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WO2008000694A2 - Stockage de gaz contenant de l'acétylène à l'aide de matériaux squelette organométalliques - Google Patents

Stockage de gaz contenant de l'acétylène à l'aide de matériaux squelette organométalliques Download PDF

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Publication number
WO2008000694A2
WO2008000694A2 PCT/EP2007/056231 EP2007056231W WO2008000694A2 WO 2008000694 A2 WO2008000694 A2 WO 2008000694A2 EP 2007056231 W EP2007056231 W EP 2007056231W WO 2008000694 A2 WO2008000694 A2 WO 2008000694A2
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WIPO (PCT)
Prior art keywords
acetylene
acid
framework material
gas
dicarboxylic acid
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PCT/EP2007/056231
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German (de)
English (en)
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WO2008000694A3 (fr
Inventor
Markus Schubert
Ulrich Mueller
Joerg Pastre
Kerstin Schierle-Arndt
Michael Triller
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BASF SE
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BASF SE
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Priority to DE112007001530T priority Critical patent/DE112007001530A5/de
Publication of WO2008000694A2 publication Critical patent/WO2008000694A2/fr
Publication of WO2008000694A3 publication Critical patent/WO2008000694A3/fr
Anticipated expiration legal-status Critical
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Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C11/00—Use of gas-solvents or gas-sorbents in vessels
    • F17C11/002—Use of gas-solvents or gas-sorbents in vessels for acetylene
    • 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]

Definitions

  • the present invention relates to processes for storing an acetylene-containing gas in a porous organometallic framework, a porous organometallic framework containing the gas, an acetylene gas pressure vessel containing the framework and their use.
  • Acetylene is an important starting material for the synthesis of numerous organic compounds, which are used among others in the production of plastics.
  • acetylene is used for burning, cutting and welding, since it generates a high temperature when it is burned.
  • acetylene is stored in compressed gas cylinders to hold this substance. It should be noted, however, that acetylene is a reactive substance. For this safety reason and the fact that compressed gas cylinders should contain as much acetylene, acetylene is usually not stored as pure substance in an otherwise empty cylinder, but it is rather acetylene in dissolved form, for example in acetone, or adsorptively attached to diatomaceous earth, in one Gas cylinder stored and stored accordingly.
  • porous materials to increase the storage capacity of gases, for example in compressed gas cylinders, is known in the art.
  • porous organometallic frameworks A particularly interesting class of substances here are porous organometallic frameworks. Their suitability for storing gases is described, for example, in WO-A 03/064030. The storage of gases in porous organometallic frameworks prepared by electrochemical means is described in WO-A 2005/049484.
  • porous organometallic framework materials for storing the special gas acetylene.
  • R. Matsuda et al. Nature 436 (2005), 238-241
  • R. Matsuda et al. describes the highly controlled acetylene incorporation in a microporous organometallic framework composed of copper and pyrazine-2,3-dicarboxylate in a pressure range up to 1 bar and at temperatures from about 0 to 40 ° C.
  • R. Matsuda et al. an organometallic framework for acetylene storage is proposed, there is a need for porous organometallic frameworks which have good properties for storing gases containing acetylene and moreover satisfy safety aspects.
  • porous organometallic frameworks are to be used, in particular in gas pressure vessels, for which the method described by R. Matsuda et al. examined pressure and temperature range is not suitable.
  • At least one object of the present invention is to provide such alternative porous organometallic frameworks as well as methods of storing acetylene-containing gases in these frameworks.
  • the object is achieved by a method for storing an acetylene-containing gas in a porous organometallic framework material, wherein the organometallic framework material contains at least one coordinated to at least one metal ion, at least bidentate organic compounds containing the step
  • organometallic framework is copper-free.
  • porous organometallic frameworks which have stored acetylene are thermally more stable if they have no copper. Since the thermal decomposition of the storage material is a critical factor in the storage and provision of acetylene, especially in gas pressure vessels, attention should be paid to an appropriate choice for the constituents of the organometallic framework.
  • the thermal decomposition temperature for example as the onset temperature in dynamic differential calometry, should be at least 110 ° C., preferably at least 125 ° C., more preferably at least 140 ° C., more preferably at least 160 ° C., even more preferably at least 200 ° C and particularly preferably at least 220 ° C, amount.
  • the term "copper-free” is to be understood as meaning that the at least one metal ion involved in the construction of the skeleton of the porous organometallic framework material is not a copper ion Copper ion is, in Essentially not be replaced by copper in the sense of a doping. Likewise, essentially no copper should be present in the pores of the porous organometallic framework.
