CN101668831A - Flash processing of asphaltic residual oil - Google Patents

Flash processing of asphaltic residual oil Download PDF

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Publication number
CN101668831A
CN101668831A CN200880013731A CN200880013731A CN101668831A CN 101668831 A CN101668831 A CN 101668831A CN 200880013731 A CN200880013731 A CN 200880013731A CN 200880013731 A CN200880013731 A CN 200880013731A CN 101668831 A CN101668831 A CN 101668831A
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China
Prior art keywords
asphalt residue
combustion gas
gas jet
hydrogen
temperature
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CN200880013731A
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Chinese (zh)
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D·P·萨切尔
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Messer North America Inc
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Linde North America Inc
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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
    • C10G31/00—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for
    • C10G31/06—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for by heating, cooling, or pressure treatment
    • 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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
    • C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
    • 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
    • C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
    • C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only

Abstract

A method to upgrade virgin and partially hydrogenated asphaltic residual oils by utilizing hot, high velocity combustion gas jets to rapidly atomize and heat the residual oil, maintaining the reactanttemperature required to achieve the desired residual oil conversion with the minimum practical residence time, rapidly separating vapor and liquid reactants, and rapidly cooling the vapor and liquidproducts. The minimum required temperature and practical residence time are used for the production of deasphalted oil and asphaltene products with minimum degradation due to thermal cracking. The maximum conversion of residual oil may be substantially increased by combining a portion of the heavy oil product with the residual oil feed and partially hydrogenating this mixture.

Description

The flash process of asphalt residue
Invention field
General field of the present invention relates to the processing of the high temperature short contact time of asphalt residue.More specifically, the present invention is a kind of flash distillation working method of removing asphaltic substances from residual oil.
Background technology
Nearest one piece of summary [Hulet (2005)] has been inquired into the principal feature and the configuration layout of the short residence time cracking technology of exploitation in 25 years in the past.Promise, the principal feature of short residence time(SRT) technology and the challenge that faces summed up in a capsule in this piece article: " there is the intensive economic motivation in short residence time cracking technology.This technology has not only improved the more productive rate of the liquids and gases product of high value, and compact more design has also reduced investment cost.In order to prevent second pyrolysis and can make charging cracking farthest that carefully the residence time of pilot-gas is very crucial.Charging not only produces dispersion uniformly with mixing fully again rapidly of thermal source, still needs the key issue of considering in the design.At last, from the thermal equilibrium angle, also must conscientiously study rapidly and separate completely; It also helps to control the residence time of product and avoids taking place second pyrolysis.”
These are deep see clearly suggestion short residence time cracking technology should the rapid heating charging, separated product to be to control the residence time of all products rapidly, cools off reaction product fast avoiding second pyrolysis, and makes full use of heat energy and improve production capacity.The most successful short residence time(SRT) technological process satisfies all these standards.But the technology that none is handled asphalt residue can satisfy these standards fully.Normal boiling point surpasses dense (typically, being higher than 25 weight %) of 524 ℃ material in the asphalt residue, and the heptane insoluble substrate concentration that normal boiling point surpasses 524 ℃ material surpasses 25 weight %.The asphalt residue that meets these judging criterions fully is the higher diasphaltene of efficient, the target of thermo-cracking and hydrocracking process.
Fluid catalytic cracking (FCC) is undoubtedly the most successful modal and industrial short residence time cracking technology.Typically, FCC technology contacts the hydrocarbon charging of diesel boiling range closely with the granules of catalyst of heat in the entrained flow riser reactor of a short residence time(SRT), the split product that generating value is higher, especially gasoline and olefines, and so not desirable dry gas and coke by-product.The developers of FCC technology have adopted improved feed nozzle design to improve the charging rate of heating.The FCC feed nozzle has improved the initial homogeneity that contacts between the regenerated catalyst of carbonaceous feed and heat, and this has improved the charging rate of heating, reduced the productive rate of so not desirable dry gas and coke by-product.For example, United States Patent (USP) the 6th, 387, No. 247 summaries utilize the improvement of feed nozzle to improve charging rate of heating and the long-term endeavour that improves the overall performance of FCC reactor.
