CN101454425A - Flash pyrolysis method for carbonaceous materials - Google Patents
Flash pyrolysis method for carbonaceous materials Download PDFInfo
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- CN101454425A CN101454425A CNA2007800191026A CN200780019102A CN101454425A CN 101454425 A CN101454425 A CN 101454425A CN A2007800191026 A CNA2007800191026 A CN A2007800191026A CN 200780019102 A CN200780019102 A CN 200780019102A CN 101454425 A CN101454425 A CN 101454425A
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Abstract
Methods are disclosed for pyrolizing carbonaceous materials to carbonaceous materials having lower boiling points by heating the carbonaceous material to a desired reaction temperature and holding the carbonaceous material in contact with the heat for a sufficient time to achieve the desired reaction to a lower boiling point carbonaceous materials, then rapidly cooling the desired reaction products. The heating source is a jet which will provide hot and high velocity gas streams to the carbonaceous material to be heated.
Description
The friendship justice of related application is quoted
The application requires in the right of priority of the U.S. Provisional Patent Application sequence number 60/808647 of submission on May 26th, 2006.
Technical field
The present invention relates to a kind of carbonaceous material is changed into and have more high temperature, the short heat treating method that stops of the material of substandard boiling point.
Background technology
Oil, Sweet natural gas and coal provide 39%, 23% and 24% of the main energy in about world at present.For many years, along with limited oil reserve is exploited, ever-increasing irreducible oil content and the hydrogen-to-carbon ratio rate that constantly reduces make petroleum crude oil more and more difficult.The speed that rises fast of Athabasca (Athabasca) pitch production at present will be accelerated this trend.In addition, along with the exhaustion of Sweet natural gas and oil reserve, the colliery resource that contains more carbon will become more important.The result is, the commercial power that continues to increase impels people to seek to save more the method for transformation of cost, and these methods can change into valuable distillment as fuel oil residuum, residual pitch oil, resinous shale and coal with increasing carbonaceous residual fuel.
Thermal cracking processes, especially coking have become the essential elements operation of upgrading Residual oil (upgrading residual oil).Please see example: " refining of petroleum handbook (the Handbook of Petroleum Processing) " of Stan Jones and Peter Pajado (editor), Springer (Dordrecht, Holland), the 447th～481 page.Present technical process clearlys show that along with the rising of service temperature, the distillment productive rate that is obtained by various thermal treatment process and raw material increases.For example, United States Patent (USP) is set forth for No. 4446004: the resid feed that hydrogen treatment is crossed is carried out thermo-cracking under high temperature and short residence time(SRT), to increase the distillment productive rate to greatest extent.United States Patent (USP) is set forth for No. 4698147: by operation hydrogen donor thermal cracking process under high temperature and short residence time(SRT) condition, also can obtain maximum Residual oils and transform distillment.Yet according to the maximum heat flow that can access with fired heater, the top temperature of this technology and short residence time(SRT) are restricted to 525 ℃ and 3 minutes.The result is that top temperature that fired heater can produce and maximum heat flow have limited the Residual oil transformation efficiency in heat cracker and the delayed coking unit operation usually.
United States Patent (USP) is set forth for No. 2906695: by the irreducible oil charging is contacted with hot coke granule stream, can obtain obviously higher thermo-cracking temperature and coking temperature.According to expectation, fluidized carbonization equipment can obtain the distillment productive rate higher than delayed coking equipment usually.But, fluidized carbonization equipment shortcoming is that its coke produced is difficult to mill and burn than delayed coking equipment product more.Obviously, people are more prone to obtain the by product of high distillment productive rate and less trouble.But better, people are willing to be intended to not have or have only under the situation that seldom coke produces obtain higher distillment productive rate.
Thermocatalyst is used in fluid catalytic cracking unit operation, so that oily charging is heated rapidly to cracking temperature, thereby improves process efficiency.United States Patent (USP) is set forth for No. 5662868: the short residence time helps the more carbon raw material of cracking.Canadian patent application is set forth for No. 02369288: by contacting with the sand-like logistics of hot particle, the higher temperature and the shorter residence time can make heavy oil or pitch farthest be converted into distillment.
Thermo-cracking and pyrogenic kinetic model also provide profound understanding to the cracked effect under high temperature and the short residence time(SRT).Figure-1 has summed up the raw material in the following table 1, utilize disclosed Athabasca (Athabasca) pitch thermo-cracking and coking model (Murray R.Gray, William C.McCaffrey, lftikhar Hug, Tuyet Le, " cracking in the Athabasca residue coking and the kinetics of devolatilization (Kinetics of Cracking and Devolatilization duringCoking of Athabasca Resides) ", Ind.Chem.Res., 2004,43, the 5438th～5445 page), resulting temperature and time is to the influence of distillment productive rate.Ratio (TI between the weight percentage of the weight percentage of the toluene soluble components in the thermal cracking process product and the toluene soluble components in the charging
p/ TI
f), can be used as guestimate to technological operation and remaining heavy oil by product quality.Lower (TI
p/ TI
f) ratio usually operates relevant with higher-quality remaining heavy oil product with more reliable thermal cracking process.The result of Fig. 1 hint will obtain the high conversion that distillment generates, and the heavy oil quality has only the variation of minimum degree, and the operation of high temperature and short residence time(SRT) is required.For example, service temperature is increased to 800 ℃ from 700 ℃, can be with 524 ℃
+The Residual oil maximum conversion percentage that is converted into distillment be increased to from about 23% about 80%, (TI
p/ TI
f) ratio is 2.Yet, obtain this advantage, need to use the heating and cooling speed more faster than traditional method.
