CN102099444A - Catalytic reforming process to produce high octane gasoline - Google Patents
Catalytic reforming process to produce high octane gasoline Download PDFInfo
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- CN102099444A CN102099444A CN2009801278859A CN200980127885A CN102099444A CN 102099444 A CN102099444 A CN 102099444A CN 2009801278859 A CN2009801278859 A CN 2009801278859A CN 200980127885 A CN200980127885 A CN 200980127885A CN 102099444 A CN102099444 A CN 102099444A
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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
- C10G59/00—Treatment of naphtha by two or more reforming processes only or by at least one reforming process and at least one process which does not substantially change the boiling range of the naphtha
- C10G59/02—Treatment of naphtha by two or more reforming processes only or by at least one reforming process and at least one process which does not substantially change the boiling range of the naphtha plural serial stages only
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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
- C10G35/00—Reforming naphtha
- C10G35/04—Catalytic reforming
- C10G35/06—Catalytic reforming characterised by the catalyst used
- C10G35/095—Catalytic reforming characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
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Abstract
The present invention is a multistage reforming process to produce high octane product from naphtha boiling range feed. In the process, an effluent product from a penultimate reforming stage is separated into at least a first stream and a second stream by boiling point. The lower boiling of the two streams is further reformed in a final reforming stage over a medium pore molecular sieve catalyst.
Description
Invention field
The present invention relates to the multistage reforming method that uses intermediate pore molecular sieve catalyst, produce high-octane naphtha with high liquid yield and high hydrogen output.
Background of invention
Catalytic reforming is to be used for one of the basic petroleum refining process that upgrading is commonly referred to the lighter hydrocarbons charging of naphtha feed.The product that obtains from catalytic reforming can comprise stop bracket gasoline, aromatic hydrocarbons (for example benzene,toluene,xylene and ethylbenzene) and/or the hydrogen that is applicable to automobile fuel.The typical case is included in dehydrocyclization, isomerization and the dehydrogenation reaction that reaction in the catalytic reforming process comprises naphtha range hydrocarbons, and the linear and dehydrocyclization of little branched alkane and the dehydrogenation reaction of dehydrogenation reaction and naphthenic hydrocarbon cause generating aromatic hydrocarbons.Dealkylation and hydrocracking reaction are not expected because of the light hydrocarbon product that obtains low value usually.
The industrial catalyzer that is usually used in reforming reaction comprises second catalytic metal that VIII family metal such as platinum and palladium or VIII family metal have added the promotor effect usually.The example that is used as the metal of promotor comprises rhenium, tin, tungsten, germanium, cobalt, nickel, rhodium, ruthenium, iridium or their combination.Catalytic metal or multiple catalytic metal can place on the carrier such as aluminum oxide, silicon oxide or sieve and silica-sesquioxide.Generally halogen such as chlorine to be introduced on the carrier to increase the acid functionality.Except that VIII family metallized metal, other reforming catalyst comprises aluminosilicate zeolite catalyst.For example, U.S. Patent number 3,761,389,3,756,942 and 3,760,024 has instructed hydrocarbon-fraction to carry out the method for virtueization with ZSM-5 type zeolite catalyst.U.S. Patent number 4,927,525 disclose and have used the catalystic reforming method that contains precious metal and alkali-metal beta-zeolite catalyst.Other reforming catalyst comprises other molecular sieve, laminar crystal loam mould layered silicate and the amorphous clays such as borosilicate and aluminosilicophosphate.
Except that the selection of reforming catalyst, the whole bag of tricks of for the reformate product of production higher-value naphtha feed being reformed in one or more processing step is well known in the art.U.S. Patent number 3,415,737 have instructed under the gentle the condition of reorganization of routine and have carried out the method that naphtha reforming improves aromaticity content and petroleum naphtha octane value with platinum-rhenium-muriate reforming catalyst.U.S. Patent number 3,770,614 disclose reformate are carried out fractionation and lightweight reformate cut (C6 cut) is flow through the method that ZSM-5 type zeolite improves the product aromaticity content.U.S. Patent number 3,950,241 disclose by petroleum naphtha is separated into low and high boiling fraction, with low boiler cut reform, with high boiling fraction and reformate merging with will merge the method that cut and ZSM-5 type catalyzer contact this petroleum naphtha of upgrading.U.S. Patent number 4,181,599 disclose the method for naphtha reforming, comprise petroleum naphtha being separated into heavy and light ends and naphtha fraction being reformed and isomerized method.U.S. Patent number 4,190,519 have instructed the method for upgrading petroleum naphtha boiling range hydrocarbon, it comprises the heavy naphtha cut that naphtha feed is separated into the light naphtha fraction that contains C6 paraffinic hydrocarbons and low boiling hydrocarbon and contains high boiling hydrocarbon, the discharging that the heavy naphtha cut is reformed and made at least a portion reformate be rich in aromatic hydrocarbons by zeolite catalyst production with light naphtha fraction.The different process step can be used different catalysts in the naphtha feed reforming process, as U.S. Patent number 4,627, and 909,4,443,326,4,764,267,5,073,250,5,169,813,5,171,691,5,182,012,5,358,631,5,376,259 and 5,407, described in 558.
Even on catalyst for reforming naphtha and method, progress has been arranged, still be necessary to develop new higher liquid yield is provided, improves hydrogen output and minimizes the lower molecular weight (C that forms low value with improved reforming method
1-C
4) product.Found that in classification reforming process inter-stage charging separates and the lower pressure of final grade of multistage reforming process can improve RON (research octane number (RON)), aromaticity content, C
5+ liquid yield, hydrogen output and catalyst life.
Summary of the invention
The present invention relates to the method for naphtha fuel charging catalytic reforming being produced product reengineering oil in multistage resurfacing operation mode.Described method be included in the penultimate stage of multistage reforming process in the first reformation pressure down contact petroleum naphtha boiling range feeds generate the penultimate stage discharging; Reformate and heavy reformate in the middle of being divided into the described penultimate stage discharging of at least a portion at least, the mid-boiling point of wherein said middle reformate is lower than the mid-boiling point of described heavy reformate; Generate the final discharging that comprises final reformate with reformate in the middle of described being contacted with the catalyzer that comprises at least a mesoporous molecular sieve under the second reformation pressure in the final level of multistage reforming process, wherein the first reformation pressure is higher than the second reformation pressure.