  • the term "copper-free” is preferably to be understood as meaning that the proportion of copper in the form of its ions or in metallic form in the porous organometallic framework is less than 100 ppm, based on the total weight of the porous organometallic framework 25 ppm and very particularly preferably the maximum content is less than 10 ppm. Particularly preferred in the porous organometallic framework material for the process according to the invention, no copper can be detected.
  • the acetylene-containing gas is a gas which, in addition to acetylene, may contain other gases.
  • inert gases such as nitrogen, helium, neon, argon or mixtures thereof may be mentioned here.
  • the proportion of acetylene in the acetylene-containing gas is preferably at least 10% by volume. More preferably, the proportion of acetylene in the acetylene-containing gas is at least 25% by volume, more preferably at least 50% by volume, more preferably at least 60% by volume, still more preferably at least 75% by volume, and still more preferably at least 80% by volume, more preferably at least 90%.
  • the acetylene-containing gas may also be pure acetylene or acetylene in the commercial purity stages.
  • the acetylene-containing gas may also contain acetylene having a purity of at least 90% by volume, more preferably at least 95% by volume, still more preferably at least 99% by volume, and most preferably at least 99.5% by volume. % be.
  • the porous organometallic framework material which serves to store the gas containing acetylene contains at least one at least one bidentate organic compound coordinated to at least one metal ion.
  • This metal organic framework is described, for example, in US Pat. No. 5,648,508, EP-A AO 790,253, MO Keeffe et al., J. Sol. State Chem., 152 (2000), pages 3 to 20, H. Li et al., Nature 402 (1999), page 276, M. Eddaoudi et al., Topics in Catalysis 9 (1999), pages 105 to 11 1 , B. Chen et al., Science 291 (2001), pages 1021 to 1023, DE-A-101 1 1 230 and AC Sudik et al., J. Am. Chem. Soc. 127 (2005), 71 10-7118.
  • the organometallic framework suitable for storing the acetylene-containing gas typically contains a metal ion that is not copper ion.
  • more than one metal ion is present in the porous metal-organic framework.
  • This at least one further metal ion can be located in the pores of the organometallic framework or be involved in the construction of the framework lattice. In the latter case, such a metal ion would also bind the at least one at least bidentate organic compound or a further at least bidentate organic compound.
  • any metal ion other than copper ions can be considered, which is suitably suitable for being part of the porous organometallic framework material. If more than one metal ion is contained in the porous organometallic framework material, these may be present in a stoichiometric or non-stoichiometric amount. If coordination sites are occupied by a further metal ion and this is in a non-stoichiometric relationship to one of the abovementioned metal ions, such a porous organometallic framework material can be regarded as a doped framework material. The preparation of such doped organometallic frameworks in general is described in 10 2005 053430.
  • porous organometallic framework may be impregnated with another metal in the form of a metal salt.
  • a method for impregnation is described for example in EP-A 1070538.
  • another metal ion is in stoichiometric relation to the first metal ion, then it is mixed organometallic frameworks. In this case, the further metal ion may be involved in the framework construction or not.
  • the framework material may be polymeric or polyhedra.
  • the organometallic framework suitable for storing the acetylene-containing gas typically contains only one metal ion which is not copper ion.
  • the metal component in the framework material according to the present invention is preferably selected from Groups Ia, IIa, IMa, IVa to Villa and Ib to VIb of the Periodic Table of the Elements without copper.
  • Mg, Ca, Sr, Ba, Sc, Y, a lanthanide Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ro, Os, Co, Rh, Ir, Ni, Pd, Pt, Au, Zn, Cd, Hg, Al, Ga, In, Tl, Si, Ge, Sn, Pb, As, Sb and Bi.
  • Mg, Sc, Y, a lanthanide, Ti, Zr, Mn, Fe, Co, Ni, Zn, Al and In further more preferred are Mg, Y, La, Zr, Ce, Sc, Fe, Co, Zn, Al and In.
  • Mg, Al, Zn, Fe, In, Sc and Y are particularly preferred.
