WO2007139885A2 - Procédé de pyrolyse flash pour matériaux carbonés - Google Patents

Procédé de pyrolyse flash pour matériaux carbonés Download PDF

Info

Publication number
WO2007139885A2
WO2007139885A2 PCT/US2007/012386 US2007012386W WO2007139885A2 WO 2007139885 A2 WO2007139885 A2 WO 2007139885A2 US 2007012386 W US2007012386 W US 2007012386W WO 2007139885 A2 WO2007139885 A2 WO 2007139885A2
Authority
WO
WIPO (PCT)
Prior art keywords
feed
carbonaceous
boiling point
hot
high velocity
Prior art date
Application number
PCT/US2007/012386
Other languages
English (en)
Other versions
WO2007139885A3 (fr
Inventor
Donald P. Satchell
Original Assignee
Linde, Inc.
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Linde, Inc. filed Critical Linde, Inc.
Priority to CA002653185A priority Critical patent/CA2653185A1/fr
Publication of WO2007139885A2 publication Critical patent/WO2007139885A2/fr
Publication of WO2007139885A3 publication Critical patent/WO2007139885A3/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B49/00—Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated
    • C10B49/02—Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated with hot gases or vapours, e.g. hot gases obtained by partial combustion of the charge
    • 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
    • C10G9/34—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert preheated fluids, e.g. with molten metals or salts
    • C10G9/36—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert preheated fluids, e.g. with molten metals or salts with heated gases or vapours
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/58—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels combined with pre-distillation of the fuel
    • C10J3/60—Processes
    • C10J3/62—Processes with separate withdrawal of the distillation products
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/58—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels combined with pre-distillation of the fuel
    • C10J3/60—Processes
    • C10J3/64—Processes with decomposition of the distillation products
    • C10J3/66—Processes with decomposition of the distillation products by introducing them into the gasification zone
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0913—Carbonaceous raw material
    • C10J2300/093—Coal
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0913—Carbonaceous raw material
    • C10J2300/094—Char
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0953—Gasifying agents
    • C10J2300/0959—Oxygen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/16—Integration of gasification processes with another plant or parts within the plant
    • C10J2300/1696—Integration of gasification processes with another plant or parts within the plant with phase separation, e.g. after condensation

