Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
  • B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
  • B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
  • B01D53/26—Drying gases or vapours
  • B01D53/28—Selection of materials for use as drying agents
• • 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
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
• • 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
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
  • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
  • B01J20/0233—Compounds of Cu, Ag, Au
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
  • B01D2253/20—Organic adsorbents
  • B01D2253/204—Metal organic frameworks (MOF's)
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2257/00—Components to be removed
  • B01D2257/80—Water
• • 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
  • B01J2220/00—Aspects relating to sorbent materials
  • B01J2220/50—Aspects relating to the use of sorbent or filter aid materials

Definitions

• the present invention relates to the use of porous organometallic frameworks as a desiccant.
• Disturbing may be traces of water in such chemical reactions, which reduce the yield of a reaction or completely avoid the occurrence of such a reaction. Therefore, numerous methods have been developed to reduce the water content of organic liquids.
• a simple possibility is to bring the solvent into contact with a desiccant so that the water in the solvent is bound to the desiccant so that the proportion of water in the organic solvent is correspondingly reduced.
• Such known agents are molecular sieves, calcium chloride, magnesium sulfate and the like.
• An object of the present invention is thus to supply new substances of such use.
• the object is achieved by the use of a porous organometallic framework material comprising at least one at least bidentate organic compounds coordinated to at least one metal ion, as a drying agent for reducing or removing water from an organic liquid.
• organometallic frameworks in addition to their adsorbent properties, are also outstandingly suitable for drying organic liquids, in particular for gases or for gas separation.
• a desiccant for use as a desiccant to reduce or remove water from an organic liquid thus serve porous organometallic frameworks.
• organometallic frameworks are known in the art and are described, for example, in US Pat. No. 5,648,508, EP-A-0 790 253, M. O'Keeffe et al., J. SoI. State Chem., 152 (2000), pages 3 to 20, H. Li et al., Nature 402, (1999), page 276, M. Eddaoudi et al., Topics in Catalysis ⁇ , (1999), pages 105 to 1 11, B. Chen et al., Science 291_, (2001), pages 1021 to 1023 and DE-A-101 11 230.
• MOF organometallic frameworks
• porous organometallic frameworks are those in which the organic compound as a ligand represents a mono-, bi- or polycyclic ring system which is selected from at least one of the heterocycles selected from the group consisting of pyrrole, alpha-pyridone and gamma-pyridone and has at least two nitrogen ring atoms.
• the electrochemical preparation of such frameworks is described in WO-A 2007/131955.
• the organometallic frameworks according to the present invention contain pores, in particular micro and / or mesopores.
• Micropores are defined as those having a diameter of 2 nm or smaller and mesopores are defined by a diameter in the range of 2 to 50 nm, each according to the definition as described by Pure & Applied Chem. 57 (1983), 603-619, in particular on page 606.
• the presence of micro- and / or mesopores can be checked by means of sorption measurements, these measurements determining the uptake capacity of the organometallic frameworks for nitrogen at 77 Kelvin according to DIN 66131 and / or DIN 66134.
• the specific surface is preferably calculated according to the Langmuir model (DIN 66131, 66134) for an organometallic framework in powder form more than 100 m 2 / g, more preferably over 300 m 2 / g, more preferably more than 700 m 2 / g, even more preferably more than 800 m 2 / g, even more preferably more than 1000 m 2 / g and especially preferably more than 1200 m 2 / g.
• Shaped bodies containing organometallic frameworks may have a lower active surface area; but preferably more than 150 m 2 / g, more preferably more than 300 m 2 / g, even more preferably more than 700 m 2 / g.
• the metal component in the framework material according to the present invention is preferably selected from the groups Ia, IIa, IIIa, IVa to Villa and Ib to VIb. Particularly preferred are Mg, Ca, Sr, Ba, Sc, Y, Ln, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ro, Os, Co, Rh, Ir , Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, Tl, Si, Ge, Sn, Pb, As, Sb and Bi, where Ln is lanthanide.
• Lanthanides are La, Ce, Pr, Nd, Pm, Sm, En, Gd, Tb, Dy, Ho, Er, Tm, Yb.
• Zn, Al, Mg, Cu, Mn, Fe, Co, Ni, Ti, Zr, Y, Sc, V, In, Ca, Cr, Mo, W, Ln are furthermore particularly preferred.