In some embodiments, the penultimate stage catalyst system therefor comprises VIII family metal and the promotor that is carried on porous high-temperature inorganic oxide carrier.In some embodiments, final level catalyzer comprises VIII family metal.
In another embodiment, reforming method be included in the penultimate stage of multistage reforming process in the first reformation pressure down contact petroleum naphtha boiling range feeds generate the penultimate stage discharging; The described penultimate stage discharging of at least a portion is divided into lightweight reformate, middle reformate and heavy reformate at least, the mid-boiling point of wherein said lightweight reformate be lower than described in the middle of reformate mid-boiling point and wherein said in the middle of the mid-boiling point of reformate be lower than the mid-boiling point of heavy reformate; Generate the final discharging that comprises final reformate with reformate in the middle of described being contacted with the catalyzer that comprises at least a mesoporous molecular sieve under the second reformation pressure in the final level of multistage reforming process, wherein the first reformation pressure is higher than the second reformation pressure.
Others, feature and advantage will from following to specific embodiments description and the Accessory Right claim see.
Brief description
Fig. 1 is the synoptic diagram of one embodiment of the invention.
Fig. 2 is the synoptic diagram of second embodiment of the present invention.
Describe in detail
In present method, the charging of petroleum naphtha boiling range hydrocarbon is handled in multistage reforming process, described method comprises at least one penultimate stage, be used for described naphtha feed is reformatted into the penultimate stage naphtha products that octane value is higher than described naphtha feed, with a final level, be used for the described penultimate stage discharging of part product is further reformed, generate the final petroleum naphtha that octane value is higher than described penultimate stage naphtha products.Thereby reforming process is carried out dehydrocyclization, isomerization and dehydrogenation reaction and low octane rating normal paraffin and naphthenic hydrocarbon is converted under the condition of high-octane rating material and the catalyzer and operates being selected from.In this way, produce the product that octane value improves and aromaticity content increases.In some embodiments, multistage reforming process be can production allowance (net positive quantity) condition and one or more catalyzer of hydrogen operate down.
Multistage reforming process of the present invention comprises refinery's materials flow by at least two placed in-line reformation levels.In general, the characteristics of each level of reforming are one or more reforming reactor containers, and each reactor is equipped with catalyzer and maintains under the reforming reaction condition.From the product of each grade before the final level, all or part of, enter the next stage (succeeding stage) of multi stage process.The temperature of coming out to enter the product of next stage from each grade can improve or reduce the concrete needs that satisfy process.Similarly, the pressure that enter the product of final level next stage before also can improve or reduce, and condition is the pressure that the pressure of described penultimate stage is higher than described final level.
Although following discussion repeatedly relates to the operation of the second from the bottom and final level of reforming for simplicity, the principle of the invention can be applicable between any two continuous levels and can be used for the level that several connect successively.Thereby in fact, if three or more individual levels are arranged, the final level of term used herein does not necessarily represent the most last level, but a back level of front (being commonly referred to " second from the bottom " for the purpose of convenient) level is followed in representative.
Definition
In the content disclosed herein, boiling temperature is according to the ASTM D-2887 standard test methods with gas Chromatographic Determination petroleum fractions boiling Range Distribution Analysis, shows unless have in addition.Mid-boiling point is defined as the 50vol% boiling temperature of being measured according to ASTM D-2887 simulation distil.
In the content disclosed herein, the carbon number value of hydrocarbon (is C
5, C
6, C
8, C
9Deng) the available standards vapor-phase chromatography determines.Except as otherwise noted, research octane number (RON) (RON) is to determine with the described method of ASTM D2699.
Except as otherwise noted, the feeding rate of sending into catalytic reaction zone is the feed volume report that will send into per unit volume catalyzer per hour.In fact, the feeding rate in this paper disclosure is called liquid hourly space velocity (LHSV), is ((to be hr with a hour inverse
-1) report.
The said C of this paper
4-materials flow comprises that a high proportion of per molecule has 4 or the hydrocarbon of carbon atom still less.Equally, C
5+ materials flow comprises that a high proportion of per molecule has the hydrocarbon of 5 or more carbon atoms.Those skilled in the art will recognize that the hydrocarbon flow in the refining process normally adopts still-process to separate with boiling range.Like this, estimate C
4-materials flow comprises a small amount of C
5, C
6Even C
7Molecule.But typical still-process will be by the C at least about 70vol%
4-materials flow comprise per molecule have 4 or still less the mode of the hydrocarbon of carbon atom design and operate.This paper is with the C of carbon number range sign
5+, C
6-C
8, C
9+ with other hydrocarbon-fraction the same meaning is arranged.
Term " silica alumina ratio " is meant silicon oxide (SiO
2) and aluminum oxide (Al
2O
3) mol ratio.
Term used herein " molecular sieve " is meant the crystalline material of the hole of containing uniform-dimension, cave, clearance space, and size is small enough to molecule by hole, cave, clearance space and is adsorbed than macromole and then can not passes through.Examples of molecular sieve comprises that zeolite and non-zeolite molecular sieve are as including but not limited to SAPO (aluminosilicophosphate), MeAPO (metallic aluminium phosphoric acid salt), AlPO
4, and ELAPO (the chloro-aluminate series of nonmetal replacement).
Being used for the related periodic table of elements of present disclosure is that Chemical AbstractService is at chemistry and physics handbook (72
NdVersion, 1991-1992) the middle CAS version of announcing.
