EP1844126A1 - Verfahren zur erhöhung der selektivität von physikalisch wirkenden lösungs mitteln bei einer absorption von gaskomponenten aus technischen gasen - Google Patents
Verfahren zur erhöhung der selektivität von physikalisch wirkenden lösungs mitteln bei einer absorption von gaskomponenten aus technischen gasenInfo
- Publication number
- EP1844126A1 EP1844126A1 EP06700913A EP06700913A EP1844126A1 EP 1844126 A1 EP1844126 A1 EP 1844126A1 EP 06700913 A EP06700913 A EP 06700913A EP 06700913 A EP06700913 A EP 06700913A EP 1844126 A1 EP1844126 A1 EP 1844126A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- gas
- absorption
- absorbent
- column
- pressure
- 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
Links
- 239000007789 gas Substances 0.000 title claims abstract description 78
- 238000000034 method Methods 0.000 title claims abstract description 18
- 230000037074 physically active Effects 0.000 title abstract 2
- 239000002904 solvent Substances 0.000 title description 6
- 238000010521 absorption reaction Methods 0.000 claims abstract description 49
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 26
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 23
- 239000002253 acid Substances 0.000 claims abstract description 22
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003345 natural gas Substances 0.000 claims abstract description 9
- 230000007423 decrease Effects 0.000 claims abstract description 3
- 230000002745 absorbent Effects 0.000 claims description 40
- 239000002250 absorbent Substances 0.000 claims description 40
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 27
- 230000008569 process Effects 0.000 claims description 6
- 238000011084 recovery Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000002826 coolant Substances 0.000 claims description 2
- 238000003795 desorption Methods 0.000 abstract description 5
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 4
- 238000001816 cooling Methods 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract 6
- 238000004064 recycling Methods 0.000 abstract 4
- 230000009102 absorption Effects 0.000 description 35
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 16
- 239000001569 carbon dioxide Substances 0.000 description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 description 8
- 230000008929 regeneration Effects 0.000 description 5
- 238000011069 regeneration method Methods 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- LCEDQNDDFOCWGG-UHFFFAOYSA-N morpholine-4-carbaldehyde Chemical compound O=CN1CCOCC1 LCEDQNDDFOCWGG-UHFFFAOYSA-N 0.000 description 2
- 125000001741 organic sulfur group Chemical group 0.000 description 2
- KYWXRBNOYGGPIZ-UHFFFAOYSA-N 1-morpholin-4-ylethanone Chemical compound CC(=O)N1CCOCC1 KYWXRBNOYGGPIZ-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- -1 morphysorb Chemical compound 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/08—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors
- C10K1/16—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with non-aqueous liquids
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/72—Other features
- C10J3/82—Gas withdrawal means
Definitions
- the invention relates to a process for increasing the selectivity of physically acting solvents in the case of absorption of gas components from industrial gases. Examples of such absorptions are:
- the physically acting solvent also triggers value components out of the technical gas.
- the conditions often have to be set in such a way that the amount of the absorbed value components is scarcely negligible, which is an unavoidable disadvantage of all physically acting solvents.
- the recovery processes are used in conjunction with a corresponding absorption device.
- Corresponding absorption devices are for raw natural gases or synthesis gases, in addition to valuable components such as methane, higher hydrocarbons, hydrogen, carbon dioxide - if desired - and carbon monoxide impurities such as hydrogen sulfide, organic sulfur components such as mercaptans and carbon dioxide sulfide, also carbon dioxide - if undesirable - and small amounts used in water vapor in different proportions, used.
- the recovered compounds can either be re-added to the respective, purified technical gas or marketed as a separate product. In general, it is necessary to remove the sulfur components contained in the raw natural gas, for example, for further technical use up to ppm levels from the gas.
- the removal of hydrogen sulfide, mercaptans, carbon dioxide and other sour gas constituents from industrial gases is generally carried out by means of chemically acting absorbent, such as amine solutions, alkali salt solutions, etc. or physically acting absorbent such as selexol, propylene carbonate, N-methyl-pyrrolidone, morphysorb, methanol among other things, in circulatory systems, wherein physically acting absorbents, in contrast to chemically acting detergents, are also able to remove organic sulfur components.
- chemically acting absorbent such as amine solutions, alkali salt solutions, etc.