• Further preferred are Al, Cu, Zr, Y, Ln, Mn and Mg. In particular, Cu is preferred.
• At least bidentate organic compound refers to an organic compound containing at least one functional group capable of having at least two coordinative bonds to a given metal ion, and / or to two or more, preferably two, metal atoms each having a coordinative bond train.
• Examples of functional groups which can be used to form the abovementioned coordinative bonds are, for example, the following functional groups: -CO 2 H, -CS 2 H, -NO 2 , -B (OH) 2 , -SO 3 H, - Si (OH) 3 , -Ge (OH) 3 , -Sn (OH) 3 , -Si (SH) 4 ,
• R for example, preferably represents an alkylene group having 1, 2, 3, 4 or 5 carbon atoms, for example a methylene, ethylene, n-propylene, i-propylene, n-butylene, i-butylene, tert-butylene or n-pentylene group, or an aryl group containing 1 or 2 aromatic nuclei such as 2 C ⁇ rings, which may optionally be condensed and may be independently substituted with at least one substituent, and / or which may each independently contain at least one heteroatom such as N, O and / or S.
• functional groups are to be mentioned in which the abovementioned radical R is absent.
• the functional groups can also be heteroatoms of a heterocycle.
• nitrogen atoms are mentioned here.
• the at least two functional groups can in principle be bound to any suitable organic compound, as long as it is ensured that the organic compound having these functional groups is capable of forming the coordinate bond and for preparing the framework material.
• the organic compounds containing the at least two functional groups are derived from a saturated or unsaturated aliphatic compound or an aromatic compound or an aliphatic as well as aromatic compound.
• the aliphatic compound or the aliphatic portion of the both aliphatic and aromatic compound may be linear and / or branched and / or cyclic, wherein also several cycles per compound are possible. More preferably, the aliphatic compound or the aliphatic portion of the both aliphatic and aromatic compound contains 1 to 15, more preferably 1 to 14, further preferably 1 to 13, further preferably 1 to 12, further preferably 1 to 1 1 and especially preferably 1 to 10 C atoms such as 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 C atoms. In particular, methane, adamantane, acetylene, ethylene or butadiene are preferred.
• the aromatic compound or the aromatic part of both the aromatic and the aliphatic compound may have one or more nuclei, for example two, three, four or five nuclei, wherein the nuclei may be present separately from each other and / or at least two nuclei in condensed form ,
• the aromatic compound or the aromatic moiety of the both aliphatic and aromatic compounds has one, two or three nuclei, with one or two nuclei being particularly preferred.
• each nucleus of the named compound may contain at least one heteroatom, such as, for example, N, O, S, B, P, Si, Al, preferably N, O and / or S.
• aromatic compound or the aromatic moiety of both the aromatic and the aliphatic compound contains one or two C 6 cores, the two being present either separately or in condensed form.
• benzene, naphthalene and / or biphenyl and / or bipyridyl and / or pyridyl may be mentioned as aromatic compounds.
• the at least bidentate organic compound an aliphatic or aromatic, acyclic or cyclic hydrocarbon having 1 to 18, preferably 1 to 10 and in particular 6 carbon atoms, which also exclusively 2, 3 or 4 carboxyl groups as functional groups.
• the at least bidentate organic compound is derived from a dicarboxylic acid such as oxalic acid, succinic acid, tartaric acid, 1,4-butanedicarboxylic acid, 1,4-butenedicarboxylic acid, 4-oxo-pyran-2,6-dicarboxylic acid, 1,6 Hexanedicarboxylic acid, decanedicarboxylic acid, 1,8-heptadecanedicarboxylic acid, 1,9-heptanecanedicarboxylic acid, heptadecanedicarboxylic acid, acetylenedicarboxylic acid, 1,2-benzenedicarboxylic acid, 1,3-benzenedicarboxylic acid, 2,3-pyridinedicarboxylic acid, pyridine-2,3 - dicarboxylic acid, 1, 3-butadiene-1, 4-dicarboxylic acid, 1, 4-benzenedicarboxylic acid, p-benzenedicarboxylic acid,
• the at least bidentate organic compound is one of the above-exemplified dicarboxylic acid as such.
• the at least bidentate organic compound may be derived from a tricarboxylic acid, such as
• the at least bidentate organic compound is one of the above-exemplified tricarboxylic acids as such.
