EP2291489A2 - Vorrichtung zur steuerung der betriebszustände in einer katalytischen cracking-einheit mit doppelter steigung - Google Patents

Vorrichtung zur steuerung der betriebszustände in einer katalytischen cracking-einheit mit doppelter steigung

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Publication number
EP2291489A2
EP2291489A2 EP09766003A EP09766003A EP2291489A2 EP 2291489 A2 EP2291489 A2 EP 2291489A2 EP 09766003 A EP09766003 A EP 09766003A EP 09766003 A EP09766003 A EP 09766003A EP 2291489 A2 EP2291489 A2 EP 2291489A2
Authority
EP
European Patent Office
Prior art keywords
riser
catalyst
catalytic cracking
propylene
cracking unit
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP09766003A
Other languages
English (en)
French (fr)
Other versions
EP2291489B1 (de
Inventor
Frédéric FEUGNET
Thierry Gauthier
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
IFP Energies Nouvelles IFPEN
Original Assignee
IFP Energies Nouvelles IFPEN
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by IFP Energies Nouvelles IFPEN filed Critical IFP Energies Nouvelles IFPEN
Publication of EP2291489A2 publication Critical patent/EP2291489A2/de
Application granted granted Critical
Publication of EP2291489B1 publication Critical patent/EP2291489B1/de
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
    • C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
    • 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
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04—Oxides
    • C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
    • 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
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
    • C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
    • C10G11/182—Regeneration
    • 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
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
    • C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
    • C10G11/187—Controlling or regulating
    • 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
    • C10G51/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more cracking processes only
    • C10G51/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more cracking processes only plural serial stages only
    • C10G51/026—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more cracking processes only plural serial stages only only catalytic cracking steps
    • 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
    • C10G2300/4006—Temperature
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/02—Gasoline
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/20—C2-C4 olefins