Except that other factor, the present invention is based on discovery in independent or other reformation level with paraffinic hydrocarbons C particularly
6-C
8Paraffinic hydrocarbons carries out the performance that the selectivity reformation can improve whole reforming process.Therefore, using the reformation level second from the bottom of traditional reforming catalyst is to operate under lower severity condition, because do not need to reach naphtha fuel or the common desired high-octane rating of fuel blending stock.Can catalysis comparatively gentle reaction of catalyzer such as hexanaphthene and alkyl cyclohexane dehydrogenation reaction and the hydrocracking reaction is minimized under these conditions.Usually, be used for the conventional catalyst of paraffin dehydrogenation cyclization more understanding the light gas that generates more amount under the severe condition, because catalyzer reacts more or less non-selectivity to dehydrocyclization.But, adopt the present invention, the middle reformate that comes out from penultimate stage be delivered to the final reformation level that intermediate pore molecular sieve catalyst is housed.The performance characteristics of intermediate pore molecular sieve catalyst allows to operate under the pressure of reduction in the final level of multistage reforming process, improves C
6-C
8The selectivity of paraffin dehydrogenation cyclisation is kept lower catalyst structure speed simultaneously.The C that comes out from penultimate stage
9The octane value of+cut will be higher than C
6-C
8Middle runnings, and it can further not reformed in final level.Otherwise, the high-octane rating C that comes out from penultimate stage
9+ cut will carry out some cracking and dealkylation reaction in final level, and this has reduced liquid yield and has expended hydrogen.Therefore, the performance characteristics of final level catalyzer provides sharp benefit of replenishing, and makes total process increase liquid yield and improve and produce the high-octane rating product under the hydrogen output.
The petroleum naphtha boiling range feeds that enters the multi stage process penultimate stage is that boiling range is the naphtha fraction of about 550 and preferred 70-450 of about 50-.In some embodiments, the reforming reactor charging is C
5+ charging.The reforming reactor charging for example can comprise virgin naphtha, belong to raffinate, C from the alkane of aromatic hydrocarbons extraction or adsorption process
6-C
10Rich paraffinic feedstock, biologically-derived petroleum naphtha, from the petroleum naphtha of the hydrocarbon building-up process that comprises Fischer-Tropsch and methyl alcohol building-up process and from the naphtha product of other oil refining process such as hydrocracking or traditional reforming process.In the reforming process process that comprises more than two-stage, reformer feed can comprise the product that is generated at least partially in the previous stage.
The used reforming catalyst of reformation level second from the bottom can be any known active catalyzer of catalytic reforming that has.In some embodiments, the penultimate stage catalyzer comprises the VIII family metal that places on the oxide carrier.The example of VIII family metal comprises platinum and palladium.Catalyzer can further comprise promotor such as rhenium, tin, tungsten, germanium, cobalt, nickel, iridium, rhodium, ruthenium or their combination.In some such embodiments, promoter metal is rhenium or tin.These metals place on carrier such as aluminum oxide, silica, the silicon oxide.In some embodiments, carrier is an aluminum oxide.Carrier also can comprise natural or artificial synthetic zeolite.Catalyzer also can comprise the muriate of 0.1-3wt%, the muriate of preferred 0.5-1.5wt%.If catalyzer comprises promoter metal, then it is fit to comprise that the capacity promoter metal provides the ratio of promotor and platinum between 0.5: 1 and 10: 1 or between 1: 1 and 6: 1.Accurate condition, compound and the operation of producing catalyzer are that those skilled in the art are well-known.Some examples of traditional catalyst are shown in U.S. Patent number 3,631, and 216,3,415,737 and 4,511,746, their full content drawn be reference.
Reforming catalyst in penultimate stage and the final level can ball shape (pills), fine granularity (pellets), macrobead shape (granules), fragment or various special shape use, be positioned in the reaction zone with the fixed bed form, charging can be with liquid phase, vapor phase or mixed phase and with up or down or the radial flow mode pass through.Perhaps, reforming catalyst adopts moving-bed or fluidized solids technology, and wherein the turbulent bed of a catalyzer in small, broken bits is upwards passed through in charging.But preferred fixed bed system or close phase shift bed system are because catalyst abrasion is few and other service advantages are arranged.In fixed bed system, with the temperature of reaction of feeding preheating (adopting any suitable heating hand level), then by catalyst fixed bed reaction zone is housed to anticipation.This reaction zone can be one or more reactor that separates, and adopts suitable equipment to keep the anticipation temperature of reaction ingress, because reforming reaction essence is so that a thermo-negative reaction is must holding temperature.
The actual the condition of reorganization of penultimate stage and final level depends in part on used charging at least, and whether aromatic hydrocarbons, paraffinic hydrocarbons or naphthene content be high and depend on desirable product octane value and desirable hydrogen output.
Penultimate stage is maintained than under the mild reaction conditions, so that suppress to want the cracking of upgrading materials flow and the work-ing life of improving catalyzer in the penultimate stage.Want the petroleum naphtha boiling range feeds of upgrading to contact with the penultimate stage catalyzer under reaction conditions in the penultimate stage, described condition is a temperature in about 1100 scopes of about 800-, pressure in the about 400psig scope of about 70-and feeding rate at the about 5hr of about 0.5-
-1The LHSV scope.In some embodiments, the pressure of penultimate stage is in the about 400psig scope of about 200-.
The discharging of penultimate stage is a upgraded product, and RON is improved in the penultimate stage reaction process.The penultimate stage discharging comprises hydrocarbon and the hydrogen that produces in the penultimate stage reaction process, and in the charging of the upstream of at least some hydrogen (if the words that have) adding penultimate stage.The discharging hydrocarbon can be characterized by C
4-hydrocarbon and C
5The mixture of+hydrocarbon is distinguished with the molecular weight of every class hydrocarbon.In embodiments, C in the discharging
5The merging RON of+hydrocarbon is 85 at least.