The developers of FCC technology have also had been found that the approach of the control residence time.For example, United States Patent (USP) the 6th, 979 has disclosed for No. 360 and implemented the method that the short contacting time hydrocarbon transforms in a FCC reactor, has adopted the rapid inertial separation of gas and FCC reactor solids product.United States Patent (USP) the 6th, 610, No. 900 by adopting the removing of sectional FCC riser reactor and intersegmental product to expand this notion.United States Patent (USP) the 5th, 762 has disclosed the method for removing reaction product by vaporization from used catalyst for No. 882.During with the overhead product charging, the heat balance that the output of by-product coke roughly needs with the FCC technological process.Make coke yield higher in the higher FCC charging of pitch slag, this has very big negative impact to processing performance.United States Patent (USP) the 4th, 415 has disclosed for No. 438 and to have adopted heat-staple catalyzer and high catalyst regeneration temperature to improve the rate of heating of heavy oil feed and reduce coke yield.United States Patent (USP) the 5th, 271, the riser tube initial temperature that realizes improving by the ratio that improves regenerated catalyzer and charging for No. 826 adds quench liquid then and regulates riser temperature, has obtained similar results.Canadian Patent the 2nd, 369, disclosed resid feed and inert solid thermo-cracking in the short contact time reactions device of FCC reaction type for No. 288 and but also caused relatively poor product yield distribution solving a catalyst deactivation difficult problem, comprised that coke output has surpassed the heat demand of technology.U.S. Patent Application Publication has disclosed the diasphaltene of FCC heavy oil feed for No. 2006/0042999 to reduce the deactivation rate that catalyzer causes because of the metal that exists in the charging and coke precursors.United States Patent (USP) the 6th, 171, disclosed for No. 471 the appropriate hydrocracking of residue FCC charging and deasphalting combination to reduce because the speed of the catalyst deactivation that metal that exists in the charging and coke precursors cause.Although there are these effort to reduce the coke yield of making the FCC technology of charging with slag pitch, the output of coke is considerably beyond to regenerated catalyzer or the needed amount of inert solid preheating.
As a result, adopt similar principle successfully to develop the short contacting time fluidized coking process, this technology makes asphalt residue change into the transformation efficiency maximization of distillate.Typically, fluidized coking process comprises the partial combustion of coke granule, contact the rapid heating resid feed closely by fluidized-bed with the burnt grain of heat, by cyclonic separator with by-product coke and the gas-phase product sharp separation carried secretly, and quenching system with gas-phase product rapidly cooling so that the secondary pyrolysis is reduced to minimum level.United States Patent (USP) the 2nd, 881 has disclosed the atomizing of resid feed and distribution for No. 130 in case the depression of fluid stopping coke bed and improve the rate of heating of resid feed.The developers of fluidized coking process have also had been found that the approach of the control residence time.For example, United States Patent (USP) the 4th, 816 has disclosed the charging order for No. 136 and contact with raising overhead product productive rate with the burnt grain of comparatively high temps in the lower fluidisation coke bed of service temperature then at riser reactor.United States Patent (USP) the 5th, 658 has been described a kind of method of the phase residence reactor that is used to lose heart for No. 455, and it can be reduced to minimum level with the secondary heat scission reaction.United States Patent (USP) the 4th, 497 has disclosed for No. 705 recycle of heavy oil has been carried out solvent treatment, selectively removes the method for carbonaceous less substance, and it has reduced undesirable second pyrolysis of these valuable products.United States Patent (USP) the 4th, 587 had disclosed before regenerating for No. 010 and valuable product have been separated the method that puts forward by partial oxidation from coke.Fluid coking and FCC process have many common characteristic, for handling the carbonaceous residual oil charging quite a lot of advantages are arranged.Fluidized coking process has been got rid of the difficult problem of catalyzer rapid deactivation, the coke of the quite big quantity that produces when also not needing to burn as FCC processing asphalt residue.Because it is to produce by evaporation that fluid coking and FCC technology all require all product liquids, for unconverted asphalt residue, these two kinds of technologies all can not operate under short residence time(SRT).
United States Patent (USP) the 3rd, 393 has disclosed high temperature short residence time(SRT) distillating method No. 133, and this method can make the distillate productive rate the highest, the degraded minimum that residual oil is caused because of heat scission reaction.Yet solvent extraction [Altgelt (1994)] is a kind of preferable methods, producing the residual oil fraction with much higher equivalence margin boiling point, and does not have the thermally splitting degraded on the substrate.Successfully developed solvent treatment technology, for example United States Patent (USP) the 4th, 810, No. 367 output deasphalted oil, resin and asphaltene from the asphalt residue charging continuously.Many reliable simply again unit operations of these process needs make residual oil contact with solvent and separate.In addition, the separating step of solvent and residual oil needs a large amount of steam heating.Therefore, this Technology is particularly useful at refinery, and at refinery, the Infrastructure of needed solvent, steam and maintenance all obtains easily.United States Patent (USP) the 6th, 357 has disclosed the method for the on-the-spot device for improving quality of a kind of solvent extraction for No. 526 and produced the synthetic crude product of deasphalted oil, and a kind of bituminous fuel produces the steam that is used for bitumen extraction.For this indirect application, flash distillation diasphaltene technology has many potential ideal features.Temperature is very high, and very short flash evaporation unit operation duration of contact might be produced deasphalted oil and pitch logistics and needn't solvent in the single unit operation of compactness.The heat energy of input can be used to separate deasphalted oil and bitumen product, produces the steam that is used for bitumen extraction, produces the heated bitumen logistics, and this logistics does not need reheat or granulation just to be burnt.Regrettably, early stage technology does not provide any method can heat bitumen feed, separates deasphalted oil and asphaltene product, and the deasphalted oil of rapid enough ground refrigerated separation and asphaltene product are to avoid the excessive thermo-cracking and the degraded of deasphalted oil product.