Definitions

  • the present invention relates to a high-temperature, short-residence thermal treatment method to convert carbonaceous material to material with lower normal boiling points.
  • Petroleum, natural gas, and coal currently provide about 39%, 23%, and 24% of the world's primary energy.
  • petroleum crude oil has become progressively more difficult to process due to increasing residual oil content and decreasing hydrogen to carbon ratio.
  • Athabasca bitumen production should accelerate this trend.
  • carbonaceous coal resource will likely become more important.
  • there is growing commercial incentive to find more cost-effective means to convert progressively more carbonaceous residual fuels e.g. petroleum residual oil, residual bitumen oil, oil shale, and coal, to valuable distillates.
  • the maximum temperature and minimum residence time of this process was limited to 525° C and three minutes by the maximum heat flux that can be achieved with fired heater.
  • resid conversion in thermal cracker and delayed coker unit operations are typically limited by the maximum temperature and heat flux that can be, achieved in a fired heater.
  • U.S. Patent No. 2,906,695 teaches that much higher thermal cracking and coking temperatures can be achieved by contacting the residual oil feed with a stream of hot coke particles.
  • fluidized bed cokers typically achieve higher distillate yields than delayed cokers.
  • one disadvantage of the fluidized bed coker is the coke product is much more difficult to grind and burn than the delayed coke product.
  • FIG. 1 summarizes the effects to temperature and time on distillate yield using a published Athabasca bitumen thermal cracking and coking model (Murray R. Gray, William C.
  • Vh Vh
  • U.S. Patent No. 4,545,890 teaches that the distillate yield from a hydrogen donor coal liquefaction process increases with increasing temperature and decreasing residence time.
  • U.S. Patent No. 4,048,053 teaches that the maximum distillate yield can by achieved by contacting coal with hot hydrogen at a temperature greater than 400 0 C and residence time between 2 milliseconds and 2 seconds.
  • U.S. Patent No. 5,110,452 maximizes distillate yield by heating to 1000° to 2000 0 F (538 to 1093 0 C) at a rate greater than 10,000° F/second (5,538° C/second) with a hot gas from a partial oxidation unit operation.
  • FIG. 1 The calculations in FIG. 1 indicate that high conversion of resid to distillates with a heavy oil by-product with reasonable toluene insoluble levels requires high temperature and short residence time operation.
  • FIG. 2 presents the characteristics of the temperature profile required to meet these requirements. Clearly, both very high heating rates and cooling rates are required. Unfortunately, earlier processes only provide methods to achieve very high heating rates or cooling rates, but not both. Fluidized bed cokers and catalytic cracking reactors achieve very high heating rates by contacting oil feed with a much larger mass of hot coke or catalyst as a thin film. However, the large thermal mass of the hot solids makes rapid quenching of the reactants impractical. Therefore, fluidized bed cokers and catalytic crackers can not achieve the cooling rates indicated in FIG. 2.
  • reaction products from a conventional fired heater thermal cracking furnace can be cooled very quickly by intimate mixing with a cool quench fluid, typically a distillate oil or water.
  • a cool quench fluid typically a distillate oil or water.
  • the coke formation rate in the thermal cracking heating coils can only be controlled by limiting the heating rate to rates that are much lower than the heating rates indicated on FIG. 2. Therefore, a conventional fired heater can achieve the required cooling rate, but not heating rate.
  • This invention uses a completely different method to achieve both the required heating and cooling rates indicated in FIG. 2.
  • the present invention provides for a method to use an annular hot, high velocity gas stream to rapidly heat a coaxial carbonaceous stream.
  • This invention utilizes hot supersonic jets with appropriate shape, mechanical energy, and thermal energy to achieve the rapid heating rate indicated on FIG. 2.
  • this invention uses an annular hot, high velocity jet that completely surrounds the cylindrical oil feed stream.
  • This large mechanical energy input dramatically increases the surface area for mass and energy transfer and increases the oil temperature by the conversion of mechanical energy to thermal energy.
  • one can achieve rapid oil heating rates, with minimum localized overheating, by using a hot, high velocity jet at the desired reaction temperature with sufficient mechanical energy to heat the oil feed to the desired reaction temperature.
  • the predominately gaseous flash pyrolysis reactor products can be very quickly cooled using atomized quench oil with a moderate boiling point.
  • a method for the conversion of a carbonaceous feed material to a carbonaceous material with lower normal boiling point comprising means to a) produce a hot gas at elevated pressure; b) convert said hot gas at elevated pressure to a hot high velocity gas jet or array of jets at lower pressure; c) feed carbonaceous feed material mesial to the hot, high velocity jet or array of jets to rapidly heat the carbonaceous feed material; d) provide sufficient residence time to achieve the desired conversion of the carbonaceous feed material to lower boiling point material; and e) rapidly cool the lower boiling point material reaction products.
  • a pyrolysis process for converting a feed carbonaceous material having a first boiling point to a carbonaceous material having a second lower norma) boiling point comprising the steps: a) heating said feed carbonaceous material to a desired reaction temperature; b) cooling the reaction products produced in step (a); and c) recovering said reaction products.
  • a process for converting a feed carbonaceous material having a first normal boiling point to a carbonaceous material having a second lower normal boiling point comprising directing a high velocity hot gas stream to said feed carbonaceous material, cooling the reaction products of the heating of said feed carbonaceous material, and recovering said reaction products.
  • FIG. 1 is a graph that summarizes the typical relationship between the resid conversion to distillates, product-to-feed mass ratio of toluene insoluble species, operating temperature, and residence time.
  • FIG. 2 is a plot of a typical temperature profile required to achieve a high resid-to-distillate with and heavy residual oil by-product.
