CN102803444B - For the method and apparatus of separate bitumen from slurry hydrocracking vacuum gas oil and composition - Google Patents
For the method and apparatus of separate bitumen from slurry hydrocracking vacuum gas oil and composition Download PDFInfo
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- CN102803444B CN102803444B CN201080035430.7A CN201080035430A CN102803444B CN 102803444 B CN102803444 B CN 102803444B CN 201080035430 A CN201080035430 A CN 201080035430A CN 102803444 B CN102803444 B CN 102803444B
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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
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
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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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1074—Vacuum distillates
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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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4081—Recycling aspects
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- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
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- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention discloses a kind of method and apparatus for being changed into by heavy hydrocarbon charge compared with lighter hydrocarbons product.By the pulp of heavy hydrocarbon charge particulate solid material with form heavy hydrocarbon slurry and in slurry hydrocracking unit hydrocracking to produce vacuum gas oil (VGO) and pitch.First vacuum column is by VGO and separated from bitumen, and the second vacuum column is further by VGO and separated from bitumen.The similar VGO of 15 % by weight is recovered and recycled to slurry hydrocracking device by the second vacuum column.Not coherent bituminous composition when obtaining can be made into particle and transport.
Description
Background of invention
The present invention relates to a kind of method and apparatus for the treatment of crude oil, relate more specifically under the existence of additive and catalyzer hydrocracking heavy hydrocarbon to provide useable products and further for the preparation of the method and apparatus of refining conversion system as the raw material of FCC or hydrocracking.
For heavy hydrocarbon oil being changed into the lightweight and medium naphtha with good quality and the hydrogenating conversion process being used for reformer feed, oil fuel and gas oil is known.The liquid that these heavy hydrocarbon oil can derive as petroleum crude oil, atmospheric tower bottom product, vacuum column bottom product, heavy cycle oil, shale oil, coal for this material, crude oil residue, topped oil and the heavy asphaltic oil produced by oil-sand.The special oil meaningfully produced by oil-sand, and it contains by petroleum naphtha to the wide boiling range material of kerosene, gas oil, pitch etc. and containing the material of most of boiling point more than 538 DEG C (1000 °F).
Because the reserves of conventional crude decline, must by these heavy oil modifications to satisfy the demands.In this upgrading, heavier material converting is become lighter fraction and most of sulphur, nitrogen and metal must be removed.Usually first in normal pressure crude still, process to provide by crude oil the fuel Products comprising petroleum naphtha, kerosene and diesel oil.Usually normal pressure crude still tower bottoms stream is delivered in vacuum tower so that obtain can for the raw material of FCC unit or the vacuum gas oil (VGO) of other purposes.VGO seethes with excitement usually in the scope of 300 DEG C of (572 °F)-538 DEG C (1000 °F).The bottoms of vacuum column usually comprise based on the ash free basis at least 9 % by weight except inorganic substance hydrogen and be less than the density of 1.05g/cc.Sending into further in refinery with before being processed into enabled production, usually in elementary reforming unit, process vacuum tower bottoms.Elementary reforming unit as known in the art includes but not limited to coking method, as postponed or fluid coking; With method of hydrotreating as ebullated bed or slurry hydrocracking (SHC).All these elementary modification technologies are as delayed coking, boiling bed hydrogenation cracking and slurry hydrocrackingly under normal pressure equivalent condition, crude oil vacuum bottom product can be changed into the VGO that boiling point is 343-538 DEG C (650-1000 °F).
Under the material converting by boiling point being more than 524 DEG C (975 °F) becomes boiling point to be the preferred level of conversion of the 80-95 % by weight of 524 DEG C (975 °F) or following material, SHC produces the asphaltic by-products based on the yield of ash free basis 5-20 % by weight.By definition, pitch is as ASTM D2887, D6352 or D7169 (all by petroleum industry use) measure the hydrocarbon material of boiling point more than 538 DEG C of (1000 °F) normal pressure equivalence values by standard gas chromatograph simulation distil method.The definition of these " transformation efficiencys " and " pitch " makes relative to bitumen conversion rate, and the scope of converted product narrows.Asphaltic by-products is at room temperature solid and the minimum pumping temperature had more than 250 DEG C, and this makes the movement carrying out any large distance be crackpot, because need pipeline deep fat to add chuck or electrically heated.It is also containing can the solid inorganic material that goes out of sedimentation.Therefore, tank storage is deposited needs to prevent the stirring of sedimentation or circulation, other fund and process cost.
When being heated to softened zone, the bonding of solid can be there is.Sticky or softening starting point is difficult to measure, and can need experience test consuming time, such as, by being merged under expection load by solid in the silo, measures thereafter the shearing force needed for mobile solid.This standard test comprises the ASTM D6773 using Schulz ring-shear test apparatus and the ASTM D6128 using Jenike ring-shear test apparatus.Pitch is not pure compound and melting in wide region.Therefore, dsc (DSC) can not obtain the clear and definite melting peak that can be used as presto tool program.
The softening temperature of pitch traditionally uses ring and ball softening point method, and ASTM D36 or Mettler softening point test method, ASTM D3104 measures.These two kinds of methods are all for measuring material by temperature during beginning liquid-flow.This can be particularly useful for the minimum temperature being provided as the pitch of liquid in the bituminous cement for the preparation of pave the way, put up a house top and other and industrial use.But this information does not tell about thing about softening beginning and not directly for determining that solid stands viscous deformation or starts coherent point.
Solidifying of pitch can be attended by dust generation, because have the pitch started compared with high softening-point may become fragility.But having the pitch started compared with low softening point may become viscosity, and this makes large quantities of difficult treatment.
Need for processing the better method of the pitch produced by SHC to provide more easy to handle pitch.In addition, the better method that can how easily to process for assessment of pitch is needed.