Residual hydrocracking is the most standing carbonaceous less material that bituminous material is changed into, and is reduced in the method for metal and coke precursor concentration in the unconverted asphaltic substances.United States Patent (USP) the 2nd, 987, the notion of introducing the boiling bed hydrogenation cracking case first No. 465.The ebullated bed hydrogenation reactor utilizes upwards flowing of carbenes residual oil and hydrogen feed, contacts with the expanded bed of hydrogenation processing catalyst particle or the colloidal state hydrotreating catalyst carried secretly.Expanded bed hydrotreating catalyst bed will be not easy blocked more than original fixed bed catalyst bed designs.United States Patent (USP) the 5th, 164 has disclosed the method for producing colloid mink cell focus catalyzer No. 075, and this catalyzer is effective especially to the hydrogenation of asphaltic substances.United States Patent (USP) the 6th, 511 has disclosed the method for recovery and recirculation colloid heavy oil hydrocracking catalyzer No. 937.All these residual hydrocracking technologies are all carried out hydrogenation and thermo-cracking to residual oil simultaneously.United States Patent (USP) the 4th, 427 has been determined a basic limit of this method No. 535.The activation energy of heat scission reaction is higher than the activation energy of hydrogenation reaction.Hydrogenation reaction has postponed to produce coke precursors and the final polyreaction that produces coke.Therefore, the residual hydrocracking device must be under the temperature more much lower than FCC or fluid coker operation to keep operability.U.S. Patent Application Publication has disclosed employing colloid molybdenum sulfide catalyst for No. 2005241993 and has improved hydrogenation reaction speed, especially the hydrogenation reaction speed of asphaltic substances.This innovation has improved the speed of asphaltic substances hydrogenation reaction, and makes exercisable temperature be put into maximum, but it does not change the fundamental characteristics of this hydrocracker service temperature limit.Hydrogen donor dilution cracking technology has been eliminated this temperature limitation basically, and it then, carries out thermo-cracking to residual oil by cycloalkyl overhead product moderate temperature hydrogenation is produced hydrogen donor solvent in the presence of this hydrogen donor solvent, greatly reduce the speed that coke precursors generates.United States Patent (USP) the 4th, 698 has disclosed for No. 147 in the temperature that improves hydrogen donor dilution cracking process and has reduced duration of contact, dullly improves the maximum conversion rate that residual oil changes into distillate.United States Patent (USP) the 4th, 002 has disclosed high temperature and short contacting time hydrogen donor dilution cracking technology for No. 556 and has reduced widely to keeping the needed hydrogen gas consumption of operability.The benefit of these high temperature and short contacting time be it seems the restriction of the speed of cooling that just is limited by actual charging rate of heating and product.Hydrogen donor dilution cracking processing requirement has sufficiently high pressure so that hydrogen donor solvent keeps the state of liquid phase under high heat cracking reaction temperature.
None can realize that the method according to this invention can produce the potential superiority of eu-bitumen product in high temperature short contact process in these technological processs.
Summary of the invention
The present invention is a kind of flash evaporation that improves the asphalt residue quality, this method utilizes combustion gas jet with resid feed atomizing and heating rapidly, adopt inertial device that gaseous state is separated rapidly with liquid reactant, and the chilling logistics is cooled off gaseous light oil product and liquid heavy oil product rapidly.
Combustion gases are through one convergent-flaring type nozzle, are also referred to as de Laval type nozzle and expand and produce combustion gas jet.Reactant is less than 400 milliseconds in the residence time more than 425 ℃, preferably is less than 100 milliseconds, most preferably less than 50 milliseconds.Because the bitumencarb metallic substance, promptly heptane insolubles is the most headachy material for the refinery unit operation of routine, so the present invention pays attention to the removal of asphaltic substances.From residual oil, remove the bitumencarb metallic substance can by with reactant at the required short residence time(SRT) internal heating of evaporation to minimum temperature with the evaporation of heptane solvend, produce minimum deasphalted oil and the pitch heavy oil product of palliating degradation degree that causes because of thermo-cracking.By improving temperature of charge, again the actual residence time more than 425 ℃ is remained on the shortest productive rate that can significantly reduce the pitch heavy oil product simultaneously, make the yield of gas and light distillate minimum.The productive rate of pitch mink cell focus can also be by the partial hydrogenation of resid feed, and operates under higher temperature of charge, is again remained on that operation reduces further under the shortest condition simultaneously the actual residence time more than 425 ℃.
In one embodiment of the invention, disclosed a kind of asphalt residue method for quality of improving, this method comprises:
A) utilize the expansion of combustion gases the time to produce combustion gas jet by convergent-gradually expanded form nozzle;
B) this combustion gas jet is contacted closely with the asphalt residue charging;
C) will contact formed gas phase by this asphalt residue and this combustion gas jet separates with liquid product;
D) with this gas-phase product and liquid product cooling, form lightweight oil and heavy oil product respectively.
The operating method of the inventive method be with asphalt residue be added to be preheating to before the described combustion gas jet about 100 ℃ to about 425 ℃ temperature range.