Discharging (or being called the penultimate stage discharging) from penultimate stage comprises the C that is divided into middle at least reformate and heavy reformate
5+ hydrocarbon.Discharging also comprises hydrogen and C
4-hydrocarbon.In some embodiments, rich hydrogen materials flow is separated from discharging in the pre-separation step, for example adopt high-pressure separator or other flash zone.C in the discharging
4-hydrocarbon also can be separated with hydrogen in the pre-separation process or be separated in follow-up flash zone.Middle reformate is characterized by the mid-boiling point that mid-boiling point is lower than the heavy reformate.In some embodiments, the boiling range of middle reformate is about 280 of about 70-.In some such embodiments, middle reformate comprises 70vol%C at least
5-C
8Hydrocarbon.In some embodiments, the boiling range of middle reformate is about 280 of about 100-, and in some such embodiments, middle reformate comprises 70vol%C at least
6-C
8Hydrocarbon.In some embodiments, the boiling range of middle reformate is about 230 of about 100-.In some such embodiments, middle reformate comprises 70vol%C at least
6-C
7Hydrocarbon.Reformate may be attended by a large amount of C in the middle of reclaiming
5The further recovery of lightweight reformate cut.The lightweight reformate is characterized by the mid-boiling point that mid-boiling point is lower than middle reformate.In some embodiments, the boiling range of lightweight reformate is about 140 of about 70-.In some such embodiments, middle reformate comprises 70vol%C at least
5Hydrocarbon.About 220 and higher of the boiling range of the heavy reformate that is produced in the upgraded products may sepn process, in some such embodiments, the heavy reformate comprises 70vol%C at least
9+ hydrocarbon.
The RON of middle reformate is the indication of gentle the condition of reorganization in the penultimate stage.Like this, the RON of middle reformate is generally greater than 65.In some embodiments, the RON of middle reformate is in about 65-100 scope.In some such embodiments, the RON of middle reformate is in the 65-95 scope.
Final level reforming catalyst comprises at least a mesoporous molecular sieve.Molecular sieve is a porous inorganic oxide, it is characterized in that having the crystalline structure that the particular geometric hole can be provided according to the concrete structure of every kind of molecular sieve.The meaning of phrase " mesopore " be porous inorganic oxide when being calcinated form the free diameter range of crystallography at about 7.1 dusts of about 3.9-.The free diameter of the crystallography of molecular sieve pore passage is published in Ch.Baerlocher, W.M.Meier and D.H.Olson, " the framework of molecular sieve atlas " of Elsevier (the 5th revised edition, 2001) 10[ndash] 15 pages, this document drawn be reference.The non-limiting example of mesoporous molecular sieve comprises ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35, ZSM-38, ZSM-48, MCM-22, SSZ-20, SSZ-25, SSZ-32, SSZ-35, SSZ-37, SSZ-44, SSZ-45, SSZ-47, SSZ-57, SSZ-58, SSZ-74, SUZ-4, EU-1, NU-85, NU-87, NU-88, IM-5, TNU-9, ESR-10, TNU-10 and their combination.In the present disclosure, the mesoporous molecular sieve that is applicable to present method is SiO
2/ M
2O
3Be at least preferably at least 200: 1 and more preferably at least 500 40: 1: 1 high silica ZSM-5 zeolite, wherein M is selected from Al, B or Ga.
Authorize the reference that discloses many disclosure ZSM-5 in the U.S. Patent number 4,401,555 of Miller.These reference comprise people's such as the aforesaid Grose of authorizing U.S. Patent number 4,061,724, authorize people's such as Dwye United States Patent (USP) second edition numbers 29,948, people such as Flanigan are at Nature, 271,512-516 discloses the physics and the absorption property of high silica ZSM-5 in (on February 9th, 1978), people such as Anderson disclose catalyzed reaction and ZSM-5 is adsorbed measuring method among the 114-130 (1979) at J.Catalysis 58.The disclosure of these reference and U.S. Patent number 4,401,555 is drawn and is reference, particularly prepares the content of the method for high silica alumina ratio ZSM-5.Also can find open source literature such as the United States Patent (USP) 5407558 and the US5376259 of some high silica alumina ratio ZSM-5 preparations and aspect of performance.
In embodiments, be used as the silica at least 40: 1 of the high-silicon ZSM-5-molecular sieve of present method catalyst component, or at least 200: 1 or at least 500: 1.The silica of exemplary high-silica zeolite was at least 1000: 1.In some embodiments, the characteristics of molecular sieve are to have less than 10 μ m or less than 5 μ m or less than the crystalline size of 1 μ m.The method of measuring crystalline size is well-known as the method that adopts scanning electron microscope.The characteristics of high silica ZSM-5 are that degree of crystallinity is at least 80% or be at least 90% or be at least 95% in some embodiments.The method of measuring degree of crystallinity is well-known as adopting X-ray diffraction method.The catalyzer middle strong acidity is undesirable, because this can promote cracking, causes C
5+ liquid product optionally reduces.For reducing acidity, preferred molecular sieve alkali metal containing and/or alkaline-earth metal.Preferably in sieve synthesis procedure or afterwards, alkali or alkaline-earth metal are introduced catalyzer.Preferred at least 90%, more preferably at least 95%, most preferably at least 99% acid site neutralizes by introducing metal.In one embodiment, mesoporous molecular sieve contains and is less than 5000ppm basic metal.This class mesoporous silicate molecular sieve for example is disclosed in U.S. Patent number 4,061,724 and 5,182,012, these patents are particularly drawn about the content of description, preparation and the analysis of molecular sieve with specific silica, particular crystal size, specific degree of crystallinity and specific alkali metal content and are reference.
Other can be used for the final molecular sieve of reforming level and comprises U.S. Patent number 4,835, list in 336, it is ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35, ZSM-38, ZSM-48 and other analogous material such as Hickson application number 166 in application on July 7th, 1980, disclosed CZH-5 in 863, this document draw and are reference.
SSZ-20 is disclosed in U.S. Patent number 4,483,835 and SSZ-23 be disclosed in U.S. Patent number 4,859,442, two pieces of documents all draw and are reference.
U.S. Patent number 3,702 is seen in the more specifically description of ZSM-5,886 and United States Patent (USP) second edition numbers 29,948, and full content draws and is reference.
U.S. Patent number 3,709,979 is seen in the more specifically description of ZSM-11, and its full content draws and is reference.
U.S. Patent number 3,832,449 is seen in the more specifically description of ZSM-12, and its full content draws and is reference.
U.S. Patent number 4,481 is seen in the more specifically description of ZSM-22,177,4,556,477 and european patent number 102,716, and the full content of every piece of document draws and is reference.
U.S. Patent number 4,076,842 is seen in the more specifically description of ZSM-23, and the full content of this document draws and is reference.
U.S. Patent number 4,016,245 is seen in the more specifically description of ZSM-35, and the full content of this document draws and is reference.
