WO2008000752A1 - Verfahren zur reinigung von cyclischen ketonen - Google Patents
Verfahren zur reinigung von cyclischen ketonen Download PDFInfo
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- WO2008000752A1 WO2008000752A1 PCT/EP2007/056391 EP2007056391W WO2008000752A1 WO 2008000752 A1 WO2008000752 A1 WO 2008000752A1 EP 2007056391 W EP2007056391 W EP 2007056391W WO 2008000752 A1 WO2008000752 A1 WO 2008000752A1
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- cyclododecatriene
- acid
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- cyclododecanone
- cyclic ketone
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/85—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to a chemical modification
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/80—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
- C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/56—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds
- C07C45/57—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom
- C07C45/58—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom in three-membered rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/62—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by hydrogenation of carbon-to-carbon double or triple bonds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C45/82—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/385—Saturated compounds containing a keto group being part of a ring
- C07C49/413—Saturated compounds containing a keto group being part of a ring of a seven- to twelve-membered ring
Definitions
- the present invention relates to a process for purifying a composition (I) containing at least one cyclic ketone having 7 to 16 carbon atoms, comprising thermally treating the composition (I) with at least one acid and further purifying by a process selected from the group consisting of distillation, extraction and crystallization.
- the present invention further relates to a process for the preparation of cyclododecanone, comprising such a purification, and the use of at least one acid for purifying a composition (I), at least containing a cyclic ketone having 7 to 16 carbon atoms, by thermally treating the composition ( I) with the acid.
- Cyclic ketones are needed for various applications in high purity. Cyclic ketones often contain impurities, for example those with oxygen-containing groups, which are difficult to remove by conventional purification processes, such as distillation, extraction or recrystallization, as a result of the preparation process. Conventional cleaning process for such separation problems are therefore complicated and expensive.
- cyclododecanone is an important intermediate for the preparation of, for example, laurolactam, dodecanedicarboxylic acid and polyamides derived therefrom such as nylon 12 or nylon 6.12.
- Cyclododecanone is prepared, for example, by air oxidation of cyclododecane in the presence of boric acid to cyclododecyl borate, hydrolysis of the borate to cyclododecanol and subsequent dehydrogenation of the cyclododecanol. Cyclododecane itself is still obtained by complete hydrogenation of cyclododecatriene. A description of this technical process for the synthesis of cyclododecanone can be found inter alia in T. Schiffer, G. Oenbrink, "Cyclododecanol, Cyclododecanone and Laurolactam" in Ullmann's Encyclopedia of Industrial Chemistry, 6th Edition, 2000, Electronic Release, Wiley VCH.
- Another method is based on the epoxidation of cyclododecatriene, wherein cyclododecanone is obtained from the epoxide after hydrogenation and rearrangement.
- cyclododecanone is obtained from the epoxide after hydrogenation and rearrangement.
- Such a process is described, for example, in EP 1 018 498 A2.
- DE 103 44 595 A and DE 103 44 594 A describe processes for the preparation of cyclododecanone, in which oxidation takes place with nitrous oxide in one process step.
- the present invention was therefore based on the object to provide a method by which cyclic ketones can be obtained easily and with little effort in high purity.
- Another object of the present invention was to provide a purification process with which in particular oxygen-containing organic compounds can be separated from the cyclic ketones.
- Another object of the present invention was to provide a cyclic ketone purification process which can be easily combined with known cyclic ketone production processes.
- this object is achieved by a process for purifying a composition (I), at least comprising a cyclic ketone having 7 to 16 carbon atoms, at least comprising the steps
- Acid further purifying by a process selected from the group consisting of distillation, extraction and crystallization.
- Cyclic ketones having a purity of, for example,> 99.5% can be obtained by the process according to the invention.
- the process according to the invention can be carried out in particular following a basically known preparation process for a cyclic ketone having 7 to 16 carbon atoms.
- the inventive method can be easily combined with existing systems, so that no costly conversions are required.
- the process of the present invention provides a way to improve the yield of cyclic ketones, since treatment with acid is generally very selective and thus less product is lost in the subsequent distillative or crystalline purification.
- treating is understood to mean contacting the composition (I) with at least one acid
- the composition (I) according to the invention is thermally treated with an acid according to step (i).
- the process according to the invention comprises stages (i) and (ii).
- the composition (I) is thermally treated with an acid.
- the thus treated composition (I) is further purified by distillation, extraction and / or crystallization.
- the distillation, extraction and / or crystallization can be carried out by all conventional methods known to the person skilled in the art.
- Suitable solvents for the crystallization according to step (ii) are, for example, alcohols, ethers, hydrocarbons, aromatic hydrocarbons, ketones, preferably toluene, xylene, methanol, ethanol, propanol, butanol, acetone, diethyl ketone or methyl tert-butyl ether. According to the invention, it is also possible that no solvent is used, but a melt crystallization is carried out.
- the distillative purification can be carried out in one or more columns. It is preferred to work at pressures between 1 and 2000 mbar. Especially with cyclic ketones having more than 8 carbon atoms, pressures between 5 and 500 mbar are preferred, with 10 to 200 mbar being particularly preferred.
- the temperatures (bottom temperature) are between 100 and 300 ° C.
- the temperature during the purification by distillation is preferably from 130 to 250 ° C., more preferably from 150 to 220 ° C.
