US20080300439A1 - Process for the Separation of C5 Hydrocarbons Present in Streams Prevalently Containing C4 Products Used for the Production of Highoctane Hydrocarbon Compounds By the Se-Lective Dimerization of Isobutene - Google Patents

Process for the Separation of C5 Hydrocarbons Present in Streams Prevalently Containing C4 Products Used for the Production of Highoctane Hydrocarbon Compounds By the Se-Lective Dimerization of Isobutene Download PDF

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US20080300439A1
US20080300439A1 US12/094,061 US9406106A US2008300439A1 US 20080300439 A1 US20080300439 A1 US 20080300439A1 US 9406106 A US9406106 A US 9406106A US 2008300439 A1 US2008300439 A1 US 2008300439A1
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alcohol
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Marco Di Girolamo
Domenico Sanfilippo
Massimo Conte
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SnamProgetti SpA
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Assigned to SNAMPROGETTI S.P.A. reassignment SNAMPROGETTI S.P.A. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: CONTE, MASSIMO, DI GIROLAMO, MARCO, SANFILIPPO, DOMENICO
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08—Catalytic processes
    • C07C2/26—Catalytic processes with hydrides or organic compounds
    • C07C2/28—Catalytic processes with hydrides or organic compounds with ion-exchange resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/34—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping with one or more auxiliary substances
    • B01D3/36—Azeotropic distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B63/00—Purification; Separation; Stabilisation; Use of additives
    • C07B63/04—Use of additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/04—Purification; Separation; Use of additives by distillation
    • C07C7/05—Purification; Separation; Use of additives by distillation with the aid of auxiliary compounds
    • C07C7/06—Purification; Separation; Use of additives by distillation with the aid of auxiliary compounds by azeotropic distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/20—Use of additives, e.g. for stabilisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C9/00—Aliphatic saturated hydrocarbons
    • C07C9/14—Aliphatic saturated hydrocarbons with five to fifteen carbon atoms
    • C07C9/16—Branched-chain hydrocarbons
    • C07C9/21—2, 2, 4-Trimethylpentane
    • 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
    • C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • C07C2531/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • C07C2531/08—Ion-exchange resins
    • C07C2531/10—Ion-exchange resins sulfonated
    • 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
    • C10G2400/22—Higher olefins