  • FIG. 3 is a sketch of a burnjector lance to produce an annular hot, high velocity gas jet to rapidly heat a coaxial carbonaceous stream.
  • FIG. 4 summarizes the effect of the steam coolant-to-oxygen feed ratio on the burnjector key stream properties.
  • FIG. 5 is a plot of the oxygen and fuel gas requirement as a function of the cooling steam-to-oxygen feed ratio.
  • FIG. 6 is a simplified process sketch of a flash pyrolysis system to convert a liquid carbonaceous material to distillates and a heavy oil.
  • FIG. 7 is a block flow diagram for a flash pyrolysis system to convert solid carbonaceous materials to distillates.
  • FIG. 1 The calculations in FIG. 1 indicate that high conversion of resid to distillates with a heavy oil by-product with reasonable toluene insoluble levels requires high temperature and short residence time operation.
  • FIG. 2 presents the characteristics of the temperature profile required to meet these requirements. Clearly, both very high heating rates and cooling rates are required. Unfortunately, earlier processes only provide methods to achieve very high heating rates or cooling rates, but not both. Fluidized bed cokers and catalytic cracking reactors achieve very high heating rates by contacting oil feed with a much larger mass of hot coke or catalyst as a thin film. However, the large thermal mass of the hot solids makes rapid quenching of the reactants impractical. Therefore, fluidized bed cokers and catalytic crackers can not achieve the cooling rates indicated in FIG. 2.
  • reaction products from a conventional fired heater thermal cracking furnace can be cooled very quickly by intimate mixing with a cool quench fluid, typically oil or water.
  • a cool quench fluid typically oil or water.
  • the coke formation rate in the thermal cracking heating coils can only be controlled by limiting the heating rate to rates that are much lower than the heating rates indicated on FIG. 2. Therefore, a conventional fired heater can achieve the required cooling rate, but not heating rate.
  • This invention uses a completely different method to achieve both the required heating and cooling rates indicated in FIG. 2.
  • FIG. 3 is used to illustrate the equipment and method used to produce an annular and hot, high velocity gas jet S8 to rapidly heat the cylindrical mesial carbonaceous stream S9.
  • This apparatus is very similar to the apparatus that is described in U.S. Patent No. 6,910,431.
  • the bumjector lance consists of an outer body 1 and inner body 2 that is separated by the annular combustion chamber 5 and convergent-divergent nozzle 6.
  • the carbonaceous material feed S1 , fuel feed S2, substantially pure oxygen feed S3, and coolant S4 feed enter the burnjector lance at the proximal end 3.
  • the carbonaceous material feed S1 can be any material that contains carbon. It may include gaseous, liquid, or solid carbon containing material or mixtures in any proportion.
  • a residual carbonaceous material has some species with a normal boiling point greater than 524° C. Carbonaceous material species with normal boiling points less than 524° C are considered distillates.
  • a liquidus residual carbonaceous material contains some species with normal boiling points greater than 524° C with an apparent viscosity less than or equal to 1000 centipoises at 300° C. Petroleum resid, petroleum tar, coal tar, bitumen, and by-products from catalytic or non-catalytic cracking processes are representative examples of residual liquid carbonaceous feed materials.
  • Solid carbonaceous material has an apparent viscosity greater than 1000 centipoises.
  • Coal and oil shale are representative examples of solid carbonaceous feed materials.
  • the solid carbonaceous material feed would typically be admixed with a gaseous and/or liquid carrier material.
  • Typical gaseous carrier materials for solid carbonaceous materials could include hydrocarbon molecules with less than eight carbon atoms per molecule, steam, nitrogen, and argon in any proportion.
  • Liquid carrier materials for solid carbonaceous materials could include petroleum liquids, coal derived liquids, or water in any proportion.
  • Typical examples of gaseous carbonaceous feed materials would include ethane, propane, and butane for the production of hydrogen and the corresponding olefin.
  • the fuel feed S2 may be any material with a heat of combustion with air at 25° C and 1 atmosphere that is greater than 5,000 joules per gram of fuel.
  • the fuel feed is preferably a gas or a liquid.
  • Typical gaseous fuel feeds would include any hydrocarbon mixture at a temperature that is above its dew point at the burnjector operating pressure and less than 400° C.
  • a hydrocarbon is any species that contains some carbon and hydrogen atoms. Hydrocarbons would typically also contain some sulfur, oxygen, and nitrogen atoms. Carbon monoxide and hydrogen are useful examples of gaseous non- hydrocarbon fuels.
  • Liquid fuel feed would include any mixture of hydrocarbon species that are fed to the burnjector lance at a temperature below its bubble point temperature at the burnjector operating pressure. Solid fuels are preferably converted to gaseous or liquid fuels via gasification, or similar process, prior to feeding to the burnjector lance.
  • the oxidant S3 feed is preferably substantially pure oxygen, which is preferably greater than 70 molar percent O 2 , more preferably greater than 90 molar percent O 2 , and most preferably greater than 95 molar percent O 2 .
  • the burnjector lance S4 coolant is preferably, water, steam, or steam with a water mist.
  • the fuel feed S2 enters the burnjector lance though a conduit 7 that is in flow communication with the fuel feed S2 radial distribution header 8.
  • a conduit 9 maintains flow communication between the fuel feed S2 radial distribution header 8 and the annular combustion chamber 6.
  • the cross- sectional area of the fuel S2 radial distribution header 8 is sufficient to maintain a substantially uniform pressure at the proximal end of the fuel feed conduit 9 to the annular combustion chamber 5.
  • the fuel feed conduit may be a continuous curvilinear conduit (as shown on FIG. 3) or roughly equally distributed discrete apertures.
  • the oxidant S3 feed enters the burnjector lance though a conduit 10 that is in flow communication with the oxidant S3 feed radial distribution header 11.
  • a conduit 12 maintains flow communication between the oxidant S3 feed radial distribution header 11 and the annular combustion chamber 5.
  • the cross-sectional area of the oxidant S3 feed radial distribution header 11 is sufficient to maintain a substantially uniform pressure at the proximal end of the oxidant feed conduit 12 to the annular combustion chamber 5.