Table-1 typical asphalt stock character
Other process modification investigator obtains the similar conclusion of relevant coal class charging.No. the 4545890th, United States Patent (USP) is set forth: the distillment productive rate that obtains from the hydrogen donor coal liquefaction craft, and along with temperature raises and residence time shortening and increasing.No. the 4048053rd, United States Patent (USP) is set forth: be higher than 400 ℃ and the residence time under the condition between 2 milliseconds and 2 seconds in temperature, by coal is contacted with hot hydrogen, can obtain the distillment productive rate of maximum.United States Patent (USP) is set forth for No. 5110452: with the speed greater than 10000 ℉/seconds (5538 ℃/second), use is from the partial oxidation device hot gas that obtains in service, material is heated to 1000～2000 ℉ (538～1093 ℃), can obtains maximum distillment productive rate.This shows once more, if can find a reliable and cost-effective method to obtain required high heating rate, then can relatively significantly find its potential benefit.
In other are used, used the supersonic velocity hot gas to spray and obtained very high heating rate.For example, United States Patent (USP) has been set forth a kind of oxygen fueled combustion that uses for No. 6910431 and has been produced the method that supersonic velocity sprays rapid heating surface.
The calculating of Fig. 1 shows: become to contain the distillment of heavy oil by product from the Residual oil high-degree of conversion, this by product contains an amount of toluene insolubles level, need operate under high temperature and short residence time(SRT).Fig. 2 has shown will reach the proterties that these require required thetagram.Clearly, both need the heating rate that is exceedingly fast, also needed the rate of cooling that is exceedingly fast.Unfortunately, early stage technology only can provide can obtain the method for heating rate or rate of cooling that is exceedingly fast, and can not both take into account.Fluidized carbonization equipment and catalytic cracking reaction device contact with a large amount of hot coke or film like catalyzer by making oily charging, reach the heating rate that is exceedingly fast.Yet the solid of a large amount of heat makes the quick cooling of reactant unrealistic.Therefore, fluidized carbonization equipment and catalytic cracking reaction device can't obtain the rate of cooling that Fig. 2 shows.On the other hand, the reaction product that obtains in conventional fired heater pyrocrack furnace can be by mixing cooling of being exceedingly fast with cooling fluid (normally distilled oil or water) closely.Unfortunately, the coke generating rate in the thermo-cracking heating collar can only be by being limited in heating rate than under the low speed that manys of heating rate shown in Figure 2, and ability is controlled.Therefore, conventional fired heater can obtain required rate of cooling, rather than heating rate.The present invention uses a kind of diverse method to obtain the required heating and cooling speed that Fig. 2 shows simultaneously.
Summary of the invention
The invention provides the method that a kind of high velocity air that uses annular heat comes the co-axial carbonaceous stream of rapid heating.
The supersonic velocity injection stream that this invention utilization has the heat of suitable shape, mechanical energy and heat energy reaches rapid heating speed shown in Figure 2.Can be efficiently be transformed in the oily charging in order to ensure mechanical energy from the high velocity jet of heat, the present invention used a kind of can be fully around the high velocity jet of the annular heat of cylindric oily incoming flow.Huge mechanical energy input has greatly increased the surface-area of material and energy transformation, also by mechanical energy being converted to the temperature that heat energy has improved oil plant.The result is, by use the high velocity jet of heat under required temperature of reaction, can obtain to have the heating rate of oil plant fast of minimum local superheating character, and this injection stream has enough mechanical energy, so that oily charging is heated to required temperature of reaction.Gaseous state accounts for most flash pyrolysis reactor products, can use the cooling oil of the atomizing with suitable boiling point to reach quick cooling.
In an embodiment of the invention, disclosed a kind of carbon-containing feeding is changed into and had the more method of the carbonaceous material of substandard boiling point, this method may further comprise the steps:
A) under elevated pressure, generate hot gas;
B) high-speed gas injection that the hot gas under the above-mentioned high pressure is changed into the heat under the lower pressure flows or the injection stream array;
C) carbon-containing feeding is joined the high velocity jet of heat or the central authorities (mesial) of injection stream array, with the rapid heating carbon-containing feeding;
D) provide enough residence time,, carbon-containing feeding is converted into more lower boiling material to obtain required transformation efficiency; With
E) cooling contains the more reaction product of low-boiling point material fast.