  • Preferred ions are Mg 2+ , Sc 3+ , Y 3+ , La 3+ , Ce 4+ , Ti 3+ , Zr 4+ , Mn 3+ , Mn 2+ , Fe 3+ , Fe 2+ , Co 3+ , Co 2+ , Ni 2+ , Ni + , Zn 2+ , Al 3+ and In 3+ . More preferred ions are Mg 2+ , Y 3+ , La 3+ , Zr 4+ , Ce 4+ , Sc 3+ , Fe 3+ , Co 2+ , Co 3+ , Zn 2+ , Al 3+ and In 3 + . Most preferred ions are Mg 2+ , Al 3+ , Zn 2+ , Fe 2+ , In 3+ , Sc 3+ and Y 3+ .
  • Lanthanides (Ln) in the context of the present invention are La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm and Yb.
  • At least bidentate organic compound refers to an organic compound containing at least one functional group capable of having at least two, preferably two coordinative, bonds to a given metal ion, and / or to two or more, preferably two, metal atoms, respectively to form a coordi- native bond.
  • 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 , -Ge (SH) 4 , -Sn (SH) 3 , -PO 3 H, -AsO 3 H , -AsO 4 H, -P (SH) 3 , -As (SH) 3 , -CH (RSH) 2 , -C (RSH) 3 -CH (RNH 2 ), -C (RNH 2 ) 3 , -CH (ROH) 2 , -C (ROH) 3 , -CH (RCN) 2 , -C (RCN) 3 where, for example, R preferably represents an alkylene group
  • 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 containing 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 an 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. Methane, adamantane, acetylene, ethylene or butadiene are particularly preferred in this case.
  • the aromatic compound or the aromatic part of both aromatic and aliphatic compound may have one or more cores, such as two, three, four or five cores, wherein the cores may be separated from each other and / or at least two nuclei in condensed form.
  • the aromatic compound or the aromatic part of the both aliphatic and aromatic compound 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.
  • the aromatic or aromatic moiety of the both aromatic and aliphatic compounds contains one or two C 6 nuclei, wherein the two nuclei are either separately or in condensed form.
  • aromatic compounds benzene, naphthalene and / or biphenyl and / or bipyridyl and / or pyridyl may be mentioned as aromatic compounds.
  • the at least one at least bidentate organic compound is preferably derived from 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.
  • 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.
  • Halides are F, Cl, Br, I; in particular F, Cl, Br.
  • 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 “inferred” means that one or more carboxylic acid functions can be replaced by a sulfone (-SO 3 H).
  • a sulfonic acid group may additionally be added to the 2, 3 or 4 carboxylic acid functions.
  • the di-, tri- or tetracarboxylic acid has, in addition to the abovementioned functional groups, an organic main body or an organic compound to which these are bonded.
  • the abovementioned functional groups may 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 coordinative bond for the preparation of the framework.
  • the organic compounds 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 compounds contains 1 to 18, 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. Methane, adamantane, acetylene, ethylene or butadiene are particularly preferred in this case.
  • the aromatic compound or the aromatic part of both the aromatic and the aliphatic compound may contain one or more nuclei, for example se have two, three, four or five cores, wherein the cores can be separated from each other and / or at least two cores in condensed form.
  • the aromatic compound or the aromatic part of the both aliphatic and aromatic compound one, two or three nuclei, with one or two nuclei being particularly preferred.
  • each nucleus of the compound mentioned may contain at least one heteroatom, such as, for example, N, O, S, B, P, Si, preferably N, O and / or S.
  • the aromatic compound or the aromatic moiety of the both aromatic and aliphatic compounds contains one or two C 6 cores, the two being either separately or in condensed form.
  • Benzene, naphthalene and / or biphenyl and / or bipyridyl and / or pyridyl may in particular be mentioned as aromatic compounds.
  • the organic compound is an aliphatic or aromatic, acyclic or cyclic hydrocarbon having 1 to 18, preferably 1 to 10 and in particular 6 carbon atoms, which additionally has only 2, 3 or 4 carboxyl groups as functional groups.
  • the at least bidentate organic compound is derived from a dicarboxylic acid, such as oxalic, succinic, tartaric, 1,4-butanedicarboxylic, 1,4-butenedicarboxylic, 4-oxo-pyran-2,6-dicarboxylic, 1 , 6- hexanedicarboxylic acid, decanedicarboxylic acid, 1,8-heptadecane dicarboxylic acid, 1,9-heptadecane dicarboxylic 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, imi
  • 2,8-dicarboxylic acid diimidedicarboxylic acid, pyridine-2,6-dicarboxylic acid, 2-methylimidazole-4,5-dicarboxylic acid, thiophene-3,4-dicar carboxylic acid, 2-isopropylimidazole-4,5-dicarboxylic acid, tetrahydropyran-4,4-dicarboxylic acid, perylene-3,9-dicarboxylic acid, perylenedicarboxylic acid, pluriol E 200-dicarboxylic acid, 3,6-dioxaoctanedicarboxylic acid, 3, 5-cyclohexadiene-1,2-dicarboxylic acid, octadicarboxylic acid, pentane-3,3-carboxylic acid, 4,4'-diamino-1,1'-diphenyl-3,3'-dicarboxylic acid, 4,4'-diaminodiphenyl 3,3'-dicar
  • 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
  • an at least bidentate organic compound derived from a tetracarboxylic acid such as
  • the at least bidentate organic compound is one of the above exemplified tetracarboxylic acids as such.