U.S. Patent number 4,046,859 is seen in the more specifically description of ZSM-38, and the full content of this document draws and is reference.
U.S. Patent number 4,397,827 is seen in the more specifically description of ZSM-48, and the full content of this document draws and is reference.
Crystalline molecular sieve can make the borosilicate form, wherein boron replaced more typical aluminosilicate form molecular sieve to small part aluminium.The borosilicate examples of molecular sieve is described in the U.S. Patent number 4,268,420,4,269,813,4,327,236 of authorizing Klotz, and the disclosure of these patents, the particularly disclosure of relevant borosilicate preparation are drawn and be reference.
Aluminosilicophosphate (SAPO) is the example of the non-zeolite molecular sieve that is applicable to that the present invention puts into practice.SAPO comprises the [SiO that drift angle is shared
4] tetrahedron, [AlO
4] tetrahedron and [PO
4] molecular skeleton that connects by Sauerstoffatom of tetrahedron.By changing P/Al and Si/Al ratio, the acidity that can improve SAPO minimizes and favourable isomerization reaction maximization undesirable hydrocracking reaction.Preferred about 0.75-1.3 of P/Al mol ratio and the preferred about 0.08-0.5 of Si/Al mol ratio.Be applicable to that aluminosilicophosphate example of the present invention comprises SAPO-11, SAPO-31 and SAPO-41, also be disclosed in U.S. Patent number 5,135, in 638.
According to the present invention, the used catalyzer of final level contains one or more VIII family metal such as nickel, ruthenium, rhodium, palladium, iridium or platinum.Preferred VIII family metal is iridium, palladium and particularly platinum.Compare other VIII family metal, their selectivity to dehydrocyclization under dehydrogenation ring structure reaction conditions are higher and more stable.In the catalyzer percentage ratio of VIII family metal such as platinum preferably between 0.1wt.% and 5wt.%, 0.3-2.5wt.% more preferably.Catalyzer can further comprise promotor such as rhenium, tin, germanium, cobalt, nickel, iridium, tungsten, rhodium, ruthenium or their combination.
In forming final level catalyzer, preferably crystalline zeolite is combined with body material.Body material does not have catalytic activity to hydrocarbon pyrolysis reaction.Satisfied body material comprises inorganic oxide such as aluminum oxide, silicon oxide, natural existence or processed conventionally clay such as wilkinite, kaolin, sepiolite, attapulgite and halloysite.Therefore even it also is that seldom acid sites has only minimum or do not have lytic activity that these materials have
The final reaction conditions of reforming level is appointed as the specific performance advantage that can effectively utilize this grade catalyst system therefor.Therefore, in the methods of the invention, final reaction pressure of reforming level preferably is lower than the pressure of penultimate stage.The final level operation under low pressure of reforming is feasible, and at least in part because the cause of the high catalytic stability of mesoporous molecular sieve of the present invention, this can allow catalyzer under low pressure to operate and significant fouling and active early ageing phenomenon can not take place.This can allow penultimate stage operating than under the mild conditions conversely again, and the high yield of long catalyst life and hydrogen and desired high-octane rating product is provided.
The naphtha feed of final level is the middle reformate of telling from the penultimate stage discharging.In the method, middle reformate is contacting with catalyzer under the reforming reaction condition in final level, described reaction conditions comprise temperature in about 1100 scopes of about 800-, pressure in the about 250psig scope of about 50-and feeding rate at the about 5hr of about 0.5-
-1The LHSV scope.The pressure of reformation level in some embodiments, is lower than 100psig.Add the additional charging of hydrogen, but this not necessarily as the final level of reforming.In some embodiments, will reclaim and loop back final level from final level discharging sepn process with the hydrogen that charging adds.Final level is being kept H
2/ hydrocarbon mol ratio is 1: 1-10: operate under the condition of 1 scope.Preferred H
2/ hydrocarbon mol ratio is 1: 1-4: 1.
According to detailed process, it (is C that the discharging of the final level of reforming (another saying is " final discharging ") can comprise lightweight
4-product and/or hydrogen) product, do further processing after in the end in the separating step it being shifted out from reformate, acting as a fuel is used for being in harmonious proportion or using.Can tell the hydrogen rich gas materials flow the discharging before separating step, for example adopt high-pressure separator or other flash zone.Also can be in the preflash district with the C in the discharging
4-hydrocarbon is separated, perhaps with hydrogen or in follow-up flash zone.The RON of the reformate of the final level output of reforming is higher than the middle reformate of sending into final reformation level.In embodiments, the RON of final level reformate is at least 90 or be at least 95 or be at least 98.In some embodiments, final level reformate seethes with excitement in about 280 scope of about 70-.In some such embodiments, final level reformate comprises 70vol%C at least
5-C
8Hydrocarbon.In some embodiments, final reformate seethes with excitement in about 280 scope of about 100-.In some such embodiments, final reformate comprises 70vol%C at least
6-C
8Hydrocarbon.In some embodiments, final reformate seethes with excitement in about 230 scopes of about 100-.In some such embodiments, final reformate comprises 70vol%C at least
6-C
7Hydrocarbon.Except that final reformate materials flow, also can from the discharging of final level, reclaim final lightweight materials flow.Under these circumstances, final lightweight materials flow is seethed with excitement in about 140 scopes of about 70-, and in some such embodiments, the materials flow of final level lightweight comprises 70vol%C at least
5Hydrocarbon.
Reformate is suitable as fuel or fuel blending stock.In some embodiments, the reformate that comes out from the final level of reforming to small part will be in harmonious proportion from the heavy reformate that the level of reforming second from the bottom reclaims to small part, temper can be used as fuel or fuel blending stock.
Referring now to Fig. 1 explanation, embodiment of the present invention.The petroleum naphtha boiling range cut 5 of boiling range in 50-550 scope sent into reaction order 10, and feeding rate is about 0.5hr
-1-Yue 5hr
-1LHSV.The reaction conditions of the level 10 of reforming is included in about 800 temperature and be higher than the total pressure of 70psig in about 400psig scope to about 1100 scopes.