Summary of the invention
We find to use the second vacuum column cannot not provide stickyly and the pitch that can more easily solidify in the product from SHC reactor reclaims.Second vacuum column is separated further with pitch by VGO and VGO can be recycled in slurry hydrocracking reactor.A part can be recycled in slurry hydrocracking reactor from the pitch of the first vacuum column.Temperature lower in two vacuum columns is allowed in the use of the second vacuum column, and this reduces coking and cracking is considered.Then asphaltic by-products can be formed as the solid particulate of free-pouring large quantities of solid, and it more easily can manage under the transport temperature of expection.The use of two vacuum columns can also give lower asphalt temperature to avoid the coking in heating installation.When standing expection transport temperature, the pitch with the VGO concentration under 14 % by weight can not become sticky with its solid form.
Accompanying drawing is sketched
For understanding the present invention better, with reference to accompanying drawing.
Fig. 1 is the indicative flowchart of display the inventive method and equipment.
Fig. 2 is the indicative flowchart of the selectable method and apparatus of display the present invention.
DESCRIPTION OF THE PREFERRED
Multiple heavy hydrocarbon feedstocks can be become comparatively lighter hydrocarbons product with equipment by the inventive method.It can be processed aromatic raw material and be very difficult to the raw material of hydrotreatment traditionally, such as, sediment etc. bottom the vacuum residuum of vacuum tower bottoms, visbreaking, diasphaltene base material, defective pitch, storage tank.Suitable charging comprises boiling point at the long residuum of 343 DEG C (650 °F) or more, boiling point at the heavy vacuum gas oil (VGO) of 426 DEG C (800 °F) or more and vacuum residuum, and the vacuum residuum of boiling point more than 510 DEG C (950 °F).In whole specification sheets, boiling temperature should be understood to basis by the boiling temperature observed and distillation calculation of pressure, it is normal pressure equivalence boiling point (atmospheric equivalentboiling point, AEBP) that equation that the ASTMD1160 appendix A 7 of " Practice for Converting ObservedVapor Temperatures to Atmospheric Equivalent Temperatures " provides calculates as used title.In addition, term " pitch " is to be understood that and refers to that vacuum residuum or AEBP are greater than the material of 538 DEG C (1000 °F).
Equipment comprises slurry hydrocracking reactor 20, first vacuum column 90 and the second vacuum column 100.Separation column 50 can for the preparation of the slurry hydrocracking product of the first vacuum column 100, and tablets press 130 can make asphalt solidification become solid particulate.
In SHC method as shown in Figure 1, the heavy hydrocarbon recycle stream in the coke suppressant additive of the particulate material in pipe 6 or catalyzer and pipe 8 such as recycle of heavy VGO (HVGO) and/or pitch are mixed the homogenous slurry forming well blend in charging stock tank 10.Many kinds of solids granules of catalyst can be used as particulate material, and in an aspect, condition is that these solids can survive method for hydrogen cracking and remain valid as the part of recirculation.Useful especially granules of catalyst is US 4,963, described in 247 those.Therefore, particle is generally granularity and is less than 45 μm and most of, i.e. at least 50 % by weight ferrous sulfate with the granularity being less than 10 μm in an aspect.Sulfuric acid monohydrate iron is preferred catalyzer.Also can preferred alum clay catalyzer.In an aspect, granules of catalyst is suppressed to add in incoming mixture in the coke based on fresh feed 0.01-4.0 % by weight.As selecting or in addition, oil soluble coke suppressant additive can being used.Oil soluble additive comprises the metallic naphthenate with molybdenum, tungsten, ruthenium, nickel, cobalt or iron based on fresh feed 50-1000wppm or sad metal-salt.
Be pumped into from the heavy hydrocarbon charge in this slurry of charging stock tank 10 and pipe 12 in fired heater 14 via pipe 16.Combined feed is heated in well heater 14 and is pumped in the entrance bottom tubular type SHC reactor 20 by inlet tube 18.In well heater 14, the usual thermolysis of ferrum-based catalyst particle newly added by pipe 6 becomes to have the less Iron sulfuret of catalytic activity.Some decomposition can be carried out in SHC reactor 20.Such as, when leaving well heater 14, sulfuric acid monohydrate iron can change into Iron sulfuret and have and be less than 0.1 or the even granularity of 0.01 μm.SHC reactor 20 can take the form of three-phase (solid-liquid-gas) reactor, and it does not have stationary solid bed, and catalyzer, the charging of hydrogen G&O with the movement that only moves upward, wherein have back-mixing to a certain degree by it.
Many mixing and pumping configuration can be suitable.Such as replace or except the heavy oil recycle stream in pipe 8, also the charging in pipe 12 can be mixed with the catalyzer from pipe 6 in tank 10.Also feed steam 8 and 12 can add in SHC reactor 20 instead of mix by expection individually.
Standing after heating, the hydrogen make-up in the hydrogen of recirculation and pipe 22 to be fed in SHC reactor 20 by pipe 24 in well heater 26.Hydrogen in pipe 24 can add position more than the charging in-position in pipe 18.Can be distributed in from the hydrogen in the charging in pipe 18 and pipe 24 in SHC reactor 20 with suitable divider.In addition, it can heated and is being transferred in pipe 18 as shown in the charging added before in SHC reactor in pipe 16 by the hydrogen in pipe 23 in well heater 14.Also expection may use single heating device 14 heated air, charging and catalyzer combination stream to produce the feed steam in pipe 18, well heater 26 and pipe 24 can be saved in this case.
Between the SHC reaction period, the formation tending to coke or other material that liquid phase, solid phase or semi-solid phase are settled out from the bulk material of reactor is importantly made to minimize.This can cause the incrustation of reactor or downstream unit.The aromatic oil of relative polarity added in raw material is make coke or the minimized a kind of means of other throw out.HVGO is polar aromatic oil.In an aspect, depend on quality and the single-pass conversion level of raw material, the recirculation HVGO in pipe 8 accounts for the 0-50 % by weight of the raw material of SHC reactor 20.The charging entered in SHC reactor 20 comprises three phases: solid catalyst, liquid hydrocarbon and gas hydrogen and volatized hydrocarbon.