Definitions

  • the present invention relates to a process for the separation of C 5 hydrocarbons present in the C 4 charges used for the production of high-octane hydrocarbon compounds by the selective dimerization reaction of isobutene and to a lesser extent of possible linear olefins, in the presence of linear and branched alcohols and alkyl ethers, which favour the production of higher selectivities on the part of the catalyst.
  • the mixture obtained can then be hydrogenated with conventional methods to obtain a product with further enhanced octane characteristics.
  • alkylated products are extremely important as they have a high octane number, a low volatility and are practically free of olefins and aromatic compounds.
  • the alkylation process in liquid phase is a reaction between isoparaffinic hydrocarbons, such as isobutane, and olefins, for example propylene, butenes, pentenes and relative mixtures thereof, in the presence of an acid catalyst for the production of C 7 -C 9 hydrocarbons with a high octane number to be used in gasolines (A. Corma, A. Martinez, Catal. Rev.-Sci. Eng., 35, (1993), 483).
  • a hydrocarbon product of this type is becoming increasingly more requested due to its octane characteristics (both the Research Octane Number (RON) and the Motor Octane Number (MON) are high) and those relating to the boiling point (limited volatility but low end-point) which position it in the group of compositions of great interest for obtaining gasolines which are more compatible with current environmental requirements.
  • octane characteristics both the Research Octane Number (RON) and the Motor Octane Number (MON) are high
  • RON Research Octane Number
  • MON Motor Octane Number
  • Oligomerization processes were widely used in the ‘30s’ and ‘40s’ for converting low-boiling C 3 -C 4 olefins into gasolines.
  • the process leads to the production of a gasoline with a high octane number (RON about 97) but with a high sensitivity (difference between RON and MON) due to the purely olefinic nature of the product (J. H. Gary, G. E. Stress, “Petroleum Refining: Technology and Economics”, 3 rd Ed., M. Dekker, New York, (1994), 250).
  • Typical olefins which are oligomerized are mainly propylene, which gives dimers or slightly higher oligomers depending on the process used, and isobutene which mainly gives dimers but is always accompanied by a considerable quantity of higher oligomers.
  • this reaction can be carried out either batchwise, semi-batchwise or in continuous, either in gas or liquid phase, generally at temperatures ranging from 50 to 300° C. and at atmospheric pressure or such pressures as to maintain the reagents in liquid phase, if necessary.
  • Typical catalysts for the industrial oligomerization process of isobutene are represented by phosphoric acid, generally supported on a solid (for example kieselguhr), or cation-exchange acid resins.
  • phosphoric acid generally supported on a solid (for example kieselguhr), or cation-exchange acid resins.
  • the latter allow blander conditions to be used compared with supported phosphoric acid both in terms of temperature and pressure (50-100° C. and 0.2-3 MPa with respect to 200-220° C. and 3-10 MPa).
  • catalysts are also claimed in literature, both liquid acids such as H 2 SO 4 and derivatives of sulfonic acids, and solids such as silico-aluminas, mixed oxides, zeolites, fluorinated or chlorinated aluminas, etc.; none of these catalysts however has so far enabled an industrial process to be set up, as in the case of supported phosphoric acid (F. Asinger, “Mono-olefins: Chemistry and Technology”, Pergamon Press, Oxford, pages 435-456) and that of cation resins (G. Scharfe, Hydrocarbon Proc., April 1973, 171).
  • the main problem of this process lies in the fact that excessive percentages of heavy oligomers such as trimers (selectivity of 20-40%) and tetramers (selectivity of 1-5%) of isobutene, are produced in the oligomerization phase. Tetramers are completely outside the gasoline fraction as they are too high-boiling and therefore represent a net loss in yield to gasoline; as far as trimers are concerned, their concentration should be greatly reduced as they have a boiling point (170-180° C.) at the limit of future specifications on the final point of reformulated gasolines.
  • the reaction product is then preferably hydrogenated to give a completely saturated end-product with a high octane number and low sensitivity.
  • the hydrogenation can be carried out with conventional methods as described, for example, in F. Asinger, “Mono-olefins: Chemistry and Technology”, Pergamon Press, Oxford, page 455.
  • Table 1 indicates the octane number and relative boiling points of some of the products obtained, by means of the process, object of the present invention.
  • the process, object of the present invention for the separation of C 5 hydrocarbons present, in a quantity ranging from 0.2 to 20% by weight, in streams prevalently containing C 4 products used for the production of high-octane hydrocarbons, by the selective dimerization reaction of isobutene, is characterized in that the reaction is carried out in the presence of linear and branched alcohols and ethers in a quantity which is such as to have a molar ratio alcohols+ethers/isobutene in the feeding higher than 0.01 and preferably lower than 0.7.
  • the process claimed herein can be applied to cuts mainly containing isobutane, isobutene, n-butane, n-butenes and saturated and olefinic C 5 hydrocarbons.
  • Saturated and olefinic C 5 hydrocarbons can be present in these streams, in various amounts (0.2-20% by weight), depending on the efficiency of the C 4 -C 5 separation step.
  • the C 5 olefins possibly present can be involved in dimerization reactions.
  • the stream sent to the reaction steps can contain branched alcohols or a blend of alcohols and alkyl ethers, in addition to the hydrocarbon components.
  • the alcohols used are linear, preferably containing a number of carbon atoms ranging from 1 to 6, preferably from 4 to 7 carbon atoms; preferred linear alcohols are methanol and/or ethanol, whereas preferred branched alcohols are tert-butyl alcohol (TBA) and/or tert-amyl alcohol (TAA).
  • preferred linear alcohols are methanol and/or ethanol
  • preferred branched alcohols are tert-butyl alcohol (TBA) and/or tert-amyl alcohol (TAA).
  • the alkyl ether used can be selected from those containing a number of carbon atoms ranging from 5 to 10: MTBE (methyl tert-butyl ether), ETBE (ethyl tert-butyl ether), MSBE (methyl sec-butyl ether), ESBE (ethyl sec-butyl ether), TAME (methyl tert-amyl ether), TAEE (ethyl tert-amyl ether) or mixtures thereof are preferred.
  • Isobutene together with the hydrocarbon stream in which it is contained, is sent with the mixture of alcohols and alkyl ethers, in stoichiometric defect, into contact with the acid catalyst where the dimerization takes place.