The discharging 11 of penultimate stage is a upgraded products may, and its RON RON in the reaction process of penultimate stage 10 is improved.Penultimate stage discharging 11 comprises hydrocarbon and the hydrogen that generates in the penultimate stage reaction process, and at least some hydrogen (if having words) will add in the charging of upstream of penultimate stage.In the embodiment of Fig. 1 explanation, 20 are divided into rich hydrogen materials flow 21, C with described discharging in the disengaging zone
4-materials flow 22, middle reformate 25 and heavy reformate 26.In some embodiments, this separating step carries out in single disengaging zone.In other embodiments, this separating step is being operated hydrogen and optional C in the multi-region continuously
4-materials flow is presorted in the abscission zone at one or more and is separated, and reformate 25 and heavy reformate 26 separates in the middle of carrying out then.
In the embodiment of Fig. 1 explanation, middle reformate 25 comprises the C in discharging of main amount
5-C
8Hydrocarbon and a spot of C
4And C
9Hydrocarbon.Reformate 25 is sent into final reformation level 30 in the middle of the near small part.Heavy reformate 26 contains the C in discharging 11 of main amount
9+ hydrocarbon, and its RON is higher than 98, preferably is higher than 100.
Middle reformate 25 is sent into final reformation level 30, under reaction conditions, contacts with the catalyzer that comprises platinum and at least a mesoporous molecular sieve, described reaction conditions comprise temperature at about 1100 scopes of about 800-and pressure in the about 250psig scope of about 50-.
The discharging 31 of the final level of reforming 40 separates in the disengaging zone, obtains rich at least hydrogen materials flow 41, C
4-materials flow 42 and final reformation materials flow 45.In some embodiments, final reformate materials flow is at C
5The boiling of+boiling range.As mentioned above, according to the particular demands of detailed process, separating step can carry out in one or more disengaging zone.In one embodiment, final reformate materials flow 45 can further merge with heavy reformate 26, further handles or be used as fuel or fuel blending stock then.Rich hydrogen materials flow 41 merges with rich hydrogen materials flow 21, is used for other oil refining process then, and C
4-materials flow 42 and C
4-materials flow 22 merges.
Referring now to Fig. 2 explanation, embodiment of the present invention.With boiling range is that 50-550 petroleum naphtha boiling range cut 5 is sent into reaction order 10, and feeding rate is about the about 5hr of 0.5-
-1LHSV.The reaction conditions of the level 10 of reforming comprises that temperature is being higher than 70psig to about 400psig scope in about 1100 scopes of about 800-and total pressure.
The discharging 11 of penultimate stage is a upgraded products may, and its RON is improved in the reaction process of penultimate stage 10.Penultimate stage discharging 11 comprises hydrocarbon and the hydrogen that generates in the penultimate stage reaction process, and at least some hydrogen (if the words that have) will add in the upstream charging of penultimate stage.In the embodiment of Fig. 2 explanation, 20 are divided into rich hydrogen materials flow 21, C with discharging in the disengaging zone
4-materials flow 22, lightweight reformate 23, middle reformate 24 and heavy reformate 26.In some embodiments, this separating step carries out in single disengaging zone.In other embodiments, this separating step is being operated hydrogen and optional C in the multi-region continuously
4-materials flow is presorted in the abscission zone at one or more and is separated, and carries out lightweight reformate 23 then, middle reformate 24 separates with heavy reformate 26.
In the embodiment of Fig. 2 explanation, lightweight reformate 23 comprises the C in discharging of main amount
5Hydrocarbon and a spot of C
4And C
6Hydrocarbon.Middle reformate comprises the C in discharging of main amount
6-C
8 Hydrocarbon.Heavy reformate 26 comprises the C in discharging 11 of main amount
9+ hydrocarbon.
The discharging 31 of the final level of reforming 40 separates in the disengaging zone, obtains rich at least hydrogen materials flow 41, C
4-materials flow 42, final C
5Materials flow 43 and final reformation materials flow 44.In some embodiments, final reformate materials flow is at C
6The boiling of+boiling range.As mentioned above, according to the particular demands of detailed process, separating step can carry out in one or more disengaging zone.Shown in the embodiment that Fig. 2 illustrates, final reformate materials flow 44 can further merge with heavy reformate 26, further handles or be used as fuel or fuel blending stock then.Rich hydrogen materials flow 41 merges with rich hydrogen materials flow 21, is used for other oil refining process then, C
4-materials flow 42 and C
4-materials flow 22 merges and final C
5Materials flow 43 and C
5Materials flow 23 merges.
The following examples only are the illustration embodiment of the present invention rather than will limit the invention to listed specific embodiments.Except as otherwise noted, all umbers and percentage ratio are weight unit.All numerical value all are to be worth approximately.When providing digital scope, be to be understood that the embodiment beyond the alleged scope still belongs to the scope of the invention.The described details of each embodiment should not be construed as essential feature of the present invention.
Embodiment
Embodiment 1
With API be 54.8, RON be 53.3 and table 1 shown in the naphtha feed of ASTM D-2887 simulation distil data reform with commercial reforming catalyst in penultimate stage, described catalyzer comprises platinum and the rhenium promotor that is carried on alumina supporter.Reaction conditions comprises that temperature is that 840, pressure are that 200psig, hydrogen/hydrocarbon mol ratio are that 5: 1 and feeding rate are 1.43hr
-1LHSV.C
5+ liquid yield is that output is 92.7wt%.Hydrogen output is 975 standard cubic feet per barrel chargings.
C from the penultimate stage collection
5The API of+liquid product is 46.6, RON be 89 and ASTMD-2887 simulation distil data as shown in table 2.