The inventive method at quite medium pressure, in an aspect at 3.5-24MPa range of operation, wherein can be formed without coke in SHC reactor 20.Temperature of reactor is generally 350-600 DEG C, and the temperature of 400-500 DEG C is preferred.LHSV is 4h based on fresh feed usually
-1below, 0.1-3hr
-1preferred, 0.2-1hr
-1particularly preferred.Every journey bitumen conversion rate can be 50-95 % by weight.Hydrogen gas feed rate is 674-3370Nm
3/ m
3(4000-20,000SCF/bbl) oil.Although SHC can multiple known to dirty or upwards carry out in flow reactor, the tubular reactor that charging and gas move upwardly through is applicable to particularly well.Therefore, the outlet of SHC reactor 20 is more than entrance.Although only one is shown in Fig. 1, one or more SHC reactor 20 can be used in parallel or in series.Because liquid feeding is changed into vapor product, therefore foaming tendency is in appearing in SHC reactor 20.Also defoamer can be added in SHC reactor 20, be added to its top in an aspect, to reduce the tendency producing foam.Suitable defoamer comprises as US 4, and 969, the siloxanes disclosed in 988.In addition, can by the top of the chilling hydrogen injecting reactor from pipe 27 to cool slurry hydrocracking product.Also expect that quench tube optionally comprises VGO, diesel oil or other hydrocarbon flow.
The hydrocracking stream of air inclusion-liquid mixture is taken out from the top of SHC reactor 20 by pipe 28.Slurry hydrocracking by the aliphatic group cracking from aromatic ring, but leave aromatic ring, thus produce that to comprise based on the ash free basis except inorganic substance be 8 % by weight or less, suitably 6 % by weight or less, the slurry hydrocracking product of hydrogen concentration of at least 4 % by weight usually.Slurry hydrocracking product can have based at least 1.1g/cc of the ash free basis except inorganic substance, suitably at least 1.15g/cc, is usually not more than the density of 1.3g/cc.The toluene insoluble organic detritus (TIOR) of slurry hydrocracking product also containing 1-10 % by weight." TIOR " represents the on-catalytic solid of a part of slurry hydrocracking product mid-boiling point more than 524 DEG C (975 °F).
Hydrocracking stream from SHC reactor 20 top is the vapour-liquid mixture be made up of several product, and described product comprises the VGO and pitch that can be separated with a large amount of different modes.In an aspect, by the hydrocracking effluent from SHC reactor 20 top under the separation temperature remaining on 200-470 DEG C (392-878 °F), and in an aspect SHC reaction pressure under high pressure hot separator 30 in be separated.Optional chilling in pipe 27 can help reaction product to be chilled in high pressure hot separator 30 temperature required.In high pressure hot separator 30, be separated into gas streams 32 and liquid stream 34 by pipe 28 from the effluent of SHC reactor 20.Gas streams is flash vaporized product under the temperature and pressure of high pressure hot separator 30 and comprises the hydrocarbon product from SHC reactor 20 of 35-80 volume %, preferred 50-70 volume %.Equally, liquid stream is the flashed liquid under the temperature and pressure of high pressure hot separator 30.Gas streams is removed at top by pipe 32 from high pressure hot separator 30, and liquid distillate is taken out bottom high pressure hot separator 30 by pipe 34.
By the liquid distillate in pipe 34 in the temperature identical with high pressure hot separator 30, but be transferred under the pressure of 690-3,447kPa (100-500psig) in heat-lightening steaming pot 36.Vapor overhead product in pipe 38 cool in water cooler 39 and pipe connecting 42 (it is the liquid bottoms product from cold high pressure separator in pipe 42) to form pipe 52.Liquid distillate leaves heat-lightening steaming pot in pipe 40.
Lower temperature is cooled in the one or more water coolers overhead leaving high pressure hot separator 30 in pipe 32 represented at water cooler 44.Water washing (not shown) on pipe 32 is generally used for washing out salt as curing ammonium or ammonium chloride.Water washing will remove nearly all ammonia and some hydrogen sulfide from stream 32.Stream 32 is delivered to cold high pressure separator 46.In an aspect, cold high pressure separator in the temperature lower than high pressure hot separator 30, but operates at the same pressure.Under cold high pressure separator 46 remains on the separation temperature of 10-93 DEG C (50-200 °F), and in an aspect under the pressure of SHC reaction.In cold high pressure separator 46, the top product of high pressure hot separator 30 is separated into gas streams 48 and liquid stream 42.Gas streams is the flash vaporized cut under the temperature and pressure of cold high pressure separator 46.Equally, liquid stream is flashed liquid product under the temperature and pressure of cold high pressure separator 46 and comprises the hydrocarbon product from SHC reactor 20 of 20-65 volume %, preferred 30-50 volume %.By using this kind of separator, gained exit gas stream is mainly containing having the hydrogen of some impurity as hydrogen sulfide, ammonia and light hydrocarbon gas.
Rich hydrogen stream in pipe 48 can be passed through fills washing tower 54, it is washed by the washings in pipe 56 to remove hydrogen sulfide and ammonia there.Renewable and the recirculation of spent scrub stream in pipe 58, and be generally amine.Washing rich hydrogen stream discharge from washer via pipe 60 and with added by pipe 62 and combined by the fresh supplemented hydrogen that circulating air compressor 64 and pipe 22 recirculation return in SHC reactor 20.Hydrogen make-up can add in compressor 64 upstream or downstream, if but use chilling, then supplementing pipe 62 should in the downstream of quench tube 27.
Liquid distillate carry fluids product in pipe 42 adjoins the flash evaporation tank top product of the cooling left in the pipe 38 of water cooler 39 to produce pipe 52, to cold flash tank 66 feed under the lower pressure of its 690-3,447kPa (100-500psig) in the temperature identical with cold high pressure separator 46 and heat-lightening steaming pot 36.Top gas in pipe 68 can for comprising the C that can be recovered and utilize
4the fuel gas of material.Liquid bottoms product in pipe 70 and flowing into separately in distillation stage 50 from the bottoms pipe 40 of heat-lightening steaming pot 36.