Definitions

  • the present invention is in the field of catalytic cracking of petroleum fractions, more particularly so-called "heavy" cuts.
  • the main FCC (fluidized catalytic cracking abbreviation) feedstock of heavy cuts is generally a hydrocarbon or hydrocarbon mixture containing essentially (i.e., at least 80%) higher boiling molecules. at 340 ° C.
  • This feed contains quantities of metals (Ni + V) limited generally less than 50 ppm, preferably less than 20 ppm, and a hydrogen content in general greater than 11% by weight, typically between 11.5% and 14.5% and preferably between 11.8% and 13%. It is also preferable to limit the nitrogen content to below 0.5% by weight.
  • CCR carbon conradson
  • These heavy cuts may in particular come from atmospheric distillation, vacuum distillation, hydrocracking unit or deasphalting.
  • the objective of the catalytic cracking unit of a refinery is to produce gasoline bases, ie cuts having a distillation range of between 35 ° C and 250 ° C. More and more this primary objective is accompanied by a new objective which is the production of light olefins, essentially ethylene and propylene.
  • Gasoline is produced by cracking the heavy load in the main reactor (called the main riser in the rest of the text due to the upward flow of the catalyst and the slender form of this reactor, in accordance with the terminology of the person skilled in the art)
  • the co-production of propylene is, for its part, generally obtained by recycling in an additional reactor, called additional riser, part of the gasoline cut produced by the unit. catalytic cracking or from an equivalent charge such as C5, C6, C7 and C8 oligomers.
  • riser principal noted (1) to designate the riser oriented to the production of gasoline
  • secondary riser noted (2) to designate the riser dedicated to the production of propylene
  • the coproduction of propylene requires a significant modification of the operating conditions of the secondary riser with respect to the operating conditions of the main riser.
  • a conventional riser operating under conditions of production of essence operates with a catalyst on charge ratio of between 4 and 15, and preferably between 5 and 10, and with riser outlet temperatures (denoted TS) of between 510 and 580 ° C., and preferably between 520 ° C. and 570 ° C. ° C.
  • the secondary riser therefore operates with operating conditions much more severe than the main riser.
  • Both risers are fed with regenerated catalyst, whose temperature results from the combustion of the coke.
  • the amount of catalyst circulating in the unit therefore depends on the regeneration temperature.
  • a change in the operation of the first riser can therefore change the regeneration temperature and directly affect the operation of the second riser.
  • the present invention makes it possible to implement an independent and optimized control of the operating conditions of each riser by independent control of the catalyst inlet temperatures in the two risers.
  • the term "cat cooler” means the heat exchanger external to the regeneration zone for cooling the catalyst taken from a point of said zone and reintroduced after cooling to another point in the regeneration zone.
  • the "cat cooler” or “coolers” used in the present invention differ from a "cat cooler” according to the prior art in that it (s) has (s) at least one specific output that brings the cooled catalyst directly to one of the risers.
  • This application does not describe the means for achieving independent and optimized control of the temperature of each of the risers.
  • FIG. 1 represents a diagram of the catalytic cracking unit according to the invention with two risers and two cat coolers, each of the risers being supplied with catalyst coming directly from the cat cooler dedicated to the corresponding riser.
  • the invention therefore consists of a process for the production of propylene gasoline and co-production using a new configuration of the catalytic cracking unit which makes it possible to independently control the temperature and time conditions. contact of the main riser fed by a conventional load dedicated to the production of gasoline and working under moderate severity conditions on the one hand, and the secondary riser fueled by a gasoline or equivalent cut, dedicated to the production of propylene and working in conditions of high severity on the other hand.
  • the main riser (1) is fed with catalyst from the regeneration zone which has been cooled in a "cat cooler” (7), called “cat cooler” principal, and directly sent out of said "cat cooler” to the base of the main riser (1) via the transfer line (10).
  • the catalyst circuit passing through the regeneration zone, the cat cooler (7), the transfer line (10) and the main riser (1) is called the main circuit.
  • the secondary riser (2) is fed with catalyst from the regeneration zone which has been cooled in a "cat cooler” (6) separate from the main “cat cooler” (7), referred to as “secondary cat cooler” (6). , and directly sent out of said secondary “cat cooler” at the base of the secondary riser (2) via the transfer line (12).
  • the catalyst circuit passing through the regeneration zone, the "cat cooler” (6), the transfer line (12), and the secondary riser (2) is called secondary circuit.
  • main (1) and a catalyst fraction cooled to optimum conditions for feeding the secondary riser (2).
  • the fact of having a "cat cooler” on each of the catalyst circuits makes it possible to independently control the temperature of the catalyst sent into each riser, and thus to independently optimize the operation of each of the risers.
  • the main riser (1) is optimized for working at moderate severity conditions, and the secondary riser (2) at high severity conditions.
  • each "cat cooler” main or secondary
  • main or secondary the fact of sending the catalyst directly out of each "cat cooler” to the corresponding riser (respectively main or secondary) is accompanied by a significant energy saving that has been quantified about 10% of the total heat exchanged by each of the "cat cooler” compared to a single “cat cooler” providing internal cooling to the regeneration zone, ie with a cooled catalyst outlet inside of the regeneration zone.
  • This gain is explained by the fact that in the configuration of the present invention, the combustion air is not cooled contrary to a traditional arrangement.
  • the present invention is compatible with any type of configuration of the regeneration zone, whether this zone is a single stage or two stages working in series. It can therefore be applied to remodeling existing units without having to modify the regeneration zone in which the air burns the coke formed during the reaction. More precisely, the present invention can therefore be defined as a fluidized catalytic cracking unit comprising two independent catalyst circuits whose temperature is controlled in a dissociated way:
  • a first "main” circuit comprising a main riser operating under conditions of moderate severity, and comprising a catalyst cooling system (“main cat cooler”) placed between the regeneration zone and the reaction zone,
  • main cat cooler a catalyst cooling system
  • a second so-called “secondary” circuit comprising a secondary riser operating under conditions of high severity, and comprising a secondary catalyst cooling system (“secondary cooler”) placed between the regeneration zone and the reaction zone.