Gas phase and liquid product are cooled to and are lower than 400 ℃ temperature.
The apparent viscosity of this asphalt residue generally is lower than 1000 centipoises (cP).
This method also provides the pre-treatment to the partial hydrogenation that comprises carbonaceous residual oil.This hydrogenation can carry out in the presence of catalyzer in ebullated bed or fixed bed hydrogenation treatment reactor, and described catalyzer is selected from cobalt molybdate and the nickel molybdate that is supported on the active aluminum oxide carrier.This catalyzer also can be a kind of colloidal hydrotreating catalyst, for example catalyzer of colloid molybdenum sulfide type.
In resid feed the add-on of hydrogen be every barrel of resid feed about 100 to about 1500 standard cubic foot hydrogen, preferred every barrel of resid feed adds about 150 to about 1000 standard cubic foot hydrogen.
By making a kind of oxygenant and a kind of fuel reaction produce combustion gases, fuel is selected from carbon monoxide, hydrogen, and gaseous hydrocarbons and their mixture, oxygenant is selected from air, oxygen-rich air and pure oxygen basically.Steam also can be used to control temperature of combustion, stops the generation of coke, and simplifies the product recovery system.
Typically, the temperature of combustion gases is about 1250 to about 2000 ℃, and pressure is about 2 to 40 crust.
Convergent-divergent nozzle can be axisymmetric, and carbonaceous residual oil can contact with gas-jet from the periphery of gas-jet.Combustion gas jet also can be formed by a conical convergent-divergent nozzle.Residual oil can axially contacting with gas-jet along this conical convergent-divergent nozzle.
In the method for the invention, inertial device can be a cyclonic separator.Reactant the residence time more than 425 ℃ less than 400 milliseconds.Can adopt the agent of liquid overhead product chilling to cool off the reactant of gas phase and liquid phase fast.In certain example, the agent of liquid distillate chilling is atomized.Can adopt sweeping gas that the loss of distillate chilling agent in heavy oil product is reduced to a minimum, the preferred steam of this sweeping gas.
Description of drawings
Fig. 1 is the synoptic diagram according to the asphalt residue flash process process of method of the present invention.
Fig. 2 is atomizing heated nozzle figure.
Fig. 3 is inertia gas-liquid separation device figure.
Embodiment
The flash distillation treatment process of handling asphalt residue is described by means of these accompanying drawings.Among Fig. 1, asphalt residue charging 1 typically contains the material that the above normal boiling point of 25 weight % is higher than 975 (524 ℃), more preferably more than the 50 weight %, preferably more than the 75 weight %.Resid feed typically has Lan Shi carbon residue (Ramsbottom carbon) and the heptane insolubles of 5-40 weight %.The more charging typical earth surface of carbon containing reveals higher Lan Shi carboloy residue and heptane insolubles value.Typical resid feed source comprises long residuum or vacuum residuum, oil-sand, pitch, Tar sands, coal tar, pyrolytic tar or the shale oil of oil.Resid feed 1 also can be by partial hydrogenation before entering atomizing-heated nozzle 2.Optionally the hydrogen gas consumption of resid feed hydrogenation step is generally every barrel of oil 100-1500 standard cubic foot (SCF/bbl) or every cubic metre of 95-285 gram mole, is 150-1000SCF/bbl more preferably, is preferably 200-700SCF/bbl.Optionally hydrogenation step preferably carries out in ebullated bed or fixed bed hydrogenation treatment reactor, adopt conventional cobalt molybdate and nickel molybdate hydrotreating catalyst and/or the colloid hydrogenation catalyst system that is supported on the active aluminum oxide carrier, preferred moly-sulfide colloid catalyst.
Cross or untreated resid feed 1 is preheated to 100-425 ℃ temperature range before being fed to atomizing-heated nozzle usually through hydrotreatment, more preferably 200-400 ℃, best 300-375 ℃ temperature range.Under feeding temperature, the apparent viscosity of resid feed preferably is lower than 1000 centipoises (cP) or 1Pas, more preferably, is lower than 100cP, preferably is lower than 10cP.Atomizing-heated nozzle 2 utilizes combustion gas jet 3 with resid feed 1 atomizing and heating rapidly, produces reactant flow 6.By the expansion formation combustion gas jet 3 of combustion gases 4 through convergent-divergent nozzle 5.Can design this convergent-divergent nozzle 5 with the method (Green-1999) of standard to obtain the kinetic energy content and the heat energy content of ideal combustion gas jet 3.Combustion chamber one heat insulation 9 makes fuel 7 and oxygenant 8 burnings produce combustion gases 4 for 10 li.Fuel 7 can be carbon monoxide, hydrogen, solid carbonaceous fuel, liquefied hydrocarbon, gaseous hydrocarbons, perhaps their mixture.Preferred gaseous state and liquid fuel.Coal, coke, refinery coke are the examples of solid carbonaceous fuel.Oxygenant can be an air, oxygen-rich air, or with the pure oxygen basically of steam dilution.The oxygen concn of pure oxygen basically preferably is higher than 0.7 molar fraction (that is, the molar fraction of argon and nitrogen is less than 0.3), more preferably, is higher than 0.85 molar fraction, preferably is higher than 0.9 molar fraction.When the target of technology is reactant flow 6 gasifications that make signal portion, and when making the thermally splitting palliating degradation degree minimum, then air is preferred oxygenant.If the target of technology is to make reactant flow 6 gasification and thermo-crackings, then the pure basically oxygen through the steam dilution is preferred oxygenant 8.