- physically acting absorbent such as selexol, propylene carbonate, N-methyl-pyrrolidone, morphysorb, methanol among other things
- physically acting absorbents in contrast to chemically acting detergents, are also able to remove organic sulfur components.
- the carbon dioxide contained in the gas is either completely, partly or as little as possible removed.
- the absorption device must be designed enlarged by the amount of the recirculated volume due to the recompressed recycle gas both with respect to the inevitably flickered sour gas and with respect to the gas volume.
- the invention solves the problem in that
- the loaded absorbent is placed on the top of a stripping column, which has a bottom reboiler and can have one or more Soaufko- cher, and operated at a slightly higher pressure than the absorption column, • in this stripping column by the interaction of sump cooker and application temperature an equilibrium is set such that the sour gas concentration in the absorbent increases towards the sump and the concentration of the hydrocarbons towards the sump decreases,
- a recycle gas rich in hydrocarbons and poor in acid gas components is withdrawn at the top of the stripping column, and
- the temperature of the coming out of the absorption device, loaded absorbent is changed before task in the stripping column.
- both a temperature increase and a temperature drop is considered.
- a device for the indirect heat exchange is selected, which can be operated both with cooling medium and with heating medium.
- Cooling of the loaded absorbent takes place during operation when a sharper separation efficiency of the stripping column is desired. This will be the case if it is desired to reduce the sour gas portions in the recycle gas or to reduce the hydrocarbon levels in the bottom draw or both.
- the cooling capacity therefore corresponds to that of a reflux condenser for the stripping columns, which can therefore be dispensed with. However, this increases the required heat output of the reboiler of the stripping column.
- a heating of the loaded absorbent takes place during operation when the physical absorbent has also mitabsorbed large amounts of lower hydrocarbons, ie, especially methane, which can easily desorb and be flashed in the head of the stripping column.
- the pressure increase when heated is best effected by a pump.
- the required in the stripping column increased pressure level can also be effected by static pressure due to different installation altitude by the absorption device is higher than the stripping column and in the liquid supply lines a liquid column is adjusted, which corresponds to the pressure difference, which Promotion of recycle gas in the absorption device is sufficient.
- the intention is to recover those hydrocarbons which have been absorbed from crude natural gas with the method according to the invention, one obtains in this way also a possibility and a degree of freedom in order to set the respective economic optimum of recovery with temporally changing, absorbed gas fractions which is another advantage of the process.
- FIG. 1 shows the process according to the invention, comprising a stripping column and the associated pumps and heat exchangers, and their interaction with an absorption column and a two-stage sour gas De - sorption device.
- the feed gas 1 is introduced into the bottom of the absorption column 2 and flows through them from bottom to top, being washed by regenerated physical absorbent 3, which is abandoned from above, and freed from acid gases.
- the clean gas 4 leaves the absorption column 2 overhead.
- the absorbent 5 loaded with acid gases, in which hydrocarbons are also absorbed, is withdrawn from the bottom of the absorption column 2 and brought to an elevated pressure by means of the pressure booster pump 6 and, depending on the operating conditions, is heated or cooled in the heat exchanger 7.
- the changed in pressure and temperature loaded absorbent 8 is abandoned in the head of the stripping column 9. It passes through the output column equipped with packing or tray 9 from top to bottom, while the desorbed gases flow in countercurrent from bottom to top.
- the absorbent which is essentially loaded only with sour gas, is drawn off at the bottom of the stripping column 9 and partly heated in the reboiler 10, some of which desorbs acid gases which support the stripping action in the lower region of the stripping column 9.
- it is expedient not to supply all the heat required in Sumpfaufkocher, but via one or more side cookers that relate their energy through the heat exchange with the hot, regenerated solution coming from the desorber. Therefore, a page deduction 11 is provided in the middle region of the stripping column, which promotes the loaded absorbent by means of the Soabzugspumpe 12 in the side boiler 13 and back into the stripping column 9.
- the rich in hydrocarbons, but sour gas components poor recycle gas 14 is withdrawn overhead of the stripping column 9, cooled in the cooler 15 and returned to the absorption column 2.
- the operating pressure is adjusted so that the pressure gradient between the head of the stripping column 9 and the feed point 16 of the absorption column 2 for conveying the Recycle gas 14 sufficient sufficient.
- the choice of the feed point 16 depends on the concentration of sour gas constituents, which should be about the same at the selected task both in the absorption column 2 and in the recycle gas 14.