  • the linear primary alcohol in addition to interacting with the catalyst, also helps to limit the possible cracking of the alkyl ether and can possibly react with the dimers and linear C 4 olefins, whereas the branched alcohol (tertiary) does not react with the olefins due to its steric hindrance.
  • the dimerization product In order to obtain the dimerization product with the desired selectivity to dimers, it is essential to maintain a constant level of oxygenated products in the reaction environment but above all the contemporaneous presence of the three oxygenated compounds (linear alcohol, branched alcohol and alkyl ether) which, due to a synergic effect are capable of forming the catalytic species with the correct activity and stability.
  • acid catalysts can be used for this process, but those preferred are styrene-divinyl benzene polymeric resins having sulphonic groups as catalytic centres.
  • a large range of operative conditions can be used to produce high-octane hydrocarbons from isobutene in the desired selectivities. It is possible to operate in vapour or liquid-vapour phase, but operating conditions in liquid phase are preferred.
  • the pressure is preferably higher than the atmospheric value, in order to maintain the reagents in liquid phase, generally below 5 MPa, more preferably between 0.2-2.5 MPa.
  • the reaction temperature preferably ranges from 30 to 120° C.
  • the feeding space velocities of the oxygenatedhydrocarbon stream are preferably lower than 30 h ⁇ 1 , more preferably ranging from 1 and 15 h ⁇ 1 .
  • Isobutene is mainly converted in the reaction zone, however part of the C 4 -C 5 olefins present can also be converted to useful product; in principle, there are no limits to the concentration of iso-olefin in the hydrocarbon fraction, even if concentrations ranging from 2 to 60% are preferred; in case of streams having a high isobutene concentration (dehydration or cracking) it is therefore convenient to dilute the charge with C 4 -C 7 hydrocarbons. There are no limits, on the contrary, for the ratio between isobutene and linear olefins.
  • the process, object of the present invention can be effected batchwise or in continuous, bearing in mind however that the latter is much more advantageous in industrial practice.
  • the reactor configuration selected is generally a double reaction step comprising one or more fixed bed reactors which can be optionally selected from a tubular and adiabatic reactor.
  • the C 5 products cannot therefore be removed from the plant together with the C 4 products, as they would introduce oxygenated products (branched alcohols and ethers) into the stream, which are difficult to remove by means of the traditional techniques used for removing methanol (water washing) and which are poisonous for the subsequent treatment processes of the streams (polymerization, alkylation and metathesis).
  • the C 5 products cannot be maintained in the oxygenated stream as they would rapidly accumulate.
  • it is therefore necessary to introduce a C 5 /branched alcohol azeotropic separation step, which can be inserted in different positions of the plant in relation to the C 5 content in the charge and also the relative concentration of the C 5 products present.
  • the separation of the C 5 /branched alcohol azeotropic product can be effected using traditional fractionation columns in which the azeotropic mixture can be recovered at the head, bottom or as side cut.
  • the C 5 products are present in the streams prevalently containing C 4 products in a quantity preferably ranging from 0.5 to 10% by weight.
  • the separation of the C 5 /branched alcohol azeotropic product is preferably carried out starting from blends of:
  • FIGS. 1-6 Six process schemes are shown in FIGS. 1-6 , in order to clearly illustrate the present invention.
  • FIG. 1 shows a process scheme wherein C 5 hydrocarbons are not present in the charge and the oxygenated products are methanol (linear alcohol), TBA (branched alcohol) and MTBE (alkyl ether).
  • the effluent ( 4 ) from the first reaction step is sent to a first separation column C 1 in which a stream ( 5 ) essentially containing C 4 hydrocarbons and methanol is removed from the head, whereas a stream ( 6 ) essentially containing the reaction product and remaining oxygenated compounds, is collected at the bottom.
  • the head stream ( 5 ) is then fed, together with the recycled streams of oxygenated products ( 16 ) and methanol ( 17 ), to a second reaction step R 2 , which can consist of one or more reactors, wherein the isobutene present is selectively converted to dimers.
  • the effluent ( 8 ) from the second reaction step is separated in a column C 2 from whose bottom a stream ( 10 ) essentially containing MTBE, TBA, the dimerization product and part of the C 4 products, is removed and sent to the column C 1 for the recovery of the product and oxygenated products.
  • the head stream ( 9 ), consisting of C 4 products and the C 4 /methanol azeotropic mixture is, on the other hand, sent to an MR unit for the recovery of the alcohol which can consist, for example, of an absorption system on molecular sieves or a water washing column.
  • the alcohol recovered ( 14 ) can be sent back to the two reaction steps (streams 17 and 18 ) whereas the hydrocarbon stream ( 13 ) can be used in subsequent operations.
  • the bottom stream ( 6 ) of the column C 1 is sent to a further separation column C 3 wherein a stream ( 11 ) essentially containing MTBE, TBA and dimers is removed at the head and is recycled to the two reaction steps (streams 15 and 16 ), whereas the reaction product ( 12 ) essentially consisting of dimers, trimers and small quantities of oligomers and ethers of dimers, is recovered at the bottom.
  • FIG. 2 therefore shows a possible process scheme which differs from the previous scheme in that the stream containing oxygenated products to be recycled ( 11 ) (ethers and TBA) is removed from the column C 3 as side cut, whereas the C 5 /TBA azeotropic product ( 19 ) is recovered from the head of the column and can optionally be joined with the reaction product.
  • the stream containing oxygenated products to be recycled ( 11 ) ethers and TBA
  • the C 5 /TBA azeotropic product 19
  • the process scheme becomes more complex when a more efficient separation of the mixture of C 5 products/oxygenated products/reaction product is to be effected, as a new fractionation column C 4 must be inserted, as shown in FIG. 3 .
  • the head stream of the column C 3 ( 11 ) is sent to a new column C 4 where the C 5 /TBA azeotropic mixture ( 20 ) is separated at the head and the stream of oxygenated products ( 19 ) is separated at the bottom and recycled to the two reaction steps.
  • the C 5 hydrocarbons can be recovered using the two fractionation columns of the C 4 products wherein the C 5 /TBA azeotropic mixture can be thus recovered as side cut ( 19 ) both in the column C 1 ( FIG. 4 ) and in the column C 2 ( FIG. 5 ).
  • a further option however consists in effecting the separation of the C 4 -C 5 products in a last new column C 5 , as shown in FIG. 6 , in which the C 5 /TBA azeotropic product is recovered as bottom stream ( 19 ).