Distillation stage and SHC reactor 20 communicating downstream." communicating downstream " means the material flowed at least partially in communicating downstream assembly can operationally from the assembly that it is communicated with." connection " means material flowing and operationally allows between listed assembly." upstream connection " means can operationally flow in the assembly of its connection from the material of upstream connection assembly at least partially.Distillation stage 50 can comprise one or several container, but it is only shown as a container in FIG.Distillation stage 50 can comprise strip vessel and atmospheric tower, but is just single tower in an aspect.Rare gas element as middle pressure steam can bottom distillation stage 50 near feed in pipe 72 with the comparatively light constituent of stripping from heavy component.Distillation stage 50 produces top gas product in pipe 74, at the naphtha products stream in pipe 76 that sides stream, in the diesel product stream in pipe 78 of sideing stream, at optional atmospheric gas oil (AGO) stream sideed stream in pipe 80 and the VOG in bottoms pipe 82 and pitch stream.
A part of hydrocracking effluent in bottom stream from distillation stage 50 to be introduced in fired heater 84 and the bottom stream of heating is transferred to and remains on 1-10kPa (7-75 holder) by pipe 82, in the first vacuum column 90 at the pressure of preferred 1-7kPa (10-53 holder) and vacuum distilling temperature, produce 371-482 DEG C (700-900 °F), preferred 398-454 DEG C (750-850 °F), the normal pressure equivalence cut point most preferably between the lightweight VGO (LVGO) of 413-441 DEG C (775-825 °F) and HVGO.First vacuum column and distillation stage 50 and SHC reactor 20 communicating downstream.First vacuum column is in an aspect for having three grades of injectors to provide the distillation tower of the vacuum in tower at top.The injector in each stage and gas streams such as steam feed the vacuum promoting injector upstream in vacuum column simultaneously.Pressure is larger in each injector stage downstream side, causes overhead in accumulator, be condensed into callable product liquid.The lighter-than-air gas leaving for the 3rd injector stage can be recovered and be used as the fuel in fired heater 84 in an aspect.Can be suitable for promoting the device of other type of vacuum.In an aspect, steam stripped can be used in the first vacuum column.Steam is transferred in the first vacuum column 90 by steam merging chamber 104 by pipe 99.
Three kinds of cuts can be separated in the first vacuum column: the diesel oil in head tube 92 and the overhead fraction compared with lighter hydrocarbons, in pipe 94 from the boiling point sideed stream not higher than 482 DEG C (900 °F), LVGO stream more than usual 300 DEG C (572 °F), pipe 96 mid-boiling point that sides stream be more than 371 DEG C (700 °F) HVGO stream and bottoms pipe 98 obtain more than 450 DEG C (842 °F) boiling pitch stream.Many HVGO in pipe 96 are recycled in SHC reactor 20 usually.The HVGO of non-recycling part is recovered usually used as product and transforms further in other refining operation.Produce (it needs larger energy to promote vacuum) for making steam to minimize, a part of LVGO stream in pipe 94 is cooled by heat exchange and in pipe 95 in pumped back tower with condensation condensable materials as much as possible.To side stream pipe less than 96 and the opposite side cut of slop wax in the pipe 97 obtained at the bottoms pipe more than 98 carrying the first pitch stream at HVGO, can be recycled to and side stream in the SHC reactor 20 of pipe 97 communicating downstream with slop wax.In this case, most of or all streams 96 can be used as the recovery of HVGO product.By sideing stream in take-off pipe 97, less charging is sent in the second vacuum column 100, require it to have more low capacity and improve the quality of HVGO in pipe 96.Slop wax stream in pipe 97 has 621 DEG C (1150 °F) below usually, preferably 607 DEG C (1125 °F) full boiling points below.VGO stream also can upstream recirculation to strengthen lock out operation.
The first pitch stream in pipe 98 is transferred to the second vacuum column 100 of the first vacuum column 90, separation column 50 and SHC reactor 20 communicating downstream in pipe 98.The first pitch stream in pipe 98 is not suitable as granular solids bulk flow.It is heat-labile, because if stand this temperature time enough, it starts cracking being low to moderate at the temperature of 300 DEG C.Pitch in pipe 98 can have can up to the inorganic solid content of 6-10 % by weight.Highly filled formation by coke makes fired heater 84 tend to fouling.Temperature required in bottom vacuum column by adding steam to reduce hydrocarbon partial pressure or to reduce by reducing vacuum pressure further, is costliness both it.Temperature in bottom vacuum column must be high to be promoted from pitch by enough HVGO.What we found to comprise the pitch of at least 14 % by weight HVGO solidifies the sticky particle providing and be not easy bulk treatment.Fired heater 84 outlet at the temperature of 385 DEG C (725 °F) can make the first vacuum column 90 produce the pitch only with 10 % by weight HVGO content, but well heater 84 may be made to live through multifocalization.
The present invention uses the second vacuum tower 100 to promote HVGO further from pitch.In an aspect, the second vacuum tower operates to obtain to produce and can be formed and can the VGO needed for pitch of particle of bulk treatment promote under the pressure lower than the first vacuum column.The use of the second vacuum column 100 provides 377 DEG C (710 °F) in the fired heater 84 of the first vacuum column 90 upstream or following, 370 DEG C in an aspect (698 °F) or following lesser temps, so more impossible from the fouling of coking.Be used in the steam stripped in the first vacuum column 90, the first pitch stream in pipe 98 can be transferred in the second vacuum column 100 under 315-350 DEG C (600-662 °F).In an aspect, the first pitch stream in pipe 98 directly can be transferred in the second vacuum column 100 without undergoing heating or refrigerating unit.In other words, pipe 98 can lack heating or refrigerating unit until it is to the second vacuum column 100 feed.But some heating or cooling may be required.As selection, in an aspect, heat adds in the second vacuum column 100 by deep fat or steam.Therefore, to the temperature in of the first pitch stream 98 in the second vacuum column 100 in an aspect than large from the temperature out of the first pitch stream 98 bottom the first vacuum column 90 or be littlely not more than 50 DEG C.