• 1, 1-Dioxidperylo [1, 12-BCD] thiophene-3,4,9,10-tetracarboxylic acid perylenetetracarboxylic acids such as perylene-3,4,9,10-tetracarboxylic acid or perylene-1,12-sulfone-3, 4,9,10-tetra carboxylic acid, butanetetracarboxylic acids such as 1,2,3,4-butanetetracarboxylic acid or meso-1,2,3,4-butanetetracarboxylic acid, decane-2,4,6,8-tetracarboxylic acid, 1,4,7,10,13,16- Hexa-oxacyclooctadecane-2,3,1,1,12-tetracarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid,
• the at least bidentate organic compound is one of the above exemplified tetracarboxylic acids as such.
• the at least one at least bidentate organic compound derives from or is a di-, tri- or tetracarboxylic acid.
• the term "derive" in the context of the present invention means that the di-, tri- or tetracarboxylic acid can be present in the framework material in partially deprotonated or completely deprotonated form. Furthermore, the di-, tri- or tetracarboxylic acid may contain a substituent or independently of one another several substituents. Examples of such substituents are -OH, -NH 2 , -OCH 3 , -CH 3 , -NH (CH 3 ), -N (CH 3 ) 2 , -CN and halides.
• the term "derive" in the context of the present invention means that the di-, tri- or tetracarboxylic acid can also be present in the form of the corresponding sulfur analogs.
• the term "derive” in the context of the present invention means that one or more carboxylic acid functions can be replaced by a sulfonic acid group (-SO 3 H).
• a sulfonic acid group may also occur in addition to the 2, 3 or 4 carboxylic acid functions.
• Preferred heterocycles as at least bidentate organic compounds in which a coordinate bond takes place via the ring heteroatoms are the following substituted or unsubstituted ring systems:
• each of the cores can contain at least one heteroatom, where two or more nuclei have identical or different heteroatoms may contain.
• Suitable heteroatoms are, for example, N, O, S, B, P. Preferred heteroatoms here are N, S and / or O.
• a suitable substituent in this regard is, inter alia, -OH, a nitro group, an amino group or an alkyl or alkoxy group.
• Particularly preferred at least bidentate organic compounds are imidazolates, such as 2-methylimidazolate, acetylenedicarboxylic acid (ADC), camphericarboxylic acid, fumaric acid, succinic acid, benzenedicarboxylic acids, such as phthalic acid, isophthalic acid, terephthalic acid (BDC), aminoterephthalic acid, triethylenediamine (TEDA), naphthalenedicarboxylic acids ( NDC), biphenyldicarboxylic acids such as 4,4'-biphenyldicarboxylic acid (BPDC), pyrazine dicarboxylic acids such as 2,5-pyrazine dicarboxylic acid, bipyridinedicarboxylic acids such as 2,2'-bipyridine dicarboxylic acids such as 2,2'-bipyridine-5,5'-dicarboxylic acid, benzene tricarboxylic acids such as 1, 2,3-, 1, 2,4-benzene
• terephthalic acid 2,6- and 1,5-naphthalenedicarboxylic acid
• isophthalic acid fumaric acid
• 1,3,5-benzenetricarboxylic acid (BTC) trimellitic acid
• glutaric acid 2,5-dihydroxyphthalphthalic acid
• BTC 1,3,5-benzenetricarboxylic acid
• the organometallic framework material may also comprise one or more monodentate ligands and / or one or more at least bidentate ligands which are not derived from a di-, tri- or tetracarboxylic acid.
• the MOF may also comprise one or more monodentate ligands.
• Suitable solvents for the preparation of the MOF include i.a. Ethanol, dimethylformamide, toluene, methanol, chlorobenzene, diethylformamide, dimethyl sulfoxide, water, hydrogen peroxide, methylamine, sodium hydroxide solution, N-methylpolidone ether, acetonitrile, benzyl chloride, triethylamine, ethylene glycol and mixtures thereof.
• Other metal ions, at least bidentate organic compounds and solvents for the production of MOF include i.a. in US Pat. No. 5,648,508 or DE-A 101 11 230.
• the pore size of the organometallic framework can be controlled by choice of the appropriate ligand and / or the at least bidentate organic compound. Generally, the larger the organic compound, the larger the pore size.
