WO2008000694A2

WO2008000694A2 - Storage of acetylene-containing gases by means of metal-organic framework materials

Info

Publication number: WO2008000694A2
Application number: PCT/EP2007/056231
Authority: WO
Inventors: Markus Schubert; Ulrich Mueller; Joerg Pastre; Kerstin Schierle-Arndt; Michael Triller
Original assignee: Basf Se
Priority date: 2006-06-26
Filing date: 2007-06-22
Publication date: 2008-01-03
Also published as: DE112007001530A5; WO2008000694A3

Abstract

The invention relates to methods for storing an acetylene-containing gas in a porous metal-organic framework material, said metal-organic framework material containing at least one, at least bidentate compound that is coordinately bound to at least one metal ion. The method according to the invention comprises the step of contacting the acetylene-containing gas with the metal-organic framework material, the metal-organic framework material being copper-free. The invention also relates to a porous metal-organic framework material which contains the acetylene-containing gas and to a corresponding acetylene gas-pressure container and the use thereof.

Description

Storage of acetylene-containing gases with the help of organometallic frameworks

description

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. In addition, acetylene is used for burning, cutting and welding, since it generates a high temperature when it is burned.

Typically, 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.

The use of porous materials to increase the storage capacity of gases, for example in compressed gas cylinders, is known in the art.

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.

The general suitability of porous organometallic framework materials for storing the special gas acetylene is also known. R. Matsuda et al., Nature 436 (2005), 238-241, describe 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. Although 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. In this case, 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

Bringing the acetylene-containing gas into contact with the organometallic framework material,

wherein the organometallic framework is copper-free.

It has been found that 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.

In this case, 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.

In the context of the present invention, 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.

Therefore, 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. In particular, 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%.

However, the acetylene-containing gas may also be pure acetylene or acetylene in the commercial purity stages.

Thus, 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.

Scaffold materials from the prior art can be used for the porous organometallic framework material to be used, which is copper-free in the sense of the invention.

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 (MOF) 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.

However, it is also possible that 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.

In principle, 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.

In addition, the 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.

If 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. Particularly preferred are 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. More preferred are 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. Particularly preferred are Mg, Al, Zn, Fe, In, Sc and Y. With respect to the ions of these elements, mention is particularly made of Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Ba ²⁺ , Sc ³⁺ , Y ^{3 +} , Ti ⁴⁺ , Zr ⁴⁺ , Hf ⁴⁺ , V ⁴⁺ , V ³⁺ , V ²⁺ , Nb ³⁺ , Ta ³⁺ , Cr ³⁺ , Mo ³⁺ , W ³⁺ , Mn ³⁺ , Mn ²⁺ , Re ³⁺ , Re ²⁺ , Fe ³⁺ , Fe ²⁺ , Ru ³⁺ , Ru ²⁺ , Os ³⁺ , Os ²⁺ , Co ³⁺ , Co ²⁺ , Rh ²⁺ , Rh ⁺ , Ir ²⁺ , Ir ⁺ , Ni ²⁺ , Ni ⁺ , Pd ²⁺ , Pd ⁺ , Pt ²⁺ , Pt ⁺ , Au ⁺ , Zn ²⁺ , Cd ²⁺ , Hg ²⁺ , Al ³⁺ , Ga ^{3 +} , In ³⁺ , Tl ³⁺ , Si ⁴⁺ , Si ²⁺ , Ge ⁴⁺ , Ge ²⁺ , Sn ⁴⁺ , Sn ²⁺ , Pb ⁴⁺ , Pb ²⁺ , As ⁵⁺ , As ³⁺ , As ⁺ , Sb ⁵⁺ , Sb ³⁺ , Sb ⁺ , Bi ⁵⁺ , Bi ³⁺ , Bi ⁺ and Ln ³⁺ . 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.

The term "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 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 Cβ rings, which may be condensed and independently of each other may be suitably substituted with at least one substituent in each case, and / or independently of one another in each case at least one heteroatom such as may contain N, O and / or S. According to likewise preferred embodiments, functional groups are to be mentioned in which the abovementioned radical R is absent. In this regard, among others rem -CH (SH) ₂ , -C (SH) ₃ , -CH (NH ₂ ) ₂ , -C (NHz) ₃ , -CH (OH) ₂ , -C (OH) ₃ , -CH (CN) ₂ or - C (CN) ₃ To name.