- the desired product is preferably obtained via a side draw. It is inventively possible to obtain the desired product liquid or gaseous. About the bottom of high boilers, preferably low boilers are preferably separated overhead. If two columns are used, the desired product, preferably together with high-boiling components, preferably passes via the bottom into the second column from which it is obtained then can be won over head or turn as side take. Partition wall columns can also be used according to the invention.
- step (ii) Prior to distillation, extraction or crystallization according to step (ii), it may be advantageous to remove the acid from the treated composition (I). This can be done in the case of heterogeneous acids, for example by filtration, in the case of homogeneous acids are, for example, extraction, for example with water, or distillation, the acid is separated, depending on the boiling point, overhead or sump.
- the acid can be reused in step (i) after separation.
- the present invention also relates to a method as described above for purifying a composition (I) containing at least one cyclic ketone having 7 to 16 carbon atoms, wherein the acid is separated after step (i) and then re-introduced into the step (i) is used.
- the treatment with acid is preferably carried out at temperatures of 60 to 350 ° C, in particular from 100 to 270 ° C, particularly preferably from 130 to 260 ° C.
- the present invention also relates to a method as described above for purifying a composition (I) containing at least one cyclic ketone having 7 to 16 carbon atoms, wherein the treatment according to step (i) at a temperature of 60 to 350 ° C is performed.
- compositions comprising at least one cyclic ketone having 7 to 16 carbon atoms with acids in a subsequent further purification, for example by distillation, extraction and / or by crystallization cyclic ketones in high yields in purities of about 99.5% can be obtained.
- the cyclic ketone itself is not attacked or only very slightly.
- the separated compounds are, in particular, alcohols, aldehydes and epoxides. Based on the cyclic ketone contained in the composition, according to the invention, less than 10% of the ketone is lost, preferably less than 5%, in particular less than 3%.
- the treatment according to step (i) can take place both in the gas phase and in the liquid phase.
- the pressure is adjustable over a wide range. It may, for example, be between 0.001 and 300 bar, preferably between 0.01 and 200 bar, more preferably between 0.1 and 100 bar. According to the invention, preference is given to a pressure at which optionally occurring low boilers can be removed from the system by distillation, ie. at a pressure of 0.25 to 70 bar, in particular 0.35 to 50 bar, preferably 0.5 to 30 bar.
- the acid treatment according to step (i) can be carried out batchwise or continuously, with a continuous treatment being preferred.
- the residence times are, for example, between 0.1 and 50 hours, preferably between 0.2 and 24 hours, for example between 0.5 and 15 hours, in particular between 1 hour and 19 hours, more preferably between 1, 5 and 10 hours.
- the present invention also relates to a method as described above for purifying a composition (I) at least comprising a cyclic ketone having 7 to 16 carbon atoms, wherein the treatment according to step (i) for a time of 0.1 until 50 hours is carried out.
- the acids used according to the invention are Bronsted or Lewis acids, it also being possible to use mixtures of two or more acids.
- the acids used can be homogeneously dissolved or heterogeneous. Heterogeneous acids can be suspended or fixed according to the invention.
- the present invention also relates to a method as described above for purifying a composition (I) at least comprising a cyclic ketone having 7 to 16 C atoms, wherein the acid is present in a homogeneous or heterogeneous manner.
- the homogeneously soluble acids used according to the invention are, for example, mineral acids or organic acids.
- Examples are sulfuric acid, sulfonic acids, nitric acid, hydrochloric acid, phosphoric acid, phosphorous acid, perchloric acid, heteropolyacids as described, for example, in EP 0 158 229 B1, C 1 - to C 30 -carboxylic acids, such as formic acid, acetic acid, propionic acid, benzoic acid or the like.
- Preferred homogeneous acids are phosphoric acid, phosphorous acid, sulfuric acid, sulfonic acids and heteropolyacids such as
- Tungstophosphoric Particularly preferred are phosphoric acid and tungstophosphoric acid.
- the content of homogeneously soluble acid is generally between 0.01 and 10 wt.% Based on the cyclic ketone.
- a homogeneously soluble acid in an amount of 0.05 to 5 wt.%, Particularly preferably 0.1 to 1 wt.% Used.
- a homogeneously soluble acid is used in an amount of 0.1 to 1% by weight.
- the acid is recycled, at least in part, to the treatment stage.
- Heterogeneous acids which are suitable according to the invention are, for example, metal oxide solids which, according to the invention, may have been treated, for example, with mineral acids such as phosphoric acid or sulfuric acid to increase their acid strength.
- mineral acids such as phosphoric acid or sulfuric acid
- oxides or mixed oxides of B, Al, Si, Sn, Ti, Cr, Zr, Fe and Zn which may contain further constituents.
- heterogeneous organic based acids e.g. acidic ion exchanger.
- heterogeneous acids in an amount of 0.5 to 20 wt.%, Particularly preferably from 1 to 10 wt.% Used.
- a catalyst loading i. the load of heterogeneous acid, adjusted from 0.01 to 10 kg of cyclic ketone / liter of catalyst x h.
- a catalyst loading of 0.05 to 2 kg of cyclic ketone / liter of catalyst x h, more preferably 0.1 to 1 kg of cyclic ketone / liter of catalyst x h is set.
- the present invention therefore relates to a method as described above, wherein a heterogeneous acid having a Catalyst load of 0.01 to 10 kg of cyclic ketone / liter of catalyst xh is used.
- the acid is separated off in step (ii).
