WO2007128994A1 - Mof-compounds as gas adsorbers - Google Patents

Mof-compounds as gas adsorbers Download PDF

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Publication number
WO2007128994A1
WO2007128994A1 PCT/GB2007/001330 GB2007001330W WO2007128994A1 WO 2007128994 A1 WO2007128994 A1 WO 2007128994A1 GB 2007001330 W GB2007001330 W GB 2007001330W WO 2007128994 A1 WO2007128994 A1 WO 2007128994A1
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metal
gas
group
organic framework
organic
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PCT/GB2007/001330
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French (fr)
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Kjell Ove Kongshaug
Richard Hamilton Heyn
Helmer Fjellvag
Richard Blom
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Universitetet I Oslo
Cockbain, Julian
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Publication of WO2007128994A1 publication Critical patent/WO2007128994A1/en

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    • 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
    • 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
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • 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
    • 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
    • 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

Definitions

  • the invention relates to the use of metal-organic frameworks as oxide gas adsorbents, in particular as carbon dioxide adsorbents .
  • Carbon dioxide is a by-product of many processes, not -least hydrocarbon combustion, which is undesirable to release into the atmosphere. Accordingly processes for carbon dioxide capture have been developed. At present the standard techniques for carbon dioxide capture involve the use of aqueous solutions of amino- alcohols with carbon dioxide-containing gas being passed through such solutions and the captured carbon dioxide subsequently being released by increasing the temperature of the solution. Such "temperature swing" processes have high energy requirements and cause loss, possibly into the environment, of the expensive and toxic amino-alcohols . There is thus a continuing need for improved and alternative carbon dioxide capturing agents and processes.
  • MOFs metal-organic frameworks having electron pair donor functions on the organic component which are uncoordinated to the metal component are particularly effective as carbon dioxide capturing agents and can be used in pressure-swing (rather than just temperature-swing) carbon dioxide capture and release.
  • the invention provides a process for oxide gas capture which process comprises contacting a gas comprising an oxide with a metal- organic framework wherein a metal-coordinating organic component carries a non-metal-coordinating electron pair donor group, and optionally releasing captured oxide gas from said metal-organic framework by raising temperature and/or reducing pressure.
  • an oxide gas capture apparatus comprising a conduit containing a metal-organic framework wherein a metal-coordinating organic component carries a non-metal-coordinating electron pair donor group.
  • the invention provides a shift reactor incorporating an apparatus according to the invention.
  • Examples of apparatus that may be modified to incorporate MOFs according to the invention are automobile exhaust silencers (see for example US Patent No. 5708237, where the damper (14) may include the MOF) and shift reactors (see for example US Patent No. 5458857) . These US Patents are hereby incorporated herein by reference .
  • Metal-organic frameworks are a category of materials in which metal atoms or metal atom containing clusters are linked into a three-dimensional framework by bi- or poly-functional organic groups. MOFs have been described for example in many publications of Yaghi et al of the University of Michigan, US, e.g. in US-A- 20040225134.
  • MOF-177 has zinc containing clusters linked together by 4 , 4 ' , 4 " -benzene-1 , 3 , 5-triyl- tri-benzoic acid, i.e. a trifunctional compound having three metal-coordinating carboxyl groups but not containing any non-metal-coordinating electron pair donor functional groups .
  • the electron pair donor group typically has the electron pair located on a heteroatom, e.g. an amino, thiol or hydroxy group, preferably an amino group.
  • the electron pair donor group is typically not a group capable of chelating a metal, i.e. of coordinating a metal via two or more atoms of the group.
  • the electron pair carrying atom is not part of a delocalized electron system.
  • the electron pair carrying atom is desirably separated by at least two atoms from the metal- coordinating groups (e.g. from the carbon of a carboxyl group) . It is especially preferred that the organic component should carry more than one electron pair donor group, e.g. 2-6 such groups, and it is also preferred that such groups be close to each other, e.g. separated by no more than 4 backbone atoms , more preferably by no more than 2 backbone atoms .
  • the spacing of the metal-coordinating groups is preferably unaffected by rotational motion within the component, eg as in terephthalic acid or the tri-benzoic acid-benzene of MOF-177.
