CA2534760A1 - Process for regenerating a hydrogenation catalyst - Google Patents

Process for regenerating a hydrogenation catalyst Download PDF

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Publication number
CA2534760A1
CA2534760A1 CA002534760A CA2534760A CA2534760A1 CA 2534760 A1 CA2534760 A1 CA 2534760A1 CA 002534760 A CA002534760 A CA 002534760A CA 2534760 A CA2534760 A CA 2534760A CA 2534760 A1 CA2534760 A1 CA 2534760A1
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Prior art keywords
catalyst
process according
thermal treatment
traces
hydrogenation
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Abandoned
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CA002534760A
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French (fr)
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Michel Strebelle
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Solvay SA
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Individual
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    • 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
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/02—Heat treatment
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C21/00—Acyclic unsaturated compounds containing halogen atoms
    • C07C21/02—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds
    • C07C21/04—Chloro-alkenes
    • C07C21/06—Vinyl chloride
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/08—Silica
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/90—Regeneration or reactivation
    • B01J23/96—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the noble metals
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B7/00—Halogens; Halogen acids
    • C01B7/01—Chlorine; Hydrogen chloride
    • C01B7/03—Preparation from chlorides
    • C01B7/035—Preparation of hydrogen chloride from chlorides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B7/00—Halogens; Halogen acids
    • C01B7/01—Chlorine; Hydrogen chloride
    • C01B7/07—Purification ; Separation
    • C01B7/0706—Purification ; Separation of hydrogen chloride
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/013—Preparation of halogenated hydrocarbons by addition of halogens
    • C07C17/02—Preparation of halogenated hydrocarbons by addition of halogens to unsaturated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/15—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination
    • C07C17/152—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination of hydrocarbons
    • C07C17/156—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination of hydrocarbons of unsaturated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/44—Palladium
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/612—Surface area less than 10 m2/g
    • 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
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
    • B01J38/12—Treating with free oxygen-containing gas
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

Process for regenerating a spent hydrogenation catalyst comprising at least one catalytic metal selected from the group consisting of Ru, Rh, Pd, Os, Ir and Pt on an inert support, the said process essentially consisting of a thermal treatment in the presence of oxygen at a temperature of between 300 and 700~C.