- the acid it is also possible within the scope of the present invention for the acid to be separated off after step (i) and before step (ii).
- Possible methods for separation are, for example, distillation, crystallization, extraction or precipitation.
- the present invention also relates to a method as described above for purifying a composition (I) comprising at least one cyclic ketone having 7 to 16 C atoms, wherein after step (i) and before step (ii) the acid is at least is partially separated.
- the composition (I) contains at least one cyclic ketone having 7 to 16 carbon atoms.
- the at least one cyclic ketone is preferably a ketone having 8 to 14 C atoms, more preferably having 9 to 12 C atoms, for example cyclodecanone, cycloundecanone or cyclododecanone.
- the present invention also relates to a method as described above for purifying a composition (I) at least comprising a cyclic ketone having 7 to 16 carbon atoms, wherein the cyclic ketone is cyclododecanone.
- composition (I) usually contains the cyclic ketone in an amount of more than 80% by weight, preferably 85 to 99.9% by weight, especially 88 to
- the composition (I) usually contains further compounds, in particular organic compounds, preferably those with oxygen-containing groups, for example alcohols, aldehydes or epoxides, which are preferably removed by the purification process according to the invention.
- the organic compounds can in particular have the same number of carbon atoms.
- the secondary components are in the composition (I) prior to carrying out the cleaning according to the invention in particular less than 20 wt.%, In particular less than 15 wt.%, Particularly preferably less than 12 wt.%.
- the minor components are contained in an amount of 0.001 to 10 wt .-%, in particular from 0.1 to 9 wt.%, Preferably from 0.5 to 5 wt.%, Particularly preferably from 1 to 4 wt.%. Therefore, according to a further embodiment, the present invention also relates to a method as described above for purifying a composition (I) comprising at least one cyclic ketone having 7 to 16 C atoms, wherein the composition (I) in addition to the at least one cyclic ketone at least one further contains oxygen-containing organic compound.
- the inventive purification process gives a cyclic ketone in a purity of> 95%, for example> 98%, in particular> 99%, determined by gas chromatographic methods.
- the cyclic ketone is preferably obtained in a purity of> 99.5%, preferably> 99.8%, particularly preferably> 99.9%.
- composition (I) containing at least one cyclic ketone having 7 to 16 carbon atoms can be obtained by any conventional production method of such cyclic ketones.
- the present invention relates to a process for the preparation of a cyclic ketone having 7 to 16 C atoms, comprising at least the steps
- composition (I) containing at least one cyclic ketone having 7 to 16 carbon atoms
- composition (I) contains cyclododecanone as the cyclic ketone, this can be obtained via all preparation processes for cyclododecanone known to the person skilled in the art.
- the present invention relates to a process for the preparation of cyclododecanone, comprising at least the steps
- composition (I ') Purification of the composition (I ') at least comprising the steps (i) thermally treating the composition (I ') with at least one acid, (ii) further purifying by a process selected from the group consisting of distillation, extraction and crystallization.
- the preparation of the composition (I ') according to step (a) can be carried out in one or more stages, i. the composition (T) is obtained by a one-step or multi-step synthesis of cyclododecanone. According to step (b), the resulting composition (I ') is purified.
- cyclododecanone can be obtained by air oxidation of cyclododecane in the presence of boric acid or Co salts.
- Cyclododecanone can also be prepared, for example, by hydrogenation of cyclododecadienone, by oxidation of cyclododecane, by oxidation of cyclododecene by means of dinitrogen monoxide or by hydrogenation of cyclododecatriene epoxide.
- the present invention also relates to a process for the preparation of cyclododecanone as described above, wherein step (a) comprises at least the steps
- cyclododecanone is preferably obtained via a hydrogenation of cyclododecadienone according to step (a3), which in turn was obtained by oxidation of a cyclododecatriene, preferably with nitrous oxide, according to step (a2).
- Cyclododecatriene is inventively preferably obtained by trimerization of butadiene according to step (a1).
- further treatments can be carried out between stages (a1), (a2) and (a3), for example purification steps.
- Step (a1) involves the trimerization of butadiene.
- 1. ⁇ . ⁇ -cyclododecatriene can be prepared, for example, by trimerization of pure 1,3-butadiene, as described, for example, in T. Schiffer, G. Oenbrink, "Cyclododecatrienes, Cyclooctadienes, and 4-Vinylcyclohexenes", Ullmann's Encyclopedia of Industrial Chemistry, 6th Edition (2000), Electronic Release, Wiley VCH.
- cis, trans, trans-1, 5,9-cyclododecatriene, cis, cis, trans-1, 5,9-cyclododecatriene and all-trans-1,5 arise, for example, during the trimerization in the presence of Ziegler catalysts , 9-cyclododecatriene, as described, for example, in H. Weber et al. "The formation of cis, trans, trans-cyclododecatriene (1.5.9) by means of titanium-containing catalysts" in: Liebigs Ann. Chem. 681 (1965) p. 10-20. Cyclododecatriene can be prepared by trimerization of 1,3-butadiene using a titanium catalyst.
- titanium catalysts for trimerization While in principle all suitable titanium catalysts for trimerization can be used, in the article by Weber et al. described titanium tetrachloride / ethylaluminum sesquichloride catalyst particularly suitable.
- the butadiene used for the trimerization particularly preferably has a degree of purity of at least 99.6% and more preferably of at least 99.65%, determined by gas chromatography.