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.

Preferably, 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. Particularly preferably, 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. Independently of each other, furthermore, 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. More preferably, 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. In particular, 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. 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. Halides are F, Cl, Br, I; in particular F, Cl, Br. In addition, 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. Sulfur analogues are the functional groups -C (= O) SH and its tautomer and C (= S) SH, which can be used instead of one or more carboxylic acid groups. Moreover, in the context of the present invention, the term "inferred" means that one or more carboxylic acid functions can be replaced by a sulfone (-SO ₃ H). In addition, 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. In this case, 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.

Preferably, 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. Particularly preferably, 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. Independently of each other, furthermore, 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. More preferably, 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.

More preferably, 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.

For example, 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, imidazole-2,4-dicarboxylic acid, 2-methylquinoline-3,4-dicarboxylic acid, quinoline-2,4-dicarboxylic acid , Quinoxaline-2,3-dicarboxylic acid, θ-chloroquinoxaline, Ⓒ, 4,4'-diaminophenylmethane-3,3'-dicarboxylic acid, quinoline-3,4-dicarboxylic acid, and 7-chloro-4-hydroxyquinoline. 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'-dicarboxylic acid, benzidine-3,3'-dicarboxylic acid, 1,4-bis (phenylamino) benzene-2,5-dicarboxylic acid, 1,1'-dinaphthyldicarboxylic acid, 7-chloro-8-methylquinoline-2 , 3-dicarboxylic acid, 1-anilinoanthraquinone-2,4'-dicarboxylic acid, polytetrahydrofuran-250-dicarboxylic acid, 1, 4-bis (carboxymethyl) -piperazine-2,3-dicarboxylic acid, 7-chloroquinoline-3, 8-dicarboxylic acid, 1- (4-carboxy) -phenyl-3- (4-chloro) -phenylpyrazoline-4,5-dicarboxylic acid, 1, 4,5,6,7,7, -hexachloro-5-norbornene 2,3-dicarboxylic acid, phenylindane dicarboxylic acid, 1, 3-dibenzyl-2-oxo-imidazolidine-4,5-dicarboxylic acid, 1 ^ -cyclohexanedicarboxylic acid, naphthalene-1, 8-dicarboxylic acid, 2-benzoylbenzene-1,3-dicarboxylic acid, 1,3-dibenzyl-2 - oxoimidazolidine-4,5-cis-dicarboxylic acid, 2,2'-biquinoline-4,4'-dicarboxylic acid, pyridine-3,4-dicarboxylic acid, 3,6,9-trioxaundecanedicarboxylic acid, hydroxybenzophenone dicarboxylic acid, Pluriol E 300 dicarboxylic acid, Pluriol E 400 dicarboxylic acid, Pluriol E 600 dicarboxylic acid, pyrazole-3,4-dicarboxylic acid, 2,3-pyrazine dicarboxylic acid, 5,6-dimethyl-2,3-pyrazine dicarboxylic acid, 4,4'-diaminodiphenyl ether diimide dicarboxylic acid, 4, 4'-diaminodiphenylmethanediimide dicarboxylic acid, 4,4'-diaminodiphenylsulfonediimide dicarboxylic acid, 1, 4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,3-adamantanedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 8- Methoxy-2,3-naphthalenedicarboxylic acid, 8-nitro-2,3-naphthalenecarboxylic acid, 8-sulfo-2,3-naphthalenedicarboxylic acid, anthracene-2,3-dicarboxylic acid, 2 ', 3'-diphenyl-p terphenyl-4,4'-dicarboxylic acid, diphenyl ether-4,4'-dicarboxylic acid, imidazole-4,5-dicarboxylic acid, 4 (1H) -oxothiochromene-2,8-dicarboxylic acid, 5-tert-butyl-1, 3 benzenedicarboxylic acid, 7,8-quinolinedicarboxylic acid, 4,5-imidazoledicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, hexatriacontanedicarboxylic acid, tetradecanedicarboxylic acid, 1,7-heptadicarboxylic acid, 5-hydroxy-1,3-benzenedicarboxylic acid, 2,5-dihydroxy- 1, 4-dicarboxylic acid, pyrazine-2,3-dicarboxylic acid, furan-2,5-dicarboxylic acid, 1-nonene-6,9-dicarboxylic acid, eicosendicarboxylic acid, 4,4'-dihydroxydiphenylmethane-3,3'-dicarboxylic acid, 1-amino-4-methyl-9,10-dioxo-9,10-dihydroanthracene-2,3-dicarboxylic acid, 2,5-pyridinedicarboxylic acid, cyclohexene-2,3-dicarboxylic acid, 2,9-dichlorofluorubin-4, 1 1 -dicarboxylic acid, 7-chloro-3-methylquinoline-6,8-dicarboxylic acid, 2,4-dichlorobenzophenone-2 ', 5'-dicarboxylic acid, 1, 3-benzenedicarboxylic acid, 2,6-pyridinedicarboxylic acid, 1-methylpyrrole -3,4-dicarboxylic acid, 1-benzyl-1 H-pyrrole-3,4-dicarboxylic acid, anthraquinone-1, 5 dicarboxylic acid, 3,5-pyrazoldicarboxylic acid, 2-nitrobenzene-1, 4-dicarboxylic acid, heptane-1, 7-dicarboxylic acid, cyclobutane-1,1-dicarboxylic acid 1, 14-tetradecanedicarboxylic acid, 5,6-dehydronorbornane-2,3-dicarboxylic acid , 5-ethyl-2,3-pyridinedicarboxylic acid or campestericarboxylic acid,