  • the fuel feed conduit 9 enters the annular combustion chamber 5 juxtaposed, and in close proximity, to oxidant feed conduit 12.
  • the fuel S2 and oxidant S3 streams are mixed at the proximal end of the annular combustion chamber 5.
  • Any conventional means may be used to initiate combustion.
  • a spark ignition source to initiate and maintain combustion.
  • one may preheat the S2 fuel stream to a temperature above its auto thermal ignition temperature at the burnjector operating oxygen partial pressure to ensure prompt ignition and reliable combustion.
  • species with low auto thermal ignition temperatures e.g., hydrogen sulfide
  • a catalyst may be added to lower the auto ignition temperature. In this case a portion or all of the S4 coolant stream would preferably be added to S2 fuel and/or the S3 oxidant streams to control the adiabatic flame temperature.
  • this catalytic combustion system would be similar to catalytic combustion systems used in stationary natural gas turbines for the production of electrical energy.
  • this catalytic combustion system would be similar to catalytic combustion systems used in aircraft fan jet engines.
  • Either catalytic combustion system could be used to preheat the S2 fuel and/or the S3 oxidant stream to a temperature in excess of the auto thermal ignition temperature to ensure stable combustion in a subsequent non-catalytic combustion step.
  • the S2 fuel and S3 oxidant feeds are contacted for a sufficient time to substantially complete combustion, typically between 10 millisecond and 2 seconds.
  • the bumjector S4 coolant feed stream typically enters the burnjector inner body 2 at the proximal end 3 through conduit 13 and flows into the inner body 2 S4 coolant feed radial header 14.
  • the cross-sectional area of the S4 coolant radial header 14 is sufficient to provide an essentially constant pressure at the proximal end of coolant conduit 15.
  • the S4 coolant leaves the S4 coolant radial header 14 and flows axially in conduit 15 toward the distal end 4 of the burnjector lance. Then, the coolant flows in 16 toward the burnjector proximal end 3 to the inner body 2 coolant product radial header 17.
  • the coolant in conduits 15 and 16 prevent overheating and coking of the carbonaceous material feed S1 in the burnjector central conduit 23.
  • the coolant flows from the inner body 2 coolant product radial header 17 to the outer body 1 coolant feed radial header 19 via conduit 18.
  • the S4 coolant flows axially in conduit 20 toward the distal end 4 of the burnjector and then flow axially in conduit 21 toward the proximal end 3 of the burnjector.
  • the S4 coolant can optionally be discharged from the proximal end of the bumjector.
  • the preferred embodiment of this invention is to discharge the S6 heated coolant through nozzle 22 in the annular combustion chamber 5. Then, the heated coolant stream 6 combines with the combustion products S5 to form the convergent- divergent nozzle 6 feed S7.
  • the temperature of the convergent-divergent nozzle 6 feed S7 is preferably between 3500° and 1000 0 C, more preferably between 2500° and 1250 0 C, most preferably between 1500° and 2000 0 C.
  • the ratio of the convergent-divergent nozzle 6 feed S7 pressure to S10 reactor exit pressure is preferably between 2:1 and 20:1, more preferably between 2:1 and 10:1, most preferably between 3:1 and 5:1.
  • the burnjector may be equipped with a curvilinear convergent-divergent nozzle 6 as shown in Section B-B on FIG. 3.
  • the curvilinear convergent-divergent nozzle 6 may form a circle as shown in the B-B section on FIG. 3.
  • the B-B section of the curvilinear convergent-divergent nozzle 6 may have unequal major axes to form an elliptical shape.
  • the B-B section of the curvilinear convergent- divergent nozzle 6 may form any closed geometric shape.
  • the axis of the convergent-divergent nozzle 6 and the S8 jet may be parallel to the axis of the carbonaceous material feed conduit 23 as shown on FIG. 3.
  • the axis of the convergent-divergent nozzle 6 may be inclined to produce a S8 jet that intersects the carbonaceous material stream downstream of the distal end 4 of the burnjector lance 1.
  • the burnjector lance may also be equipped with an array of discrete convergent-divergent nozzles as shown in B-B' section on FIG. 3. These convergent nozzles may be equally spaced along the circumference of a circle, as shown in B-B' section on FIG. 3, or in any other arrangement.
  • the axis of the discrete convergent-divergent nozzles may be positioned to maximize mechanical and thermal energy transfer to the carbonaceous material S9 stream. Any combination of or arrangement of curvilinear and discrete convergent-divergent nozzles may be used.
  • the S8 jet temperature is preferably in the 500° to 2500° C temperature range, more preferably in the 600° to 2000 0 C temperature range, most preferably in the 700 0 C to 1500° C temperature range.
  • the jet velocity is preferably greater than 500 meters per second, more preferably greater than 1000 meters per second, and most preferably greater than 1500 meters per second.
  • a means 24 is provided to attach the burnjector lance to a reaction vessel 25.
  • burnjector mechanical designs that are capable of producing hot and high velocity gas stream S8 that can rapidly heat the carbonaceous stream S9.
  • one could utilize a cylindrical combustion chamber, rather than the annular combustion chamber shown on FIG. 3, to further decrease the heat transfer rate to the carbonaceous material feed S1.
  • the scope of this invention includes any means to produce an annular, hot, high velocity gas jet to rapidly heat a mesial carbonaceous stream.
  • the burnjector coolant S4 coolant feed provides cooling for the burnjector lance outer body 1 and inner body 2.
  • the S4 coolant feed rate also affects the thermal and mechanical energy content of the stream S8 jet.
  • FIG. 4 summarizes the typical effect of changes in the S4 coolant to S3 oxidant feed ratio. Increasing the S4 coolant to S3 oxidant feed ratio decreases the heat transferred from the annular combustion chamber 5 to the burnjector outer body 1 and inner body 2, increases the burnjector outer body 1 and inner body 2 cooling, and increases the mechanical energy of the S8 jet.
  • FIG. 5 shows that higher oxygen and fuel feed rates are required to achieve these benefits.
  • FIG. 6 is a simplified process flow sketch for a flash pyrolysis system 30 that uses the hot, high velocity gas stream S8 (see FIG. 3) to convert liquid carbonaceous materials in stream S1 to distillates.