- the 1,3-butadiene used contains no 1,2-butadiene and no 2-butyne within the scope of the accuracy of detection.
- mixtures are generally obtained which contain at least 95% by weight, preferably at least 96% by weight and more preferably at least 97% by weight, of cis, trans, trans-1, 5,9-cyclododecatriene.
- the mixtures contain about 98 wt .-% cis, trans, trans-1, 5,9-cyclododecatriene.
- This mixture containing ice, trans, trans-1, 5,9-cyclododecatriene can be used as such for the reaction according to step (a2). It is likewise possible, via at least one suitable method, for example preferably via at least one distillation, to remove the ice, trans, trans-1, 5,9-cyclododecatriene from the mixture and to use it in the reaction according to step (a2).
- the oxidation according to step (a2) can be carried out by any suitable method known to the person skilled in the art.
- the oxidation according to step (a2) is preferably carried out in the context of the process according to the invention by means of dinitrogen monoxide.
- cyclododecatriene is oxidized, preferably by reaction with dinitrogen monoxide.
- At least one suitable solvent or diluent may be used for the reaction of cyclododecatriene with dinitrogen monoxide.
- cyclododecane or cyclododecanone or saturated aliphatic or aromatic, optionally alkyl-substituted hydrocarbons may be mentioned, wherein substantially all conventional solvents and / or diluents are suitable, provided that they neither a CC double bond, nor a CC triple bond , still have an aldehyde group.
- the temperatures in the reaction of cyclododecatriene with dinitrogen monoxide are preferably in the range of 140 to 350 ° C, more preferably in the range of 180 to 320 ° C and particularly preferably in the range of 200 to 300 ° C.
- the pressures in the reaction of cyclododecatriene with dinitrogen monoxide are preferably higher than the autogenous pressure of the educt or product mixture at the selected reaction temperature or the selected reaction temperatures.
- the pressures are preferably in the range from 1 to 1000 bar, more preferably in the range from 40 to 300 bar and particularly preferably in the range from 50 to 200 bar.
- the reactors which can be used for the reaction of cyclododecatriene with dinitrogen monoxide.
- the reaction can be carried out in batch mode or in continuous mode.
- at least one CSTR Continuous Stirred Tank Reactor
- at least one tubular reactor or at least one loop reactor can be used.
- the reaction of cyclododecatriene with dinitrogen monoxide is preferably carried out in a single reactor.
- the residence time of the reaction mixture in the at least one reactor in the reaction of cyclododecatriene with dinitrogen monoxide is generally in the range of up to 20 h, preferably in the range of 0.1 to 20 hours, more preferably in the range of 0.2 to 15 hours and more preferably in the range of 0.25 to 10 hours.
- the molar ratio of nitrous oxide to cyclododecatriene is generally in the range of 0.05 to 4, preferably in the range of 0.06 to 1, more preferably in the range of 0.07 to 0.5 and more preferably in the range of 0.1 to 0.4.
- the reaction of cyclododecatriene with dinitrogen monoxide can be carried out so that at a very high selectivity with respect to cyclododecadienone, a conversion of cyclododecatriene in the range of up to 50%, preferably in the range of 5 to 30% and particularly preferably in the range of 10 to 20% becomes.
- the selectivity, based on cyclododecadienone is generally at least 90%, preferably at least 92.5% and particularly preferably at least 95%.
- any cyclododecatriene or any mixture of two or more different cyclododecatrienes can be reacted with dinitrogen monoxide.
- These include, for example, 1, 5,9-cyclododecatrienes, for example cis, trans, trans-1, 5,9-cyclododecatriene or cis, cis, trans-1, 5,9-cyclododecatriene or all-trans-1, 5, 9-cyclododecatriene, to name a few.
- the cyclododecatriene used is preferably cis, trans, trans-1, 5,9-cyclododecatriene.
- the reaction of cis, trans, trans-1, 5,9-cyclododecatriene with dinitrogen monoxide results in a cyclododeca-4,8-dienone isomer mixture comprising at least two of the isomers cis, trans-cyclododeca-4,8-dienone, trans, cis-cyclododeca-4,8-dienone and trans, trans -cyclododeca-4,8-dienone.
- An example of a typical isomer mixture accordingly has the isomers in molar ratios of about 1: 1: 0.08. This mixture of isomers may be present in the composition (I) used in the process according to the invention.
- the reaction of cyclododecatriene with dinitrogen monoxide can in principle be carried out in the presence of a catalyst, but also without the addition of a catalyst.
- all suitable catalysts can be used.
- at least one homogeneous or at least one heterogeneous or both at least one homogeneous and at least one heterogeneous catalyst can be used.
- the catalysts which can be used preferably contain at least one metal from the 7th, the 8th, the 9th, the 10th or the 1 st subgroup of the Periodic Table of the Elements.
- catalysts which can be used according to the invention comprise at least one element selected from the group consisting of Re, Fe, Ru, Co,
- the catalysts which can be used according to the invention contain at least one element selected from the group consisting of Fe, Ni, Pd, Pt and Cu.
- the catalysts which can be used according to the invention particularly preferably comprise Pd, Pt, Ru or Ni.
- Suitable examples are homogeneous catalysts containing at least one element of the 8th, 9th or 10th subgroup. More preferred are homogeneous catalysts containing Ru, Rh, Ir and / or Ni. For example, here, for example, RhCl (TTP) 3 or Ru 4 H 4 (CO) - to name I a. Particularly preferred are those homogeneous catalysts containing Ru. For example, homogeneous catalysts are used, as described in US 5,180,870, US 5,321,176, US 5,177,278, US 3,804,914, US 5,210,349 US 5,128,296, US B 316,917 and DR Fahey in J. Org. Chem. 38 (1973) p.
