WO2008151759A2 - Process and apparatus for mixing gases - Google Patents
Process and apparatus for mixing gases Download PDFInfo
- Publication number
- WO2008151759A2 WO2008151759A2 PCT/EP2008/004511 EP2008004511W WO2008151759A2 WO 2008151759 A2 WO2008151759 A2 WO 2008151759A2 EP 2008004511 W EP2008004511 W EP 2008004511W WO 2008151759 A2 WO2008151759 A2 WO 2008151759A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- mixing chamber
- gas
- gas flow
- connecting tube
- converter
- Prior art date
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
- B01J8/0496—Heating or cooling the reactor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
- B01F23/10—Mixing gases with gases
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F25/00—Flow mixers; Mixers for falling materials, e.g. solid particles
- B01F25/20—Jet mixers, i.e. mixers using high-speed fluid streams
- B01F25/23—Mixing by intersecting jets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
- B01J8/0446—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical
- B01J8/0461—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical in two or more cylindrical annular shaped beds
- B01J8/0469—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical in two or more cylindrical annular shaped beds the beds being superimposed one above the other
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
- B01J8/0492—Feeding reactive fluids
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/74—Preparation
- C01B17/76—Preparation by contact processes
- C01B17/765—Multi-stage SO3-conversion
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/74—Preparation
- C01B17/76—Preparation by contact processes
- C01B17/80—Apparatus
- C01B17/803—Converters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F25/00—Flow mixers; Mixers for falling materials, e.g. solid particles
- B01F2025/91—Direction of flow or arrangement of feed and discharge openings
- B01F2025/915—Reverse flow, i.e. flow changing substantially 180° in direction
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F25/00—Flow mixers; Mixers for falling materials, e.g. solid particles
- B01F2025/91—Direction of flow or arrangement of feed and discharge openings
- B01F2025/918—Counter current flow, i.e. flows moving in opposite direction and colliding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00008—Controlling the process
- B01J2208/00017—Controlling the temperature
- B01J2208/00106—Controlling the temperature by indirect heat exchange
- B01J2208/00168—Controlling the temperature by indirect heat exchange with heat exchange elements outside the bed of solid particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00796—Details of the reactor or of the particulate material
- B01J2208/00823—Mixing elements
- B01J2208/00831—Stationary elements
- B01J2208/00849—Stationary elements outside the bed, e.g. baffles
Definitions
- the present invention relates to a process for mixing two gases of different temperature and/or composition in a converter for producing SO 3 from an SO 2 - containing gas, and to an apparatus for performing this process.
- the present invention is concerned with the production of sulfuric acid.
- sulfuric acid mostly is produced by the so-called double absorption process, which is described in Ullmann's Encyclopedia of Industrial Chemistry, 5 th edition, Vol. A25, pp. 635 to 700.
- a starting gas containing sulfur dioxide is at least partly reacted with oxygen in a plurality of successive contact stages of a converter corresponding to the formula
- the produced gas containing sulfur trioxide then is supplied to an absorber and converted there to sulfuric acid.
- the oxidation of the sul- fur dioxide to sulfur trioxide is effected in the presence of a catalyst, which usually contains vanadium pentoxide as active component and has a working range of about 380 to 640 0 C. While at temperatures above 64O 0 C an irreversible damage of the catalyst occurs, the same is inactive at temperatures below 380 0 C.
- the gas inlet temperature into the contact stage must be about 400 0 C. At a distinctly lower inlet temperature, the reaction is not initiated, whereas at a much higher inlet temperature the temperature rises so much during the process that the catalyst is damaged.
- the reac- tion is performed in several stages, between which the process gas each is cooled by means of integrated heat exchangers, in order to achieve a suitable gas inlet temperature for the next contact stage.
- such converter includes four to five contact stages, and in the above-mentioned double absorption process the process gas having passed through a number of, e.g. three, contact stages is supplied to an intermediate absorption tower, in which the SO 3 is converted to sulfuric acid, oleum or liquid SO 3 , and the SO 3 concentration in the process gas thereby is decreased again.
- the process gas Upon heating to the required process temperature, the process gas then is supplied to the next contact stages of the converter and thereafter to the final absorption.
- the process gas supplied to the converter suffers from frequent fluctuations of the quantity and SO2 concentration. While in conventional converters the SO 2 concentration usually is restricted to about 12 vol-% due to the high temperatures achieved in the first step of catalysis, the process described in DE 102 49 782 A1 provides for using higher SO 2 concentrations by recirculating SO 3 -containing gas. This recirculation limits the reaction in the first contact stage and as a result the heat generated there.