The bottom communicating downstream of the second vacuum column 100 and the first vacuum column 90.Second vacuum column 100 remains on 0.1-3.0kPa (1-23 holder), at the pressure of preferred 0.2-1.0kPa (1.5-7.5 holder) and the vacuum distilling temperature of 300-370 DEG C (572-698 °F), produce 454-593 DEG C (850-1100 °F), preferred 482-579 DEG C (900-1075 °F), the normal pressure equivalence cut point most preferably between the HVGO of 510-552 DEG C (950-1025 °F) and pitch.Second vacuum column 100 and the first vacuum column 90, distillation stage 50 and SHC reactor 20 communicating downstream.
Second vacuum column 100 can for conventional vacuum tower or it can have by producing the special function of to drive away VGO for the asphalt membrane promoting low boiling component to evaporate from pitch from pitch.The vaporizer producing dedicated film can promote that VGO evaporation is to avoid coking fast enough.Film generates vaporizer can comprise vaporizer stripper, thin-film evaporator, wiped film evaporator, falling film evaporator, rising-film evaporator and wiped surface vaporizer.In these films generation vaporizer, some can comprise the moving part for upgrading the asphalt surface in the second vacuum column 100.It can be suitable that the film of other type generates vaporizer.Such as thin-film evaporator (TFE) by the asphalt heating on heating tube internal surface until VGO start evaporation.By having ground, fixed interval (FI) rotating vane, pitch retains on the inside pipe surface as film.Then VGO steam liquefies on the cooling tube of condenser.Wiped film evaporator (WFE) is different from TFE part and is that its uses and has and stir the pitch that flows to be separated with the hinged blades of the minimum clearance of internal surface.In TFE and WFE, pitch tangentially to be entered in unit more than managing in heating and is evenly distributed on the inner periphery of pipe by rotating vane.Pitch spirals down on wall, and the bow wave (bow wave) of rotor blade development simultaneously produces height eddy current and best hot-fluid.VGO rapid evaporation and steam can relative to pitches and stream or counter-current flow.In simple TFE and WFE design, VGO can be arranged in outside but as far as possible close to the condenser condensation of vaporizer.Short-path distillation unit is another kind of TFE or WFE with internal condensation device.Wiped surface vaporizer (SSE) is similar to the operate of WFE.But SSE inexertion only keeps film on inner heating surface, but the asphalt membrane frequently being removed by scraper and remain on as possible on hot surface is not overheated.
In falling film evaporator (FFE), pitch to enter at top in vaporizer and is distributed to equably in heating tube.Film enters in heating tube and also flows downward at boiling temperature and part evaporation.Rare gas element such as steam can be used for the heating tube by the external contact with pipe.Pitch and VGO steam all flow into downwards in Lower separator in pipe, wherein by steam VGO and separated from bitumen.
Rising-film evaporator (RFE) operates based on thermosiphon principle.Pitch enters through the bottom of the steam-heated heating tube provided in the outside of pipe.When asphalt heating, steam VGO starts to be formed and rises.The raising force of this gasification VGO causes liquid and steam upwards to flow with parallel flow.Meanwhile, the output increased of VGO steam and pitch when rising as thin film on tube wall.Relative to gravity and stream moves up the advantageous effects having and produce in pitch and promote the high turbulence that heat trnasfer and coke suppress.
In an aspect, special second vacuum column 100 for generation of film can be can by Artisan Industries of Waltham, the vaporizer stripper that Maryland obtains.Second vacuum column 100 is shown as the vaporizer stripper in Fig. 1.First pitch stream 98 can be passed through optional preevaporator 102, and described preevaporator can for RFE be to evaporate most of VGO from pitch.Vaporizer stripper can not have the operation of preevaporator 102 ground.Steam or other rare gas element enter the upper end of preevaporator 102 by steam merging chamber 104 and condensation product leaves in lower end.Pitch and VGO enter in the major diameter flash zone 108 of vaporizer stripper 100 via pipe 106.Steam VGO can by entrainment trap as mist eliminator leaves vaporizer stripper top to be separated condensables.Steam leaves and enters in condenser 112 and possibility accumulator 114 in pipe 110.Vacuum is pulled out by condenser 112, can by stage injector or other appropriate device.Pipe 116 takes out VGO, in an aspect mainly HVGO, to be recycled in SHC reactor 20 in pipe 8.Therefore, the top communicating downstream of SHC reactor 20 and the second vacuum column 100.In pipe 116, a part of HVGO can be recovered, and flows out in pipe 124 as clean product.The downward level of pitch in vaporizer stripper 100 is associated in heating or the column plate that do not heat as on pipe-disc type column plate, simultaneously all the other volatile matters by rising steam by stripping.Column plate provides the new liq film in each stage, upgrades for evaporating the surface with steam stripped asphalt membrane.In an aspect, column plate can limit and the inner chamber be communicated with through the heating fluid of the pitch of column plate for indirect heating from pipe 126.Heating fluid leaves the second vacuum column 100 to reheat in pipe 128.Rare gas element can be sprayed onto in tower with stripping pitch by pipe 118 as steam or nitrogen and to strengthen mass transfer further.Second pitch stream removes by the second vacuum column 100 in pipe 120, and comprises and be less than 14 % by weight VGO, is preferably not more than 13 % by weight VGO.In the present context, be less than 14 % by weight from the second vacuum tower bottoms, be not more than 13 % by weight in an aspect, be preferably not more than the second pitch stream in the pipe 120 of 10 % by weight at 538 DEG C (1000 °F) or seethe with excitement below.In addition, be less than 14 % by weight, be not more than 13 % by weight in an aspect, the second pitch stream be preferably not more than in the pipe 120 of 10 % by weight seethes with excitement in 300 DEG C (572 °F)-538 DEG C of (1000 °F) scopes.In an aspect, at least 1 % by weight pipe 120 in the second pitch stream be or be less than the VGO of boiling under 538 DEG C (1000 °F).The second pitch stream in pipe 120 also comprises based on the ash free basis 8 % by weight or less except inorganic substance, and suitably 6 % by weight or less, the hydrogen concentration of at least 4 % by weight usually.Second pitch stream can have based at least 1.1g/cc of the ash free basis except inorganic substance, suitably at least 1.15g/cc, is usually not more than the density of 1.3g/cc.Second pitch stream also can contain the toluene insoluble organic residue (TIOR) of 1-10 % by weight.Second vacuum column 100 can reclaim the similar VGO of 15 % by weight from pitch.The VGO of this recovery leaves vacuum column 100 in head tube 110, and it can return in SHC reactor 20 in pipe 116,8,16 and 18 in recirculation.