- Such catalysts are about (TPP) 2 (CO) 3 Ru, [Ru (CO) 4 ] 3 , (TPP) 2 Ru (CO) 2 Cl 2 , (TPP) 3 (CO) RuH 2 , (TPP) 2 ( CO) 2 RuH 2 , (TPP) 2 (CO) 2 RUCIH or (TPP) 3 (CO) RUCI 2 .
- at least one heterogeneous catalyst is suitable, wherein at least one of the abovementioned metals can be used as metal as such, as Raney catalyst and / or applied to a conventional support.
- Preferred support materials are, for example, activated carbons or oxides such as, for example, aluminum oxides, silicon oxides, titanium oxides or zirconium oxides. Also to be mentioned among other things as support materials bentonites. If two or more metals are used, they may be present separately or as an alloy. In this case, it is possible to use at least one metal as such and at least one other metal as Raney catalyst or at least one metal as such and at least one other metal applied to at least one support, or at least one metal as Raney catalyst and at least one other metal applied to at least one support, or at least one metal as such and at least one metal other than Raney's catalyst and at least one other metal applied to at least one support.
- the catalysts used may, for example, also be so-called precipitation catalysts.
- Such catalysts can be prepared by reacting their catalytically active components from their salt solutions, in particular from the solutions of their nitrates and / or acetates, for example by adding solutions of alkali metal and / or alkaline earth metal and / or carbonate solutions, for example poorly soluble Hydroxides, oxide hydrates, basic salts or carbonates precipitates, the resulting precipitates then dried and then converted by calcination at generally 300 to 700 ° C, especially 400 to 600 ° C in the corresponding oxides, mixed oxides and / or mixed-valent oxides by a treatment with hydrogen or hydrogen-containing gases in the range of generally 50 to 700 ° C, in particular 100 to 400 ° C to the respective metals and / or oxidic compounds lower oxidation state reduced and converted into the actual catalytically active form.
- the precipitation of the catalytically active components can be carried out in the presence of the relevant support material.
- the catalytically active components can advantageously be precipitated simultaneously with the carrier material from the relevant salt solutions.
- Hydrogenation catalysts are preferably used which contain the hydrogenation-catalyzing metals or metal compounds deposited on a support material.
- the Processes according to the invention generally include those support materials in which the catalytically hydrogenating component has been applied to a support material, for example by impregnation.
- the manner of applying the catalytically active metal to the support is generally not critical and can be accomplished in a variety of ways.
- the catalytically active metals can be applied to these support materials, for example, by impregnation with solutions or suspensions of the salts or oxides of the elements concerned, drying and subsequent reduction of the metal compounds to the respective metals or compounds of lower oxidation state by means of a reducing agent, preferably with hydrogen or complex hydrides .
- a reducing agent preferably with hydrogen or complex hydrides
- Another possibility for applying the catalytically active metals to these carriers is to impregnate the carrier with solutions of thermally easily decomposable salts, for example with nitrates or thermally easily decomposable complex compounds, for example carbonyl or hydrido complexes of the catalytically active metals, and the like impregnated carrier for thermal decomposition of the adsorbed metal compounds to temperatures in the range of 300 to 600 ° C to heat.
- This thermal decomposition is preferably carried out under a protective gas atmosphere.
- Suitable shielding gases are, for example, nitrogen, carbon dioxide, hydrogen or the noble gases.
- the catalytically active metals can be deposited on the catalyst support by vapor deposition or by flame spraying.
- the content of these supported catalysts on the catalytically active metals is in principle not critical to the success of the process according to the invention. In general, higher levels of catalytically active metals of these supported catalysts result in higher space-time conversions than lower levels.
- supported catalysts are used whose content of catalytically active metals in the range of 0.1 to 90 wt .-%, preferably in the range of 0.5 to 40 wt .-% based on the total weight of the catalyst.
- these content data refer to the entire catalyst including carrier material, but the different carrier materials have very different specific weights and specific surface areas, it is also conceivable that these data can be exceeded or exceeded, without adversely affecting the result of the process according to the invention.
- the catalytically active metals may be applied to the respective carrier material.
- the catalytically active metals can be applied to the carrier, for example, by the process of DE-OS 25 19 817, EP 1 477 219 A1 or EP 0 285 420 A1.
- the catalytically active metals are present as alloys which are obtained by thermal treatment and / or reduction of, for example, by impregnation of the carrier material with a salt or complex of the aforementioned metals.
- Both the activation of the precipitation catalysts and of the supported catalysts can also be carried out in situ at the beginning of the reaction by the hydrogen present. Preferably, these catalysts are activated separately before use.
- support materials in general, the oxides of aluminum and titanium, zirconium dioxide, silica, clays such as montmorillonites, silicates such as magnesium or aluminum silicates, zeolites such as the structural types ZSM-5 or ZSM-10, or activated carbon can be used.
- Preferred support materials are aluminas, titanium dioxides, silica, zirconia and activated carbon.
- mixtures of different carrier materials can also serve as carriers for catalysts which can be used in the process according to the invention.
- Very particularly preferred catalysts according to the invention are those which contain Ni, Pt and / or Pd and are applied to a carrier.