- a first gas flow is introduced into a mixing chamber in a first direction, in particular from below, that a second gas flow is countercurrently introduced into the mixing chamber in a direction opposite to the first direction, in particular from above, and that the gas mixture obtained in the mixing chamber is discharged from the mixing chamber via a connecting tube extending in the first direction, in particular directed from the bottom to the top, and supplied to a heat exchanger integrated in the converter.
- the second gas flow is in- traduced into the converter from below through a central supply conduit and then deflected radially to the outside by substantially 180°, so that it flows downwards into the mixing chamber surrounding the supply conduit.
- the second gas flow here en- ters the mixing chamber through a hole arrangement, so that it is divided and en- ters the mixing chamber as a multitude of small gas flows. Mixing with the first gas flow coming from below thereby is promoted.
- the first gas is an SO 2 - and SO 3 -containing process gas in accordance with the invention, which for instance is recirculated from the intermediate absorption
- the second gas is either an SO 2 -containing gas of another, e. g. lower temperature or an SO 3 -containing gas having another, e. g. a higher, concentration of SO 3 or has differences in both to the first gas.
- the second SO 2 -containing gas can also con- tain SO 3 , e. g. 1 to 10 vol-% SO 3 , but preferably contains less than 1 % SO 3 .
- the SO 3 -containing gas normally contains a certain amount of SO 2 , too.
- the second gas flow is smaller than the first gas flow and amounts to 20 to 70%, preferably ⁇ 50% of the first gas flow.
- An inventive apparatus for mixing two gases in a converter for producing SO 3 from an SO 2 -containing gas which can be used in particular for performing the process described above, includes a mixing chamber, to which a first gas flow is supplied in a first direction, in particular from below, a supply conduit for a second gas flow, wherein the mixing chamber is provided in the form of a ring around the supply conduit and is connected with the supply conduit, and a connecting tube, which extends from the mixing chamber in the first direction, in particular to the top, and connects the mixing chamber with the integrated heat exchanger.
- the connecting tube protrudes into the mixing chamber as an immersion tube. Therefore, the second gas flow must first traverse the mixing chamber by overcoming the resistance of the first (main) gas flow, before it is discharged from the mixing chamber via the connecting tube. The homogeneous mixing of the two gas flows thereby is promoted.
- a pre- chamber is provided above the mixing chamber, into which opens the supply conduit for the second gas flow and which is separated from the mixing chamber by a permeable dividing device, e. g. a perforated plate. By means of a perforated plate, the second gas flow is divided into a multitude of smaller gas flows, which promotes thorough mixing with the first gas flow.
- the connecting pipe extending from the mixing chamber in the first direction, in particular to the top extends through the perforated plate and the prechamber.
- perforated plate should not necessarily be understood to be a plate with openings, but can rather be a variety of arrangements, e.g. welded grids, riveted strips of metal or other materials placed one on top of the other.
- the openings can be round, angular or be present as slots or in different shapes.
- the openings likewise can have different sizes and shapes, e.g. in dependence on the distance of the opening from the immersion tube.
- fur- ther gas conducting means or structures are present on the so-called perforated plate, e.g. sheets, welding seams.
- the gas flow in the mixing chamber can be guided e. g. by guiding plates or by the gas inlet of the permeable dividing de- vice, so that e. g. a stream like a swirl in the mixing chamber results or the stream has different directions inside the mixing chamber.
- the permeable dividing device and/or the supply conduits for the first gas can be controlled in the cross sectional area to maintain a uniform mixing if the volume flow of the gases are changed.
- a ring disk is provided on the outside of the connecting tube. It thereby is prevented that the part of the second gas flow flowing along the connecting tube is directly diverted at the end of the immersion tube and is discharged via the connecting tube without mix- ing. This part of the first gas flow impinges on the ring disk, so that additional turbulences are generated and thorough mixing with the first gas flow is ensured.
- the ring disk is not necessarily like an annulus around the connecting tube. It is possible, that this ring disk has an irregular boundary e. g. a saw tooth or sinusoidal. This ring disk also can have some further guiding plates or the like to create e. g. a curled stream in the mixing chamber or different flow directions.
- a plurality of connecting tubes preferably uniformly distributed around the periphery of the mixing chamber are provided in accordance with the invention, through which the gas mixture is discharged.
- Fig. 1 schematically shows a sectional representation of a converter for producing SO 3 from an SO 2 -containing gas with an apparatus for mixing gases in accordance with the present invention
- Fig. 2 shows an enlarged section in accordance with detail Il of Fig. 1 with the apparatus for mixing gases, in which the gas flows are illustrated.
- the converter 1 for converting SO 2 to SO 3 as shown in Fig. 1 includes a total of five contact stages K1 to K5, in which a catalyst, in particular a catalyst containing vanadium pentoxide, is provided for converting SO 2 to SO 3 .