The second pitch stream in vacuum tower bottoms pipe 120 can directly be discharged in tablets press 130.In an aspect, do not need by the asphalt temperature in heat exchange Correctional tube 120 with the pitch for the preparation of granulation.Useful especially tablets press 130 is by Sandvik Process Systems ofSandviken, and the ingot device processed of what Sweden provided be called Rotoformer, it produces the hemi-spherical granule being called ingot.Other tablets press can be melt line material tablets press, underwater melt cutter, the forcing machine with mouth template, granulating system, spray-drier etc.The particle produced should have circle or semicircle appearance, and this makes them move freely in bulk treatment and transfer system.Circular or semicircle particle comparatively can not stick together, because they have less point of contact, and the less dust that tends to is formed, because they lack the sharp edges of sheeting.
The tablets press 130 of ingot type processed comprises the cylinder shape stator 134 of heating, and it provides the molten asphalt from the second pitch stream 120 or storage tank 132.Tablets press 130 is via the bottom communicating downstream of pipe 120 and the second vacuum column 100.Rotate porose cylindrical wall 136 around stator 134 Concentric rotation with by have hole wall 136 perforate launch and the asphaltogenic particle of shape or ingot.Ingot is deposited on the whole operation width of metal belt 138, and in an aspect, described travelling belt is stainless.Solidify at the ingot dripped and shifted by band 138 with the heat of cooling period release, described band is by cooling as the water indirect heat exchange of being sprayed by pipe 140 under being with heat-eliminating medium.The water coolant of spraying to be collected in tank and in pipe 142, to be recycled to water cooling system and not to contact pitch particle.The too much pitch be retained in the perforate of rotational circle cylindrical wall 136 can be forced into the position it dropped in again on band 138 by the rod of charging again of heating.Ingot is sent in collector 144 by band 138.Present pitch ingot can easily bulk treatment also transport for consuming.Pitch ingot can store or transport now and not need other cooling of having a mind to.Ingot can not stick together, because enough VGO have been separated that softening starting point temperature is increased to more than the highest expection transport temperature from pitch.Highest expected temperature in transport must depend on the weather of route and the type of container.The reliable global maximum of 66 DEG C (150 °F) can by InternationalSafe Transit Association, the data estimation of Ocean Container Temperature and HumidityStudy, Preshipment Testing Newsletter (second quarter in 2006).
Fig. 2 describes the selectable schema of the present invention, is wherein recycled in SHC reactor 20 from the pitch recycle stream in the pipe 150 of the first pitch stream in pipe 98.Fig. 2 and Fig. 1 is identical, and difference is to regulate the pitch recirculation pipe 150 of a part of first pitch stream 98 of transfer to be combined with feed-pipe 8 to make pipe 116 to walk around the second vacuum column 100 by control valve 142.Therefore, the bottoms communicating downstream of SHC reactor 20 and the first vacuum column 100.All other sides of Fig. 2 embodiment are identical with Fig. 1.First pitch stream can optionally be recycled in SHC reactor 20 in pipe 8 as a part of charging at least partially.All the other granules of catalyst from SHC reactor 20 in SHC effluent in pipe 28 will be present in the first pitch stream 98.Part catalyzer can return in SHC reactor 20 together with a part of first pitch stream recirculation expediently.This selection scheme will preserve SHC catalyzer.Rest part first pitch stream in pipe 98 is transferred in the second vacuum column 100 in pipe 146.In in this selection, the first vacuum column 90 can for not having the flashing tower of heat input or cooling.
Embodiment
For measuring bituminous material solidifiable and transport, considering acceptable safe operating limits, taking the top temperature that 66 DEG C (150 °F) expose as In transit bituminous material.Bituminous material must can transport and not start to be bonded together under this maximum temperature at the most.That is, the softening beginning temperature of pitch must be greater than 66 DEG C (150 °F).
The program of thermodynamic analyzer (TMA) is used to be similar to McNally, and McCourt G., M., Density Measurement of Thermoplastic Powders During Heating andCooling Cycles Using Thermal Mechanical Analysis, the program of the density for measuring powdery molded polymeric of ANTEC 2002Conference Proceedings, 1956-1960 report.TMA ModelQ400 from TA Instruments of New Castle, Delaware starts temperature and temperature of fusion for measuring melting.The non-classification asphalt powder of 10mg hand lapping is introduced in 7mm aluminium dish.Powder bed Aluminum cover is covered.The quartzy plunger covered measures the position of lid.By 5g load applying on powder and by powder with 5 DEG C/min of heating.Pitch softens and collapses when temperature is raised.Assembling position relative to the tabular data of temperature, and as the function of temperature, draws the first order derivative of changes in skew relative to the temperature variation at 5 DEG C of intervals.When the speed of thermal expansion is caught up with speed that powder collapses and seen as clearly sharp-pointed paddy on rate diagram, melting or fusing point are the temperature of maximum negative displacement.This paddy occurs it being because after collapsing, and when it is liquid, powdered sample starts rise with temperature and expand now.The starting of melting be defined as first order derivative relative to paddy 1% detected skew.
The beginning melt temperature of 1% distortion is expressed as T (1%), defines as follows:
T (1%) is (Z-Z
liq)/(Z
0-Z
liqtemperature during)=0.01 (1)
Wherein:
The position that Z=measures under temperature T;
Z
0=there is the starting position of the plunger of sample at ambient temperature; And
Z
liq=be the position under the fusing point at the peak of rate diagram.