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US12/094,061 2005-11-17 2006-11-13 Process for the Separation of C5 Hydrocarbons Present in Streams Prevalently Containing C4 Products Used for the Production of Highoctane Hydrocarbon Compounds By the Se-Lective Dimerization of Isobutene Abandoned US20080300439A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
IT002198A ITMI20052198A1 (it) 2005-11-17 2005-11-17 Procedimento per la separazione di idrocarburi c5 presenti nelle correnti contenenti prevalentemente c4 da utilizzare per la produzione di composti idrocarburici altoottanici mediante dimerizzazione selettiva di isobutene
ITMI2005A002198 2005-11-17
PCT/EP2006/010893 WO2007057151A2 (en) 2005-11-17 2006-11-13 Process for the separation of c5 hydrocarbons present in streams prevalently containing c4 products used for the production of high-octane hydrocarbon compounds by the se- lective dimerization of isobutene

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PCT/EP2006/010893 A-371-Of-International WO2007057151A2 (en) 2005-11-17 2006-11-13 Process for the separation of c5 hydrocarbons present in streams prevalently containing c4 products used for the production of high-octane hydrocarbon compounds by the se- lective dimerization of isobutene

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US14/589,465 Active US10618857B2 (en) 2005-11-17 2015-01-05 Process for the separation of C5 hydrocarbons present in streams prevalently containing C4 products used for the production of high-octane hydrocarbon compounds by the selective dimerization of isobutene