Adopt suitable normal burner 11 to mix and fire fuel 7 and oxygenant 8.Regulate the flow velocity of oxygenant 8, make this flow velocity for fuel 7 is changed into CO 2, H 2O, H 2S and N 2Theoretical desirable value 0.9-1.05 doubly, better is 0.95-1 is doubly.Adjust the character of fuel 7 and oxygenant 8, make the temperature of combustion gases 4 reach 1000-2500 ℃, more preferably, reach 1250-2000 ℃, preferably reach 1500-1750 ℃.The pressure of combustion gases 4 be preferably reactant flow 6 pressure 2-20 doubly, more preferably, 3-15 is doubly.The volume of combustion chamber 10 will be enough to make combustion reactions, finishes substantially in about 1 second usually.
As shown in Figure 2, atomizing-heated nozzle 2 preferably has conical convergent-divergent nozzle 5, and as shown in the figure, resid feed `1 axially enters along conical convergent-divergent nozzle 5.This convergent-divergent nozzle also can be a kind of rotational symmetry convergent-divergent nozzle of routine, and resid feed enters through around it.Can adopt convergent-divergent nozzle array.Preferred conical convergent-divergent nozzle 5 can interior atomizing-heated nozzle body 12 and outside form easily between the atomizing-heated nozzle body 13.Interior atomizing-heated nozzle body 12 is all controlled by nozzle coolant flow 15 with the temperature of outer atomizing-heated nozzle body 13.Nozzle coolant flow 15 can be the refrigerant of liquid phase for example, water or Dowtherm A thermal barrier for example.Nozzle coolant flow 15 can advantageously contain liquid and gas to improve temperature control, improves the dimensional stability of interior and outer atomizing-heated nozzle body, thereby has also improved the dimensional stability of conical convergent-divergent nozzle 5.The two-phase coolant pressure is preferably set to the temperature that keeps refrigerant 100-350 ℃ scope, more preferably, and in 200-300 ℃ scope.Nozzle refrigerant 15 contacts with ectosome 13 closely with the endosome 12 of atomizing-heated nozzle in annular refrigerant feeding-passage 16 and refrigerant backward channel 17.Feeding-passage 16 and backward channel 17 can be advantageously provided with helical baffle, with speed that improves refrigerant and the uniform distribution of guaranteeing coolant flow.
Combustion gases 4 enter atomizing-heated nozzle 2 by gas feed hole 19, and are dispensed to the ingress of annular convergent-divergent nozzle 5 by annular header 20.Combustion gases 4 quicken by conical convergent-divergent nozzle 5, produce combustion gas jet 3.Angle 21 between combustion gas jet 3 and the resid feed 1 is preferably 30-75 °, more preferably 45-60 °.Adjust the flow velocity ratio of combustion gas jet 3 and resid feed 1, to the adiabatic temperature of reactant flow 6 acquisitions for 500-850 ℃.Conduit 22 will atomize-and heated nozzle 2 couples together with inertia gas-liquid separation device 23.Preferred inertial separator 23 is the cyclonic separators with several supplementary features.Determine the separation performance of the design variable and the assessment cyclonic separator of cyclonic separator, and as the operational condition of cyclonic separator with to design the method for the residence time of relevant variable be (Green-1999) that obtains easily.Can adopt the thermo-cracking kinetic model (Gray-2004) that obtains easily to assess the extent of thermal degradation relevant with operational condition.
As further describing among Fig. 3, inertial device charging 24 tangentially enters the cylindrical sections 25 of inertial device 23 through a rectangular conduit 26.Vapor components 27 is followed helicoidal flow mode to steam and is discharged cylinder 28.Vapor components 27 is lower than 400 ℃ by contacting to be cooled to rapidly closely with chilling agent liquid stream 29, is more preferably to be lower than 300 ℃ temperature, forms vapor phase product stream 30.Increase the interfacial area of chilling agent liquid with the fog nozzle 30 of routine, and the small droplets of chilling agent liquid is dispersed in the round shape steam discharges on the cross section of conduit 28.Spraying gun can move fluid as mobile fluid or steam with chilling agent liquid stream 29.The chilling logistics 29 of steam or vaporization is that conventional steam moves fluid.The normal boiling point of distillate chilling agent liquid stream 29 preferably hangs down 25-150 ℃ than the service temperature of lightweight oil 31, is more preferably than the service temperature of lightweight oil 31 to hang down 50-100 ℃.