- Most preferred carriers are or include activated carbon, alumina, titania and / or silica.
- the at least one heterogeneous catalyst can be used, for example, as a suspension catalyst and / or as a fixed bed catalyst.
- step (a3) is carried out with at least one suspension catalyst
- reactors denotes both different types of reactors as well as reactors of the same type, which differ for example by their geometry such as their volume and / or their cross-section and / or by the hydrogenation conditions in the reactors.
- the hydrogenation according to (a3) is carried out with at least one fixed catalyst, then preferably at least one tubular reactor such as at least one shaft reactor and / or at least one tube bundle reactor is used, wherein a single reactor operated in liquid or trickle mode can be. at The use of two or more reactors can be operated in at least one mode and at least one in trickle mode.
- Invention preferably separated by at least one filtration step.
- the thus separated catalyst can be recycled to the hydrogenation or fed to at least one of any other method. It is also possible to use the
- a homogeneous catalyst is used as catalyst in the hydrogenation according to step (a3), this is preferably separated off in the context of the present invention by at least one distillation step. In this distillation, one or two or more distillation columns can be used. The thus separated catalyst can be recycled to the hydrogenation or fed to at least one of any other method. It is also possible to work up the catalyst in order, for example, to recover the metal contained in the catalyst.
- both the at least one homogeneous and the at least one heterogeneous catalyst may, if necessary, be regenerated by at least one suitable process.
- the heat can be dissipated internally, for example via cooling coils, and / or externally, for example via at least one heat exchanger. If, for example, at least one tubular reactor is preferably used for the hydrogenation, the reaction is preferably conducted over the outer circulation, in which the heat removal is integrated.
- the residence time is generally in the range from 0.05 to 50 h, for example in the range from 0.5 to 50 h, preferably in the range from 1 to 30 h and more preferably in the range of 1, 5 to 25 h, most preferably in the range of 1, 5 to 10 h. It is irrelevant whether according to the invention a main reactor and a post-reactor or in addition further reactors are used. For all of these embodiments, the total residence time is within the ranges given above.
- the catalyst loading (kg feed / liter of catalyst xh) is generally in the range from 0.03 to 20, preferably in the range from 0.05 to 5 and more preferably in the range of 0.1 to 2. It is irrelevant whether according to the invention a main reactor and a post-reactor or in addition further reactors are used. For all of these embodiments, the total load is in the above ranges.
- the hydrogenation temperature in the main reactor is in the range of 0 to 350 ° C, preferably in the range of 20 to 300 ° C, more preferably in the range of 50 to 250 ° C, and most preferably in the range of 80 to 220 ° C.
- the hydrogen pressure in the hydrogenation according to the invention in the main reactor is generally in the range from 1 to 325 bar, preferably in the range from 5 to 300 bar, more preferably in the range from 10 to 250 bar and particularly preferably in the range from 15 to 150 bar.
- At least one suitable solvent or diluent can be used.
- suitable solvents and diluents which are not hydrogenated or otherwise reacted under the hydrogenation conditions, e.g. Alcohols, ethers, hydrocarbons, water, aromatics or ketones, in particular toluene or cyclododecane.
- the hydrogenation according to step (a3) is carried out without addition of a solvent or diluent.
- the composition (I ') may be obtained by trimerization of butadiene to cyclododecatriene, hydrogenation of cyclododecatriene Cyclododecane and subsequent oxidation of cyclododecane to cyclododecanone can be obtained.
- the present invention therefore also relates to a process for the preparation of cyclododecanone as described above, wherein step (a) comprises at least the steps
- stages (a-1), (a-II) and (a-III) can be carried out between stages (a-1), (a-II) and (a-III), for example purification steps.
- stage (a-1) the above-described statements apply to stage (a1).
- step (a-II) and step (a-III) reference is made to DE 103 44 594 A, the content of which is incorporated herein in its entirety into the context of the present application.
- cyclododecanone is obtained by trimerization of butadiene to cyclododecatriene, oxidation of cyclododecatriene to cyclododecatriene epoxide and subsequent hydrogenation and rearrangement of cyclododecatriene epoxide to cyclododecanone.
- the present invention also relates to a process for the preparation of cyclododecanone as described above, wherein step (a) comprises at least the steps
- stages (aA), (aB) and (aC) further treatments can take place between stages (aA), (aB) and (aC), for example purification steps.
- stage (aA) the above-described statements apply to stage (a1).
- stage (aB) and stage (aC) reference is made to EP 1 018 498 A2, the contents of which are incorporated in their entirety into the context of the present application.
- cyclododecanone is obtained by trimerization of butadiene to cyclododecatriene, selective hydrogenation of cyclododecatriene to cyclododecene and subsequent oxidation of cyclododecene to cyclododecanone.
- the present invention also relates to a process for the preparation of cyclododecanone as described above, wherein step (a) comprises at least the steps
- stage (a- ⁇ ) further treatments can take place between the stages (a- ⁇ ), ( ⁇ - ⁇ ) and ( ⁇ - ⁇ ), for example purification steps.
- stage (a- ⁇ ) the above-described statements apply to stage (a1).
- stage (a- ⁇ ) and stage ( ⁇ - ⁇ ) reference is made to DE 103 44 594 A1, the content of which relating thereto being fully incorporated into the context of the present application.
- the present invention relates to the use of at least one acid for purifying a composition containing at least one cyclic ketone.