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US (2) US20080300439A1 (ko)
EP (1) EP1948576B1 (ko)
KR (1) KR101376942B1 (ko)
AR (1) AR057597A1 (ko)
BR (1) BRPI0618598B1 (ko)
HU (1) HUE044972T2 (ko)
IT (1) ITMI20052198A1 (ko)
SA (1) SA06270421B1 (ko)
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20210101851A1 (en) * 2019-10-07 2021-04-08 Lummus Technology Llc Co-production of high purity isobutane and butene-1 from mixed c4s

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8753503B2 (en) 2008-07-24 2014-06-17 Uop Llc Process and apparatus for producing a reformate by introducing isopentane

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4447668A (en) * 1982-03-29 1984-05-08 Chemical Research & Licensing Company Process for producing high purity isoolefins and dimers thereof by dissociation of ethers
US5030768A (en) * 1990-03-30 1991-07-09 Air Products And Chemicals, Inc. Process for preparing alkyl tert-alkyl ethers
US5908964A (en) * 1996-02-22 1999-06-01 Neste Oy Process for preparing alkyl ethers and mixtures thereof
US6011191A (en) * 1997-05-15 2000-01-04 Snamprogetti S.P.A. Process for the production of hydrocarbons with a high octane number by the selective dimerization of isobutene
US6433238B1 (en) * 1999-08-05 2002-08-13 Snamprogetti S.P.A. Process for the production of hydrocarbons with a high octane number by the selective dimerization of isobutene
US6590132B1 (en) * 2001-04-27 2003-07-08 Uop Llc Separation of monomer from oligomer with lower bottoms temperature
US6613108B1 (en) * 1998-10-16 2003-09-02 Fortum Oil & Gas Oy Process for producing a fuel component
US6734333B2 (en) * 2001-02-23 2004-05-11 Catalytic Distillation Technologies Recovery of tertiary butyl alcohol
US20060122444A1 (en) * 2003-01-23 2006-06-08 Udo Peters Method for producing butene oligomers and tert-butylethers from c4 flows containing isobutene

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4447668A (en) * 1982-03-29 1984-05-08 Chemical Research & Licensing Company Process for producing high purity isoolefins and dimers thereof by dissociation of ethers
US5030768A (en) * 1990-03-30 1991-07-09 Air Products And Chemicals, Inc. Process for preparing alkyl tert-alkyl ethers
US5908964A (en) * 1996-02-22 1999-06-01 Neste Oy Process for preparing alkyl ethers and mixtures thereof
US6011191A (en) * 1997-05-15 2000-01-04 Snamprogetti S.P.A. Process for the production of hydrocarbons with a high octane number by the selective dimerization of isobutene
US6613108B1 (en) * 1998-10-16 2003-09-02 Fortum Oil & Gas Oy Process for producing a fuel component
US6433238B1 (en) * 1999-08-05 2002-08-13 Snamprogetti S.P.A. Process for the production of hydrocarbons with a high octane number by the selective dimerization of isobutene
US6734333B2 (en) * 2001-02-23 2004-05-11 Catalytic Distillation Technologies Recovery of tertiary butyl alcohol
US6590132B1 (en) * 2001-04-27 2003-07-08 Uop Llc Separation of monomer from oligomer with lower bottoms temperature
US20060122444A1 (en) * 2003-01-23 2006-06-08 Udo Peters Method for producing butene oligomers and tert-butylethers from c4 flows containing isobutene

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20210101851A1 (en) * 2019-10-07 2021-04-08 Lummus Technology Llc Co-production of high purity isobutane and butene-1 from mixed c4s
US11505512B2 (en) * 2019-10-07 2022-11-22 Lummus Technology Llc Co-production of high purity isobutane and butene-1 from mixed C4s

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US10618857B2 (en) 2020-04-14
HUE044972T2 (hu) 2019-12-30
ITMI20052198A1 (it) 2007-05-18
BRPI0618598B1 (pt) 2016-08-02
WO2007057151A2 (en) 2007-05-24
EP1948576B1 (en) 2019-03-20
KR20080069191A (ko) 2008-07-25
WO2007057151A3 (en) 2007-07-26
SA06270421B1 (ar) 2011-01-24
US20150225312A1 (en) 2015-08-13
EP1948576A2 (en) 2008-07-30
BRPI0618598A2 (pt) 2011-09-06
AR057597A1 (es) 2007-12-05
KR101376942B1 (ko) 2014-03-20

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