Table 1: the ASTM D-2887 simulation distil of penultimate stage charging
| Vol％ | Temperature, °F |
| IBP | ?182 |
| 10 | ?199 |
| 30 | ?227 |
| 50 | ?258 |
| 70 | ?291 |
| 90 | ?336 |
| EP | ?386 |
Table 2: the C that penultimate stage is collected
5The ASTM D-2887 simulation distil of+liquid product
| Vol.％ | Temperature, °F |
| IBP | ?165 |
| 10 | ?189 |
| 30 | ?234 |
| 50 | ?257 |
| 70 | ?289 |
| 90 | ?336 |
| EP | ?411 |
Embodiment 2
C with embodiment 1
5Reformate and heavy reformate in the middle of+liquid product is distilled into.Reformate contains the C from embodiment 1 of 80vol% in the middle of analyzing
5+ liquid product.The API of middle reformate is 55.7, RON be 85 and ASTM D-2887 simulation distil data as shown in table 3, used as the charging of the final level of reforming of embodiment 3 and comparing embodiment 1.Analyze the C that the heavy reformate contains 20vol% from embodiment 1
5+ liquid product.The API of heavy reformate be 28.9 and RON be 105, more descriptions see Table 5.
Table 3: from the ASTM D-2887 simulation distil of the middle reformate of the level of reforming second from the bottom
| Vol.％ | Temperature, °F |
| IBP | ?168 |
| 10 | ?190 |
| 30 | ?235 |
| 50 | ?240 |
| 70 | ?284 |
| 90 | ?296 |
| EP | ?336 |
Embodiment 3
Middle the reformate that embodiment 2 is produced is as the charging of the final level of reforming, and the final level catalyst system therefor of reforming is based on the ZSM-5 zeolite, is compounded with the catalyzer of 35% alumina binder material.The SiO of ZSM-5
2/ Al
2O
3Mol ratio be about 2000 and ion-exchange to become the ammonium form aftershaping be 65% zeolite/35% alumina extrudate.Extrudate flooded with 0.8%Pt, 0.3%Na and 0.3%Mg prepare finished catalyst.Reaction conditions and experimental result are listed in table 4.
Table 4: the embodiment 3 and the result of comparing embodiment 1 compare
Comparing embodiment 1
At the final middle reformate and the embodiment 1 described commercial platinum/rhenium that be carried on aluminum oxide catalyst based contact of level of reforming with embodiment 2 productions.Reaction conditions and experimental result are shown in table 4 and compare with the embodiment 3 that uses the ZSM-5 zeolite based catalysts.
Embodiment 3 shows with the commercial platinum catalyst that is carried on aluminum oxide with comparing embodiment 1 and compares, at similar C
5The ZSM-5 zeolite based catalysts is at C under the+RON
5The favourable part of+liquid yield and hydrogen output aspect.
Embodiment 4
With product that reformation is generated in final level of the middle reformate among the embodiment 3 and heavy reformate (embodiment 2) mediation of reforming without final level.The C of the final product that is in harmonious proportion
5+ total RON, C
5+ total recovery and total hydrogen output are shown in table 5, to use whole C
5The discharging of+penultimate stage is the basis meter as charging (it is distilled into middle reformate and heavy reformate in embodiment 2).The result that result and comparing embodiment 2 are obtained compares, whole C in the comparing embodiment 2
5+ product is with whole C
5The discharging of+penultimate stage is that charging is produced, reformate and heavy reformate in the middle of not being distilled into.
Comparing embodiment 2
Whole C that embodiment 1 produces
5+ product, reformate and heavy reformate in the middle of not being distilled into, described ZSM-5 is catalyst based contacts at final reform level and embodiment 3, and reaction conditions is that 930,80psig, hydrogen/hydrocarbon mol ratio are that 2: 1 and feeding rate are 1.5hr
-1LHSV.The final C of level that reforms
5+ liquid yield is 89.9wt, %, C
5The RON of+liquid product is 97.4.Hydrogen output is 190 standard cubic feet per barrel chargings.In table 5, the result of embodiment 4 and the result of comparing embodiment 2 are contrasted, among the embodiment 4 the finished product be among temper (i) embodiment 3 of following oil plant in the middle of reformate at final level reform product of being produced and the heavy reformate (embodiment 2) of (ii) reforming and handling, whole C in the comparing embodiment 2 without final level
5+ product is from whole C
5The discharging of+penultimate stage is that charging is produced, and is not distilled into middle and heavy reformate.
Table 5: the embodiment 4 and the result of comparing embodiment 2 contrast
The note of table 5:
(1) embodiment 3: the C that provides
5+ RON, C
5+ yield and product H
2Output is charging based on middle reformate.
(2) embodiment 2: the C that provides
5+ RON and C
5+ yield is based on the heavy reformate of reforming without final level.
(3) comparing embodiment 2: the C of the product that provides
5+ RON, C
5+ yield and product H
2Output is based on whole C
5The discharging of+penultimate stage is charging.
(4) embodiment 4: the total C that provides
5+ RON, total C
5+ yield and total H
2Output is based on whole C
5The discharging of+penultimate stage is charging (it is distilled into middle reformate and heavy reformate in embodiment 2).The finished product of embodiment 4 are in harmonious proportion by following oil plant and form the product that (i) middle reformate is reformed in final level; (ii) without the final grade of heavy reformate of reforming.
Embodiment 4 and comparing embodiment 2 show and adopt the ZSM-5 zeolite based catalysts, with middle reformate as the final grade charging of reforming at C
5+ yield, hydrogen output and C
5+ RON aspect and the full boiling range C of use
5The favourable part that+charging is compared.
The RON value of being reported in embodiment 3-4 and comparing embodiment 1 and 2 is the value that mixed interconnection is applied to use the composition analysis of gas-chromatography to be calculated according to RON above.Described method is corrected to the difference of measurement and RON value that calculate in ± 0.8.
Claims (15)
1. reforming method comprises:
A. in the penultimate stage of multistage reforming process, under the first reformation pressure, contact the petroleum naphtha boiling range feeds and generate the penultimate stage discharging;
B. reformate and heavy reformate in the middle of the described penultimate stage discharging of at least a portion being divided at least, the mid-boiling point of wherein said middle reformate is lower than the mid-boiling point of heavy reformate; With
C. in the final level of multistage reforming process under the second reformation pressure near small part described in the middle of reformate contact with the catalyzer that comprises at least a mesoporous molecular sieve and generate the final discharging that comprises final reformate, the wherein said first reformation pressure is higher than the described second reformation pressure.
2. the process of claim 1 wherein that described middle reformate comprises 70vol%C at least
5-C
8Hydrocarbon.