  • the organic and metal components of the MOFs of the invention may otherwise be components typical of known MOFs, e.g. as described in US-A-20040225134. Introduction of electron pair donor groups onto such organic components is chemically straightforward and many electron pair donor group carrying organic compounds suitable for MOF production are available commercially or known from the literature.
  • the metal of the MOF will be selected from Group 1 through 16 metals, e.g. Li, Na, K, Rb, Be, Mg, Ca, Sr, Ba, Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Rn, 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.
  • it is Al, Zn or Ni, especially Ni and Al .
  • the metal may form part of a M n X 1n cluster where M is the metal and X is a Group 14 to 17 atom, e.g. 0, N or S, especially 0, m is 1 to 10 and n is a number selected to balance the charge of the cluster.
  • the organic component is preferably a polycarboxylate, especially a material containing at least one cyclic group which may be aromatic or non- aromatic.
  • the metal component in the MOF will typically be coordinated by at least one non-linking ligand (i.e. one which does not form part of the backbone of the MOF) , e.g. sulphate, nitrate, halide, phosphate etc.
  • non-linking ligand i.e. one which does not form part of the backbone of the MOF
  • the gas treated in the process of the invention is one containing or consisting of a gaseous oxide, e.g. a sulphur, nitrogen or carbon oxide, in particular carbon dioxide.
  • a gaseous oxide e.g. a sulphur, nitrogen or carbon oxide, in particular carbon dioxide.
  • this may be a gas resulting from combustion (e.g. of hydrocarbons), natural gas or the product of a shift reactor (i.e. reactors used in production of hydrogen from methane) .
  • the apparatus of the invention will typically comprise a conduit filled or lined with the MOF.
  • the MOF optionally with a binder or diluent may itself be formed into a gas absorbent structure, e.g. a brick or perforated brick and such structures, which may be used in or to construct conduits, form a further aspect of the present invention.
  • a gas adsorbent structure eg a brick, tube, ring, tablet or pellet, typically having a maximum dimension (eg length or diameter) of at least 5mm
  • a metal-organic framework as hereinbefore defined.
  • Such structures may be produced by compressing the MOF, optionally together with a filler or binder, eg calcium carbonate, silica, or polyvinylpyrrolidone.
  • a filler or binder eg calcium carbonate, silica, or polyvinylpyrrolidone.
  • the structure may comprise a porous cage (eg of metal, glass or ceramic) containing the MOF in powder or pelletised form.
  • the process of the invention will typically comprise passing the gas from which the oxide gas is to be extracted through such a conduit in a gas uptake phase and ceasing such gas flow and raising the temperature in the conduit and/or reducing the pressure in the conduit to release the adsorbed oxide gas.
  • the apparatus will contain at least two such conduits with gas flow divertible into either so that one may operate in adsorption mode while the other is operating in desorption mode.
  • adsorption as used herein to refer to oxide gas uptake by the MOF should be considered to cover any form of gas sorption
  • gas oxide-saturated MOF elements may be replaced by fresh MOF elements and sent to a remote location for oxide gas desorption (e.g. where the MOF elements are in an exhaust gas system ' of a hydrocarbon- fuelled vehicle) .
  • Gas release from the MOF may be achieved by temperature increase - however the MOF is preferably not exposed to temperatures above 500 0 C, more preferably not to temperatures above 400 0 C. More preferably however gas release is achieved by reducing the ambient pressure at the MOF, e.g. by 1 to 100 bar (0.1 to 10 MPa), more preferably 10 to 40 bar (1 to 4 MPa) .
  • Figure 1 shows powder X-ray diffraction patterns for the MOFs of Examples 1 and 2;
  • Figure 2 shows powder X-ray diffraction patterns for the MOFs of Examples 3 and 4;
  • Figure 3 shows thermogravimetric traces for the MOFs of Examples 1 and 2;
  • Figure 4 shows thermogravimetric traces for the MOFs of Examples 3 and 4;
  • Figure 5 shows CO 2 adsorption-disorption isotherms, measured at 25°C, for the MOFs of Examples 1 and 2; and
  • Figure 6 shows CO 2 adsorption-disorption isotherms, measured at 25°C, for the MOFs of Examples 3 and 4.
  • Example 4 USO-2-Ni-A 0.29g of Ni(NO) 3 ' 6H 2 O, 0,18g of 2-aminotere ⁇ hthalic acid, 0.28g l,4-diazabic ⁇ clo[2.2.2]octane and 18.88g of dimethylformamide were mixed and transferred to a teflon-lined steel autoclave.
