Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
  • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
• • A—HUMAN NECESSITIES
  • A62—LIFE-SAVING; FIRE-FIGHTING
  • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
  • A62D9/00—Composition of chemical substances for use in breathing apparatus
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
  • B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
  • B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • 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
  • B01J20/30—Processes for preparing, regenerating, or reactivating
  • B01J20/34—Regenerating or reactivating
  • B01J20/3425—Regenerating or reactivating of sorbents or filter aids comprising organic materials
• • 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
  • B01J20/30—Processes for preparing, regenerating, or reactivating
  • B01J20/34—Regenerating or reactivating
  • B01J20/3483—Regenerating or reactivating by thermal treatment not covered by groups B01J20/3441 - B01J20/3475, e.g. by heating or cooling
• • 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
  • B01J20/30—Processes for preparing, regenerating, or reactivating
  • B01J20/34—Regenerating or reactivating
  • B01J20/3491—Regenerating or reactivating by pressure treatment
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B63—SHIPS OR OTHER WATERBORNE VESSELS; RELATED EQUIPMENT
  • B63C—LAUNCHING, HAULING-OUT, OR DRY-DOCKING OF VESSELS; LIFE-SAVING IN WATER; EQUIPMENT FOR DWELLING OR WORKING UNDER WATER; MEANS FOR SALVAGING OR SEARCHING FOR UNDERWATER OBJECTS
  • B63C11/00—Equipment for dwelling or working underwater; Means for searching for underwater objects
  • B63C11/02—Divers' equipment
  • B63C11/18—Air supply
  • B63C11/22—Air supply carried by diver
  • B63C11/24—Air supply carried by diver in closed circulation
• • C—CHEMISTRY; METALLURGY
  • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
  • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
  • C25B3/00—Electrolytic production of organic compounds
  • C25B3/01—Products
  • C25B3/13—Organo-metallic compounds
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
  • B01D2253/20—Organic adsorbents
  • B01D2253/204—Metal organic frameworks (MOF's)
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2257/00—Components to be removed
  • B01D2257/50—Carbon oxides
  • B01D2257/504—Carbon dioxide
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2220/00—Aspects relating to sorbent materials
  • B01J2220/50—Aspects relating to the use of sorbent or filter aid materials
  • B01J2220/56—Use in the form of a bed
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
  • Y02C20/00—Capture or disposal of greenhouse gases
  • Y02C20/40—Capture or disposal of greenhouse gases of CO2
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P20/00—Technologies relating to chemical industry
  • Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2

Definitions

• the present invention relates to methods for removing carbon dioxide and optionally water from breathing air in closed or partially closed systems by means of a porous organometallic framework, such systems with at least one respirator and their use and method for regenerating the porous organometallic framework.
• the diver is supplied via a mouthpiece oxygen from the pressure bottle, which this can breathe.
• the exhaled air is released to the surrounding water. This allows the diver to stay underwater longer than the air volume of the diving mask would dictate.
• adsorbents described in the prior art which can be used consist of different materials.
• a soda lime bed is used for a dipping device.
• a breathing apparatus wherein the carbon dioxide absorber should be reactivated by heat or reduced carbon dioxide pressure.
• the carbon dioxide absorber is called calcium hydroxide.
• DE-A 33 03 420 describes methods and devices for purifying the respiratory air of CO 2 , wherein molecular sieves serve as adsorbers, which can be regenerated by a pressure swing process.
• the object is achieved by a method for removing carbon dioxide and optionally water from breathing air in closed or partially closed systems containing the step
• the framework material contains at least one, at least one bidentate organic compound coordinately bound to at least one metal ion.
• the object is further achieved by a closed or partially closed system containing at least one respirator and a respiratory mask, a suit or other life support systems, further containing a porous organometallic framework, wherein the framework material at least one at least one metal ion coordinatively bound, at least bidentate organic Contains connection.
• porous organometallic frameworks in closed or partially closed systems containing at least one breathing apparatus contain or are particularly efficient in processes for removing carbon dioxide and optionally water from breathing air and also can be easily regenerated.