3. the process of claim 1 wherein that described middle reformate comprises 70vol%C at least
6-C
8Hydrocarbon.
4. the process of claim 1 wherein that described heavy reformate comprises 70vol%C at least
9+ hydrocarbon.
5. the process of claim 1 wherein that the RON of described middle reformate is higher than the RON of described petroleum naphtha boiling range feeds.
6. the process of claim 1 wherein described in the middle of the RON of reformate 65 in less than 100 scope.
7. the process of claim 1 wherein that the RON of described heavy reformate is at least 95.
8. the process of claim 1 wherein the described first reformation pressure in the scope of 200psig to 400psig, the described second reformation pressure is in the scope of 50psig-150psig.
9. the process of claim 1 wherein that the described catalyzer in described penultimate stage comprises VIII family metal and the promotor that is carried on the porous high-temperature inorganic oxide carrier.
10. the method for claim 9, wherein said catalyzer comprise be carried on the alumina supporter as the platinum of VIII family metal with as the rhenium of promoter metal.
11. the process of claim 1 wherein that described mesoporous molecular sieve is selected from ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35, ZSM-38, ZSM-48, MCM-22, SSZ-20, SSZ-25, SSZ-32, SSZ-35, SSZ-37, SSZ-44, SSZ-45, SSZ-47, SSZ-57, SSZ-58, SSZ-74, SUZ-4, EU-1, NU-85, NU-87, NU-88, IM-5, TNU-9, ESR-10, TNU-10 and their combination.
12. the process of claim 1 wherein that described mesoporous molecular sieve comprises the ZSM-5 that silica was at least 200: 1.
13. the process of claim 1 wherein that described mesoporous molecular sieve includes is less than the alkali-metal ZSM-5 of 5000ppm.
14. reforming method comprises:
A. in the penultimate stage of multistage reforming process, under the first reformation pressure, contact the petroleum naphtha boiling range feeds and generate the penultimate stage discharging;
B. the described penultimate stage discharging of at least a portion is divided into lightweight reformate, middle reformate and heavy reformate at least, the mid-boiling point of wherein said lightweight reformate is lower than the mid-boiling point of described middle reformate, and the mid-boiling point of wherein said middle reformate is lower than the mid-boiling point of described heavy reformate; With
C. the final level of multistage reforming process under the second reformation pressure with at least a portion described in the middle of reformate contact with the catalyzer that comprises at least a mesoporous molecular sieve and generate the final discharging that comprises final reformate, the wherein said first reformation pressure is higher than the described second reformation pressure.
15. the method for claim 15 further comprises:
A. described final discharging is divided into final at least C
5Materials flow and final reformate materials flow;
B. with described final C
5Materials flow and described lightweight reformate materials flow merge; With
C. described final reformate and described heavy reformate are merged.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US12/134,131 US20090301933A1 (en) | 2008-06-05 | 2008-06-05 | Catalytic reforming process to produce high octane gasoline |
| US12/134,131 | 2008-06-05 | ||
| PCT/US2009/043586 WO2009148773A1 (en) | 2008-06-05 | 2009-05-12 | Catalytic reforming process to produce high octane gasoline |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102099444A true CN102099444A (en) | 2011-06-15 |
Family
ID=41165127
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009801278859A Pending CN102099444A (en) | 2008-06-05 | 2009-05-12 | Catalytic reforming process to produce high octane gasoline |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US20090301933A1 (en) |
| EP (1) | EP2310475A1 (en) |
| JP (1) | JP2011522927A (en) |
| CN (1) | CN102099444A (en) |
| AU (1) | AU2009255498A1 (en) |
| CA (1) | CA2726912A1 (en) |
| WO (1) | WO2009148773A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107971016A (en) * | 2016-10-21 | 2018-05-01 | 中国石油化工股份有限公司 | A kind of catalytic cracking catalyst containing phosphorous IMF structure molecular screens and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8658021B2 (en) | 2008-06-05 | 2014-02-25 | Chevron U.S.A. Inc. | Multi-stage reforming process to produce high octane gasoline |
| US8366909B2 (en) * | 2009-02-26 | 2013-02-05 | Chevron U.S.A. Inc. | Reforming process at low pressure |
| US8222473B1 (en) * | 2011-12-22 | 2012-07-17 | Chevron U.S.A. Inc. | Isomerization of light paraffins |
| US9266091B2 (en) * | 2012-03-29 | 2016-02-23 | Uop Llc | Reforming catalysts with tuned acidity for maximum aromatics yield |
| US8926735B1 (en) * | 2014-01-30 | 2015-01-06 | Chevron U.S.A. Inc. | Separation of gases using zeolite SSZ-45 |
| US20160145507A1 (en) * | 2014-11-20 | 2016-05-26 | Chevron U.S.A. Inc. | Two-stage reforming process configured for increased feed rate to manufacture reformate and benzene |
| US20160145506A1 (en) * | 2014-11-20 | 2016-05-26 | Chevron U.S.A. Inc. | Two-stage reforming process configured for increased feed rate to manufacture reformate |
| CN109569714B (en) * | 2017-09-28 | 2021-11-16 | 中国石油化工股份有限公司 | Fischer-Tropsch synthesis naphtha conversion catalyst and preparation method thereof |
| RU2748456C1 (en) * | 2020-07-13 | 2021-05-25 | Общество с ограниченной ответственностью "ЭНЕРДЖИ ЭНД ИНЖИНИРИНГ" | Method for processing hydrocarbon raw materials |
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- 2009-05-12 AU AU2009255498A patent/AU2009255498A1/en not_active Abandoned
- 2009-05-12 WO PCT/US2009/043586 patent/WO2009148773A1/en active Application Filing
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Also Published As
| Publication number | Publication date |
|---|---|
| EP2310475A1 (en) | 2011-04-20 |
| JP2011522927A (en) | 2011-08-04 |
| WO2009148773A1 (en) | 2009-12-10 |
| US20090301933A1 (en) | 2009-12-10 |
| CA2726912A1 (en) | 2009-12-10 |
| AU2009255498A1 (en) | 2009-12-10 |
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Application publication date: 20110615 |