  • the autoclave was heated at HO 0 C for 24 hours, and then it was quenched to room temperature.
  • the product was collected by filtration and washed with dimethylformamide. The product was dried at ambient temperature overnight.
  • Powder X-ray diffraction patterns were recorded for the MOFs of Examples 1 to 4 using radiation of wavelength 1.5406 A. These are shown in Figures 1 and 2.
  • the unit cell of the compounds of Examples 3 and 4 were determined, and the two cells were similar indicating isostructurality between the two compounds , Furthermore the ⁇ nit cells of the two compounds were similar to that of a Zn compound published recently in literature (D.N. Dybtsev, H. Chun, K. Kim, Angew. Chem. Int. Ed. 2004, 43, 5033), so it can be assumed that the two compounds are isostructural with this compound.
  • the crystal structure of the Zn compound shows a 3D metal-organic framework (MOF) structure containing a 3D channel system with channel sizes of about 0.8x0.8nm 2 .
  • MOF metal-organic framework
  • the structure of the amine functionalized material (USO-2-Ni-A) of Example 4 shows disorder in the placement of the amine groups .
  • Example 6 Thermocrravimetric Analysis About 20mg of USO-A-Al and USO-I-Al-A were separately heated to 700 0 C at a rate of 5°C/min. Both compounds show, a continuous weight loss starting at room temperature and ending at about 300 0 C resulting from the solvent removal (Figure 3). The second weight loss is representing the decomposition of the structures.
  • the specific surface areas were measured by multipoint BET analyses using nitrogen as probe gas at 77K on a Quantachrome Autosorb-1 instrument. After de-solvating the materials at 300 0 C under reduced pressure the specific surface areas were measured to: USO-I- Al: 130OmVg and USO-I-Al-A: 980m7g. ' The results are shown in Figure 3.
  • Example 7 C(X Adsorption-Desorption Isotherms CO 2 isotherms were measured at 25 0 C by keeping the compounds of Examples 1 and 2 in a thermostated water bath using a Quantachrome Autosorb-1 instrument.
  • the CO 2 adsorption-desorption isotherms measured at 25 0 C on USO- 1-Al and USO-I-Al-A show a CO 2 adsorption capacity of about 10 and 12 weight percent, respectively, for the two compounds at 1 atmosphere partial pressure of carbon dioxide (Figure 5) .
  • the amine functionalized material (USO-I-Al-A) showing significantly higher CO 2 adsorption capacity than the unfunctionalized material despite the fact that the functionalized material has a lower specific surface area. The results are shown in Figure 5.
  • CO 2 isotherms were measured at 25 0 C by keeping the compounds of Examples 3 and 4 in a thermostated water bath using a Quantachrome Autosorb-1 instrument.
  • the CO 2 adsorption-desorption isotherms measured at 25 0 C on USO- 2-Ni and USO-2-Ni-A show a CO 2 adsorption capacity of about 10 and 14 weight percent, respectively, for the two compounds ( Figure 6) at 1 atmosphere partial pressure of carbon dioxide.
  • the amine functionalized material USO-2-Ni-A

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Abstract

The invention provides a process for oxide gas capture which process comprises contacting a gas comprising an oxide with a metal -organic framework wherein a metal- coordinating organic component carries a non-metal- coordinating electron pair donor group, and optionally releasing captured gas from said metal-organic framework by raising temperature and/ or reducing pressure.

Description

MOF-compounds as gas adsorbers
The invention relates to the use of metal-organic frameworks as oxide gas adsorbents, in particular as carbon dioxide adsorbents .
Carbon dioxide is a by-product of many processes, not -least hydrocarbon combustion, which is undesirable to release into the atmosphere. Accordingly processes for carbon dioxide capture have been developed. At present the standard techniques for carbon dioxide capture involve the use of aqueous solutions of amino- alcohols with carbon dioxide-containing gas being passed through such solutions and the captured carbon dioxide subsequently being released by increasing the temperature of the solution. Such "temperature swing" processes have high energy requirements and cause loss, possibly into the environment, of the expensive and toxic amino-alcohols . There is thus a continuing need for improved and alternative carbon dioxide capturing agents and processes.