- the withdrawn from the stripping column 9, loaded with sour gas absorbent 17 is further heated in the heater 18 and passed into the medium-pressure flash tank 19 where a significant pressure release takes place.
- a first part of the desorbed sour gas 24 is released.
- the partially desorbed absorbent 20 is then passed into the low pressure stripper 21, where further pressure release takes place and almost complete expulsion of the still absorbed acid gases 27 from the absorbent is effected by a gaseous stripping medium 22, such as CO 2 or N 2 .
- the desorbed acid gases 23 and 24 are cooled in the sour gas coolers 25 and 26, combined as sour gas 27 and fed to a further use.
- the complete regeneration could also take place in a desorption column without the external supply of stripping gas, the regeneration then being effected by a sump cooker which generates the necessary stripping steam.
- the regenerated absorbent 28 is first conveyed by the feed pump 29 to the side cooker 13, where it is used for heating, and then to the cooler 30, where it is brought to the desired absorption temperature and then as a regenerated absorbent 3 to the top of the absorption column. 2 is given up. If further heat consumers can be served, even more heat utilization is possible, for example, the bottom reboiler 10 and the heat exchanger 7 can be supplied with waste heat.
- the absorption medium was a mixture of n-formyl morpholine and n-acetylmorpholine selected according to the use of the Morphosorb method.
- Stripping medium desorbed sour gas desorbed sour gas
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Gas Separation By Absorption (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102005004948A DE102005004948B3 (de) | 2005-02-02 | 2005-02-02 | Verfahren zur Erhöhung der Selektivität von physikalisch wirkenden Lösungsmitteln bei einer Absorption von Gaskomponenten aus technischen Gasen |
PCT/EP2006/000208 WO2006081921A1 (de) | 2005-02-02 | 2006-01-12 | Verfahren zur erhöhung der selektivität von physikalisch wirkenden lösungs mitteln bei einer absorption von gaskomponenten aus technischen gasen |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1844126A1 true EP1844126A1 (de) | 2007-10-17 |
EP1844126B1 EP1844126B1 (de) | 2018-03-21 |
Family
ID=35745945
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP06700913.4A Active EP1844126B1 (de) | 2005-02-02 | 2006-01-12 | Verfahren zur erhöhung der selektivität von physikalisch wirkenden lösungs mitteln bei einer absorption von gaskomponenten aus technischen gasen |
Country Status (6)
Country | Link |
---|---|
US (1) | US7824542B2 (de) |
EP (1) | EP1844126B1 (de) |
CA (1) | CA2595967C (de) |
DE (1) | DE102005004948B3 (de) |
NO (1) | NO20074454L (de) |
WO (1) | WO2006081921A1 (de) |
Families Citing this family (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8002952B2 (en) * | 2007-11-02 | 2011-08-23 | Uop Llc | Heat pump distillation |
US7981256B2 (en) * | 2007-11-09 | 2011-07-19 | Uop Llc | Splitter with multi-stage heat pump compressor and inter-reboiler |
JP4803470B2 (ja) * | 2009-10-05 | 2011-10-26 | 独立行政法人産業技術総合研究所 | 熱交換型蒸留装置 |
US8673135B2 (en) * | 2010-05-28 | 2014-03-18 | Axens | Coal liquefaction complex with minimal carbon dioxide emissions |
US20120085126A1 (en) * | 2010-10-06 | 2012-04-12 | Exxonmobil Research And Engineering Company | Low energy distillation system and method |
DE102011108308A1 (de) | 2011-07-25 | 2013-01-31 | Thyssenkrupp Uhde Gmbh | Wärmerückgewinnung bei Absorptions- und Desorptionsprozessen bei reduzierter Wärmeaustauschfläche |
EP2599536A1 (de) * | 2011-11-29 | 2013-06-05 | Nederlandse Organisatie voor toegepast -natuurwetenschappelijk onderzoek TNO | Verfahren zur Entfernung von sauren Gasen aus Abgasen |