More preferably, the at least bidentate organic compound is one of the above exemplified dicarboxylic acid as such.

For example, the at least bidentate organic compound may be derived from a tricarboxylic acid, such as

2-Hydroxy-1,2,3-propanetricarboxylic acid, 7-chloro-2,3,8-quinolinetricarboxylic acid, 1,2,3-, 1,4-benzene tricarboxylic acid, 1,2,4-butanetricarboxylic acid, 2-phosphono 1, 2,4-butanetricarboxylic acid, 1, 3,5-benzenetricarboxylic acid, 1-hydroxy-1,2,3-propanetricarboxylic acid, 4,5-dihydro-4,5-dioxo-1H-pyrrolo [2, 3-F] quinoline-2,7,9-tricarboxylic acid, 5-acetyl-3-amino-6-methylbenzene-1, 2,4-tricarboxylic acid, 3-amino-5-benzoyl-6-methylbenzene-1, 2, 4-tricarboxylic acid, 1, 2,3-propanetricarboxylic acid or aurintricarboxylic acid. Furthermore, more preferably, the at least bidentate organic compound is one of the above-exemplified tricarboxylic acids as such.

Exemplary of an at least bidentate organic compound derived from a tetracarboxylic acid, such as

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-tetracarboxylic 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-hexaoxacyclooctadecane-2,3,11,12-tetracarboxylic acid, 1, 2,4,5-benzenetetracarboxylic acid, 1,2,11,12-dodecantetracarboxylic acid, 1, 2,5,6-hexane-tetracarboxylic acid, 1, 2,7,8-octanetetracarboxylic acid, 1, 4,5,8-naphthalenetetracarboxylic acid, 1,2,9,10-decantetracarboxylic acid, benzophenonetetracarboxylic acid, 3,3 ', 4,4'-benzophenetetracarboxylic acid, Tetrahydrofurantetracarboxylic acid or cyclopentanetetracarboxylic acids such as cyclopentane-1, 2,3,4-tetracarboxylic acid.

More preferably, the at least bidentate organic compound is one of the above exemplified tetracarboxylic acids as such.