In yet another embodiment of the present invention, disclosed a kind of method for pyrolysis that the carbon-containing feeding with first boiling point can be converted into the carbonaceous material with second lower normal boiling point, this method may further comprise the steps:
A) above-mentioned carbon-containing feeding is heated to required temperature of reaction;
B) with the reaction product cooling that produces in the step (a); With
C) reclaim above-mentioned reaction product.
In yet another embodiment of the present invention, disclosed a kind of method that the carbon-containing feeding with first normal boiling point can be converted into carbonaceous material with second lower normal boiling point, this method comprises guides the high speed hot gas flow into above-mentioned carbon-containing feeding, cooling is by heating the reaction product that above-mentioned carbon-containing feeding obtains, and reclaims above-mentioned reaction product.
Description of drawings
Fig. 1 has summed up the transformation efficiency of Residual oil to distillment, the mass ratio of the toluene insolubles in product and the charging, service temperature and the typical relation between the residence time.
Fig. 2 is for reaching the high required representative temperature graphic representation of Residual oil-distillment transformation efficiency, and this distillment comprises remaining heavy oil by product.
Fig. 3 is the sketch of a burning spray gun (burnjector lance), and this spray gun produces the high-speed gas injection stream of annular heat, comes the co-axial carbonaceous stream of rapid heating.
Fig. 4 has summed up the crucial air-flow Effect on Performance of the ratio of vapor refrigerant and oxygen input to spray gun.
Fig. 5 is the figure that shows the relation between the ratio of oxygen and fuel gas requirement and cooling steam amount and oxygen input.
Fig. 6 is the simplification process sketch of flash pyrolysis system, and this system is converted into distillment and heavy oil with liquid carbonaceous material.
Fig. 7 is the block flow diagram of flash pyrolysis system, and this system is converted into distillment with solid carbonaceous substance.
Embodiment
The calculating of Fig. 1 shows: become to contain the distillment of heavy oil by product from the Residual oil high-degree of conversion, this by product contains an amount of toluene insolubles level, need operate under high temperature and short residence time(SRT).Fig. 2 has shown will reach the proterties that these require required thetagram.Very clear, both needed the heating rate that is exceedingly fast, also need the rate of cooling that is exceedingly fast.Unfortunately, early stage technology only can provide can obtain the method for heating rate or rate of cooling that is exceedingly fast, and can not both take into account.Fluidized carbonization equipment and catalytic cracking reaction device by oily charging and a large amount of hot coke or film like catalyzer are contacted, reach the heating rate that is exceedingly fast.Yet the solid of a large amount of heat makes the quick cooling of reactant unrealistic.Therefore, fluidized carbonization equipment and cat cracker can't obtain the rate of cooling that Fig. 2 shows.On the other hand, the reaction product that obtains in conventional fired heater pyrocrack furnace can be by mixing cooling of being exceedingly fast with cooling fluid (normally oil or water) closely.Unfortunately, the coke generating rate in the thermo-cracking heating collar can only be by being limited in heating rate than under the much lower speed of heating rate shown in Figure 2, could be controlled.Therefore, conventional fired heater can obtain required rate of cooling, rather than heating rate.The present invention uses a kind of diverse method to obtain the required heating and cooling speed that Fig. 2 shows simultaneously.
Fig. 3 has illustrated equipment and the method for the high-speed gas injection stream S8 that is used to produce annular heat, and this gas injection stream S8 is used for columniform its central carbon containing stream S9 that is positioned at of rapid heating.The equipment of describing in No. the 6910431st, this equipment and the United States Patent (USP) is closely similar.Spray gun is by by toroidal combustion chamber 5 with hold back diffusing type (convergent-divergent) nozzle 6 separated exocoels 1 and inner chamber 2 constitutes.Carbon-containing feeding S1, combustion gas charging S2, high purity oxygen gas charging S3 and refrigerant charging S4 enter spray gun from near-end 3.
Carbon-containing feeding S1 can be any material that contains carbon.Can comprise gaseous state, liquid state or solid-state carbonaceous material or the mixture of their arbitrary proportion.The normal boiling point of some substance classes is higher than 524 ℃ in the remaining carbonaceous material.It is overhead product that normal boiling point is lower than that 524 ℃ carbon containing species is taken as.Liquid residual carbonaceous material comprises some substance classes, and they had both had the normal boiling point that is higher than 524 ℃ and have also had the apparent viscosity of being less than or equal to 1000 centipoises under 300 ℃.The by product of fuel oil residuum, petroleum tar, coal tar, pitch and catalysis or on-catalytic cracking process is the representative of the liquid carbon-containing feeding of remnants.The apparent viscosity of solid carbon-contg material is greater than 1000 centipoises.Coal and resinous shale are exactly the representative example of solid carbon-contg charging.Usually, solid carbon-contg charging meeting mixes with the solid support material of gasiform and/or liquid state.The gaseous carrier material that is usually used in the solid carbon-contg material can comprise: the per molecule of arbitrary proportion contains hydrocarbon molecule, water vapour, nitrogen and the argon gas of 8 following carbon atoms.The liquid carrier material that is used for the solid carbon-contg material may comprise: the petroleum liquid of arbitrary proportion, coal derived liquid, or water.The example of typical gaseous state carbon-containing feeding comprises: ethane, propane and butane, and to produce hydrogen and corresponding alkene.