- the thermal treatment with an acid allows for easier separation of impurities, especially organic oxygenated compounds, having a similar or identical number of C atoms as the cyclic ketone contained in the composition (I).
- the present invention relates to the use of at least one acid for purifying a composition (I), at least containing a cyclic ketone having 7 to 16 carbon atoms, by thermally treating the composition (I) with the acid.
- the present invention also relates to a use of at least one acid as described above for purifying a composition (I) containing at least one cyclic ketone of 7 to 16 carbon atoms, wherein the cyclic ketone is cyclododecanone.
- the invention relates to the use of a soluble acid in an amount of 0.01 to 10% by weight, based on the cyclic ketone, for purifying a composition containing at least one cyclic ketone having 7 to 16 carbon atoms.
- the inventive method is characterized in particular by the fact that pure products are obtained with high catalyst life and a simple process control.
- the apparatus design for the inventive method is simple and inexpensive.
- a cyclododecanone crude product prepared by the process as described in DE 103 44 595 A, wherein in the hydrogenation a Cyclododecadienon was used, which had a purity of about 97.5%, contains 97% cyclododecanone and a variety of other components (0 , 2% cyclododecane, 0.5% cyclododecanol, 0.6% dodecanol, 0.3% dodecanal, 0.6% hydroxymethylcycloundecane, 0.1% formylcycloundecane and 0.2% of a large number of other products whose individual contents are each below 0, 05%), is heated with 0.5 wt.% Of 85% aqueous phosphoric acid for 5 h at 200 ° C and then at 10 mbar via a thin film evaporator in a top stream (about 95% of the total) and a bottom stream (approx 5% of the total) containing the phosphoric acid, separated.
- the bottoms stream can be
- Comparative Example 1 Analogous to Example 1, crude cyclododecanone product is worked up, but without the treatment with phosphoric acid. Cyclododecanone is obtained in purities of 99.3 to 99.5% in a distillation yield of about 60%. The remaining fractions contain cyclododecanone with purities 60 to 99.3%.
- a cyclododecanone crude product analogous to Example 1 was passed over acidic alumina (100 ml) at 220 ° C. and a catalyst loading of 0.5 kg feed / liter of catalyst x h. The reaction was collected over 24 h and then distilled as in Example 1. Cyclododecanone was obtained with a distillation yield of 96% in purities between 99.7 and 99.8.
- Example 2 was repeated, with the difference that the catalyst used was acidic titanium dioxide. Cyclododecanone was obtained with a purity of 99.8% and a distillation yield of 94%.
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Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
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JP2009517181A JP2009541439A (ja) | 2006-06-29 | 2007-06-27 | 環状ケトンの精製方法 |
EP07765649A EP2038245B1 (de) | 2006-06-29 | 2007-06-27 | Verfahren zur reinigung von cyclischen ketonen |
AT07765649T ATE510812T1 (de) | 2006-06-29 | 2007-06-27 | Verfahren zur reinigung von cyclischen ketonen |
US12/306,807 US7714171B2 (en) | 2006-06-29 | 2007-06-27 | Method for purifying cyclic ketones |
KR1020087031569A KR101361288B1 (ko) | 2006-06-29 | 2007-06-27 | 시클릭 케톤의 정제 방법 |
CN200780023854XA CN101479227B (zh) | 2006-06-29 | 2007-06-27 | 提纯环酮的方法 |
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EP06116262.4 | 2006-06-29 | ||
EP06116262 | 2006-06-29 |
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WO2008000752A1 true WO2008000752A1 (de) | 2008-01-03 |
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PCT/EP2007/056391 WO2008000752A1 (de) | 2006-06-29 | 2007-06-27 | Verfahren zur reinigung von cyclischen ketonen |
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US (1) | US7714171B2 (de) |
EP (1) | EP2038245B1 (de) |
JP (1) | JP2009541439A (de) |
KR (1) | KR101361288B1 (de) |
CN (1) | CN101479227B (de) |
AT (1) | ATE510812T1 (de) |
ES (1) | ES2363614T3 (de) |
WO (1) | WO2008000752A1 (de) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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EP3153493A1 (de) | 2015-10-08 | 2017-04-12 | Basf Se | Verfahren zur reinigung von cyclohexadec-8-en-1-on |
Families Citing this family (6)
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PL2391596T3 (pl) * | 2009-01-28 | 2018-12-31 | Basf Se | Sposób wyodrębniania dodekatrienalu i jego zastosowanie jako substancji zapachowej |
WO2011115132A1 (ja) | 2010-03-15 | 2011-09-22 | 宇部興産株式会社 | アミド化合物の製造方法 |
EP2723842B2 (de) * | 2011-06-22 | 2017-12-06 | Firmenich SA | Cyclododecadienonderivate als parfümstoffe |