Very particular preference is given to using at least mono-, di-, tri-, tetra- or higher-nuclear aromatic di-, tri- or tetracarboxylic acids, where each of the cores can contain at least one heteroatom, where two or more nuclei have identical or different heteroatoms may contain. For example, preference is given to monocarboxylic dicarboxylic acids, monocarboxylic tricarboxylic acids, monocarboxylic tetracarboxylic acids, dicercaric dicarboxylic acids, dicercaric tricarboxylic acids, dicerous tetracarboxylic acids, tricyclic dicarboxylic acids, tricarboxylic tricarboxylic acids, tricarboxylic tetracarboxylic acids, tetracyclic dicarboxylic acids, tetracyclic tricarboxylic acids and / or tetracyclic tetracarboxylic acids. 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 as the 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 (ATC), adamantane dibenzoate (ADB), benzene tribenzoate (BTB), methanetetrabenzoate (MTB), adamantane tetrabenzoate or dihydroxyterephthalic acids such as, for example, 2,5-dihydroxyterephthalic acid (DHBDC).

Amongst others, 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.

In addition to these at least bidentate 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.

As already stated, one or more carboxylic acid functions can be replaced by a sulfonic acid function. In addition, a sulfonic acid group may additionally be present. Finally, it is also possible that all carboxylic acid functions are replaced by a sulfonic acid function.

Such sulfonic acids or their salts, which are commercially available, 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, 8-dihydroxynaphthalene-3,6-disulfonic acid, 2,2'-dihydroxy-1,1 '-azaphthalene-3', 4,6'-trisulfonic acid.

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.

Preferably, 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.

In a shaped body of the organometallic framework, however, 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. Preferably, however, 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. Accordingly, another aspect of the present invention is a molded article containing the organometallic framework suitable for storing the acetylene-containing gas.

The production of moldings from organometallic frameworks is described for example in WO-A 03/102000.

Preferred processes for the production of moldings are extruding or tableting. In molded article production, 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.

There are essentially no restrictions with regard to the possible geometries of the shaped bodies. For example, pellets such as disc-shaped pellets, pills, spheres, granules, extrudates such as strands, honeycomb, mesh or hollow body may be mentioned.

In principle, all suitable processes are possible for producing these shaped bodies. In particular, the following procedures are preferred:

Kneading / hulling of the framework material alone or together with at least one binder and / or at least one pasting agent and / or at least one template compound to obtain a mixture; Shaping the resulting mixture by at least one suitable method such as extrusion; Optional washing and / or drying and / or calcination of the extrudate; Optional assembly. - Tabletting together with at least one binder and / or other excipient.

Applying the framework material to at least one optionally porous support material. The material obtained can then be further processed according to the method described above to give a shaped body. - Applying the framework material on at least one optionally porous substrate.

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). For example, 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.

Most preferably, 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.

The kneading and / or shaping is carried out according to a further embodiment with the addition of at least one binder, wherein as a binder in principle any chemical compound can be used which ensures the kneading and / or deformation desired viscosity of the kneading and / or deforming mass. Accordingly, for the purposes of the present invention, 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. Pat WO 94/13584, 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, tetrabutox ytitanate, or, for example, tri-alkoxy titanates such as, for example, trimethoxy titanate, triethoxy titanate, tripropoxy titanate, tributoxy titanate, alkoxy zirconates, for example tetraalkoxyzirconates such as, for example, tetramethoxyzirconate, tetraethoxyzirconate, tetrapropoxyzirconate, tetrabutoxycirccon- nat, or, for example, trialkoxyzirconates such as trimethoxyzirconate, triethoxyzirconate, tripropoxyzirconate, tributoxyzirconate, silica sols, amphiphilic substances and / or graphites.

As a viscosity-increasing compound, for example, optionally in addition to the above-mentioned compounds, 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.

As 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.

Other additives that can be used for kneading and / or shaping include amines or amine derivatives such as tetraalkylammonium compounds or amino alcohols, and carbonate containing compounds such as calcium carbonate. Such further additives are described for example in EP 0 389 041 A1, EP 0 200 260 A1 or WO 95/19222.

The order of the additives such as template compound, binder, pasting agent, viscosity-increasing substance in the molding and kneading is basically not critical.

According to a further preferred embodiment, 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.

According to a particularly preferred embodiment, as part of this drying process, at least one of the compounds added as additives is at least partially removed from the shaped body. 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.

Due to the fact that 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.

The 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.