- SO 2 -containing gas is introduced into the converter 1 from above and deflected by 180° via a deflector plate 3, so that it traverses an integrated heat exchanger WT1 arranged in the form of a ring around the central supply conduit 2 from the bottom to the top.
- a gas can be supplied via a supply means 4 not described here in detail, in order to ad- just the temperature and/or composition of the gas mixture supplied to the first contact stage K1.
- the process gas then passes through the contact stages K1 to K3, and after the conact stages K1 and K2 it is cooled by means of the integrated heat exchangers WT1 and WT2 to an inlet temperature of about 400 0 C suitable for the inlet region of each succeeding contact K2 and K3, respectively, and then is supplied to a non-illustrated heat recovery means and intermediate absorption via the outlet 5.
- the present invention is directed to the mixing of gases in the lower part of the converter 1 with the contact stages 4 and 5, so that the upper part of the converter 1 need not be described here in greater detail.
- the process parameters in the contact stages K1 to K3 and in the heat exchangers WT1 and WT2 correspond to those of usual sulfuric acid plants.
- SO 2 - and possibly SO 3 - containing process gas with a temperature of e.g. 300 to 320 0 C is introduced into a ring duct 7 via an inlet 6 at the lower end of the converter 1 and traverses the integrated heat exchanger WT3 from the bottom to the top.
- cooler SO 2 -containing gas with a temperature of e.g. 100 to 200 0 C is fed into the converter from below and traverses the same from the bottom to the top, until the second gas is passed via a deflector plate 9 to the outside into a prechamber 10, which is provided in the form of a ring around the central supply conduit 8.
- the prechamber 10 is closed by a perforated plate 11 , which includes a multitude of openings in the form of bores, slots or the like.
- the perforated plate 11 separates the prechamber 10 from a mixing chamber 12, which is provided above the integrated heat exchanger WT3 and surrounds the central supply conduit 8 in the form of a ring.
- the first gas supplied via the ring duct 7 enters the mixing chamber 12 from below, whereas the second gas supplied via the prechamber 10 enters from above.
- the two gas flows coun- tercurrently impinge on each other, which leads to a thorough mixing.
- a connecting tube 13 extending through the prechamber 10 and the perforated plate 11 opens into the mixing chamber 12 from above, which connecting tube constitutes an immersion tube and, for instance with a diameter of about 800 mm, distinctly protrudes into the mixing chamber 12 by 500 mm.
- a ring disk 14 is provided below the perforated plate 11 on the outside of the connecting tube 13. Therefore, the second gas entering the mixing chamber 12 through the perforated plate 11 impinges on the ring disk 14, so that additional turbulences are generated, which promote mixing with the first gas.
- the second gas whose volumetric flow rate is distinctly smaller than that of the first gas, for instance by 50%, first must traverse the mixing chamber 12, before it can be discharged to the top with the first gas flow via the connecting tube 13. In this way, a homogeneous incorporation of the second gas flow into the first gas flow is achieved.
- the gas mixture is discharged from the mixing cham- ber 12 to the top and passed through the integrated heat exchanger WT2, in which the gas mixture is heated up by heat exchange with the process gas leaving the second contact stage K2, so that it has a temperature suitable for entering the contact stage K4.
- S ⁇ 2 -containing gas can be supplied through a central conduit 14 coming from above, in order to adjust the inlet temperature for the fourth contact stage K4.
- the gas then traverses the contact stage K4 and is again cooled in the integrated heat exchanger WT3 to a temperature of about 400°C suitable for entering the fifth contact stage K5, before it is supplied via the outlet 15 to a non-illustrated heat recovery system and to the final absorption.