We have now found that metal-organic frameworks (MOFs) having electron pair donor functions on the organic component which are uncoordinated to the metal component are particularly effective as carbon dioxide capturing agents and can be used in pressure-swing (rather than just temperature-swing) carbon dioxide capture and release.
Thus viewed from one aspect the invention provides a process for oxide gas capture which process comprises contacting a gas comprising an oxide with a metal- organic framework wherein a metal-coordinating organic component carries a non-metal-coordinating electron pair donor group, and optionally releasing captured oxide gas from said metal-organic framework by raising temperature and/or reducing pressure. Viewed from a yet still further aspect the invention provides an oxide gas capture apparatus comprising a conduit containing a metal-organic framework wherein a metal-coordinating organic component carries a non-metal-coordinating electron pair donor group. Viewed from a further aspect the invention provides a shift reactor incorporating an apparatus according to the invention. Examples of apparatus that may be modified to incorporate MOFs according to the invention are automobile exhaust silencers (see for example US Patent No. 5708237, where the damper (14) may include the MOF) and shift reactors (see for example US Patent No. 5458857) . These US Patents are hereby incorporated herein by reference .
Metal-organic frameworks (MOFs) are a category of materials in which metal atoms or metal atom containing clusters are linked into a three-dimensional framework by bi- or poly-functional organic groups. MOFs have been described for example in many publications of Yaghi et al of the University of Michigan, US, e.g. in US-A- 20040225134.
Other publications by Yaghi et al relating to MOFs, and which are incorporated herein by reference, include US Patents Nos 5648508, 6624318, 6893564, 6929679 and 6930193 and published US Patent Applications Nos 2003 0004364, 2003 0078311, 2003 0148165, 2003 0222023, 2004 0249189, 2004 0265670, 2005 0004404, 2005 0124819, 2005 0154222, and 2005 0192175.
US-A-20040225134, the contents of which are incorporated by reference, discloses the preparation of one MOF, MOF-177, which has been proposed for use in carbon dioxide capture. MOF-177 has zinc containing clusters linked together by 4 , 4 ' , 4 " -benzene-1 , 3 , 5-triyl- tri-benzoic acid, i.e. a trifunctional compound having three metal-coordinating carboxyl groups but not containing any non-metal-coordinating electron pair donor functional groups .
In the MOFs of the invention, the electron pair donor group typically has the electron pair located on a heteroatom, e.g. an amino, thiol or hydroxy group, preferably an amino group. The electron pair donor group is typically not a group capable of chelating a metal, i.e. of coordinating a metal via two or more atoms of the group. The electron pair carrying atom is not part of a delocalized electron system.
The electron pair carrying atom is desirably separated by at least two atoms from the metal- coordinating groups (e.g. from the carbon of a carboxyl group) . It is especially preferred that the organic component should carry more than one electron pair donor group, e.g. 2-6 such groups, and it is also preferred that such groups be close to each other, e.g. separated by no more than 4 backbone atoms , more preferably by no more than 2 backbone atoms .
In the organic component of the MOF, the spacing of the metal-coordinating groups (eg carboxyl groups) is preferably unaffected by rotational motion within the component, eg as in terephthalic acid or the tri-benzoic acid-benzene of MOF-177.
The organic and metal components of the MOFs of the invention may otherwise be components typical of known MOFs, e.g. as described in US-A-20040225134. Introduction of electron pair donor groups onto such organic components is chemically straightforward and many electron pair donor group carrying organic compounds suitable for MOF production are available commercially or known from the literature.
Typically the metal of the MOF will be selected from Group 1 through 16 metals, e.g. Li, Na, K, Rb, Be, Mg, Ca, Sr, Ba, Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Rn, 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. Preferably it is Al, Zn or Ni, especially Ni and Al . The metal may form part of a MnX1n cluster where M is the metal and X is a Group 14 to 17 atom, e.g. 0, N or S, especially 0, m is 1 to 10 and n is a number selected to balance the charge of the cluster.
The organic component is preferably a polycarboxylate, especially a material containing at least one cyclic group which may be aromatic or non- aromatic.
The metal component in the MOF will typically be coordinated by at least one non-linking ligand (i.e. one which does not form part of the backbone of the MOF) , e.g. sulphate, nitrate, halide, phosphate etc.