  • 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.
  • At least bidentate organic compounds are acetylenedicarboxylic acid (ADC), campherdicarboxylic acid, fumaric acid, succinic acid, benzenedicarboxylic acids, naphthalenedicarboxylic acids, biphenyldicarboxylic acids such as 4,4'-biphenyldicarboxylic acid (BPDC), pyrazinedicarboxylic acids such as 2,5-pyrazinedicarboxylic acid, bipyridinedicarboxylic acids such as 2, 2'-bipyridine dicarboxylic acids such as, for example, 2,2'-bipyridine-5,5'-dicarboxylic acid, benzene tricarboxylic acids such as 1,2,3-, 1, 2,4-benzenetricarboxylic acid or 1,3,5-benzenetricarboxylic acid (BTC), Benzene tetracarboxylic acid, adamantane tetracarboxylic acid (BTC
  • phthalic acid isophthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,2,3-benzenetricarboxylic acid, 1, 2,4-benzenetricarboxylic acid, 1, 3,5-benzenetricarboxylic acid or 1, 2,4,5-benzenetetracarboxylic acid.
  • the organometallic framework suitable for storing the acetylene-containing gas may contain one or more of the above-identified at least diazo-dense organic compounds.
  • 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 at least one at least bidentate organic compound preferably contains no hydroxyl or phosphonic acid groups.
  • one or more carboxylic acid functions can be replaced by a sulfonic acid function.
  • a sulfonic acid group may additionally be present.
  • all carboxylic acid functions are replaced by a sulfonic acid function.
  • Such sulfonic acids or their salts are, for example, 4-amino-5-hydroxynaphthalene-2,7-disulfonic acid, 1-amino-8-naphthol-3,6-disulfonic acid, 2-hydroxynaphthalene-3, 6-disulfonic acid, benzene-1,3-disulfonic acid, 1,8-dihydroxynaphthalene-3,6-disulfonic acid, 1,2-dihydroxybenzene-3,5-disulfonic acid, 4,5-dihydroxynaphthalene-2,7- disulfonic acid, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthrolinedisulfonic acid, 4,7-diphenyl-1,10-phenanthrolinedisulfonic acid, ethane-1,2-disulfonic acid, naphthalene-1, 5 disulfonic acid, 2- (4-nitrophenylazo) -1,
  • the organometallic frameworks which are suitable for storing the acetylene-containing gas 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 (1985), pages 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 area - calculated according to the Langmuir model (DIN 66131, 66134) - for a MOF in powder form is more than 5 m 2 / g, more preferably more than 10 m 2 / g, more preferably more than 50 m 2 / g, more preferably more than 500 m 2 / g, more preferably more than 1000 m 2 / g, in particular more than 1500 m 2 / g.
  • Moldings of organometallic frameworks may have a lower specific surface area; but preferably more than 10 m 2 / g, more preferably more than 50 m 2 / g, even more preferably more than 500 m 2 / g, in particular more than 1000 m 2 / g.
  • the pore size of the porous 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, more preferably the pore size is in the range from 0.3 nm to 3 nm, based on the crystalline material.
  • pores also occur whose size distribution can vary.
  • 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 in a diameter range of up to 10 nm.
  • the pore distribution can be determined by means of mercury porosimetry.
  • the organometallic framework material can be present in powder form or as an agglomerate.
  • the framework material may be used as such or it may be placed in a mold body transformed.
  • another aspect of the present invention is a molded article containing the organometallic framework suitable for storing the acetylene-containing gas.
  • the framework material may include other materials such as binders, lubricants, or other additives added during manufacture. It is also conceivable that the framework material has further constituents, such as absorbents such as activated carbon or the like.
  • pellets such as disc-shaped pellets, pills, spheres, granules, extrudates such as strands, honeycomb, mesh or hollow body may be mentioned.