  • the secondary riser works with a contact time between 50 and 200 ms, and with a catalyst flow of between 150 kg / m2.s and 600 kg / m2.s (ms is the abbreviation of milliseconds or 10 "3 s
  • the cooling of the catalyst feeding the main riser (1) is done with a single "cat cooler” having two separate outputs of cooled catalyst, a first output to the regeneration zone, and a second output to the secondary riser by means of of a specific conduct.
  • the catalyst feed of the main riser (1) is made from a sampling point of said catalyst located in the regeneration zone.
  • Controlling the thermal level of the secondary riser (2) is done by mixing a portion of the catalyst leaving the regeneration zone with another part of the catalyst leaving the "cat cooler" directly via the specific pipe.
  • the "cat cooler” in this variant has two separate catalyst outlets, one that returns the cooled catalyst to one point in the regeneration zone, the other that returns the cooled catalyst to the riser. secondary (2) via the specific line.
  • the adjustment of the ratio of the two catalyst streams makes it possible to ensure the desired conditions of the secondary riser.
  • the temperature of the catalyst sent to the main riser is influenced by that of the secondary riser.
  • the realization of the optimal conditions for each riser is then ensured by the adapted design of the unique "cat cooler".
  • FIG. 1 corresponds to the basic case of the present invention.
  • the catalytic cracking unit according to the invention has a first riser said main riser (1) treating a conventional vacuum distillate type charge or hydro-treated residue or not and a second riser said secondary riser (2) treating a light load in view of olefin production.
  • This light load can consist of a gasoline cut, in particular a part of the gasoline produced by the cracking unit itself, which is then recycled to the base of the secondary riser (2), or by any cut whose distillation range is between 35 ° C and 250 ° C, such as oligomers C5, C6, C7 and C8.
  • the main riser (1) works under conventional cracking conditions which can be summarized as follows:
  • Riser output temperature between 550 0 C and 650 ° C, preferably between 580 0 C and 610 0 C.
  • each riser The conditions of severity specific to each riser are obtained by means of a cooling system specific to each riser, called “cat cooler” principal (10) for the main riser (1) and “cat cooler” secondary (12). ) for the secondary riser (2).
  • the term “cat cooler” means an exchanger external to the regeneration zone, working in a fluidized bed and allowing the catalyst removed in the regeneration zone to be cooled before being reintroduced into the reaction zone, via a line bringing back the cooled catalyst leaving the reactor. "cat cooler "at the base of the riser.This transfer line is noted (10) for feeding the main riser (1) and denoted (12) for feeding the secondary riser (2).
  • the catalyst is generally taken from the second stage at a temperature of between 715 and 800. ° C, and preferably close to 75O 0 C.
  • the catalyst is taken to said stage at a temperature between 650 ° C and 780 0 C, and preferably close to 750 0 C.
  • the solid gas separation in the reaction zone can be carried out by any system known to those skilled in the art such as those described in the patent application FR06 / 10.982.
  • the catalyst recovered after the solid-gas separation system is sent to a stripping zone (8) and then to the regeneration zone via a so-called standpipe pipe (5) in which the catalyst circulates with a density of between 450 and 600 kg / m3.
  • the catalyst system used for this invention contains at least one base zeolite usually dispersed in a suitable matrix such as, for example, alumina, silica or silica-alumina, to which at least one zeolite with a shape selectivity can be added. .
  • the most commonly used basic zeolite is zeolite Y, but another zeolite can be advantageously used, alone or as a mixture with zeolite Y.
  • the catalyst may comprise in particular, in the process according to the invention, at least one zeolite having a shape selectivity, said zeolite comprising silicon and at least one element selected from the group consisting of aluminum, iron, gallium, phosphorus, boron and preferably aluminum.
  • the zeolite having a shape selectivity can be of one of the following structural types: MEL (eg ZSM-11), MFI (eg ZSM5), NES, EUO, FER, CHA.
  • the proportion of zeolite having a shape selectivity with respect to the total amount of zeolite may vary depending on the charges used and the spectrum of the desired products. In the present invention, from 2% to 60%, preferably from 3% to 40%, and more preferably from 3% to 30% by weight of zeolite (s) having a shape selectivity are used.
  • Example 1 and 2 are according to the prior art
  • Example 3 is according to the invention.
  • the main riser charge is a hydrotreated atmospheric residue having the following properties:
  • the catalyst is a zeolite Y additive containing 10% by weight of ZSM5.
  • the light cut recycled to the secondary riser is a C6 + -220 ° C cut from the main heavy duty conversion riser, recycled to 50% of all gasoline produced in the two-riser cracking unit. .
  • This example illustrates the case of a catalytic cracking unit with 2 risers and 1 "cat cooler", and a 2-stage regeneration zone, the riser 1 being optimized for gasoline production, and the non-optimized riser 2 and fed by a portion of the catalytic gasoline from the main riser.
  • This example illustrates the case of a catalytic cracking unit with 2 risers and 1 "cat cooler", and a regeneration zone with 2 stages, the riser 1 not being optimized, and the riser 2 optimized for the production of olefins.
  • Temperature Regenerator stage 2 651 ° C
  • Temperature catalyst inlet riser principal 651 0 C
  • the decrease in this ratio reflects the fact that the gain in propylene does not compensate for the associated increase in dry gases. Dry gases are not recoverable products and their production is to be minimized.
  • This example according to the invention illustrates the case of a catalytic cracking unit with two risers, each having a dedicated "cat cooler” that allows it to operate under optimized conditions.
  • the 2-stage regeneration zone is the same as in Examples 1 and 2.
  • Temperature Regenerator stage 2 732 0 C
  • This case illustrates the invention which allows to independently adjust the C / O of each riser.
  • a C / O of 25 is reached for the main riser, and a C / O of 8 is maintained in the main riser.
  • the temperatures of 681 ° C and reg2 of 732 ° C are found in the desired operating ranges and ensure optimal regeneration of the catalyst.
  • the selectivity C3 / dry gas is maintained or even improved with a ratio of 1.60 against 1.56 for the conventional case.
  • the increase in dry gases in case 3 is therefore offset by the associated propylene gain.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
EP09766003A 2008-06-17 2009-06-03 Vorrichtung zur steuerung der betriebszustände in einer katalytischen cracking-einheit mit doppelter steigung Active EP2291489B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0803384A FR2932495B1 (fr) 2008-06-17 2008-06-17 Dispositif de controle des conditions operatoires dans une unite de craquage catalytique a deux risers.
PCT/FR2009/000639 WO2009153441A2 (fr) 2008-06-17 2009-06-03 Dispositif de controle des conditions operatoires dans une unite de craquage catalytique a deux risers