The gas treated in the process of the invention is one containing or consisting of a gaseous oxide, e.g. a sulphur, nitrogen or carbon oxide, in particular carbon dioxide. Typically this may be a gas resulting from combustion (e.g. of hydrocarbons), natural gas or the product of a shift reactor (i.e. reactors used in production of hydrogen from methane) .
The apparatus of the invention will typically comprise a conduit filled or lined with the MOF. However the MOF, optionally with a binder or diluent may itself be formed into a gas absorbent structure, e.g. a brick or perforated brick and such structures, which may be used in or to construct conduits, form a further aspect of the present invention. Viewed from this aspect the invention provides a gas adsorbent structure (eg a brick, tube, ring, tablet or pellet, typically having a maximum dimension (eg length or diameter) of at least 5mm) , comprising a metal-organic framework as hereinbefore defined. Such structures may be produced by compressing the MOF, optionally together with a filler or binder, eg calcium carbonate, silica, or polyvinylpyrrolidone. Alternatively, the structure may comprise a porous cage (eg of metal, glass or ceramic) containing the MOF in powder or pelletised form.
The process of the invention will typically comprise passing the gas from which the oxide gas is to be extracted through such a conduit in a gas uptake phase and ceasing such gas flow and raising the temperature in the conduit and/or reducing the pressure in the conduit to release the adsorbed oxide gas. Typically the apparatus will contain at least two such conduits with gas flow divertible into either so that one may operate in adsorption mode while the other is operating in desorption mode. (The term adsorption as used herein to refer to oxide gas uptake by the MOF should be considered to cover any form of gas sorption) . Alternatively gas oxide-saturated MOF elements may be replaced by fresh MOF elements and sent to a remote location for oxide gas desorption (e.g. where the MOF elements are in an exhaust gas system' of a hydrocarbon- fuelled vehicle) .
Gas release from the MOF may be achieved by temperature increase - however the MOF is preferably not exposed to temperatures above 5000C, more preferably not to temperatures above 4000C. More preferably however gas release is achieved by reducing the ambient pressure at the MOF, e.g. by 1 to 100 bar (0.1 to 10 MPa), more preferably 10 to 40 bar (1 to 4 MPa) .
Embodiments of the invention will now be described further with reference to the following non-limiting Examples and the accompanying drawings, in which: Figure 1 shows powder X-ray diffraction patterns for the MOFs of Examples 1 and 2;
Figure 2 shows powder X-ray diffraction patterns for the MOFs of Examples 3 and 4;
Figure 3 shows thermogravimetric traces for the MOFs of Examples 1 and 2;
Figure 4 shows thermogravimetric traces for the MOFs of Examples 3 and 4; Figure 5 shows CO2 adsorption-disorption isotherms, measured at 25°C, for the MOFs of Examples 1 and 2; and Figure 6 shows CO2 adsorption-disorption isotherms, measured at 25°C, for the MOFs of Examples 3 and 4.
Example 1 (Comparative) - USO-I-Al
0.36g of A1C13-6H2O, 0.17g of terephthalic acid, 1.58g of ethanol and 9.08g of diethylformamide were mixed and transferred to a teflon-lined steel autoclave. The autoclave was heated at 1100C for 24 hours, and then it was quenched to room temperature. The product was collected by filtration and washed with dimethylformamide. The product was dried at ambient temperature overnight.
Example 2 - USO-I-Al-A
0.36g of A1C13 '6H2O, 0.14g of 2-aminoterephthalic acid, 1.58g of ethanol and 9.08g of diethylformamide were mixed and transferred to a teflon-lined steel autoclave. The autoclave was heated at 1100C for 24 hours, and then it was quenched to room temperature. The product was collected by filtration and washed with dimethylformamide. The product was dried at ambient temperature overnight .
Example 3 (Comparative) - USO-2-Ni
0.49g of Ni(NO)3 '6H2O, 0.28g of terephthalic acid, 0.14g l,4-diazabicyclo[2.2.2]octane and 18.88g of dimethylformamide were mixed and transferred to a teflon-lined steel autoclave. The autoclave was heated at 1100C for 24 hours, and then it was quenched to room temperature. The product was collected by filtration and washed with dimethylformamide. The product was dried at ambient temperature.