• Closed systems are, in particular, those which have no opening to the environment through which atmospheric oxygen is to be introduced or exported.
• Partially closed systems are in particular those in which no atmospheric oxygen is to be absorbed by the environment into the system.
• any environment that has no ambient gas or that has an ambient gas whose inhalation does not ensure the necessary life-support or integrity of a human or higher animal comes into consideration as the environment of the closed or partially closed system.
• an environment that does not contain ambient gas can be found under water or in space.
• An ambient gas whose inhalation does not ensure the necessary life or integrity of a human or higher animal is, for example, air whose oxygen content or partial pressure is too low to breathe and / or which has other harmful components.
• the breathing mask may be, for example, one that is used during dive - that is, as a diving mask. However, it may also be an anti-masks, such as those used in the event of fire, a chemical accident, painting or handling hazardous chemicals or biological material, extreme mountaineering or high altitude (for example, in the aircraft).
• such systems may also contain suits.
• the life support system is a helmet. Typically, such a helmet can also be integrated into a corresponding suit. Often, protective suits are used in this context. in this connection are also space suits to call.
• the systems may be rooms or corridors of buildings, for example shelters, or of vehicles, for example in submarines, aircraft, in tunnels, production shafts or the like.
• the closed or partially closed system may further comprise a filter in which the porous organometallic framework is present at least as part of an adsorber bed.
• a filter in which the porous organometallic framework is present at least as part of an adsorber bed.
• adsorbents such as zeolites.
• the filter can be interchangeable or permanently installed in the system.
• the filters to be used are known from the prior art. These are typically components of the systems also known in the art.
• the closed or partially closed system according to the invention is used to remove carbon dioxide and optionally water from breathing air.
• the advantage here is that in addition to CO 2 , the water in the air can be removed. However, this is not a prerequisite for the functioning of CO 2 adsorption.
• the porous organometallic framework material is advantageous, inter alia, because it allows for easy regeneration.
• Another object of the present invention is a process for regenerating a porous organometallic framework from a closed or partially closed system, as described above, comprising the steps
• organometallic framework material optionally removing the organometallic framework material and subjecting the framework material to a gas.
• the gas may be, for example, air, nitrogen, an inert gas or a mixture thereof.
• Suitable inert gases are, for example, helium or argon.
• the regeneration can be carried out, for example, by simply passing the gas through the organometallic framework material.
• regeneration takes place under pressure and / or temperature swing adsorption. Therefore, it is preferable if the regeneration method according to the invention is carried out such that the application takes place with the change of at least one parameter selected from pressure and temperature.
• pressure is to be understood in the context of the present invention, the total pressure and / or the carbon dioxide partial pressure.
• the regeneration of the organometallic framework material can take place during the use of the closed or partially closed system according to the invention.
• porous organometallic framework to be used is known in the art.
• the suitability of porous organometallic frameworks to store carbon dioxide is described, for example, by A.R. Millward et al., J. Am. Chem. Soc. 127 (2005), 17998-17999.
• the porous organometallic framework contains at least one at least one metal ion coordinated at least bidentate organic compound.
• This metal-organic framework (MOF) is described for example in US 5,648,508, EP-AO 790 253, M. O'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 and DE-A-101 11 230.
• MOF metal-organic framework
• the MOFs according to the present invention contain pores, in particular micro and / or mesopores.
• Micropores are defined as those having a diameter of 2 nm or smaller and mesopores are defined by a diameter in the range of 2 to 50 nm, each according to the definition as described by Pure & Applied Chem. 57 (1985), 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 absorption 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 preferably 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, even more preferably more than 1000 m 2 / g and particularly preferably more than 1500 m 2 / g.
• MOF shaped bodies can have a lower specific surface; 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.
• the metal component in the framework of the present invention is preferably selected from Groups Ia, IIa, MIa, IVa to Villa and Ib to VIb. Particularly preferred are Mg, Ca, Sr, Ba, Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ro, Os, Co, Rh, Ir, Ni , Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, Tl, Si, Ge, Sn, Pb, As, Sb and Bi. More preferred are Zn, Cu, Ni, Pd, Pt, Ru, Rh and Co. Zn, Al, Ni and Cu are particularly preferred.