Fuel-feed S2 can be in 25 ℃, 1 atmospheric air when burning produce any material greater than the heat of 5000 joules/every gram fuel.Fuel-feed is gas or liquid preferably.Typical gaseous fuel charging may comprise any hydrocarbon mixture that is under certain temperature, and this temperature is higher than its dew point under the spray gun working pressure, and is lower than 400 ℃.Hydrocarbon refers to contain any kind compound of carbon atom and hydrogen atom.Hydrocarbon also comprises some sulphur, oxygen and nitrogen-atoms usually.Carbon monoxide and hydrogen are the examples of gaseous state nonhydrocarbon fuel.The liquid fuel charging can comprise that the temperature under the spray gun working pressure of importing spray gun is lower than any mixture of the hydrocarbons of its bubble point.Solid fuel is more prone to by gasification or similar technology, be converted into gaseous state or liquid fuel earlier before the input spray gun.
The oxygen that oxygenant S3 charging is preferably pure basically, the molar content of its oxygen preferably are higher than 70 moles of %, more preferably are higher than 90 moles of %, most preferably are higher than 95 moles of %.Spray gun S4 refrigerant is water, water vapor or contain the water vapor of water smoke preferably.
Fuel-feed S2 enters spray gun by conduit 7, and fluid is communicated with between the radial distribution termination 8 of conduit 7 and fuel-feed S2.Conduit 9 has been kept the radial distribution termination 8 of fuel-feed S2 and has been communicated with fluid between the toroidal combustion chamber 6.The section area of the radial distribution termination 8 of fuel-feed S2 is enough to keep the pressure of the basic homogeneous of fuel-feed conduit 9 proximal ends of leading to toroidal combustion chamber 5.This fuel-feed conduit may be a curved conduit of successive (as shown in Figure 3) or the dispersion hole that roughly is equally spaced.Similar, oxidant feed S3 enters spray gun by conduit 10, and fluid is communicated with between the radial distribution termination 11 of conduit 10 and oxidant feed S3.Conduit 12 has been kept the radial distribution termination 11 of oxidant feed S3 and has been communicated with fluid between the toroidal combustion chamber 5.The section area of the radial distribution termination 11 of oxidant feed S3 is enough to keep the pressure of the basic homogeneous of oxidant feed conduit 12 proximal ends of leading to toroidal combustion chamber 5.Fuel-feed conduit 9 and oxidant feed conduit 12 are adjacent to enter toroidal combustion chamber 5 side by side and closely.The steam of fuel S2 and oxygenant S3 mixes in the proximal end of toroidal combustion chamber 5.
Any ordinary method can be used for causing burning.For example, can use spark ignition sources to cause and keep burning.Perhaps, fuel can be flowed S2 and be preheating to and be higher than its automatic heat combustion temperature under spray gun operation oxygen partial pressure, ignite rapidly and burning reliably guaranteeing.In addition, have the material of low automatic heat combustion temperature,, can when beginning or in the course of normal operation, advantageously add among the fuel feed stream S2, to reach combustion-supporting and purpose stationary flame S5 as hydrogen sulfide.Perhaps, can add catalyzer to reduce spontaneous ignition temperature.In this case, preferably part or all of coolant flow S4 is joined among fuel sulfur S2 and/or the oxidant stream S3, with the control adiabatic flame temperature.When using gaseous fuel S2, this catalytic combustion system is similar to the catalytic combustion system of the static Sweet natural gas turbine that is used for generating electricity.When using liquid fuel S2, this catalytic combustion system is similar to the catalytic combustion system that is used for the fan-shaped jet engine of aircraft.Any one catalytic combustion system all can be used for pre-heating fuel stream S2 and/or oxidant stream S3, makes it surpass spontaneous ignition temperature, with the stable burning in non-the breaking combustion step after guaranteeing.Make fuel-feed S2 contact the sufficiently long time, so that it almost completely burns, usually between 10 milliseconds to 2 seconds with oxidant feed S3.