In addition, 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. Depending on the maximum filling pressure to be used, free-form containers but also cylindrical containers are possible. Typically, such gas pressure vessels are provided with an inlet and / or outlet valve. Here, the acetylene-containing gas is pressed to the desired filling pressure in the container. For this purpose, a pressure gradient between see a filling and the container to be filled sufficient. Typically, however, compressors are used for filling. Suitable compressed gas containers are, for example, compressed gas cylinders or boilers.

In general, 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. By pressing in the acetylene-containing gas, it is stored in the organometallic framework so that an organometallic framework according to the invention is present.

A gas pressure vessel may be completely or partially filled with the organometallic framework. This is available as a powder or shaped bed. In addition, 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. Likewise, 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. Typically, 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. In addition, 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.

In addition, 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.

Due to the storage of the acetylene-containing gas in a porous metal-organic framework which is copper-free, the reactivity of the acetylene is reduced, as shown by the elevated onset temperatures of the DSC. As a result, 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.

Dynamic Differential Scalometry (DSC)

The DSC is a screening method that allows the detection of temperatures at which potentially hazardous exothermic reactions occur.

For this purpose, the samples must be representative of the substance to be examined.

According to TRAS 410 (technical regulation for plant safety), a substance can be safely handled if 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.

This simple rule can not be applied to self-accelerating reactions. The finding based on an isothermal step measurement that a reaction is not self-accelerating is only valid for statements on time periods of the order of one day. Weak self-accelerating reaction behavior, which may be relevant in terms of safety during storage for longer periods of time, is not recognized by this method.

An exothermic reaction with an energy release of less than 100 J / g, which corresponds approximately to an adiabatic temperature increase of 50 K, according to TRAS 410 is not a safety problem. Experience shows that even reactions with an energy content of 200 J / g are handled safely if the process takes place in an open system or if there is an effective discharge system.

In exothermic reactions with an energy content below 200 J / g is not tested for self-accelerating reaction behavior. Further investigations are required under transport law at decomposition energies above 300 J / g and after right of access at decomposition energies above 500 J / g.

DSC measurement

Dynamic Differential Scalometry (DSC) is a thermoanalytical method for quantifying caloric effects. Here, the sample to be examined in a pressure-tight crucible (for example, V4A) a predetermined temperature program (for example, 2.5 K / min.) Subjected. Depending on the furnace temperature, 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.

The invention will be explained in more detail with reference to the following examples and figures, without the subject matter of the invention being limited to these.

Examples

Example 1: DSC of acetylene in Al-terephthalic acid MOF

In a kettle, 23.9 kg of terephthalic acid and 28.0 kg of Al ₂ (SO ₄ ) ₃ ^* 18H ₂ O are suspended in 150 kg of DMF, heated to 130 ° C and left at this temperature for 24 h with stirring. After cooling and filtration, it is washed with 4 × 40 kg of methanol. 12 kg of the preliminary product obtained are then suspended in 200 liters of methanol and refluxed at 65 ° C. for 24 h. Furthermore, the filtered product is washed several times with methanol and blown dry with a dry stream of N ₂ . The product is finally calcined in a muffle furnace under an air atmosphere at 330 ° C for 72 h. The product has after activation in a high vacuum at 200 ° C for several hours an N ₂ surface of about 1400 m ² / g (Langmuir).

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 μl) 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.

19.0 mg are weighed from the AI-MOF. The amount of acetylene in the crucible is 0.7 mg. An exothermic reaction is observed with an onset temperature of 200 ° C (T ₁ ) (peak temperature T ₂ = 302 ° C). The course is shown in FIG. 1.

As in the other figures, 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.

It will receive 17 kg of material. 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.

In the DSC experiment (19.6 mg MOF and 1, 0 mg acetylene) two peaks are observed in the DSC diagram.

A first reaction takes place already at an onset temperature of 95 ° C (T ₁ ) (peak temperature T ₂ = 139 ° C), a second at an onset temperature of 170 ° C (T ₃ ) (peak temperature T ₄ = 307 ° C). The course is shown in FIG.