• the pore size is preferably from 0.2 nm to 30 nm, and the pore size is particularly preferably in the range from 0.3 nm to 3 nm, based on the crystalline material. However, in a shaped body containing an organometallic framework material, larger pores also occur whose size distribution can vary. Preferably, however, more than 50% of the total pore volume, in particular more than 75%, of pores having a pore diameter of up to 1000 nm is formed.
• a majority of the pore volume is formed by pores of two diameter ranges. It is therefore further preferred if more than 25% of the total pore volume, in particular more than 50% of the total pore volume, is formed by pores which are in a diameter range of 100 nm to 800 nm and if more than 15% of the total pore volume, in particular more than 25% of the total pore volume is formed by pores ranging in diameter or up to 10 nm.
• the pore distribution can be determined by means of mercury porosimetry.
• organometallic frameworks The following are examples of organometallic frameworks.
• the metal and the at least bidentate ligands the solvent and the cell parameters (angles ⁇ , ⁇ and ⁇ as well as the distances A, B and C in A) are also indicated. The latter were determined by X-ray diffraction.
• Other organometallic frameworks are MOF-2 to 4, MOF-9, MOF-31 to 36, MOF-39, MOF-69 to 80, MOF103 to 106, MOF-122, MOF-125, MOF-150, MOF-177, MOF-178, MOF-235, MOF-236, MOF-500, MOF-501, MOF-502, MOF-505, IRMOF-1, IRMOF-61, IRMOP-13, IRMOP-51, MIL-17, MIL 45, MIL-47, M
• organometallic frameworks are MIL-53, Zn-t-isophthalic acid, Al-BDC, MOF-5, IRMOF-8, Cu-BTC, Al-NDC, Al-AminoBDC, Cu-BDC-TEDA, Zn-BDC-TEDA , Al-BTC, Al-NDC, Mg-NDC, Al-fumarate, Zn-2-methylimidazolate, Zn-2-aminoimidazolate, Cu-biphenyldicarboxylate-TEDA, MOF-177, MOF-74. Further more preferred are Al-BDC and Al-BTC.
• organometallic frameworks are Al terephthalate, Al fumarate, Mn terephthalate, Mg-NDC, Y-BDC, Y-imidazoledicarboxylate, Al-imidazoledicarboxylate, Cu-BTC and Zn-dihydroxyphthalate.
• organometallic frameworks prepared in this way have particularly good properties in connection with the adsorption and desorption of chemical substances, in particular of gases.
• the organometallic framework material precipitates in a powdery or crystalline form. This can be used as such as a desiccant in the inventive use alone or together with other desiccants or other materials. Furthermore, the organometallic framework material can be converted into a shaped body.
• Another object of the present invention is therefore the use of an organometallic framework according to the invention as a shaped body.
• Preferred methods here are the extrusion or tableting.
• other materials such as binders, lubricants or other additives may be added to the organometallic framework.
• mixtures of framework material and other desiccants are prepared as shaped articles or separately give shaped articles, which are then used as shaped-body mixtures.
• pellets such as disc-shaped pellets, pills, spheres, granules, extrudates such as strands, honeycomb, mesh or hollow body may be mentioned.
• Component B is preferably present as a shaped body.
• Preferred embodiments are tablets and strand-like extrudates.
• the shaped bodies preferably extend in at least one dimension of the space in the range from 0.2 mm to 30 mm, more preferably from 0.5 mm to 5 mm, in particular from 1 mm to 3 mm.
• the middle weight of the mixture is typically in the range of 0.2 to 0.7 Kg / L.
• the framework material can then be further processed according to the method described above to give a shaped body.
• Kneading and molding may be done according to any suitable method as described, for example, in Ullmanns Enzyklopadie der Technischen Chemie, 4th Edition, Volume 2, pp. 313 et seq. (1972), the contents of which are incorporated by reference in the context of the present application in its entirety ,
• pellets and / or tablets are produced.
• the kneading and / or shaping can be at elevated temperatures such as in the range of room temperature to 300 0 C and / or at elevated pressure such as in the range of atmospheric pressure up to some hundred bar and / or in an inert gas atmosphere such as in the presence of at least one noble gas, nitrogen or a mixture of two or more thereof.
• binders may be both viscosity-increasing and viscosity-reducing compounds.