The refrigerant incoming flow S4 of spray gun generally enters the inner chamber 2 of spray gun by conduit 13 from near-end 3, and flows into the radially termination 14 of the refrigerant charging S4 of inner chamber 2.The section area of the radially termination 14 of refrigerant S4 is enough to be provided at the constant substantially pressure in proximal end of coolant duct 15.Refrigerant S4 leaves radially termination 14 of refrigerant S4, axially flows to then in the conduit 15 that leads to spray gun far-end 4.Then, refrigerant flows to spray gun near-end 3 along conduit 16, and the refrigerant product that enters inner chamber 2 is termination 17 radially.Refrigerant in the conduit 15 and 16 has been avoided the overheated and coking of the carbon-containing feeding S1 in the spray gun center conduit 23.Can improve temperature control by using the coolant flow S4 of saturated water vapor-water smoke as spray gun.Refrigerant is by conduit 18, from the refrigerant product of the inner chamber 2 refrigerant charging termination 19 radially that flows to exocoel 1, termination 17 radially.Then, refrigerant S4 is inflow catheter 20 axially, flows to spray gun far-end 4, and inflow catheter 21 axially again flows to spray gun near-end 3 then.Refrigerant S4 can be randomly in the near-end discharging of spray gun.Yet preferred implementation of the present invention is by the refrigerant S6 after the 22 discharging heating of the nozzle in the toroidal combustion chamber 5.Then, coolant flow after the heating 6 and products of combustion S5 form the charging S7 of converging diverging nozzle 6 together.The temperature of the charging S7 of converging diverging nozzle 6 is preferably between 3500 and 1000 ℃, more preferably between 2500 and 1250 ℃, most preferably between 1500 and 2000 ℃.The ratio of the pressure between the charging S7 of converging diverging nozzle 6 and the reactor exhaust S10 is preferably between 2: 1 and 20: 1, more preferably between 2: 1 and 10: 1, most preferably between 3: 1 and 5: 1.
Technology early provides at the guidance of design and assessment converging diverging nozzle performance (sees example: RobertH.Perry ﹠amp; Cecil H.Chilton, " chemical engineering handbook (Chemical Engineer ' sHandbook) ", the 5th edition, McGraw Hill (New York), 1973, the 5～29 pages).Shown in the B-B sectional view of Fig. 3, spray gun can be equipped with curved converging diverging nozzle 6.This curved converging diverging nozzle 6 is shown as a circle on the B-B of Fig. 3 sectional view.The B-B cross section of curved converging diverging nozzle 6 also can have unequal main shaft, to form an ellipse.The B-B cross section of curved converging diverging nozzle 6 can form closed geometric shape arbitrarily.As shown in Figure 3, the axis of this converging diverging nozzle 6 can be parallel with the axis of carbonaceous material feed conduit 23 with injection stream S8.The axis of converging diverging nozzle 6 is more prone to produce and flow to the crossing injection stream S8 of carbonaceous material stream of spray gun 1 far-end 4.
Shown in the B-B ' sectional view of Fig. 3, spray gun can also be equipped with the array of discrete converging diverging nozzle.Shown in the B-B ' sectional view of Fig. 3, these convergent nozzles may be arranged on the circumference of a circle equally spacedly, or distribute with other arrangement mode.The axis of the converging diverging nozzle that these are discrete is placed in and can conducts mechanical energy and the heat energy place to the carbonaceous material stream S9 substantially.Can use the arbitrary combination or the arrangement of curved shape, discrete converging diverging nozzle.The temperature of injection stream S8 is preferably in 500 ℃ to 2500 ℃ scopes, more preferably in 600 ℃ to 2000 ℃ scopes, most preferably in 700 ℃ to 1500 ℃ scope.The speed of injection stream is preferably greater than 500 meter per seconds, more preferably greater than 1000 meter per seconds, most preferably greater than 1500 meter per seconds.Device 24 is used for making spray gun to be fixed on the reaction vessel 25.
Obviously, much other spray gun Machine Designs are arranged, the high velocity air S8 that can produce heat comes rapid heating carbon containing stream S9.People also can improve the size of spray gun.For example, under can be in the combustion chamber constant gas residence time, the diameter by increasing spray gun reduces the ratio of the surface-area of combustion chamber to volume to length ratio, and reduces heat passage to spray gun exocoel 2 and inner chamber 1.Also can produce S8 and S9 logistics with different substantially lance configuration.For example, can utilize columniform combustion chamber, rather than toroidal combustion chamber shown in Figure 3, heat transfer rate further reduced to carbon-containing feeding S1.Thereby this scope of invention comprises any device of its central carbon containing stream of high-speed gas injection stream rapid heating that can produce annular heat.
Spray gun refrigerant charging S4 provides the cooling to spray gun exocoel 1 and inner chamber 2.The feeding rate of refrigerant S4 also influences heat energy and the mechanical energy content of injection stream S8.Fig. 4 has summed up refrigerant S4 the ratio of oxidant feed S3 has been changed the typical effects of being brought.Increase the ratio of refrigerant S4, can reduce from toroidal combustion chamber 5 to spray gun exocoel 1 and inner chamber 2 heat passage, strengthen the cooling of spray gun exocoel 1 and inner chamber 2, and increase the mechanical energy of injection stream S8 oxidant feed S3.Fig. 5 shows that will reach above-mentioned advantage needs higher oxygen and fuel-feed speed.Can increase the operational condition scope of spray gun by spray gun exocoel 1 is set up exterior cooling.