- the gas streams are introduced in an inverted manner, i.e., the first gas flow is introduced from above while the second gas flow is introduced from below.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Accessories For Mixers (AREA)
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2008800197686A CN101687641B (en) | 2007-06-13 | 2008-06-06 | Process and apparatus for mixing gases |
MX2009013477A MX2009013477A (en) | 2007-06-13 | 2008-06-06 | Process and apparatus for mixing gases. |
AU2008261291A AU2008261291B2 (en) | 2007-06-13 | 2008-06-06 | Process and apparatus for mixing gases |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102007027841.3 | 2007-06-13 | ||
DE102007027841A DE102007027841B4 (en) | 2007-06-13 | 2007-06-13 | Method and apparatus for mixing gases |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2008151759A2 true WO2008151759A2 (en) | 2008-12-18 |
WO2008151759A3 WO2008151759A3 (en) | 2009-02-12 |
Family
ID=39938100
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2008/004511 WO2008151759A2 (en) | 2007-06-13 | 2008-06-06 | Process and apparatus for mixing gases |
Country Status (7)
Country | Link |
---|---|
CN (1) | CN101687641B (en) |
AU (1) | AU2008261291B2 (en) |
CL (1) | CL2008001717A1 (en) |
DE (1) | DE102007027841B4 (en) |
MX (1) | MX2009013477A (en) |
PE (1) | PE20090340A1 (en) |
WO (1) | WO2008151759A2 (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103072956B (en) * | 2012-12-31 | 2015-04-15 | 中国瑞林工程技术有限公司 | Flue gas processing method and system |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2846291A (en) * | 1951-10-10 | 1958-08-05 | Basf Ag | Process and apparatus for the production of gases containing sulfur trioxide |
GB2139914A (en) * | 1980-09-19 | 1984-11-21 | Chemetics Int | Catalytic converter |
RU2174945C2 (en) * | 1999-12-15 | 2001-10-20 | Кобяков Анатолий Иванович | Method of processing concentrated sulfur dioxide |
DE10249782A1 (en) * | 2002-10-24 | 2004-05-06 | Outokumpu Oyj | Process and plant for the production of sulfuric acid from sulfur dioxide-rich gases |
DE202006016783U1 (en) * | 2006-11-03 | 2007-01-18 | Heilig, Hubert | Contamination-insensitive gas mixer, with mechanically fixed mixing geometry and temperature adaptation, has pipes of longer, thin-walled construction, and formed out in funnel form in flow direction |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2104858A (en) * | 1935-01-23 | 1938-01-11 | Gen Chemical Corp | Manufacture of sulphuric acid |
AT195406B (en) * | 1955-10-01 | 1958-02-10 | Chemie Linz Ag | Method and device for mixing two or more gases or liquids with one another |
DE1926239U (en) * | 1964-01-31 | 1965-11-04 | Uhde Gmbh Friedrich | DEVICE FOR MIXING GASES OF DIFFERENT DENSITY. |
US5480620A (en) * | 1994-08-17 | 1996-01-02 | Cameron; Gordon M. | Catalytic converter |
DE19800800C2 (en) | 1998-01-13 | 2001-05-23 | Metallgesellschaft Ag | Process for the production of sulfuric acid |
WO2001036324A1 (en) * | 1999-11-01 | 2001-05-25 | Monsanto Company | Method for making sulfur trioxide, sulfuric acid, and oleum from sulfur dioxide |
DE10023178A1 (en) | 2000-05-11 | 2001-11-15 | Mg Technologies Ag | Two-stage catalytic production of sulfur trioxide gas with low sulfur dioxide content from high sulfur dioxide-content gas comprises use of two catalyst layers with temperature at each layer controlled |
-
2007
- 2007-06-13 DE DE102007027841A patent/DE102007027841B4/en active Active
-
2008
- 2008-06-06 CN CN2008800197686A patent/CN101687641B/en active Active
- 2008-06-06 AU AU2008261291A patent/AU2008261291B2/en active Active
- 2008-06-06 MX MX2009013477A patent/MX2009013477A/en active IP Right Grant
- 2008-06-06 WO PCT/EP2008/004511 patent/WO2008151759A2/en active Application Filing
- 2008-06-11 CL CL200801717A patent/CL2008001717A1/en unknown
- 2008-06-11 PE PE2008000996A patent/PE20090340A1/en active IP Right Grant
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2846291A (en) * | 1951-10-10 | 1958-08-05 | Basf Ag | Process and apparatus for the production of gases containing sulfur trioxide |
GB2139914A (en) * | 1980-09-19 | 1984-11-21 | Chemetics Int | Catalytic converter |
RU2174945C2 (en) * | 1999-12-15 | 2001-10-20 | Кобяков Анатолий Иванович | Method of processing concentrated sulfur dioxide |
DE10249782A1 (en) * | 2002-10-24 | 2004-05-06 | Outokumpu Oyj | Process and plant for the production of sulfuric acid from sulfur dioxide-rich gases |
DE202006016783U1 (en) * | 2006-11-03 | 2007-01-18 | Heilig, Hubert | Contamination-insensitive gas mixer, with mechanically fixed mixing geometry and temperature adaptation, has pipes of longer, thin-walled construction, and formed out in funnel form in flow direction |
Also Published As
Publication number | Publication date |
---|---|
DE102007027841B4 (en) | 2012-02-16 |
CN101687641B (en) | 2013-11-13 |
CL2008001717A1 (en) | 2008-08-01 |
DE102007027841A1 (en) | 2008-12-18 |
PE20090340A1 (en) | 2009-04-23 |
AU2008261291B2 (en) | 2013-08-01 |
WO2008151759A3 (en) | 2009-02-12 |
AU2008261291A1 (en) | 2008-12-18 |
CN101687641A (en) | 2010-03-31 |
MX2009013477A (en) | 2010-01-18 |
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