Liquid ingredient in the logistics 24 is flowed through cylindrical section 25 and conical section 32 downwards to mink cell focus relief outlet 33 in the helicoidal flow mode.Conical section 32 utilizes mass force that mink cell focus is accelerated to the conduit of mink cell focus relief outlet 33, and has increased the thickness of heavy oil film at the duct entry place of mink cell focus relief outlet 33.Conical section 32 typically adopts a straight line taper, and the difference of its bottom radius and top radius is substantially equal to the width 40 of mink cell focus relief outlet 33 conduits.
It is favourable adopting a cooling jacket 35 that the wall temperature of cylindrical section 25 and conical section 32 is cooled to 400-200 ℃, is more preferably and is cooled to 350-250 ℃.Hydrocarbon stream that obtains from process or heat-conducting fluid, for example, Dowtherm A can be used as cyclonic separator chuck refrigerant 34 easily.The hydrocarbon mixture that the preferred boiling range of chuck refrigerant is narrow, its bubble point are substantially equal to ideal wall temperature under suitable chuck working pressure, to improve the temperature control of cylindrical section 25 and conical section 32.The hydrocarbon steam that refrigerant returns in the stream 36 can be condensed, and produces steam and makes chuck refrigerant incoming flow 34 regeneration.Distillate chilling agent liquid 39 can be added to the cylindrical section 25 of cyclonic separator 23 or conical section 32 or mink cell focus and discharge in the conduit 33 (as shown in Figure 3), be favourable with the liquid portion that quickens cooling cyclonic separator charging 24.The conical section 32 (as shown in Figure 3) that can be advantageously sweeping gas 37 be added to cyclonic separator cleans the vapor components of cyclonic separator charging 24, so that the condensation on the wall of the cylindrical section 25 of cyclonic separator and conical section 32 is reduced to a minimum.In addition, the flow velocity of discharging by mink cell focus discharge conduit 33 by the control steam can be controlled at the thickness of the heavy oil film on conical section 32 walls.The preferred steam of sweep gas.
Fig. 1, the equipment in 2,3 can be operated with three kinds of patterns: flash distillation diasphaltene, flash distillation pyrolysis, the cracking of flash distillation hydrogen donor.The technology purpose of flash distillation diasphaltene unit operation is mainly by the pitch mink cell focus of flash distillation from carbonaceous residual oil charging production desired number, and the thermal destruction of lightweight oil product and heavy oil product to be reduced to a minimum.Reach this purpose, the residence time of operation is the shortest, realizes that required separation necessary operations temperature is minimum.
The technology purpose of flash pyrolysis unit operation is that the raising service temperature to combine by evaporating with the thermally splitting of mink cell focus, realizes higher lightweight oil productive rate.Because the productive rate of the low boiling point hydrocarbon that this technology produces is very high, preferably with the pure basically oxygen of steam dilution as oxygenant.
By with homogeneous catalyst to the resid feed hydrotreatment with more effectively to the asphaltic substances hydrogenation, produce hydrogen donor solvent, can also further improve the productive rate of lightweight oil.Hydrogen transfer reactions in homogeneous hydrogenation catalyzer that hydrogenation step is carried secretly also can the catalysis flash vaporization process, the speed that generates with further reduction coke precursors.Adopt the residual oil pretreatment process can further improve the productive rate of lightweight oil, this method comprises the colloid molybdenum sulfide catalyst joined in the carbonaceous residual oil goes, part circulation with heavy oil product, resid feed and circulation carbonaceous mink cell focus are merged, this mixture is input in the hydrotreating reactor, adds 100-1500SCF H 2/ bbl more preferably, adds 150-1000SCF H 2/ bbl preferably adds 200-700SCFH 2/ bbl.Reactant the residence time more than 425 ℃ preferably less than 50 milliseconds, the transformation efficiency that temperature of charge is configured to make asphaltic substances change into the heptane solvend is lower than 85%, is more preferably to be lower than 75%.
Embodiment 1
Present embodiment has illustrated that employing flash distillation treatment process produces deasphalting oily product from typical oil sands bitumen, and the by product steam that q.s is arranged simultaneously is for the pitch production of adopting SAGD technology.In the present embodiment, the feed rate of oil sands bitumen is 33.5 tonnes/hour.Combustion chamber demand for fuel amount is 1.7 tonnes of lightweight oil products per hour.The combustion chamber working pressure is 5.3 crust.Burning gas temperature anoxic 10% time for being 2000 ℃.The angle of the resid feed-gas-jet of circular cone convergent-gradually expanded form nozzle is 60 °, and the Road narrows area is 130 centimetres 2The reactant medial temperature is about 540 ℃, pressure 2.2 crust.Cyclonic separator has the feed conduit of a 14x29cm, 58 centimetres of cylindrical section diameters, high 36 centimetres, 29 centimetres of pneumatic outlet diameters, high 36 centimetres, the flow of chilling agent liquid of spraying gun of being used to pressurize is 24.4 tonnes/hour, the lightweight oil temperature is 400 ℃, 58 centimetres of conical section minimum diameters, 65 centimetres of maximum diameters are high 80 centimetres, it is wide 3.5 centimetres that mink cell focus is discharged conduit, high 7 centimetres, the flow of stripped vapor is 9.4 tonnes/hour, 5.7 tonnes/hour of heavy oil product flow velocitys (equaling the asphalt content in the oil sands bitumen charging haply).Heat cracking reaction causes about 1% the lighter product of asphaltenes conversion one-tenth.The burning of mink cell focus provides steam, the about 2.65 kg/kg oil sands bitumen chargings of its net production, and this steam production is the typical steam requirement of producing by the oil-sand of SAGD method.The flow of deasphalted oil product is about 26.2 tonnes/hour.