Fig. 6 is the simplification process flow sheet of flash pyrolysis system 30, and the high velocity air S8 (see figure 3) of this system's utilization heat changes into distillment with the liquid carbonaceous material among the logistics S1.The liquid carbon containing stream of tool commercial significance is pitch and heavy crude oil.At present, these carbonaceous materials partly are converted into distillment by coking or Residual oil hydrocracking unit operation usually.Residual oil hydrocracking produces high-quality liquid product, but costliness comparatively speaking very.On the other hand, coking is a more cost effective unit operation, but generates the petroleum coke by product that productive rate is lower and generation bothers of distillment.The flash pyrolysis system utilizes high temperature and short duration of contact, generate light oil product S 16 and heavy oil product S13 economically, they can further be refined in the purifier of petroleum refining source mill generates synthetic crude product, or further the refinement generates the petroleum products that can sell.
Flash pyrolysis system 30 uses spray gun 1, and reactor 25 and quench region 26 obtain the pyrolysis operations condition of high temperature and short residence time(SRT).Reactor 25 is refractory material 26 linings preferably, and is overheated to prevent the cylindrical wall wall.The height and the diameter ratio of reactor are preferably greater than 1: 1, more preferably greater than 5: 1, most preferably greater than 10: 1.Reactor 25 preferably has circular cylindrical cross section.
The service temperature of reactor is preferably in 500 ℃ to 1000 ℃ scopes, more preferably in 550 ℃ to 900 ℃ scopes, most preferably in 600 ℃ to 800 ℃ scopes.The working pressure of reactor 25 is preferably in 0.2 to 6 crust absolute pressure scope, more preferably in 1 to 5 crust absolute pressure scope, most preferably in 2 to 3 crust absolute pressure scopes.The ratio of the pressure of the absolute pressure of combustion chamber 5 and 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 in the spray gun 1.Steam partial pressure during the reactor operation is preferably greater than 0.1 crust, more preferably greater than 0.5 crust, most preferably greater than 1 crust.Water vapor has two functions in pyrolysis reactor 25.The first, water vapor can be by the terminating free-radical polymerisation processes coking rate that slows down.The second, water vapor can be by a reaction [2H who sets up under the pyrolysis reactor operational condition
2O (g)+C → CO
2(g)+4H
2(g)] remove cigarette ash on the pyrolytic reaction wall.
The residence time in the limited reactions device 25, to guarantee that normal boiling point among the charging S1 is by being converted into massfraction less than those materials of 524 ℃ preferably in 0.5 to 0.95 scope greater than 524 ℃, more preferably in 0.6 to 0.9 scope, most preferably in 0.7 to 0.85 scope.Fig. 2 provides guidance, at typical Athabasca (Athabasca) the pitch required residence time of carbon-containing feeding.In case reach the required residence time, cooling oil stream S11 just is used to the product stream S10 of pyrolysis reactor 25 is cooled fast between 425 ℃ to 200 ℃, and more preferably between 400 ℃ to 250 ℃, optimum is chosen between 375 ℃ to 300 ℃.Higher cooling temperature helps generating in the downstream equipment coke.And lower cooling temperature has reduced the solubleness of coke precursors in the heavy oil.The pressurization atomizing of cooling oil charging S11 can advantageously be used for increasing the interfacial area between cooling oil S11 and the pyrolysis reactor product stream S10.Heat absorption vaporization with more lower boiling cooling fluid S11 can be used to further increase the rate of cooling of logistics S10.
Conventional phase separator 27 is used to remove the heavy oil S13 of generation.The gaseous product S12 that remains can advantageously be used for producing coolant flow S4 and the exhaust vapour S15 that uses in the spray gun 1.Water smoke maker 29 can advantageously be used for improving the temperature control performance in the spray gun inner chamber 2.The part of unconverted residual material among the heavy oil S13 can advantageously be recycled among the carbon-containing feeding S1.The balance of this unconverted salvage stores can advantageously produce hydrogen by utilization standard partial oxidation technology and purification technique, comes refining distillment product.
Add the hydrogen donor solvent by the hydrogenation of liquid towards carbonaceous material S1 or in the S1 charging, can increase maximum obtainable distillment productive rate.When carbon-containing feeding was solid such as coal, adding considerable hydrogen was the requirement that acquisition has the distillment productive rate of commercial appeal.Scheme the-7th, powdery coal S17 is converted into the block flow diagram of the process of product of distillation S26.Basic skills is exactly that the Residual oil hydrogen donor solvent S18 that will derive from technology adds among the powdery coal charging S17, is formed for the charging S1 of flash pyrolysis system 30.The gun design notion of Fig. 3 and the flash pyrolysis system 30 of Fig. 6 also are fit to handle solid-state carbonaceous material.The anti-solvent S23 of relevant aliphatic series with intermediate molecular weight in conventional solid-liquid separating device 32, is used to remove ash and coke among the heavy oil product S22 that flash pyrolysis system 30 produces.The overflow 24 of this solid-liquid separating device, the light oil S21 that flash pyrolysis system 30 produces are introduced in the Distallation systm 33, to produce fuel gas, the anti-solvent oil S23 of recirculation, product of distillation S26 and irreducible oil S27.The underflow stream S25 that is rich in coke and ash content that will obtain from the solid-liquid separator introduces coke pervaporation step 35, offers the hydrogen 28 of step of hydrogenation 34 with generation, and the postcombustion gas 20 that offers spray gun 1 in the flash pyrolysis system 30.Step of hydrogenation 34 has increased the α-H content among the aromatics Residual oil S27, to produce the effectively hydrogen donor solvent S18 of recirculation.This recycle hydrogen donor solvent S18 has promoted the liquefaction of powdery coal charging S17.