Publications (2)

Publication Number Publication Date
EP2291489A2 true EP2291489A2 (de) 2011-03-09
EP2291489B1 EP2291489B1 (de) 2012-01-18

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Application Number Title Priority Date Filing Date
EP09766003A Active EP2291489B1 (de) 2008-06-17 2009-06-03 Vorrichtung zur steuerung der betriebszustände in einer katalytischen cracking-einheit mit doppelter steigung

Country Status (11)

Country Link
US (1) US8957267B2 (de)
EP (1) EP2291489B1 (de)
JP (1) JP5814115B2 (de)
KR (1) KR101610052B1 (de)
CN (1) CN102066528B (de)
AT (1) ATE541915T1 (de)
ES (1) ES2379938T3 (de)
FR (1) FR2932495B1 (de)
RU (1) RU2500790C2 (de)
SA (1) SA109300382B1 (de)
WO (1) WO2009153441A2 (de)

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EP3167026B1 (de) * 2014-07-07 2019-05-15 Albemarle Europe Sprl. Alkylierungsverfahren mit verwendung eines katalysators mit ceriumreicher seltenerde mit zeolithen und einem hydrierungsmetall
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KR20110034594A (ko) 2011-04-05
WO2009153441A3 (fr) 2010-02-25
ES2379938T3 (es) 2012-05-07
JP5814115B2 (ja) 2015-11-17
JP2011524453A (ja) 2011-09-01
FR2932495B1 (fr) 2011-03-25
RU2011101430A (ru) 2012-07-27
KR101610052B1 (ko) 2016-04-07
CN102066528A (zh) 2011-05-18
CN102066528B (zh) 2013-09-25
US20110178347A1 (en) 2011-07-21
RU2500790C2 (ru) 2013-12-10
EP2291489B1 (de) 2012-01-18
FR2932495A1 (fr) 2009-12-18
ATE541915T1 (de) 2012-02-15
US8957267B2 (en) 2015-02-17
SA109300382B1 (ar) 2013-05-18
WO2009153441A2 (fr) 2009-12-23

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