DE102012223370A1 (de) * | 2012-12-17 | 2014-06-18 | Evonik Industries Ag | Aufarbeitung eines CDON/CDOL-Gemisches mittels einer Sequenz von Seitenabzugskolonnen |
DE102012223367A1 (de) * | 2012-12-17 | 2014-06-18 | Evonik Industries Ag | Aufarbeitung eines CDON/CDOL-Gemisches mittels einer "gelochten" Trennwandkolonne |
KR102609700B1 (ko) * | 2019-10-29 | 2023-12-06 | 한화솔루션 주식회사 | 사이클로도데카논 및 이의 제조방법 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1018498A2 (de) | 1998-12-28 | 2000-07-12 | Ube Industries, Ltd. | Verfahren zur Hydrierung von epoxidierten C6-C12-Cyclokohlenwassterstoff-Verbindungen |
EP1270538A1 (de) * | 2000-04-04 | 2003-01-02 | Japan Energy Corporation | Verfahren zur herstellung makrozyklischer ketone |
EP1329448A1 (de) * | 2002-01-16 | 2003-07-23 | Ube Industries, Ltd. | Verfahren zur Herstellung von Laurolactam aus Zyklododecanon |
DE10344595A1 (de) | 2003-09-25 | 2005-05-12 | Basf Ag | Verfahren zur Herstellung eines Ketons |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US316917A (en) * | 1885-04-28 | Cord-spool and tension device for grain-binders | ||
US3804914A (en) * | 1972-05-25 | 1974-04-16 | Phillips Petroleum Co | Ruthenium(ii)complexes as catalysts for selective hydrogenation of cyclic polyenes to cyclic monoenes |
DE2519817A1 (de) | 1975-05-03 | 1976-11-11 | Hoechst Ag | Verfahren zur herstellung von butandiol-(1.4) |
DE3563447D1 (en) | 1984-03-28 | 1988-07-28 | Asahi Chemical Ind | Process for producing polyether polyol, the produced polyether polyol and polyurethane |
GB8707595D0 (en) | 1987-03-31 | 1987-05-07 | British Petroleum Co Plc | Chemical process |
US5210349A (en) * | 1991-07-01 | 1993-05-11 | Phillips Petroleum Company | Selective hydrogenation of cyclic polyenes |
US5128296A (en) * | 1991-07-01 | 1992-07-07 | Phillips Petroleum Company | Selective hydrogenation of cyclic polyenes |
US5177278A (en) * | 1991-10-23 | 1993-01-05 | E. I. Du Pont De Nemours And Company | Preparation of cyclododecene |
US5180870A (en) * | 1991-10-23 | 1993-01-19 | E. I. Du Pont De Nemours And Company | Hydrogenation of polyenes |
US5321176A (en) * | 1992-12-22 | 1994-06-14 | E. I. Du Pont De Nemours And Company | Hydrogenation of polyenes |
EP1477219A1 (de) | 2003-05-16 | 2004-11-17 | Tuttle Prilling Systems | Vorrichtung zur Granulierung |
DE10344594A1 (de) * | 2003-09-25 | 2005-05-12 | Basf Ag | Verfahren zur Herstellung von Cyclododecanon |
-
2007
- 2007-06-27 JP JP2009517181A patent/JP2009541439A/ja active Pending
- 2007-06-27 AT AT07765649T patent/ATE510812T1/de active
- 2007-06-27 CN CN200780023854XA patent/CN101479227B/zh not_active Expired - Fee Related
- 2007-06-27 EP EP07765649A patent/EP2038245B1/de active Active
- 2007-06-27 WO PCT/EP2007/056391 patent/WO2008000752A1/de active Search and Examination
- 2007-06-27 US US12/306,807 patent/US7714171B2/en not_active Expired - Fee Related
- 2007-06-27 ES ES07765649T patent/ES2363614T3/es active Active
- 2007-06-27 KR KR1020087031569A patent/KR101361288B1/ko not_active IP Right Cessation
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1018498A2 (de) | 1998-12-28 | 2000-07-12 | Ube Industries, Ltd. | Verfahren zur Hydrierung von epoxidierten C6-C12-Cyclokohlenwassterstoff-Verbindungen |
EP1270538A1 (de) * | 2000-04-04 | 2003-01-02 | Japan Energy Corporation | Verfahren zur herstellung makrozyklischer ketone |
EP1329448A1 (de) * | 2002-01-16 | 2003-07-23 | Ube Industries, Ltd. | Verfahren zur Herstellung von Laurolactam aus Zyklododecanon |
DE10344595A1 (de) | 2003-09-25 | 2005-05-12 | Basf Ag | Verfahren zur Herstellung eines Ketons |
Non-Patent Citations (1)
Title |
---|
T. SCHIFFER; G. OENBRINK: "Ullmann's Encyclopedia of Industrial Chemistry", 2000, WILEY VCH, article "Cyclododecanol, Cyclododecanon and Laurolactam" |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3153493A1 (de) | 2015-10-08 | 2017-04-12 | Basf Se | Verfahren zur reinigung von cyclohexadec-8-en-1-on |
WO2017060437A1 (de) | 2015-10-08 | 2017-04-13 | Basf Se | Verfahren zur reinigung von cyclohexadec-8-en-1-on |
US20180312458A1 (en) * | 2015-10-08 | 2018-11-01 | Basf Se | Method f0r the purification of cyclohexadec-8-en-1-one |
Also Published As
Publication number | Publication date |
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KR101361288B1 (ko) | 2014-02-11 |
US7714171B2 (en) | 2010-05-11 |
US20090326277A1 (en) | 2009-12-31 |
CN101479227A (zh) | 2009-07-08 |
KR20090023414A (ko) | 2009-03-04 |
EP2038245A1 (de) | 2009-03-25 |
EP2038245B1 (de) | 2011-05-25 |
CN101479227B (zh) | 2012-09-05 |
ATE510812T1 (de) | 2011-06-15 |
ES2363614T3 (es) | 2011-08-10 |
JP2009541439A (ja) | 2009-11-26 |
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