  • Kneading / mulling and shaping can be carried out according to any suitable method, as described, for example, in Ullmanns Enzyklopadie der Technischen Chemie, 4th edition, volume 2, p. 313 et seq. (1972).
  • the kneading / hulling and / or shaping by means of a reciprocating press, roller press in the presence or absence of at least one binder material, compounding, pelleting, tableting, extrusion, co-extruding, foaming, spinning, coating, granulation, preferably spray granulation, spraying, spray drying or a combination of two or more of these methods.
  • pellets and / or tablets are produced.
  • Kneading and / or molding may be carried out at elevated temperatures such as, for example, in the range of room temperature to 300 ° C and / or elevated pressure such as in the range of normal pressure up to a few hundred bar and / or in a protective gas atmosphere such as in the presence of at least one Noble gas, nitrogen or a mixture of two or more thereof.
  • elevated temperatures such as, for example, in the range of room temperature to 300 ° C and / or elevated pressure such as in the range of normal pressure up to a few hundred bar and / or in a protective 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, dickite, nacrit and anauxite, alkoxysilanes, as described for example in EP 0 102 544 B1, for example tetraalkoxysilanes such as, for example, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane or, for example, trialkoxysilanes such as trimethoxysilane, triethoxysilane, tripropoxysilane, tributoxysilane, alkoxytitanates, for example tetraalkoxytitanates such as tetramethoxytitanate, tetraethoxytitanate, tetrapropoxytitanate, tetrabut
  • an organic compound and / or a hydrophilic polymer such as cellulose or a CeIIU losederivat such as methylcellulose and / or a polyacrylate and / or a polymethacrylate and / or a polyvinyl alcohol and / or a polyvinylpyrrolidone and / or a polyisobutene and / or a polytetrahydrofuran and / or a polyethylene oxide.
  • 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 glyco
  • the order of the additives such as template compound, binder, pasting agent, viscosity-increasing substance in the molding and kneading is basically not critical.
  • the molding obtained according to kneading and / or molding is subjected to at least one drying, generally at a temperature in the range of 25 to 500 ° C, preferably in the range of 50 to 500 ° C and more preferably in the range of 100 to 350 ° C is performed. It is also possible to dry in vacuo or under a protective gas atmosphere or by spray drying.
  • the inventive method of storing an acetylene-containing gas includes the step of contacting the acetylene-containing gas with the organometallic framework described above. This can be done by methods known to those skilled in the art. Typically, the storage is carried out by appropriately passing or pressing on the gas so that it is adsorbed by the porous organometallic framework material for the purpose of storage. As well as the delivery, the recording can be done by appropriate change in temperature and / or pressure.
  • the contacting of the acetylene-containing gas with the organometallic framework material leads to the absorption of the acetylene-containing gas in the organometallic framework material, so that the gas is stored in the framework material.
  • the organometallic framework material is copper-free, the acetylene-containing gas can be provided in stored form in a technically secure manner.
  • Another object of the present invention is therefore a porous metallor- ganisches scaffold material containing at least one coordinated to at least one metal ion, at least bidentate organic compound, wherein in the organic framework material, an acetylene-containing gas is stored, wherein the framework material is copper-free.
  • the porous organometallic framework according to the invention therefore differs from the above-described framework materials used in the inventive method for storing an acetylene-containing gas in that the framework materials according to the invention have stored the acetylene-containing gas.
  • organometallic framework materials according to the invention can thus be obtained by the process according to the invention for storing an acetylene-containing gas.
  • a further subject of the present invention is an acetylene gas pressure vessel containing the inventive at least one porous organometallic framework material, which contains the acetylene-containing gas in stored form.
  • the gas pressure tank should be designed so that the maximum filling pressure at room temperature can be at least 10 bar (absolute). Typically, however, the maximum storage pressure of the acetylene, ie the pressure with which a gas pressure vessel is exposed to acetylene, will often be lower.
  • the maximum storage pressure should be at least 2 bar (absolute), preferably at least 5 bar (absolute) and in particular at least 10 bar (absolute), but less than the maximum filling pressure.
  • a maximum gas density of at least 10 g of acetylene per liter of container volume should be possible. More preferably, the maximum gas density is at least 15 g, more preferably at least 20 g, even more preferably at least 25 g, even more preferably at least 35 g, in particular at least 50 g per liter of container volume.
  • Suitable gas pressure vessels are known in the art.
  • the shape of the gas pressure vessel can be adapted to the respective intended use.