Seven kinds of residual pitch products by the mixture of slurry hydrocracking device heavy product prepare with sets forth obtain do not glue, method needed for free-pouring pitch particle.The raw material produced for each residual pitch is the heavy ends of the product obtained after 87 % by weight transformation efficiencys, and described transformation efficiency is by by by slurry hydrocracking for pitch vacuum tower bottoms and to change into boiling point be the boiling point of 524 DEG C of (975 °F) materials is below that the material of more than 524 DEG C (975 °F) limits.Vacuum tower bottoms by from SlaveLake, Alberta, the pitch preparation that the cold process of Peace River (Seal) rock stratum near Canada is produced.In continuous-stirring reactor, under 13.79MPa (2000psi), use ferric sulfate catalyst based slurry hydrocracking in the presence of hydrogen gas this pitch bottoms.To the isocrackate flash distillation of reactor be left to remove the product lighter than middle distillate and stripping hydrogen and all uncondensable products.For the raw material of further fractionation hereinafter referred to as heavy end cut (heavy ends, HE).
The pitch ingot of sample 1 for preparing by making HE stand conventional vacuum fractionation.The coagulated ingot of sample 1 does not move freely and is obviously at room temperature viscosity.Measure distortion by TMA to start to be 44 DEG C.Sample 1 is unacceptable for bulk treatment and transport.
Sample 2 is the clarification pitch produced by the following method: make HE sedimentation in holder, then by the liquid vacuum flashing under 380 DEG C and 5 holders (0.7kPa) without solid.The heavy vacuum flashed liquid of clarification is not made to stand further process.It is obviously not viscosity and has the softening starting point of 72.5 DEG C, and its border land is more than maximum transport temperature.Therefore, material 2 is that border land is acceptable.
Sample 3 is the de-oiling sludge produced from the HE settling operation for the preparation of sample 2.Physical sepn discharges oil by sieve plate from vacuum flashing liquid, makes volatile matter evaporate composition simultaneously.Then de-oiling sludge is made under the high vacuum of 0.3kPa (2 holder), to stand vacuum-evaporation by falling-film evaporator, but without undergoing further process.As sample 1, it is obviously viscosity, and does not move freely.The softening starting point of 52.7 DEG C of material 3 is unacceptable.Its VGO content is determined as 14 % by weight by mass balance.
Sample 4 and 5 is wherein by HE vacuum fractionation under deeper vacuum in Laboratory batch still kettle, simultaneously churned mechanically bitumen samples.Sample 4 and 5 is acceptable, because they have the softening starting point temperature higher than maximum transport temperature.But, sample 5 is heated to the temperature of 320 DEG C to drive away more VGO.At such a temperature, there are some thermally splitting.Bituminous material partial thermal decomposition can be improved its softening starting point temperature.But pitch more can be difficult to process, because its high fluid viscosity and high temperature can cause coking on heat exchange surface.In addition, especially under low absolute pressure, thermally splitting can produce the gas of higher volume, and it can surpass the ability of vacuum system rapidly.
Sample 6 and 7 by by the first step of HE vacuum fractionation and be fed in 300 DEG C of inner flash vaporization points and respectively 0.1 and 0.3kPa (0.7 and 2.5 holder) under second step in the wiped film evaporator that runs and preparing.Subsequently sample 6 and 7 passed through melting again and on Sandvik Rotoformer, form the semicircle ingot of 7mm and be granulated.Ingot is not viscosity and free-pouring and gather without any, is also even like this at 100 DEG C, thus determines that granulated materials can process under the temperature more than any possible transport temperature.
The result of following table display test.VGO mark is by the mark definition of the pitch at 538 DEG C (1000 °F) or following boiling.The pitch that VGO mark is less than 14 % by weight has the acceptable softening starting point temperature being generally used for bulk treatment.
Table
| Specimen coding | Fusing point, DEG C | Softening starting point temperature, DEG C | VGO mark, % by weight |
| 1 | 86.1 | 43.7 | 18 |
| 2 | 96.4 | 72.5 | 13 |
| 3 | 88.1 | 52.7 | 14 |
| 4 | 116.5 | 72.2 | 2 |
| 5 | 169.5 | 118.5 | 2 |
| 6 | 153.5 | 113.8 | 1 |
| 7 | 143.7 | 95.0 | 1.5 |
Bitumen product in expection sample 1-7 has the hydrogen concentration of 5 % by weight and the density of 1.2g/cc based on the ash free basis except inorganic substance.
Do not further describe, believe that those skilled in the art can use previous description, most integrated degree ground uses the present invention.Therefore, aforementioned preferred specific embodiments is interpreted as being only illustrative, and the rest part of limit publicity content never in any form.
In the preceding article, unless otherwise noted, all temperature are with a DEG C description, and all parts and percentage ratio are weighing scale.
In previously describing, those skilled in the art can easily determine principal character of the present invention, and make various changes and modifications of the present invention with can not departing from its spirit and scope be suitable for various uses and condition to make it.
Claims (10)
1., for heavy hydrocarbon charge being changed into the method compared with lighter hydrocarbons product, it comprises:
By with the slurried described heavy hydrocarbon charge of particulate solid material in hydrocracking reactor in the presence of hydrogen gas hydrocracking to produce the hydrocracking stream comprising vacuum gas oil VGO and pitch;
To be separated to provide the first pitch stream and a VGO stream by described hydrocracking stream in the first vacuum column at least partially; With
To be separated to provide the second pitch stream and the 2nd VGO stream in the second vacuum column by described first pitch stream at least partially.
2. method according to claim 1, the inlet pressure wherein in the first vacuum column is greater than the inlet pressure in the second vacuum column.
3. method according to claim 1, it comprises further makes the pitch in described second pitch stream cannot not form stickyly solid particulate at the temperature of 66 DEG C at the most.
4. method according to claim 1, the slop wax stream recirculation wherein obtained below HVGO cut turns back in hydrocracking reactor.