  • the commercially most important liquid carbonaceous streams are bitumen and heavy crude oil.
  • these very carbonaceous materials are typically partially converted to distillates via coking or resid hydrocracking unit operations. Resid hydrocracking produces high quality liquid products, but is relatively very expensive. Coking, on the other hand, is a much less costly unit operation, but produces a lower distillate yield and a problematic petroleum coke by-product.
  • the flash pyrolysis system uses high temperature and short contact time to cost-effectively produce S16 light oil and 13 heavy oil products that can be further upgraded in an upgrader to produce a synthetic crude product or further upgraded to salable petroleum products in a petroleum refinery.
  • the flash pyrolysis system 30 uses the combination of a burnjector lance 1, reactor 25, and quench zone 26 to achieve high-temperature and short residence time thermal cracking operating conditions.
  • the reactor 25 is preferably refractory 26 lined to prevent overheating of cylindrical wall.
  • the reactor preferably has a height to diameter ratio greater than 1 :1, more preferably greater than 5:1 , most preferably greater than 10: 1.
  • the reactor 25 preferably has a cylindrical cross section.
  • the reactor operating temperature is preferably in the 500° to 1000 0 C temperature range, more preferably in the 550° to 900 0 C temperature range, most preferably in the 600° C to 800° C temperature range.
  • the reactor 25 operating pressure is preferably in the 0.2 to 6 bar range absolute pressure range, more preferably in the 1 to 5 bar absolute pressure range relative, most preferably in the 2 to 3 bar absolute pressure range.
  • the ratio of the absolute pressure of the combustion chamber 5 of the burnjector lance 1 to the pressure of reactor 25 is preferably between 2:1 and 20:1, more preferably between 2:1 and 10:1 , most preferably between 3:1 and 5:1.
  • the reactor operates with a steam partial pressure preferably greater than 0.1 bar, more preferably greater than 0.5 bar, and most preferably greater than 1 bar.
  • Steam has two functions in the pyrolysis reactor 25. First, steam is known to decrease the coking rate by termination of free radical polymerization reactions. Second, steam can remove soot from the pyrolysis reactor walls via a well established reaction [2H 2 O (g) + C -> CO 2 (g) + 4 H 2 (g)] at the pyrolysis reactor operating conditions.
  • the residence time in the reactor 25 is limited to ensure that the mass fraction of the material in the S1 feed with normal boiling points greater than 524° C that is converted to material with normal boiling points less than 524 0 C is preferably in the 0.5 to 0.95 range, more preferably in the 0.6 to 0.9 range, most preferably in the 0.7 to 0.85 range.
  • FIG. 2 provides guidance for required residence time for a typical Athabasca bitumen carbonaceous feed material.
  • a quench oil stream S11 is used to very rapidly cool the pyrolysis reactor 25 product stream S10 to a temperature that is preferably between 425° and 200° C 1 more preferably between 400° and 250° C, and most preferably 375° and 300° C.
  • a conventional phase separator 27 is used to remove the resulting heavy oil S13 stream.
  • the remaining vapor product S12 may be advantageously used to produce S4 steam coolant stream for the burnjector lance 1 and S15 export steam.
  • a mist generator 29 may be advantageously used to improve the temperature control of the burnjector inner body 2.
  • a portion of the unconverted residual material in the heavy oil S13 may be advantageously recycled to the carbonaceous feed S1.
  • the balance of the unconverted residual material may advantageously be used to produce hydrogen, using standard partial oxidation and purification techniques, to upgrade the distillate products.
  • FIG. 7 is a block flow diagram for a process to convert pulverized coal S17 to a distillate product S26.
  • the basic approach is to add a process derived residual oil hydrogen donor solvent S18 to the pulverized coal S17 feed to form the S1 feed to the flash pyrolysis system 30.
  • the burnjector design concept on FIG. 3 and the flash pyrolysis system 30 on FIG. 6 are also appropriate for treating solid carbonaceous materials.
  • a moderate molecular weight and relative aliphatic anti- solvent S23 are used to remove ash and char from the heavy oil S22 product from the flash pyrolysis system 30 in a conventional solid-liquid separator 32.
  • the solid-liquid separator overflow 24, flash pyrolysis system 30 light oil S21 are fed to the distillation system 33 to produce fuel gas, recycle anti-solvent oil S23, distillate product S26, and residual oil S27.
  • the char and ash rich underflow S25 from the solid-liquid separator is fed to the char gasification step 35 to produce hydrogen 28 for the hydrogenation step 34 and supplemental fuel gas 20 for the flash pyrolysis system 30 bumjector lance 1.
  • the hydrogenation step 34 increases the alpha hydrogen content of the aromatic residual oil 27 to produce an effective recycle hydrogen donor solvent S18.
  • the recycle hydrogen donor solvent S18 facilitates liquefaction of the S17 pulverized coal feed.
  • Table 1 summarizes the vacuum bitumen resid feed properties.
  • Table 2 presented below shows a component material balance for flash pyrolysis system treating 10,000 barrels per day of the bitumen in Table 2.
  • This example selects operating conditions capable of achieving 85 weight percent conversion of species in the feed with normal boiling points greater than 525 0 C to species with boiling points less than 525° C with toluene insoluble production equal to the feed toluene insoluble content.
  • high performance coking processes would a coke yield ⁇ 25 weight percent of the resid feed in Table 1.
  • the spatial efficiency of refining unit operations are usually express in terms of liquid hourly space velocity, the ratio of the volume of oil treated per hour to the reactor volume.
  • the flash pyrolysis reactor has a space velocity of 6.4 hours "1 , which is much greater than conventional thermal cracking or coking processes.
  • the unconverted residual oil from the flash pyrolysis reactor is advantageously used to produce hydrogen, using standard partial oxidation and purification techniques, to upgrade the distillate products.
  • the partial oxidation plants treating liquid carbonaceous feeds are substantially less costly and troublesome than the corresponding plant treating a solid carbonaceous feed.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Materials Engineering (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