• 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 form a coordinative 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, 3 H -AsO , -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
• functional groups are to be mentioned in which the abovementioned radical R is absent.
• R is absent.
• functional groups are, inter alia, -CH (SH) 2, -C (SH) 3, -CH (NH 2) 2, - C (NH 2) 3, -CH (OH) 2, -C (OH) 3, -CH (CN) 2 or -C (CN) 3 TO call.
• the at least two functional groups can in principle be bound to any suitable organic compound as long as it is ensured that the organic compound having these functional groups is capable of forming the coordinative bond and the preparation of the framework.
• the organic compounds containing the at least two functional groups derived from a saturated or unsaturated aliphatic compound o- of an aromatic compound or an aliphatic as well as aromatic compound are preferred.
• 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 see compound 1 to 15, more preferably 1 to 14, more preferably 1 to 13, more preferably 1 to 12, more preferably 1 to 11 and particularly preferably 1 to 10 C atoms, for example 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 moiety of the both aliphatic and aromatic compounds has one, two or three nuclei, with one or two nuclei being particularly preferred.
• each nucleus of the named compound may contain at least one heteroatom, such as, for example, N, O, S, B, P, Si, Al, preferably N, O and / or S.
• 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 be mentioned as aromatic compounds.
• the at least bidentate organic compound is particularly preferably derived from a di-, tri- or tetracarboxylic acid or its sulfur analogs.
• the term "derive" in the context of the present invention means that the at least bidentate organic compound can be present in the framework material in partially deprotonated or completely deprotonated form.
• the at least bidentate organic compound may contain further substituents, such as -OH, -NH 2 , - OCH 3 , -CH 3 , -NH (CH 3 ), -N (CH 3 J 2 , -CN and halides.
• dicarboxylic acids such as oxalic acid, succinic acid, tartaric acid, 1,4-butanedicarboxylic acid, 4-oxo-pyran-2,6-dicarboxylic acid, 1,6-hexanedicarboxylic acid, decanedicarboxylic acid, 1,8-heptadecanedicarboxylic acid bonic acid, 1,9-heptadecane dicarboxylic acid, heptadecanedicarboxylic acid, acetylenedicarboxylic acid, 1,2-benzenedicarboxylic acid, 2,3-pyridinedicarboxylic acid, pyridine-2,3-dicarboxylic acid, 1,3-butadiene-1,4-dicarboxylic acid, 1,4.
• dicarboxylic acids such as oxalic acid, succinic acid, tartaric acid, 1,4-butanedicarboxylic acid, 4-oxo-pyran-2,6-dicarboxylic
• Diaminodiphenyl ether diimide dicarboxylic acid 4,4'-diaminodiphenylmethanediimide dicarboxylic acid, 4,4'-diaminodiphenylsulfonediimide dicarboxylic 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,
• Tricarboxylic acids such as
• each of the cores can contain at least one heteroatom, where two or more nuclei have identical or different heteroatoms may contain.
• monocarboxylic dicarboxylic acids preference is given to monocarboxylic dicarboxylic acids, monocarboxylic tricarboxylic acids, monocarboxylic tetracarboxylic acids, dicercaric dicarboxylic acids, dicercaric tricarboxylic acids, dicercaric 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, Si, Al, 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 To name alkoxy group.
• At least bidentate organic compounds to acetylenedicarboxylic acid (ADC), benzenedicarboxylic acids, naphthalenedicarboxylic acids, biphenyldicarboxylic acids such as, for example, 4,4'-biphenyldicarboxylic acid (BPDC), bipyridinedicarboxylic acids, for example 2,2'-bipyridinedicarboxylic acids, for example 2,2'-biphenylcarboxylic acids.
• ADC acetylenedicarboxylic acid
• BPDC 4,4'-biphenyldicarboxylic acid
• bipyridinedicarboxylic acids for example 2,2'-bipyridinedicarboxylic acids, for example 2,2'-biphenylcarboxylic acids.