  • free-form containers but also cylindrical containers are possible.
  • such gas pressure vessels are provided with an inlet and / or outlet valve.
  • the acetylene-containing gas is pressed to the desired filling pressure in the container.
  • a pressure gradient between see a filling and the container to be filled sufficient.
  • compressors are used for filling.
  • Suitable compressed gas containers are, for example, compressed gas cylinders or boilers.
  • the empty gas pressure vessel is filled with the above-described, still containing no acetylene-containing gas, organometallic framework material before the acetylene-containing gas is pressed. It can be received via a separate opening of the gas pressure tank. It is also possible to use the opening which is provided for receiving a valve, for filling the organometallic framework material.
  • a gas pressure vessel may be completely or partially filled with the organometallic framework. This is available as a powder or shaped bed.
  • the gas pressure vessel according to the invention may contain other sorbents, gases and / or solvents, such as acetone, DMF, for the acetylene-containing gas or other gases.
  • the organometallic framework material may already contain a solvent such as acetone or DMF before filling the gas pressure vessel. This solvent may already be present by the preparation of the organometallic framework.
  • a filter is provided in or on the gas pressure vessel according to the invention, which prevents organometallic framework material from escaping from the gas pressure vessel in an uncontrolled manner and optionally clogging an existing valve.
  • the filter or at least one further filter can serve to ensure that the storage capacity of the organometallic framework material negatively influencing substances come into contact with the framework material.
  • This may be, for example, residual water, which may be part of the acetylene-containing gas.
  • Another object of the present invention is the use of an organometallic framework material containing at least one at least one metal ion coordinate bound, at least bidentate organic compound, wherein the framework material is copper-free, for storing an acetylene-containing gas.
  • another object of the present invention is the use of an acetylene gas pressure vessel according to the invention for the storage, supply and delivery of acetylene for at least one technical application that requires acetylene.
  • Such applications may be burning, cutting, welding or chemical reaction.
  • the combustion of the acetylene-containing gas can also be carried out under low oxygen, whereby acetylene black is obtained, which can be used as a filter cloth and in the production of water and oil paints.
  • the chemical reaction may be the polymerization of acetylene.
  • Other chemical reactions in which the acetylene-containing acetylene containing acetylene can be used as starting material are the preparation of vinyl chloride, acyl nitrile, chlorophen rubber, vinyl acetate, 1, 4-butanediol, tetrahydrofuran (THF), acrylic acid and esters thereof.
  • the porous organometallic frameworks according to the invention which contain acetylene, are suitable as security explosive.
  • Safety explosives are typically characterized by the fact that their ignition requires an external energy source, such as another conventional ignition charge. Therefore, another object of the present invention is the use of a framework according to the invention as a security explosive.
  • DSC Dynamic Differential Scalometry
  • the DSC is a screening method that allows the detection of temperatures at which potentially hazardous exothermic reactions occur.
  • the samples must be representative of the substance to be examined.
  • TRAS 410 technical regulation for plant safety
  • the maximum temperature to be assumed is at least 100 K below the onset temperature.
  • Deviation from this rule is possible if sufficient additional information about, for example, the activation energy or the sensitivity of the DSC devices used is available and taken into account as judged by the experts.
  • Adhering to the recommended safety margin this is roughly equivalent to an adiabatic induction time of one day. In general, this time is sufficient to detect a "runaway" of the reaction and initiate countermeasures, and in the case of large-scale storage and gas-forming systems, the safety margin may need to be significantly increased.
  • DSC Dynamic Differential Scalometry
  • V4A pressure-tight crucible
  • a predetermined temperature program for example, 2.5 K / min.
  • the heat flow from and to the sample is determined from the temperature difference between the sample and an inert comparative sample in a defined thermal contact with the sample. Onset and peak temperatures can be determined here.
  • the onset temperature is the oven temperature at which the beginning of a noticeable exothermic reaction can be detected in the sample.
  • the peak temperature is the oven temperature at which the deflection of the measurement signal from the baseline becomes maximum.
  • Example 1 DSC of acetylene in Al-terephthalic acid MOF
  • the experimental apparatus for the DSC measurement is a commercial instrument from Mettler (TA 8000).
  • the test substance is filled into a pressure-tight crucible (300 ⁇ l) of Hastelloy C. Subsequently, the crucible is filled from a gas cylinder with acetylene at a pressure of 1, 1 bar. Purely mathematically, an empty crucible should be at this pressure take only about 0.38 mg of acetylene.