Example 3: DSC of acetylene in a Mg-2,6-naphthalenedicarboxylic acid MOF

1, 0 g of Mg (NO ₃ ) ₂ ^* 6H ₂ O and 6.7 g of 2,6-naphthalenedicarboxylic acid (NDC) are suspended in 137 g of DEF and reacted for 48 h at 130 ° C with stirring. The resulting water of reaction is discharged via a distillation bridge by means of a N ₂ stream. The filtrate is washed twice with DMF and twice with chloroform and calcined after drying in air for 48 h at 250 ° C in a muffle furnace. The resulting MOF has after activation in a high vacuum for several hours an N ₂ surface of about 130 m ² / g. In a DSC experiment with a Mg-NDC-MOF (19.2 mg MOF and 0.4 mg acetylene), the onset temperature is 325 ° C (T ₁ ) (peak temperature T ₂ = 386 ° C). The course is shown in FIG. 3.

Example 4: DSC of Acetylene in a Zn-Terephthalic Acid MOF (MOF-5)

96.7 g of Zn (NOs) ₂ MH ₂ O and 20.8 g of terephthalic acid are suspended in 2825 g of DEF (water content according to K. Fischer 0.02%). The reaction mixture (total water content according to K. Fischer 1%) is maintained at 130 ° C for 3.5 h. Vapors generated during the reaction are separated by a gentle stream of nitrogen via a distillation bridge. After cooling, the solid is filtered off and washed with 4 x 500 ml of anhydrous acetone. The solid is first pre-dried at room temperature in a stream of nitrogen for 2 to 4 days - the exact drying time is not critical - and then evacuated in a vacuum oven for 16 h (<1 mbar). The resulting MOF-5 has after activation at 200 ° C in a high vacuum for several hours N ₂ Oberflcheche of about 2940 m ² / g.

In a DSC experiment with MOF-5 (21, 4 mg MOF and 1.7 mg acetylene) the onset temperature is 235 ° C (T ₁ ) (peak temperature T ₂ = 301 ° C). The course is shown in FIG. 4.

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).

There are obtained 3.51 g of a uniform-looking, pale yellow powder. 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).

In a DSC experiment with the Sc-BDC MOF (22.0 mg MOF and 1, 3 mg acetylene) is the onset temperature at 315 ° C (T ₁₎ (peak temperature T ₂ = 441 ⁰ C). The course is shown in FIG. 5.

Claims

claims

A method of storing an acetylene-containing gas in a porous organometallic framework, wherein the organometallic framework contains at least one at least one metal ion coordinate bound, at least bidentate organic compound containing the step

Contacting the acetylene-containing gas with the organometallic framework,

characterized in that the organometallic framework material is copper-free.

2. The method according to claim 1, characterized in that the gas is acetylene.

3. The method according to claim 1 or 2, characterized in that the at least one metal ion is the ion of a metal selected from the group consisting of magnesium, scandium, yttrium, a lanthanide, titanium, zirconium, manganese, iron, cobalt, nickel, zinc, Aluminum and indium is.

4. The method according to any one of claims 1 to 3, characterized in that derives at least one at least bidentate organic compound of a di-, tri- or tetracarboxylic acid.

5. Porous organometallic framework 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, characterized in that the framework material is copper-free.

6. acetylene gas pressure vessel containing at least one porous organometallic framework material according to claim 5.

7. Gas pressure vessel according to claim 6, characterized in that the maximum filling pressure at room temperature is at least 10 bar (absolute).

8. Gas pressure vessel according to claim 6 or 7, characterized in that the maximum gas density is at least 10 g of acetylene per liter of container volume.

9. Gas pressure vessel according to one of claims 6 to 8, characterized in that it further comprises a filter.

10. Use of an organometallic framework material containing at least one coordinatively bound to at least one metal ion, at least bidentate organic compound, wherein the framework material is copper-free, for storing an acetylene-containing gas.

1 1. Use of an acetylene gas pressure vessel according to one of claims 6 to 9 for the storage, supply and delivery of acetylene for at least one technical application that requires acetylene.

12. Use according to claim 1 1, characterized in that the technical application of the burning, cutting, welding or chemical

Implementation is.

13. Use of a framework material according to claim 5, as a security explosive.