Embodiment
Table 1 has been summed up the character of vacuum pitch resid feed.Below table 2 shown 10000 barrels of bituminous component material balances in flash pyrolysis system every day of the processing list 2.
The heat of table-2 components and the example of material balance
1Cut 1: with reference under the condition, the reaction heat of the segmental C-C key of hydrocarbon is 0 kilojoule/Gram-mole at 0 ℉ and 1 standard atmospheric pressure
Other materials use based on 25 ℃, and 1 standard atmospheric pressure is with reference to the HSC chemical data under the condition.
The spray gun explanation:
The water cooling carrying capacity of spray gun=0% combustion heat, the feed material ratio of logistics/oxygen: 2, oily inlet amount=10245bbl/ days
Fuel heat value=1.02GJ/bbl524+ cracked, MT oxygen/bbl524+ cracked=0.076, logistics/bituminous material is than=0.41
The flash pyrolysis explanation:
TI product=100% charging TI, effectively cracking temperature T=690 ℃, reactor volume=10.6 cubic metre, the residence time=279 millisecond
Pitch space time=9.37 minute, reactor mechanical energy input=1153 Jiao/gram pitch, %524C+ pitch transformation efficiency=84.7%
Table-2 (continuous table)
This embodiment has selected a kind of operational condition, can make the normal boiling point that accounts for charging 85 weight % change into normal boiling point less than 525 ℃ material greater than 525 ℃ material, the toluene insoluble thing content in the product equates with toluene insoluble thing content in the charging simultaneously.In contrast, the high-performance coking process can produce more than or equal to the coke yield that accounts for the resid feed amount 25 weight % shown in the table 1.The space efficiency of refinery unit operation represents with the liquid hourly space velocity rate that generally promptly the volume of the oil of per hour handling is to the ratio of reactor volume.In this embodiment, the space velocity of flash pyrolysis reactor is 6.4 hours
-1, more much bigger than the thermo-cracking or the coking process of routine.Unconverted irreducible oil from the flash pyrolysis reactor obtains can use standard partial oxidation technology and purification technique, advantageously is used for producing hydrogen, with the refining product of distillation.The partial oxidation equipment of treatment liq carbon-containing feeding is compared with the equipment of corresponding processing solid carbon charging, save cost and more convenient more.
Though invention has been described according to above embodiment, obviously various other forms of the present invention and improvement it will be apparent to those skilled in the art that.Claims of the present invention are interpreted as covering all these conspicuous form and improvement within the spirit and scope of the present invention.
Claims (37)
1. one kind is converted into the method for the carbonaceous material with lower normal boiling point with carbon-containing feeding, and this method may further comprise the steps:
A) under elevated pressure, generate hot gas;
B) high-speed gas injection that the hot gas under the described high pressure is converted into the heat under the low pressure flows or the injection stream array;
C) carbon-containing feeding is incorporated into the high velocity jet of heat or the central authorities of injection stream array, with the described carbon-containing feeding of rapid heating;
D) provide the competent residence time, be converted into the required transformation efficiency of the lower material of boiling point to realize described carbon-containing feeding; With
E) cooling contains the more reaction product of low-boiling point material fast.
2. the method for claim 1 is characterized in that, described carbon-containing feeding comprises the component that normal boiling point is higher than 524 ℃.
3. the method for claim 1 is characterized in that, described carbon-containing feeding mainly is selected from: heavy crude oil, fuel oil residuum, petroleum tar, coal tar, pitch, coal, resinous shale and their mixture.
4. the method for claim 1 is characterized in that, described have more that the carbonaceous material of substandard boiling point mainly is selected from distillment.
5. the method for claim 1 is characterized in that, the high velocity air of described heat is between 500 ℃ to 2500 ℃.
6. the method for claim 1 is characterized in that, described injection stream or injection stream array are produced by spray gun.
7. the method for claim 1 is characterized in that, the described competent residence time is enough to the remaining heavy oil feed of about 0.5-0.95 massfraction is converted into distillment.
8. the method for claim 1 is characterized in that, described reaction product is cooled off fast by distillatory carbonaceous material, water, water vapor or their mixture.
9. the method for claim 1 is characterized in that, described reaction product is cooled to below about 400 ℃ temperature.
10. the method for claim 1 is characterized in that, the speed of the high-speed gas of described heat is greater than 500 meter per seconds.
11. the method for claim 1 is characterized in that, described hot gas produces by fuel and high purity oxygen gas burning.
12. method as claimed in claim 11 is characterized in that, described high purity oxygen gas comprises the oxygen greater than 70 moles of %.