  • the reference crucible is empty. It is then heated at a rate of 2.5 K / min.
  • the energy E (mW / mg) is plotted as a function of the temperature in ° C.
  • Comparative Example 2 DSC of acetylene in a Cu-benzenetricarboxylic acid MOF 27.8 kg of anhydrous CuSO 4 are suspended together with 12.84 kg of 1,3,5-benzenetricarboxylic acid in 330 kg of ethylene glycol and covered with N 2 .
  • the kettle is brought to 110 ° C and the synthesis mixture kept at this temperature for 12 h with stirring.
  • the solution is cooled to 50 ° C and filtered under N 2 - cover with a pressure filter.
  • the filter cake is washed with 4 ⁇ 50 l of methanol and blown dry with nitrogen for 96 h.
  • the sample Before the surface determination, the sample is evacuated at 1 10 0 C for 2 h each.
  • the N 2 surface is 2096 m 2 / g.
  • T 1 peak temperature of 95 ° C
  • T 2 139 ° C
  • T 3 peak temperature of 170 ° C
  • T 4 307 ° C
  • Example 3 DSC of acetylene in a Mg-2,6-naphthalenedicarboxylic acid MOF
  • Example 4 DSC of Acetylene in a Zn-Terephthalic Acid MOF (MOF-5)
  • Example 5 DSC of acetylene in a sc-terephthalic acid MOF 4 g of Sc (NO 3) 3 * H 2 O and 4 g of terephthalic acid (BDC) are dissolved in 350 ml of DMF and stirred at 130 ° C. for 19 h. The resulting solid is filtered off, washed with 2 x 50 ml of DMF and 3 x 50 ml of methanol for 17 h pre-dried in a vacuum oven at 200 ° C. Finally, the material is calcined for 48 hours at 290 ° C in a muffle furnace (100 l / h air).
  • the framework material has after activation at 200 ° C in a high vacuum for several hours in the surface determination with N 2 68 m 2 / g (Langmuir evaluation).

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Filling Or Discharging Of Gas Storage Vessels (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

L'invention concerne des procédés permettant le stockage d'un gaz contenant de l'acétylène dans un matériau squelette organométallique poreux, ce dernier contenant au moins un composé au moins bidenté, organique, qui est fixé par liaison de coordinatin à un ion métallique. Le procédé de l'invention comprend l'étape de mise en contact du gaz contenant l'acétylène avec un matériau squelette organométallique, ce dernier étant exempt de cuivre. L'invention concerne également un matériau squelette organométallique poreux qui contient le gaz contenant de l'acétylène et un récipient à pression gazeuse d'acétylène correspondant ainsi que leur utilisation.
PCT/EP2007/056231 2006-06-26 2007-06-22 Stockage de gaz contenant de l'acétylène à l'aide de matériaux squelette organométalliques Ceased WO2008000694A2 (fr)

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DE112007001530T DE112007001530A5 (de) 2006-06-26 2007-06-22 Speicherung von acetylenhaltigen Gasen mit Hilfe von metallorganischen Gerüstmaterialien

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EP06116016.4 2006-06-26
EP06116016 2006-06-26

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Cited By (11)

* Cited by examiner, † Cited by third party
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DE102008023481A1 (de) * 2008-05-14 2009-11-19 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Wärmeleitfähige Komposit-Adsorbentien sowie Verfahren zu deren Herstellung
US8507406B2 (en) 2010-08-12 2013-08-13 The Board Of Regents Of The University Of Texas System Zn4(OH)2(1,2,4-BTC)2—a rod packing microporous metal-organic framework with open metal sites for selective separation and sensing of small molecules
US8597406B2 (en) 2010-04-27 2013-12-03 Board Of Regents, The University Of Texas System Isoreticular metal-organic framework of the formula Zn4O(FMA)3
US8664419B2 (en) 2010-04-30 2014-03-04 The Board Of Regents Of The University Of Texas System Acetylene storage using metal-organic frameworks of the formula M2(2,5-dihydroxyterephthalate)
US9114348B2 (en) 2008-04-29 2015-08-25 Universitetet I Oslo Metal organic framework compounds
US9120080B2 (en) 2010-02-10 2015-09-01 The Board Of Regents Of The University Of Texas System Acetylene storage using metal-organic frameworks with open metal sites