5. method according to claim 1, wherein has the softening starting point temperature of at least 66 DEG C from the pitch of the second vacuum column.
6. method according to claim 1, it comprises further makes the described first pitch stream of a part be recycled to hydrocracking step.
7. method according to claim 1, it comprises further makes the 2nd VGO stream be recycled to hydrocracking step.
8., for heavy hydrocarbon charge being changed into the equipment compared with lighter hydrocarbons product, it comprises:
For the slurry hydrocracking reactor making described heavy hydrocarbon charge and hydrogen contact with particulate solid material;
The first vacuum column be communicated with described slurry hydrocracking reactor; With
The second vacuum column be communicated with described first vacuum column.
9. equipment according to claim 8, wherein said second vacuum column is that film generates vaporizer.
10. equipment according to claim 8, wherein said second vacuum column comprises the moving part of the material surface in renewal second vacuum column.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US12/491,439 | 2009-06-25 | ||
| US12/491,444 | 2009-06-25 | ||
| US12/491,439 US8540870B2 (en) | 2009-06-25 | 2009-06-25 | Process for separating pitch from slurry hydrocracked vacuum gas oil |
| US12/491,444 US8202480B2 (en) | 2009-06-25 | 2009-06-25 | Apparatus for separating pitch from slurry hydrocracked vacuum gas oil |
| PCT/US2010/038759 WO2010151463A2 (en) | 2009-06-25 | 2010-06-16 | Process and apparatus for separating pitch from slurry hydrocracked vacuum gas oil and composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102803444A CN102803444A (en) | 2012-11-28 |
| CN102803444B true CN102803444B (en) | 2015-09-02 |
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| CN201080035430.7A Active CN102803444B (en) | 2009-06-25 | 2010-06-16 | For the method and apparatus of separate bitumen from slurry hydrocracking vacuum gas oil and composition |
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|---|---|
| CN (1) | CN102803444B (en) |
| BR (1) | BRPI1014342A2 (en) |
| CA (1) | CA2765954C (en) |
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| US9150470B2 (en) | 2012-02-02 | 2015-10-06 | Uop Llc | Process for contacting one or more contaminated hydrocarbons |
| US10041011B2 (en) * | 2014-11-06 | 2018-08-07 | Uop Llc | Processes for recovering hydrocarbons from a drag stream from a slurry hydrocracker |
| RU2681527C1 (en) | 2016-12-30 | 2019-03-07 | Бейджинг Хуаши Юнайтед Энерджи Технолоджи энд Девелопмент Ко., Лтд. | Light petroleum products from heavy oil production method and device by the hydrogenation in the fluidized bed method |
| RU2640198C1 (en) * | 2017-01-19 | 2017-12-27 | Роман Иванович Якименко | Rotation-percussion evaporator and method of vacuum transfer of complex liquids on its basis |
| US10799857B2 (en) * | 2018-09-26 | 2020-10-13 | Uop Llc | Process for making and using metal catalyst for slurry hydrocracking |
| CN113061466A (en) * | 2021-02-04 | 2021-07-02 | 洛阳瑞华新能源技术发展有限公司 | Combined distillation method for generating oil by tail liquid circulating hydrocarbon material upflow type hydrogenation thermal cracking |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3968023A (en) * | 1975-01-30 | 1976-07-06 | Mobil Oil Corporation | Production of lubricating oils |
| US4525267A (en) * | 1981-06-09 | 1985-06-25 | Chiyoda Chemical Engineering & Construction Co., Ltd. | Process for hydrocracking hydrocarbons with hydrotreatment-regeneration of spent catalyst |
| CN100489061C (en) * | 2003-11-14 | 2009-05-20 | 艾尼股份公司 | Integrated process for the conversion of feedstocks containing coal into liquid products |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5755955A (en) * | 1995-12-21 | 1998-05-26 | Petro-Canada | Hydrocracking of heavy hydrocarbon oils with conversion facilitated by control of polar aromatics |
| RU2145971C1 (en) * | 1998-12-15 | 2000-02-27 | Леонтьевский Валерий Георгиевич | Method of in-line distillation of mazout and device for realization of this method |
| FR2854163B1 (en) * | 2003-04-25 | 2005-06-17 | Inst Francais Du Petrole | METHOD FOR ENHANCING HEAVY LOADS BY DISASPHALTING AND BOILING BED HYDROCRACKING |
| JP2008163097A (en) * | 2006-12-27 | 2008-07-17 | Kobe Steel Ltd | Method for hydrocracking heavy oil |
-
2010
- 2010-06-16 RU RU2012102378/04A patent/RU2504575C2/en active
- 2010-06-16 CA CA2765954A patent/CA2765954C/en active Active
- 2010-06-16 CN CN201080035430.7A patent/CN102803444B/en active Active
- 2010-06-16 BR BRPI1014342A patent/BRPI1014342A2/en not_active IP Right Cessation
- 2010-06-16 WO PCT/US2010/038759 patent/WO2010151463A2/en active Application Filing
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3968023A (en) * | 1975-01-30 | 1976-07-06 | Mobil Oil Corporation | Production of lubricating oils |
| US4525267A (en) * | 1981-06-09 | 1985-06-25 | Chiyoda Chemical Engineering & Construction Co., Ltd. | Process for hydrocracking hydrocarbons with hydrotreatment-regeneration of spent catalyst |
| CN100489061C (en) * | 2003-11-14 | 2009-05-20 | 艾尼股份公司 | Integrated process for the conversion of feedstocks containing coal into liquid products |
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| RU2012102378A (en) | 2013-07-27 |
| BRPI1014342A2 (en) | 2016-04-05 |
| CA2765954C (en) | 2014-10-07 |
| RU2504575C2 (en) | 2014-01-20 |
| WO2010151463A3 (en) | 2011-04-28 |
| WO2010151463A2 (en) | 2010-12-29 |
| CA2765954A1 (en) | 2010-12-29 |
| CN102803444A (en) | 2012-11-28 |
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