13. the method for claim 1 is characterized in that, the ratio of the pressure of described hot gas and described reaction product is between 20: 1 to 2: 1.
Have second carbonaceous material of substandard boiling point more 14. a method for pyrolysis, the carbon-containing feeding that is used for having first boiling point are converted into, this method may further comprise the steps:
A) described carbon-containing feeding is heated to required temperature of reaction;
B) with the reaction product cooling that produces in the step a); With
C) reclaim described reaction product.
15. method as claimed in claim 14 is characterized in that, described heat-processed is provided by the high velocity jet or the injection stream array of heat.
16. method as claimed in claim 14 is characterized in that, described carbon-containing feeding comprises the component that normal boiling point is higher than 524 ℃.
17. method as claimed in claim 14 is characterized in that, described carbon-containing feeding mainly is selected from: heavy crude oil, fuel oil residuum, petroleum tar, coal tar, pitch, coal, resinous shale and their mixture.
18. method as claimed in claim 14 is characterized in that, described have more that the carbonaceous material of substandard boiling point mainly is selected from distillment.
19. method as claimed in claim 15 is characterized in that, the high velocity air of described heat is between 500 ℃ to 2500 ℃.
20. method as claimed in claim 15 is characterized in that, described injection stream or injection stream array are produced by spray gun.
21. method as claimed in claim 14 is characterized in that, described reaction product is cooled off fast by distillatory carbonaceous material, water, water vapor or their mixture.
22. method as claimed in claim 14 is characterized in that, the speed of the high-speed gas of described heat is greater than 500 meter per seconds.
23. method as claimed in claim 14 is characterized in that, described hot gas is produced by fuel and high purity oxygen gas burning.
24. method as claimed in claim 23 is characterized in that, described high purity oxygen gas comprises the oxygen greater than 70 moles of %.
25. method as claimed in claim 18 is characterized in that, the described competent residence time allows to make the remaining heavy oil feed of about 0.5-0.95 massfraction be converted into distillment after step a).
26. changing into, the carbon-containing feeding that will have first normal boiling point has second method of the carbonaceous material of substandard boiling point more, this method comprises: guide the high speed hot gas flow into described carbon-containing feeding, cooling is by heating the reaction product that described carbon-containing feeding obtains, and reclaims described reaction product.
27. method as claimed in claim 26 is characterized in that, described carbon-containing feeding comprises the component that normal boiling point is higher than 524 ℃.
28. method as claimed in claim 26 is characterized in that, described carbon-containing feeding mainly is selected from: heavy crude oil, fuel oil residuum, petroleum tar, coal tar, pitch, coal, resinous shale and their mixture.
29. method as claimed in claim 26 is characterized in that, described have more that the carbonaceous material of substandard boiling point mainly is selected from distillment.
30. method as claimed in claim 26 is characterized in that, the high-speed gas injection stream of described heat is between 500 ℃ to 2500 ℃.
31. method as claimed in claim 26 is characterized in that, described heat is provided by injection stream or injection stream array.
32. method as claimed in claim 26 is characterized in that, described injection stream or injection stream array are produced by spray gun.
33. method as claimed in claim 26 is characterized in that, described reaction product is cooled off fast by distillatory carbonaceous material, water, water vapor or their mixture.
34. method as claimed in claim 26 is characterized in that, the speed of the high-speed gas of described heat is greater than 500 meter per seconds.
35. method as claimed in claim 26 is characterized in that, described hot gas is produced by fuel and high purity oxygen gas burning.
36. method as claimed in claim 34 is characterized in that, described high purity oxygen gas comprises the oxygen greater than 70 moles of %.
37. method as claimed in claim 29 is characterized in that, the described competent residence time allows to make the remaining heavy oil feed of about 0.5-0.95 massfraction be converted into distillment after step a).
Applications Claiming Priority (3)
| 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 |
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| CN101454425A true CN101454425A (en) | 2009-06-10 |
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| CNA2007800191026A Pending CN101454425A (en) | 2006-05-26 | 2007-05-22 | Flash pyrolysis method for carbonaceous materials |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102686705A (en) * | 2009-07-14 | 2012-09-19 | C20技术有限责任公司 | Process for treating agglomerating or bituminous coal by removing volatile components |
| CN108463537A (en) * | 2015-12-24 | 2018-08-28 | 伊维诺维奇·多马诺夫 | The method for handling heavy hydrocarbon feeds |
-
2007
- 2007-05-22 CN CNA2007800191026A patent/CN101454425A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102686705A (en) * | 2009-07-14 | 2012-09-19 | C20技术有限责任公司 | Process for treating agglomerating or bituminous coal by removing volatile components |
| CN102686705B (en) * | 2009-07-14 | 2015-01-14 | C20技术发展公司 | Process for treating agglomerating or bituminous coal by removing volatile components |
| CN108463537A (en) * | 2015-12-24 | 2018-08-28 | 伊维诺维奇·多马诺夫 | The method for handling heavy hydrocarbon feeds |
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Application publication date: 20090610 |