• Bipyridine-5,5-dicarboxylic acid benzene tricarboxylic acids such as 1, 2,3-
• DABDC Dihydroxyterephthalic acid
• Isophthalic acid, terephthalic acid, 2,5-dihydroxyterephthalic acid, 1,2,3-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid or 2,2-bipyridine-5,5'-dicarboxylic acid are very particularly preferably used.
• the MOF may also comprise one or more monodentate ligands.
• Suitable solvents for the preparation of the MOF include ethanol, dimethylformamide, toluene, methanol, chlorobenzene, diethylformamide, dimethyl sulfoxide, water, hydrogen peroxide, methylamine, sodium hydroxide, N-methylpolidone ether, acetonitrile, benzyl chloride, triethylamine, ethylene glycol and mixtures thereof.
• Further metal ions, at least bidentate organic compounds and solvents for the preparation of MOF are described inter alia in US Pat. No. 5,648,508 or DE-A 101 11 230.
• the pore size of the MOF can be controlled by choice of the appropriate ligand and / or the at least bidentate organic compound.
• the larger the organic compound the larger the pore size.
• the pore size is preferably from 0.2 nm to 30 nm, and the pore size is particularly preferably in the range from 0.3 nm to 3 nm, based on the crystalline material.
• 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.
• MOFs The following are examples of MOFs.
• the metal and the at least bidentate ligands, the solvent and the cell parameters are also indicated. The latter were determined by X-ray diffraction.
• organometallic frameworks are MOF-2 to 4, MOF-9, MOF-31 to 36, MOF-39, MOF-69 to 80, MOF103 to 106, MOF-122, MOF-125, MOF-150, MOF-177, MOF-178, MOF-235, MOF-236, MOF-500, MOF-501, MOF-502, MOF-505, IRMOF-1, IR-MOF-61, IRMOP-13, IRMOP-51, MIL-17, MIL-45, MIL-47, MIL-53, MIL-59, MIL-60, MIL-61, MIL-63, MIL-68, MIL-79, MIL-80, MIL-83, MIL-85, CPL 1 to 2, SZL-1 which are described in the literature.
• a porous organometallic framework material in which Zn, Al or Cu as the metal ion and the at least bidentate organic compound is terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid or 1,3,5-benzenetricarboxylic acid.
• MOFs In addition to the conventional method for producing the MOF, as described for example in US 5,648,508, they can also be prepared by electrochemical means. In this regard, reference is made to DE-A 103 55 087 and WO-A 2005/049892.
• the MOFs produced in this way have particularly good properties in connection with the adsorption and desorption of chemical substances, in particular of gases. They thus differ from those produced conventionally, even if they are formed from the same organic and metal ion constituents, and are therefore to be considered as new frameworks. In the context of the present invention, electrochemically produced MOFs are particularly preferred.
• the electrochemical preparation relates to a crystalline porous organometallic framework material containing at least one coordinated to at least one metal ion at least bidentate organic compound which is obtained in a reaction onsmedium containing the at least one bidentate organic compound in that at least one metal ion by Oxidation of at least one metal containing the corresponding metal is generated.
• electrochemical preparation refers to a production process in which the formation of at least one reaction product is associated with the migration of electrical charges or the occurrence of electrical potentials.
• At least one metal ion refers to embodiments according to which at least one ion of a metal or at least one ion of a first metal and at least one ion of at least one second metal different from the first metal by anodic Oxidation be provided.
• the electrochemical preparation comprises embodiments in which at least one ion of at least one metal is provided by anodic oxidation and at least one ion of at least one metal via a metal salt, wherein the at least one metal in the metal salt and the at least one metal, which via anodic oxide tion as metal ion can be the same or different from each other.
• the present invention encompasses an embodiment in which the reaction medium contains one or more different salts of a metal and the metal ion contained in that salt or salts is additionally provided by anodic oxidation of at least one anode containing that metal , Likewise, the reaction medium may contain one or more different salts of at least one metal and at least one metal other than these metals may be provided via anodic oxidation as the metal ion in the reaction medium.
• the at least one metal ion is provided by a-node oxidation of at least one of said at least one metal-containing A-node, wherein no further metal is provided via a metal salt.