Description

Process for re~eneratin",~ a hydrogenation catal ~~st The present invention relates to a process for regenerating a specific hydrogenation catalyst and to an industrial process using such a regenerated catalyst.
Numerous industrial processes employ a catalytic hydrogenation step.
Catalysts highly suitable for this purpose are those comprising a metal from group VIII of the Periodic Table, selected from the elements Ru, Rh, Pd, Os, Ir and Pt, on an inert support (silica, alumina, etc.).
An example of such a process is the production of vinyl chloride monomer (VCM) by coupling a direct chlorination and an oxychlorination of ethylene (CZH4) to form 1,2-dichloroethane (DCEa), which is subjected to pyrolysis to form VCM on the one hand and HCl on the other. In the course of this pyrolysis a small amount of acetylene (C2H2), of the order of approximately 2000 ppm (by volume relative to the volume of HCl), is co-produced, but cannot easily be separated from the HCI, owing to their very similar volatilities. The pyrolysis HCl is then recycled to the oxychlorination, in the course of which the C2H2 reacts to give various worthless by-products, which are detrimental to the profitability of the process. One known method, an elegant one, for removing this C2H2 consists in converting it into ethylene (C2H4) by hydrogenation, using an appropriate catalyst. One such catalyst is described in patent application DE 24 38 153, which illustrates in particular a catalyst based on Pd supported on non-porous silica. In service, however, this catalyst undergoes gradual deactivation and, although the abovementioned application records the possibility in theory of regenerating it, in practice such regeneration has proved to be fruitless, owing in particular to the contamination of this catalyst with heavy metals (H. Muller et al., Chem.-Ing.-Tech. 59 (1987) No. 8, pp. 645-7).
The applicant, however, has surprisingly found that if such a contaminated catalyst is treated in the presence of oxygen, at a temperature sufficient to remove the contaminations but not too high, so as not to impair the catalyst, the said catalyst can nevertheless be regenerated satisfactorily.
The present invention accordingly provides a process for regenerating a hydrogenation catalyst comprising at least one catalytic metal selected from the group consisting of Ru, Rh, Pd, Os, Ir and Pt on an inert support, the said regeneration process consisting essentially of a thermal treatment in the presence of oxygen at a temperature between 300 and 700°C.
Of the aforementioned catalytic metals preference is given to Pt and Pd. Pd is particularly preferred on account of its high hydrogen adsorption capacity.
The concentration of the catalytic metal in the catalyst is generally greater than or equal to 0.01 % by weight (relative to the total weight of the catalyst), preferably greater than or equal to 0.05%, or even greater than or equal to 0.1%. This concentration is, however, generally less than or equal to 10%, or even less than or equal to 5%, or even less than or equal to 1%.
The inert support of the catalyst which is regenerable by the process according to the present invention is preferably selected from porous and non-porous silica, alumina and silica-alumina. Supports based primarily on silica (in other words composed of more than 50%, preferably of more than 95%, of Si02) give good results. The support is preferably non-porous or of low porosity, in other words having a specific surface area (measured in accordance with the BET method with nitrogen) of less than 5 m2/g, and preferably less than 3 m2/g, or even less than 1 mZJg. The average pore volume of this support is advantageously less than 0.01 ml/g. Its particle size is advantageously between 1 and 20 mm, or even between 2 and 10 mm, and preferably between 3 and 7 mm.
On this support the catalytic metal is generally present in a layer of less than or equal to a micron. It is generally in the form of crystallites having a size of between 0.1 and 0.5 Vim. In particular the non-porous silica as described in the aforementioned references (DE 24 38 153 and the article by Miiller) gives good results.
By the fact that the process according to the invention "essentially consists of a thermal treatment" is meant that the major part of the regeneration of the catalyst (in other words at least 50% of the gain in selectivity and/or in degree of conversion) is realized by the thermal treatment. Preferably at least 75% of the regeneration is the outcome of the thermal treatment, or even at least 90%, and with particular preference the entirety of the regeneration is the outcome thereof, implying that according to this version of the invention the process takes place in the absence of any regenerative treatment (with steam or H2, for example) preceding or following the said thermal treatment, and therefore that the catalyst obtained from the thermal treatment is reused as it is in a hydrogenation reaction.
However, care is generally taken to remove the reactants still present on the surface of the catalyst (by flushing with nitrogen, for example) before the thernlal regeneration according to the invention.
Similarly, by "reuse of the catalyst as it is" is meant a use identical to that of a fresh catalyst. Such use may include, for example, prior activation by flushing with H2.
The thermal treatment in question consists in a residence at a high temperature (of between 300 and 700°C) in the presence of oxygen. The temperature during the thermal treatment is preferably greater than or equal to 400°C, or even greater than or equal to 500°C, in order to increase the efficiency of the regeneration. It is, however, preferably less than or equal to 600°C, or even less than or equal to 550°C, so as not to impair the catalyst (since it is known that, at too high a temperature, supported catalysts may undergo "fritting", or agglomeration of the catalytic metal, resulting in a loss of activity by reduction of the active surface). The thermal treatment may take place in the presence of pure oxygen. Preferably, however, the oxygen is diluted, with an inert gas for example. Accordingly air gives good results.