Cette invention concerne des procédés permettant de pyrolyser des matériaux carbonés afin d'obtenir des matériaux carbonés présentant des points d'ébullition plus bas. Le procédé décrit dans cette invention consiste à chauffer le matériau carboné à une température de réaction souhaitée puis à maintenir ce matériau carboné en contact avec la chaleur pendant un laps de temps suffisant pour obtenir une réaction souhaitée jusqu'à obtention de matériaux carbonés à point d'ébullition plus bas, puis à refroidir rapidement les produits de la réaction souhaitée. La source de chaleur est un jet qui applique des flux de gaz chauds et à grande vitesse au matériau carboné devant être chauffé.
PCT/US2007/012386 2006-05-26 2007-05-22 Procédé de pyrolyse flash pour matériaux carbonés WO2007139885A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CA002653185A CA2653185A1 (fr) 2006-05-26 2007-05-22 Procede de pyrolyse flash pour materiaux carbones

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US80864706P 2006-05-26 2006-05-26
US60/808,647 2006-05-26
US11/709,546 2007-02-22
US11/709,546 US20070272538A1 (en) 2006-05-26 2007-02-22 Flash pyrolosis method for carbonaceous materials

Publications (2)

Publication Number Publication Date
WO2007139885A2 true WO2007139885A2 (fr) 2007-12-06
WO2007139885A3 WO2007139885A3 (fr) 2008-03-06

Family

ID=38748513

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2007/012386 WO2007139885A2 (fr) 2006-05-26 2007-05-22 Procédé de pyrolyse flash pour matériaux carbonés

Country Status (3)

Country Link
US (1) US20070272538A1 (fr)
CA (1) CA2653185A1 (fr)
WO (1) WO2007139885A2 (fr)