US9127025B2 (en) 2011-08-19 2015-09-08 The Board Of Regents Of The University Of Texas System Zn5(BTA)6(TDA)2—a robust highly interpenetrated metal-organic framework constructed from pentanuclear clusters for selective sorption of gas molecules
US9296773B2 (en) 2012-01-17 2016-03-29 The Board Of Regents Of The University Of Texas System Zn3(BDC)3[Cu(SalPycy)] and Zn3(CDC)3[Cu(SalPycy)]—enantiopure mixed metal-organic frameworks for selective separations and enantioselective recognition
CN112661594A (zh) * 2020-12-11 2021-04-16 太原理工大学 一种混合气中乙炔的高效分离方法
US11958034B2 (en) 2020-03-31 2024-04-16 Numat Technologies, Inc. Activated amino containing metal organic framework (MOF) compositions, process of making and process of use thereof
US11958033B2 (en) 2020-03-31 2024-04-16 Numat Technologies, Inc. Modified metal-organic framework (MOF) compositions, process of making and process of use thereof

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US5648508A (en) * 1995-11-22 1997-07-15 Nalco Chemical Company Crystalline metal-organic microporous materials
US6929679B2 (en) * 2002-02-01 2005-08-16 Basf Aktiengesellschaft Method of storing, uptaking, releasing of gases by novel framework materials
DE10355087A1 (de) * 2003-11-24 2005-06-09 Basf Ag Verfahren zur elektrochemischen Herstellung eines kristallinen porösen metallorganischen Gerüstmaterials
DE102005039623A1 (de) * 2005-08-22 2007-03-01 Basf Ag Verfahren zur Herstellung von metallorganischen Gerüstmaterialien Hauptgruppen Metallionen enthaltend
DE102005053430A1 (de) * 2005-11-09 2007-05-16 Basf Ag Dotierte metallorganische Gerüstmaterialien
DE102005054636A1 (de) * 2005-11-16 2007-05-24 Basf Ag Metallorganische Gerüstmaterialien der III. Nebengruppe
US8115024B2 (en) * 2006-02-10 2012-02-14 Basf Aktiengesellschaft Process for preparing porous metal-organic framework materials

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9114348B2 (en) 2008-04-29 2015-08-25 Universitetet I Oslo Metal organic framework compounds
DE102008023481B4 (de) * 2008-05-14 2013-10-10 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Wärmeleitfähige Komposit-Adsorbentien sowie Verfahren zu deren Herstellung und deren Verwendung
DE102008023481A1 (de) * 2008-05-14 2009-11-19 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Wärmeleitfähige Komposit-Adsorbentien sowie Verfahren zu deren Herstellung
US9120080B2 (en) 2010-02-10 2015-09-01 The Board Of Regents Of The University Of Texas System Acetylene storage using metal-organic frameworks with open metal sites
US8597406B2 (en) 2010-04-27 2013-12-03 Board Of Regents, The University Of Texas System Isoreticular metal-organic framework of the formula Zn4O(FMA)3
US8664419B2 (en) 2010-04-30 2014-03-04 The Board Of Regents Of The University Of Texas System Acetylene storage using metal-organic frameworks of the formula M2(2,5-dihydroxyterephthalate)
US8507406B2 (en) 2010-08-12 2013-08-13 The Board Of Regents Of The University Of Texas System Zn4(OH)2(1,2,4-BTC)2—a rod packing microporous metal-organic framework with open metal sites for selective separation and sensing of small molecules
US9127025B2 (en) 2011-08-19 2015-09-08 The Board Of Regents Of The University Of Texas System Zn5(BTA)6(TDA)2—a robust highly interpenetrated metal-organic framework constructed from pentanuclear clusters for selective sorption of gas molecules
US9296773B2 (en) 2012-01-17 2016-03-29 The Board Of Regents Of The University Of Texas System Zn3(BDC)3[Cu(SalPycy)] and Zn3(CDC)3[Cu(SalPycy)]—enantiopure mixed metal-organic frameworks for selective separations and enantioselective recognition
US11958034B2 (en) 2020-03-31 2024-04-16 Numat Technologies, Inc. Activated amino containing metal organic framework (MOF) compositions, process of making and process of use thereof
US11958033B2 (en) 2020-03-31 2024-04-16 Numat Technologies, Inc. Modified metal-organic framework (MOF) compositions, process of making and process of use thereof
CN112661594A (zh) * 2020-12-11 2021-04-16 太原理工大学 一种混合气中乙炔的高效分离方法
CN112661594B (zh) * 2020-12-11 2023-04-21 太原理工大学 一种混合气中乙炔的高效分离方法

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