• MOF metal
• metal as used in the context of the present invention in connection with the electrochemical preparation of MOFs includes all elements of the periodic table which can be provided via anodic oxidation by electrochemical means in a reaction medium and with at least one at least bidentate organic compounds at least one organometallic porous GeStocking are able to form. Regardless of its production, the resulting MOF is obtained in powder form or as an agglomerate. This can be used as such as a sorbent in the process according to the invention alone or together with other sorbents or other materials. This is preferably done as bulk material, in particular in a fixed bed. Furthermore, the MOF can be converted into a shaped body. Preferred methods here are the extrusion or tableting.
• MOF metal-organic compound
• binders lubricants
• other additives such as binders, lubricants, or other additives may be added to the MOF.
• mixtures of MOF and other adsorbents, for example activated carbon are produced as shaped articles or separately give shaped articles, which are then used as shaped-body mixtures.
• pellets such as disc-shaped pellets, pills, spheres, granules, extrudates such as strands, honeycombs, lattices or hollow bodies may be mentioned.
• the framework material can then be further processed according to the method described above to give a shaped body.
• Foaming in porous plastics such as e.g. Polyurethane.
• Kneading 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 contents of which are incorporated by reference into the context of the present application in its entirety.
• kneading and / or shaping by means of a piston press, roll press in the presence or absence of at least one binder material, compounding, pelleting, tabletting, extrusion, coextrusion, foaming, spinning, coating, granulation, preferably spray granulation, spraying may be preferred , Spray-drying or a combination of two or more of these methods.
• pellets and / or tablets are produced.
• Kneading and / or shaping may be carried out at elevated temperatures, for example in the range from room temperature to 300 ° C. and / or at elevated pressure, for example in the range from atmospheric pressure to several hundred bar and / or in a protective gas atmosphere such as in the presence 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, as described, for example, in WO 94/29408, silica, as described, for example, in EP 0 592 050 A1, mixtures of silica and alumina, such as For example, in WO 94/13584, clay minerals, as described for example in JP 03-037156 A, for example, montmorillonite, kaolin, bentonite, halloysite, Dickit, Nacrit and anauxite, alkoxysilanes, as described for example in EP 0,102 544 B1, for example tetraalkoxysilanes such as, for example, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane or trialkoxysilanes such as trimethoxysilane, triethoxysilane, tripropoxysilane, tributoxysi
• an organic compound and / or a hydrophilic polymer such as cellulose or a cellulose derivative such as methylcellulose and / or a polyacrylate and / or a polymethacrylate and / or a polyvinyl alcohol and / or or a polyvinylpyrrolidone and / or a polyisobutene and / or a polytetrahydrofuran.
• a pasting agent inter alia, preferably water or at least one alcohol such as a monoalcohol having 1 to 4 carbon atoms such as methanol, ethanol, n-propanol, iso-propanol, 1-butanol, 2-butanol, 2-methyl-1 - propanol or 2-methyl-2-propanol or a mixture of water and at least one of said alcohols or a polyhydric alcohol such as a glycol, preferably a water-miscible polyhydric alcohol, alone or as a mixture with water and / or at least one of said monohydric alcohols be used.
• a monoalcohol having 1 to 4 carbon atoms such as methanol, ethanol, n-propanol, iso-propanol, 1-butanol, 2-butanol, 2-methyl-1 - propanol or 2-methyl-2-propanol or a mixture of water and at least one of said alcohols or a polyhydric alcohol such as a glycol
• 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, which is generally carried out at a temperature in the range of 25 to 300 ° C, preferably in the range of 50 to 300 ° C and more preferably in the range of 100 to 300 ° 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.
• Figure 1 shows the adsorption isotherm of CO 2 at 20 ° C on the organometallic framework aluminum terephthalate in the form of 3x3 mm tablets, where P is the absolute pressure in mbar and A is the amount of adsorbed gas in mg per g of adsorbent.
• the partial pressure of CO 2 (4% * 3 bar) is 120 mbar (see point 1 in Fig. 1). This corresponds to a loading of 24 to 27 mg / g (see point 2 in Fig. 1).

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