Families Citing this family (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007112570A1 (fr) 2006-04-03 2007-10-11 Pharmatherm Chemicals Inc. Procédé et produit d'extraction thermique
US7905990B2 (en) 2007-11-20 2011-03-15 Ensyn Renewables, Inc. Rapid thermal conversion of biomass
US20100038288A1 (en) * 2008-08-12 2010-02-18 MR&E, Ltd. Refining coal-derived liquid from coal gasification, coking, and other coal processing operations
US8470134B2 (en) * 2009-07-14 2013-06-25 C2O Technologies, Llc Process for treating coal by removing volatile components
WO2011008832A2 (fr) * 2009-07-14 2011-01-20 C20 Technologies, Llc Processus permettant de traiter le charbon agglomérant ou le charbon bitumeux en supprimant les composants volatils
US8366882B2 (en) * 2009-07-14 2013-02-05 C20 Technologies, Llc Process for treating agglomerating coal by removing volatile components
WO2011060539A1 (fr) 2009-11-18 2011-05-26 G4 Insights Inc. Procédé et système d'hydrogazéification de la biomasse
CA2781204C (fr) 2009-11-18 2018-05-01 G4 Insights Inc. Methanisation de la biomasse amelioree par sorption
SE534818C2 (sv) * 2010-05-06 2012-01-10 Cortus Ab Förfarande och anordning för införande av pulverformigt material i en förgasningsreaktor, varvid anordningen innefattar en lavaldysa
US20110284359A1 (en) 2010-05-20 2011-11-24 Uop Llc Processes for controlling afterburn in a reheater and for controlling loss of entrained solid particles in combustion product flue gas
US8499702B2 (en) 2010-07-15 2013-08-06 Ensyn Renewables, Inc. Char-handling processes in a pyrolysis system
US8383871B1 (en) 2010-09-03 2013-02-26 Brian G. Sellars Method of hydrogasification of biomass to methane with low depositable tars
WO2012037454A2 (fr) 2010-09-16 2012-03-22 Rinker Franklin G Traitement du charbon avec, en plus, régulation de la biomasse et des matières volatiles
US9441887B2 (en) 2011-02-22 2016-09-13 Ensyn Renewables, Inc. Heat removal and recovery in biomass pyrolysis
US8968520B2 (en) 2011-06-03 2015-03-03 National Institute Of Clean And Low-Carbon Energy (Nice) Coal processing to upgrade low rank coal having low oil content
US9005322B2 (en) 2011-07-12 2015-04-14 National Institute Of Clean And Low-Carbon Energy (Nice) Upgrading coal and other carbonaceous fuels using a lean fuel gas stream from a pyrolysis step
US9347005B2 (en) 2011-09-13 2016-05-24 Ensyn Renewables, Inc. Methods and apparatuses for rapid thermal processing of carbonaceous material
US9074138B2 (en) 2011-09-13 2015-07-07 C2O Technologies, Llc Process for treating coal using multiple dual zone steps
US10400175B2 (en) 2011-09-22 2019-09-03 Ensyn Renewables, Inc. Apparatuses and methods for controlling heat for rapid thermal processing of carbonaceous material
US9044727B2 (en) 2011-09-22 2015-06-02 Ensyn Renewables, Inc. Apparatuses and methods for controlling heat for rapid thermal processing of carbonaceous material
US10041667B2 (en) 2011-09-22 2018-08-07 Ensyn Renewables, Inc. Apparatuses for controlling heat for rapid thermal processing of carbonaceous material and methods for the same
US9109177B2 (en) 2011-12-12 2015-08-18 Ensyn Renewables, Inc. Systems and methods for renewable fuel
US9670413B2 (en) 2012-06-28 2017-06-06 Ensyn Renewables, Inc. Methods and apparatuses for thermally converting biomass
AU2014205416A1 (en) 2013-01-09 2015-07-09 C2O Technologies Llc Process for treating coal to improve recovery of condensable coal derived liquids
US20140197072A1 (en) * 2013-01-14 2014-07-17 Conocophillips Company Oil upgrading within combustion exhaust
CN104162399B (zh) * 2013-05-20 2017-10-31 宁波凯诚环保科技有限公司 酯化反应釜及酯化反应方法
WO2014210150A1 (fr) 2013-06-26 2014-12-31 Ensyn Renewables, Inc. Systèmes et procédés pour carburant renouvelable
US9327320B1 (en) 2015-01-29 2016-05-03 Green Search, LLC Apparatus and method for coal dedusting
US10337726B2 (en) 2015-08-21 2019-07-02 Ensyn Renewables, Inc. Liquid biomass heating system
BR112019013387B1 (pt) 2016-12-29 2023-03-28 Ensyn Renewables, Inc Desmetalização de biomassa
CA3075302A1 (fr) * 2017-09-07 2019-03-14 Mcfinney, Llc Procedes de traitement biologique de substances contenant des hydrocarbures et systeme permettant leur mise en oeuvre