The treatment in question therefore in fact typically involves what is generally referred to as an oxidizing atmosphere, which may be either static or moving (which is to say that a gaseous stream containing oxygen is passed over the catalyst to be regenerated). A moving oxidizing atmosphere gives good results. A simple residence in a stove or electric oven, preferably with a fan, may serve for thernzal treatment according to the present invention. Another way which gives good results consists in passing the oxidizing atmosphere through the bed of catalyst, in situ for example, in the hydrogenation reactor.
Better results are generally obtained when the catalyst is dispersed during the treatment: that is, when it presents a maximum surface area to the oxidizing atmosphere. Hence the catalyst will advantageously be spread in a layer, ranging from a monolayer of catalyst (whose thickness depends on the particle size of the catalyst) to a layer of approximately 20 cm, although, preferably, the thickness of this layer does not exceed 10 cm, or even 5 cm.
The duration of the said treatment is readily determined by the skilled person and will be adapted to the desired degree of regeneration. It is generally greater than or equal to 1 h, or even to 5 h. This duration is, however, generally less than or equal to 48 h, or even to 24 h. The same applies to the ventilation flow rate, which is preferably greater than or equal to 0.011/min.lcg cata (or litre per minute per kg of catalyst), or even greater than or equal to 0.1 1/min.leg cata, but is generally less than or equal to 1001/min.lcg cata, or even less than or equal to 101/min.kg cata.
The catalyst that it is intended should be regenerated by the process according to the invention is a "spent" catalyst, (i.e. a catalyst which has served in a hydrogenation reaction) subsequent to which its catalytic activity (in terms of selectivity and/or degree of conversion) has dropped. Such a drop in catalytic activity is generally ascribed to the deposition of carbonaceous substances and/or to contamination with chlorine compounds and/or traces of at least one heavy metal. The teen "heavy metal" is intended to denote one of the following metals:
Al, As, Cd, Cr, Ni, Cu, Sn, Fe, Mn, Hg, Pb, Zn and Ti (although the latter is not generally considered to be a heavy metal, it nevertheless constitutes a disruptive contamination for hydrogenation catalysts and, as such, is considered to be a heavy metal in the context of the present invention). The traces of heavy metals are particularly disruptive and, among them, Fe and Ti in particular, since they are commonly present in industrial fluids, owing to the nature of the equipment used to convey/treat them. Similarly, traces of Hg, which may be encountered in certain sources of H2, are also disruptive. By "traces" are meant amounts of the order of ppm, or even tens of ppm. It is not uncommon for the starting catalyst already to include traces of certain heavy metals (Fe in particular, but generally less than 50 ppm), but in the course of use an increase in the amount thereof (for example to an amount greater than or equal to 50 ppm in the case of Fe) generally contributes to a drop in the catalytic activity.
The hydrogenation reaction in which the catalyst has been used is preferably an acetylene hydrogenation reaction. It applies preferably to traces of a acetylene (C2H2) which are present in a fluid and, preferably, in a gas mixture consisting essentially of HCl and obtained from the pyrolysis of DCEa, as described above. Such a mixture generally contains between 1500 and 2500 ppm of acetylene. It often also contains of the order of tens to hundreds of ppm of chlorinated organic products such as VCM and methyl or ethyl chloride, and/or non-chlorinated organic products such as ethylene (C2H4), methane and butadiene. These contaminants result from imperfect separation during operations to separate pyrolysis products from HCI, the said separation generally being carried out by distillation. For this type of reaction, as described above, catalysts based on Pd on a non-porous silica support give good results and are readily regenerable by the process according to the invention.
The catalyst regenerated by the process according to the invention may be used in any hydrogenation reaction for which it has a catalytic activity.
Preferably it is reused in a process similar to that in which it was used beforehand. Thus the present invention lilcewise provides a process for synthesizuzg VCM by coupling of a direct chlorination and an oxychlorination of ethylene to form DCEa, which is primarily converted into VCM and into HCl by pyrolysis, the said HCl containing traces of acetylene and being recycled to the oxychlorination following hydrogenation of these traces of acetylene in the presence of a catalyst regenerated by a process as described above.
The present invention is illustrated non-limitatively by the following example:
Catalyst E39H (beads of silica 3 to 5 mm in diameter with 0.15% of Pd supported at the surface and with a specific surface area of less than 1 m2/g), sold by Degussa and as described in the aforementioned article by Miiller, was used for four and a half years (54 months) in contact with HCl containing approximately 2000 ppm of C2H2 under 10 bars and at a temperature of between 120 and 180°C. The residence time (ratio between the number of m3 (s.t.p.) of HCl/h and the volume of the catalyst bed in m3) was 1680 h-1. The quantity of employed was 3.8 mol per mole of CZH2.
The thus-spent catalyst was analyzed and compared with the virgin catalyst. The results of these analyses are given in the table below:
Element analyzed Fresh catalyst Spent catalyst (content) Pd (wei ht % 0.15 0.14 Cl (wei ht % 0.015 1.090 Fe ( m < 50 84 Traces - ~ Co,Zn,Cu,Ti,Pb,Zr A batch of 150 kg of this spent catalyst was spread over 18 plates each with a surface area of 0.3 m2. The temperature of the oven was taken to S00°C
and held for 18 h. The ventilation of the oven is controlled by an air input of 1001/min.
This batch was subsequently reused under conditions similar to those described above, at a temperature of 173°C, and its catalytic activity was compared with that of the spent catalyst at end of life (used at 180°C) in the following table:
Spent catalyst Regenerated catalyst Degree of conversion 82 94.6 of C2H2 (%