Embodiment 2
Embodiment 2 adopts the equipment of describing among the embodiment 1, and asphaltic substances is converted into deasphalted oil and heavy fraction, makes gasiform and coke precursors material generate minimumly simultaneously.23 kilograms/hour temperature is the moly-sulfide colloid catalyst that oil-sand vacuum residuum (the about 33 weight % of asphalt content) more than 535 ℃ is equipped with 1000ppm, and with 10.4 kilograms/hour circulation mink cell focus blending, in the boiling bed hydrogenation treater, under 100 crust, carry out the hydrotreatment of enough liquid residence times, in residual oil, add the hydrogen of about 640SCF/bbl.3 kilograms/hour gas fuel is oxidized dose of oxidation under 5.3 bar pressures, and this oxygenant comprises 11.3 kilograms/hour pure oxygen and steam diluent, and the ratio of steam diluent and oxygen is 1.2: 1.The combustion gases that produce are expanded to 2.2 crust through a conical convergent-gradually expanded form nozzle from 5.3 crust, contact with the circulation mink cell focus with the vacuum residuum of partial hydrogenation.This process has realized the highest about 700 ℃ thermo-cracking temperature, makes in the vacuum resid feed about 93% bitum transformation efficiency.Unconverted pitch mink cell focus by product comprises the whole metals in vacuum residuum and catalyst charge except that the coke precursors of this process generation and any coke.This material preferably is added in the gasification installation to produce hydrogen and to reclaim metal.
Though described the present invention with regard to embodiment, many other form and changes of the present invention to those skilled in the art are conspicuous.Claims of the present invention generally should be believed to comprise whole these conspicuous form and changes, and these forms and change are within spirit of the present invention and scope.
Claims (according to the modification of the 19th of treaty)
1. the method for modifying of an asphalt residue, it comprises:
A) utilize combustion gases by convergent-gradually expanded form nozzle the time, to expand and produce combustion gas jet,
B) described asphalt residue is contacted with described combustion gas jet, reaches 500-850 ℃ adiabatic temperature,
C) use the inertial separator will be by the gas phase and the liquid phase separation of described contact formation,
D) with the cooling of described gas-phase product and liquid product, form lightweight oil product and heavy oil product, reactant is being higher than residence time of 425 ℃ less than 400 milliseconds.
2. the method for claim 1 is characterized in that, described cooling is meant to be cooled to and is lower than 400 ℃ temperature.
3. the method for claim 1 is characterized in that, the apparent viscosity of described asphalt residue charging is less than 1000cP.
4. the method for claim 1 is characterized in that, described asphalt residue is being about 100-425 ℃ with temperature before described combustion gas jet contacts.
5. the method for claim 1, this method also comprise make described asphalt residue with contact so that this asphalt residue is carried out hydrotreatment with homogeneous catalyst before described combustion gas jet contacts.
6. the method for claim 1 is characterized in that, described homogeneous catalyst is a molybdenum sulfide catalyst.
7. the method for claim 1 is characterized in that, described hydrotreatment is to carry out in being selected from the hydrotreating reactor of organizing down: ebullated bed, upflowing and fixed-bed reactor.
8. the method for claim 1 is characterized in that, adds hydrogen in described asphalt residue.
9. the method for claim 1 is characterized in that, adding amounts of hydrogen in described asphalt residue is that every barrel of asphalt residue adds about 100 hydrogen to about 1500 standard cubic foots.
10. the method for claim 1 is characterized in that, adding amounts of hydrogen in described asphalt residue is that every barrel of asphalt residue adds about 150 hydrogen to about 1000 standard cubic foots.
11. the method for claim 1 is characterized in that, described combustion gas jet is by oxygenant and fuel reaction are formed.
12. the method for claim 1 is characterized in that, described oxygenant is selected from down group: air, oxygen-rich air and pure basically oxygen.
13. the method for claim 1 is characterized in that, described fuel is selected from down group: carbon monoxide, hydrogen, gaseous hydrocarbons and their mixture.
14. the method for claim 1, this method also comprise steam are added in the described fuel.
15. the method for claim 1 is characterized in that, the pressure ratio scope of described combustion gases and described reacting gas stream is 2-20.
16. the method for claim 1 is characterized in that, the temperature of described combustion gas jet is about 1250 ℃ to about 2000 ℃.
17. the method for claim 1 is characterized in that, described convergent-gradually expanded form nozzle is axisymmetric.
18. the method for claim 1, this method also comprise the array of convergent-gradually expanded form nozzle.