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4326944A (en) * 1980-04-14 1982-04-27 Standard Oil Company (Indiana) Rapid hydropyrolysis of carbonaceous solids
US6910431B2 (en) * 2002-12-30 2005-06-28 The Boc Group, Inc. Burner-lance and combustion method for heating surfaces susceptible to oxidation or reduction

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4003820A (en) * 1975-10-07 1977-01-18 Cities Service Company Short residence time hydropyrolysis of carbonaceous material
US3997423A (en) * 1975-10-20 1976-12-14 Cities Service Company Short residence time low pressure hydropyrolysis of carbonaceous materials
US4048053A (en) * 1975-10-30 1977-09-13 Cities Service Company Upgrading solid fuel-derived tars produced by short residence time low pressure hydropyrolysis
US4278446A (en) * 1979-05-31 1981-07-14 Avco Everett Research Laboratory, Inc. Very-high-velocity entrained-bed gasification of coal
US4446004A (en) * 1982-12-23 1984-05-01 Mobil Oil Corporation Process for upgrading vacuum resids to premium liquid products
US4545890A (en) * 1984-04-30 1985-10-08 Lummus Crest, Inc. Coal liquefaction and hydrogenation
US4698147A (en) * 1985-05-02 1987-10-06 Conoco Inc. Short residence time hydrogen donor diluent cracking process
US5110452A (en) * 1987-06-08 1992-05-05 Carbon Fuels Corporation Method of refining coal by catalyzed short residence time hydrodisproportionation to form a novel coal-derived fuel system
US5662868A (en) * 1994-09-22 1997-09-02 Stone & Webster Engineering Corporation Short residence time cracking apparatus and process

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4326944A (en) * 1980-04-14 1982-04-27 Standard Oil Company (Indiana) Rapid hydropyrolysis of carbonaceous solids
US6910431B2 (en) * 2002-12-30 2005-06-28 The Boc Group, Inc. Burner-lance and combustion method for heating surfaces susceptible to oxidation or reduction

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CAMERON: 'Optimised energy injection for the Electric Arc Furnace: the replacement of part of the electrical power used in an electric arc?' STEEL TIMES INTERNATIONAL 01 February 2002, *

Also Published As

Publication number Publication date
US20070272538A1 (en) 2007-11-29
CA2653185A1 (fr) 2007-12-06
WO2007139885A3 (fr) 2008-03-06

Similar Documents

Publication Publication Date Title
WO2007139885A2 (fr) Procédé de pyrolyse flash pour matériaux carbonés
US8748686B2 (en) Conversion of co-fed methane and low hydrogen content hydrocarbon feedstocks to acetylene
US9487400B2 (en) Process to prepare a mixture of hydrogen and carbon monoxide from a liquid hydrocarbon feedstock containing a certain amount of ash
US20100059411A1 (en) Flash processing of asphaltic residual oil
JPH0421717B2 (fr)
CN107429175B (zh) 用于制备合成气体的方法和设施
JPH0329112B2 (fr)
EP2326700A2 (fr) Dispositif convertissant une matière carbonée en gaz de synthèse et procédés associés
CA2708048A1 (fr) Methode de craquage des huiles lourdes
US4952743A (en) Process and apparatus for the conversion of hydrocarbons
JPH0416512B2 (fr)
US4159238A (en) Integrated coal liquefaction-gasification process
GB2024847A (en) Cracking hydrocarbons
CA1127574A (fr) Methode de reformage du naphte a liquefaction-gazeification integree de la houille
US4159237A (en) Coal liquefaction process employing fuel from a combined gasifier
US4159236A (en) Method for combining coal liquefaction and gasification processes
CN101454425A (zh) 含碳物质的闪热裂方法
US20040104147A1 (en) Heavy oil upgrade method and apparatus
WO1980001281A1 (fr) Procede de liquefaction-gazeification du charbon comprenant le reformage du naphta produit
RU2340654C2 (ru) Способ и реактор для облагораживания тяжелой нефти и полученный с помощью них продукт
EP0005900A1 (fr) Installation intégrée de liquéfaction-gazéification de charbon
Robinson Coking and Visbreaking
Platvoet et al. Refining and petrochemical industries
US20110132805A1 (en) Heavy oil cracking method
JPS60255889A (ja) 炭化水素から石油化学製品を製造する熱分解法

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 200780019102.6

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 07795286

Country of ref document: EP

Kind code of ref document: A2

WWE Wipo information: entry into national phase

Ref document number: 2653185

Country of ref document: CA

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 07795286

Country of ref document: EP

Kind code of ref document: A2