Yield (molar % C2H4/C2H248.7 62.9 It is found that the catalytic activity was highly regenerated (improved conversion and improved yield despite the lower operating temperature).

Claims (9)

1. Process for regenerating a spent hydrogenation catalyst comprising at least one catalytic metal selected from the group consisting of Ru, Rh, Pd, Os, Ir and Pt on an inert support, characterized in that the spent catalyst has been used in a reaction of hydrogenation of traces of acetylene which are present in a gas mixture consisting essentially of HCl and obtained from the pyrolysis of 1,2-dichloroethane (DCEa) and in that the said process consists essentially of a thermal treatment in the presence of oxygen at a temperature of between 300 and 700°C.
2. Process according to the preceding claim, characterized in that the catalytic metal is Pd.
3. Process according to either of the preceding claims, characterized in that the inert support is based primarily on silica.
4. Process according to any one of the preceding claims, characterized in that the inert support has a BET surface area of less than 5 m2/g.
5. Process according to any one of the preceding claims, characterized in that the temperature during the thermal treatment is between 400 and 600°C.
6. Process according to any one of the preceding claims, characterized in that the thermal treatment takes place in the presence of air.
7. Process according to the preceding claim, characterized in that the thermal treatment consists in a residence in a stove or a ventilated electric oven.
8. Process according to any one of the preceding claims, characterized in that the catalyst is contaminated with traces of heavy metals.
9. Process for synthesizing vinyl chloride monomer (VCM) by coupling a direct chlorination and an oxychlorination of ethylene to form DCEa, which is converted primarily into VCM and into HCl by pyrolysis, the said HCl containing traces of acetylene and being recycled to the oxychlorination following hydrogenation of these traces of acetylene in the presence of a catalyst regenerated by a process according to any one of the preceding claims.
CA002534760A 2003-08-08 2004-08-05 Process for regenerating a hydrogenation catalyst Abandoned CA2534760A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR0309800 2003-08-08
FR03.09800 2003-08-08
PCT/EP2004/051723 WO2005014168A1 (en) 2003-08-08 2004-08-05 Process for regenerating a hydrogenation catalyst

Publications (1)

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CA2534760A1 true CA2534760A1 (en) 2005-02-17

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EP (1) EP1658137A1 (en)
JP (1) JP2007501691A (en)
KR (1) KR20060056980A (en)
CN (1) CN1832801A (en)
AR (1) AR045336A1 (en)
BR (1) BRPI0413286A (en)
CA (1) CA2534760A1 (en)
EA (1) EA008672B1 (en)
EG (1) EG24366A (en)
MX (1) MXPA06001446A (en)
MY (1) MY149389A (en)
NO (1) NO20060496L (en)
TW (1) TW200510062A (en)
UA (1) UA84436C2 (en)
WO (1) WO2005014168A1 (en)

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CN100355718C (en) * 2005-09-21 2007-12-19 扬子石油化工股份有限公司 Regeneration method of catalyst of hydrofinishing terephthalic acid
US7718158B2 (en) 2005-10-13 2010-05-18 Lyondell Chemical Technology, L.P. Polymer-encapsulated ion-exchange resin
CA2641348C (en) 2006-02-03 2014-12-23 Grt, Inc. Continuous process for converting natural gas to liquid hydrocarbons
MY153701A (en) 2006-02-03 2015-03-13 Grt Inc Separation of light gases from halogens
KR101236099B1 (en) * 2006-12-12 2013-02-21 주식회사 엘지화학 Novel method for the production of vinyl chloride monomer
US8921625B2 (en) 2007-02-05 2014-12-30 Reaction35, LLC Continuous process for converting natural gas to liquid hydrocarbons
WO2008148113A1 (en) 2007-05-24 2008-12-04 Grt, Inc. Zone reactor incorporating reversible hydrogen halide capture and release
US8282810B2 (en) 2008-06-13 2012-10-09 Marathon Gtf Technology, Ltd. Bromine-based method and system for converting gaseous alkanes to liquid hydrocarbons using electrolysis for bromine recovery
JP4610664B1 (en) 2009-07-09 2011-01-12 Ｊｘ日鉱日石エネルギー株式会社 Method for producing regenerated hydrotreating catalyst and method for producing petroleum product
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US9193641B2 (en) 2011-12-16 2015-11-24 Gtc Technology Us, Llc Processes and systems for conversion of alkyl bromides to higher molecular weight hydrocarbons in circulating catalyst reactor-regenerator systems
CN104399492A (en) * 2014-11-17 2015-03-11 张立军 Palladium catalyst roasting regenerating process
CN105712835A (en) * 2014-12-03 2016-06-29 青岛海晶化工集团有限公司 Method for preparing VCM via balanced oxychlorination

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NL243457A (en) * 1958-09-20
DE2438153A1 (en) * 1974-08-08 1976-02-19 Degussa Selective acetylene removal from hydrogen chloride - by hydrogenation at platinum metal catalyst on non-porous silica-contg. carrier
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BRPI0413286A (en) 2006-10-10
EG24366A (en) 2009-03-05
WO2005014168A1 (en) 2005-02-17
KR20060056980A (en) 2006-05-25
NO20060496L (en) 2006-03-07
EP1658137A1 (en) 2006-05-24
TW200510062A (en) 2005-03-16
CN1832801A (en) 2006-09-13
MY149389A (en) 2013-08-30
MXPA06001446A (en) 2006-05-19
AR045336A1 (en) 2005-10-26
EA008672B1 (en) 2007-06-29
UA84436C2 (en) 2008-10-27
JP2007501691A (en) 2007-02-01
EA200600378A1 (en) 2006-06-30

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