19. the method for claim 1 is characterized in that, described asphalt residue contacts with combustion gas jet from the periphery of described combustion gas jet.
20. the method for claim 1 is characterized in that, described convergent-gradually expanded form nozzle is conical.
21. the method for claim 1 is characterized in that, described asphalt residue axially contacts with described combustion gas jet along described conical convergent-gradually expanded form nozzle.
22. the method for claim 1 is characterized in that, described inertial separator is a cyclonic separator.
23. the method for claim 1 is characterized in that, adopts the agent of distillate chilling to cool off described gas phase rapidly.
24. the method for claim 1 is characterized in that, with described chilling agent atomizing.
25. the method for claim 1 is characterized in that, adopts sweep gas that the loss of the described liquid distillate in the described mink cell focus is reduced to a minimum.
26. the method for claim 1 is characterized in that inertial separator has conical section, quickens mink cell focus to the mink cell focus discharge tube to produce mass force.
27. the method for claim 1 is characterized in that, the wall of inertial separator is cooled to 400-200 ℃ temperature.
28. the method for claim 1 is characterized in that, uses the wall temperature of boiling liquid control inertial separator.
29. the method for claim 1 is characterized in that, uses the agent of distillate chilling to come quick cooling heavy oil.

Claims (27)

1. the method for modifying of an asphalt residue, it comprises:
A) utilize combustion gases by convergent-gradually expanded form nozzle the time, to expand and produce combustion gas jet,
B) described asphalt residue is contacted with described combustion gas jet,
C) gas phase and the liquid phase separation that will form by described contact,
D) with described gas-phase product and liquid product cooling, form lightweight oil product and heavy oil product.
2. the method for claim 1 is characterized in that, described cooling is meant to be cooled to and is lower than 400 ℃ temperature.
3. the method for claim 1 is characterized in that, the apparent viscosity of described asphalt residue charging is less than 1000cP.
4. the method for claim 1 is characterized in that, described asphalt residue is being about 100-425 ℃ with temperature before described combustion gas jet contacts.
5. the method for claim 1, this method also comprise make described asphalt residue with contact so that this asphalt residue is carried out hydrotreatment with homogeneous catalyst before described combustion gas jet contacts.
6. the method for claim 1 is characterized in that, described homogeneous catalyst is a molybdenum sulfide catalyst.
7. the method for claim 1 is characterized in that, described hydrotreatment is to carry out in ebullated bed or the fixed bed hydrogenation treatment reactor.
8. the method for claim 1 is characterized in that, adds hydrogen in described asphalt residue.
9. the method for claim 1 is characterized in that, adding amounts of hydrogen in described asphalt residue is that every barrel of asphalt residue adds about 100 hydrogen to about 1500 standard cubic foots.
10. the method for claim 1 is characterized in that, adding amounts of hydrogen in described asphalt residue is that every barrel of asphalt residue adds about 150 hydrogen to about 1000 standard cubic foots.
11. the method for claim 1 is characterized in that, described combustion gas jet is by oxygenant and fuel reaction are formed.
12. the method for claim 1 is characterized in that, described oxygenant is selected from down group: air, oxygen-rich air and pure basically oxygen.
13. the method for claim 1 is characterized in that, described fuel is selected from down group: carbon monoxide, hydrogen, gaseous hydrocarbons and their mixture.
14. the method for claim 1, this method also comprise steam are added in the described fuel.
15. the method for claim 1 is characterized in that, the pressure ratio scope of described combustion gases and described reacting gas stream is 2-20.
16. the method for claim 1 is characterized in that, the temperature of described combustion gas jet is about 1250 ℃ to about 2000 ℃.
17. the method for claim 1 is characterized in that, described convergent-gradually expanded form nozzle is axisymmetric.
18. the method for claim 1, this method also comprise the array of convergent-gradually expanded form nozzle.
19. the method for claim 1 is characterized in that, described asphalt residue contacts with combustion gas jet around described combustion gas jet.
20. the method for claim 1 is characterized in that, described convergent-gradually expanded form nozzle is conical.
21. the method for claim 1 is characterized in that, described asphalt residue axially contacts with described combustion gas jet along described conical convergent-gradually expanded form nozzle.
22. the method for claim 1 is characterized in that, described being separated in the cyclonic separator carried out.
23. the method for claim 1 is characterized in that, described reactant the residence time more than 425 ℃ less than 400 milliseconds.
24. the method for claim 1 is characterized in that, adopts the agent of distillate chilling to cool off described vapor phase and gas phase rapidly.
25. the method for claim 1 is characterized in that, with described chilling agent atomizing.
26. the method for claim 1 is characterized in that, adopts sweep gas that the loss of the described distillate in the described mink cell focus is reduced to a minimum.
27. the method for claim 1 is characterized in that, adjusts the throughput ratio of described combustion gas jet and described asphalt residue, so that the adiabatic temperature scope of described reactant flow is between 500 ℃ to 850 ℃.
CN200880013731A 2007-04-24 2008-04-22 Flash processing of asphaltic residual oil Pending CN101668831A (en)

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