JP5956772B2 (ja) * | 2012-02-20 | 2016-07-27 | 東洋エンジニアリング株式会社 | 熱交換型蒸留装置 |
JP5923335B2 (ja) * | 2012-02-24 | 2016-05-24 | 東洋エンジニアリング株式会社 | 熱交換型蒸留装置 |
JP5923367B2 (ja) * | 2012-03-30 | 2016-05-24 | 東洋エンジニアリング株式会社 | 熱交換型蒸留装置 |
US10940432B2 (en) | 2016-04-27 | 2021-03-09 | Dow Global Technologies Llc | Process for selective removal of acid gases from fluid streams using a hybrid solvent mixture |
WO2018160206A1 (en) | 2017-03-03 | 2018-09-07 | Dow Global Technologies Llc | Process for separating hydrogen sulfide from gaseous mixtures using a hybrid solvent mixture |
WO2018164705A1 (en) | 2017-03-06 | 2018-09-13 | Dow Global Technologies Llc | Energy efficient process for separating hydrogen sulfide from gaseous mixtures using a hybrid solvent mixture |
WO2018164704A1 (en) | 2017-03-07 | 2018-09-13 | Dow Global Technologies Llc | Process for reducing energy consumption in the regeneration of hybrid solvents |
DE102019000803A1 (de) | 2019-02-05 | 2020-08-06 | Hans-Jürgen Maaß | Verfahren zur Erzeugung von Synthesegas |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2813126A (en) | 1953-12-21 | 1957-11-12 | Pure Oil Co | Process for selective removal of h2s by absorption in methanol |
US3205164A (en) * | 1962-09-24 | 1965-09-07 | Universal Oil Prod Co | Hydrogen sulfide removal |
US3490865A (en) * | 1964-11-17 | 1970-01-20 | Phillips Petroleum Co | Treatment of fluid streams |
US3473903A (en) * | 1967-12-04 | 1969-10-21 | Texaco Inc | Recovery of carbon from synthesis gas |
US3656887A (en) * | 1969-08-21 | 1972-04-18 | Chevron Res | Method of removing hydrogen sulfide from gaseous mixtures |
US4085192A (en) * | 1973-05-11 | 1978-04-18 | Shell Oil Company | Selective removal of hydrogen sulfide from gaseous mixtures |
EP1201290A4 (de) * | 1999-07-19 | 2002-09-04 | Ebara Corp | Verfahren und vorrichtung zur reinigung von saurem gas |
FR2796858B1 (fr) * | 1999-07-28 | 2002-05-31 | Technip Cie | Procede et installation de purification d'un gaz et produits ainsi obtenus |
US6508863B1 (en) * | 2001-10-11 | 2003-01-21 | Engelhard Corporation | Claus feed gas hydrocarbon removal |
GB0220791D0 (en) * | 2002-09-06 | 2002-10-16 | Boc Group Plc | Nitrogen rejection method and apparatus |
WO2005044955A1 (de) | 2003-11-10 | 2005-05-19 | Basf Aktiengesellschaft | Verfahren zur gewinnung eines unter hohem druck stehenden sauergasstroms durch entfernung der sauergase aus einem fluidstrom |
DE10352878A1 (de) * | 2003-11-10 | 2005-06-16 | Basf Ag | Verfahren zur Gewinnung eines unter hohem Druck stehenden Sauergasstroms durch Entfernung der Sauergase aus einem Fluidstrom |
DE10357324B4 (de) * | 2003-12-05 | 2008-11-13 | Uhde Gmbh | Verfahren zur Verschiebung von Sauergasanteilen innerhalb eines Erdgasnetzwerkes |
-
2005
- 2005-02-02 DE DE102005004948A patent/DE102005004948B3/de not_active Expired - Fee Related
-
2006
- 2006-01-12 EP EP06700913.4A patent/EP1844126B1/de active Active
- 2006-01-12 CA CA2595967A patent/CA2595967C/en not_active Expired - Fee Related
- 2006-01-12 US US11/883,522 patent/US7824542B2/en not_active Expired - Fee Related
- 2006-01-12 WO PCT/EP2006/000208 patent/WO2006081921A1/de active Application Filing
-
2007
- 2007-08-31 NO NO20074454A patent/NO20074454L/no not_active Application Discontinuation
Non-Patent Citations (1)
Title |
---|
See references of WO2006081921A1 * |
Also Published As
Publication number | Publication date |
---|---|
EP1844126B1 (de) | 2018-03-21 |
NO20074454L (no) | 2007-10-19 |
CA2595967C (en) | 2013-04-23 |
CA2595967A1 (en) | 2006-08-10 |
DE102005004948B3 (de) | 2006-03-02 |
US7824542B2 (en) | 2010-11-02 |
WO2006081921A1 (de) | 2006-08-10 |
US20080314801A1 (en) | 2008-12-25 |
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