• Preferred binders include, for example, alumina or alumina-containing binders such as those described in WO 94/29408, silica such as described in EP 0 592 050 A1, mixtures of silica and alumina, such as those described in U.S.
• clay minerals as described for example in JP 03-037156 A, for example, montmorillonite, kaolin, bentonite, halloysite, Dickit, Nacrit and anauxite, alkoxysilanes, as described for example in EP 0 102 544 B1
• tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, or trialkoxysilanes such as trimethoxysilane, triethoxysilane, tripropoxysilane, tributoxysilane, alkoxytitanates, for example Tetraalkoxytitanate such as tetra methoxytitanat, tetraethoxy titanate, tetrapropoxy titanate, tetrabutox ytitanat, or, for example, trialkoxy
• an organic compound and / or a hydrophilic polymer such as cellulose or a cellulose derivative such as methylcellulose and / or a polyacrylate and / or a polymethacrylate and / or a polyvinyl alcohol and / or or a polyvinylpyrrolidone and / or a polyisobutene and / or a polytetrahydrofuran.
• a pasting agent inter alia, preferably water or at least one alcohol such as a monoalcohol having 1 to 4 carbon atoms such as methanol, ethanol, n-propanol, iso-propanol, 1-butanol, 2-butanol, 2-methyl-1 propanol or 2-methyl-2-propanol or a mixture of water and at least one of said alcohols or a polyhydric alcohol such as a glycol, preferably a water-miscible polyhydric alcohol, alone or in admixture with water and / or at least one of said monohydric alcohols are used.
• a monoalcohol having 1 to 4 carbon atoms such as methanol, ethanol, n-propanol, iso-propanol, 1-butanol, 2-butanol, 2-methyl-1 propanol or 2-methyl-2-propanol or a mixture of water and at least one of said alcohols or a polyhydric alcohol such as a glycol, preferably
• the order of the additives is basically not critical.
• the molding obtained according to kneading and / or molding is subjected to at least one drying, which generally takes place at a temperature in the range from 25 to 300 ° C., preferably in the range from 50 to 300 ° C. and more preferably in the range from 100 to 300 0 C is performed. It is also possible to dry in vacuo or under a protective gas atmosphere or by spray drying.
• At least one of the compounds added as additives is at least partially removed from the shaped body.
• the use according to the invention for drying takes place in that the organic liquid is brought into contact with the metal-porous organometallic framework material. This can be done by static or dynamic drying. In the static drying of the organic liquid, the desiccant is set and removed again, wherein in the dynamic drying, the organic liquid flows through the desiccant.
• the porous organometallic framework material may itself be subjected to a drying step by heating prior to the use according to the invention.
• the porous organometallic framework material is activated in the sense of the present invention.
• the metal-organic framework materials are activated by that they are heated to about 100 0 C to 200 0 C. This may be accompanied by application of vacuum or use of inert gas such as nitrogen. This can be removed in addition to traces of water and carbon dioxide, thus increasing the water absorption capacity.
• porous organometallic framework material may be regenerated by heating after it has absorbed water.
• the degree of water absorption can be determined by a change in color.
• the organic liquid may be any organic liquid. Typically, it is an organic solvent or mixture of organic solvents having a certain degree of water.
• the organic liquid is preferably an alcohol, an ether, an ester, a ketone, an amide, an optionally halogenated hydrocarbon, a nitrile, an amine, a sulfur-containing organic liquid, a nitro compound or a mixture thereof.
• organic liquid examples include disinfectants, inorganic or organic solvents, fuels - in particular gasoline or diesel -, hydraulic Nk-, radiator fluid, brake fluid or an oil, especially machine oil.
• the organic liquid may be halogenated aliphatic or aromatic, cyclic or acyclic hydrocarbons or mixtures thereof.
• heptanol 100 g of heptanol are placed in an Erlenmeyer flask and 1 g of water was added. 10 g of the framework obtained according to Example 1 are predried at 140 ° C in a vacuum oven for 16 h and added to the heptanol. The suspension is stirred by means of a magnetic stirrer for 3 h at room temperature. The water content of the organic phase is determined at the start of the experiment (before the addition of the organometallic see framework material) and determined titrimetrically according to Karl Fischer at the end of the experiment. It is found that the water content of the organic phase has decreased by the drying of 1, 0 to 0.51 wt .-%.

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• 2009
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