Example 4 - USO-2-Ni-A 0.29g of Ni(NO)3 '6H2O, 0,18g of 2-aminotereρhthalic acid, 0.28g l,4-diazabicγclo[2.2.2]octane and 18.88g of dimethylformamide were mixed and transferred to a teflon-lined steel autoclave. The autoclave was heated at HO0C for 24 hours, and then it was quenched to room temperature. The product was collected by filtration and washed with dimethylformamide. The product was dried at ambient temperature overnight.
Example 5 - X-Rav Diffraction
Powder X-ray diffraction patterns were recorded for the MOFs of Examples 1 to 4 using radiation of wavelength 1.5406 A. These are shown in Figures 1 and 2.
Indexation of the powder patterns indicated very similar unit cells for the compounds of Examples 1 and 2, and furthermore the cells are similar to that of two compounds based on Al and Cr published in the literature (C. Serre, F. Millange, C. Thouvenot, M. Nogues, G. Marsolier, D. Louer, G. Ferey, J". Am. Chem. Soc. 2002, 124, 13519) . The structure of the amine functionalized material (USO-I-Al-A) shows disorder in the placement of the amine groups .
On basis of the powder X-ray data the unit cell of the compounds of Examples 3 and 4 were determined, and the two cells were similar indicating isostructurality between the two compounds , Furthermore the μnit cells of the two compounds were similar to that of a Zn compound published recently in literature (D.N. Dybtsev, H. Chun, K. Kim, Angew. Chem. Int. Ed. 2004, 43, 5033), so it can be assumed that the two compounds are isostructural with this compound. The crystal structure of the Zn compound shows a 3D metal-organic framework (MOF) structure containing a 3D channel system with channel sizes of about 0.8x0.8nm2. As for the compound of Example 2, the structure of the amine functionalized material (USO-2-Ni-A) of Example 4 shows disorder in the placement of the amine groups .
Example 6 - Thermocrravimetric Analysis About 20mg of USO-A-Al and USO-I-Al-A were separately heated to 7000C at a rate of 5°C/min. Both compounds show, a continuous weight loss starting at room temperature and ending at about 3000C resulting from the solvent removal (Figure 3). The second weight loss is representing the decomposition of the structures. The specific surface areas were measured by multipoint BET analyses using nitrogen as probe gas at 77K on a Quantachrome Autosorb-1 instrument. After de-solvating the materials at 3000C under reduced pressure the specific surface areas were measured to: USO-I- Al: 130OmVg and USO-I-Al-A: 980m7g. ' The results are shown in Figure 3.
About 20mg of USO-2-Ni and USO-2-Ni-A were separately heated to 7000C at a rate of 5°C/min. The two compounds show the first weight loss in the range 200 to 2500C consistent with the removal of the solvent molecules
(Figure 4) . After the first weight- loss, both compounds show a plateau in their TGA curves indicating the presence of porous compounds. The second weight loss is then due to decomposition of the frameworks. High temperature powder X-ray diffraction data for both compounds indicate that the structural integrity of the compounds are maintained after the first weight loss, and this is further supported by the measurements of high internal BET surface areas for the two compounds when they were desolvated under reduced pressure at 2000C: USO-2-Ni-A: 1529m7g and USO-2-Ni: 191OmVg.
(Specific surface areas were measured by multipoint BET analyses using nitrogen as probe gas at 77K on a Quantachrome Autosorb-1 instrument) .
Example 7 - C(X Adsorption-Desorption Isotherms CO2 isotherms were measured at 250C by keeping the compounds of Examples 1 and 2 in a thermostated water bath using a Quantachrome Autosorb-1 instrument. The CO2 adsorption-desorption isotherms measured at 250C on USO- 1-Al and USO-I-Al-A show a CO2 adsorption capacity of about 10 and 12 weight percent, respectively, for the two compounds at 1 atmosphere partial pressure of carbon dioxide (Figure 5) . The amine functionalized material (USO-I-Al-A) showing significantly higher CO2 adsorption capacity than the unfunctionalized material despite the fact that the functionalized material has a lower specific surface area. The results are shown in Figure 5.
CO2 isotherms were measured at 250C by keeping the compounds of Examples 3 and 4 in a thermostated water bath using a Quantachrome Autosorb-1 instrument. The CO2 adsorption-desorption isotherms measured at 250C on USO- 2-Ni and USO-2-Ni-A show a CO2 adsorption capacity of about 10 and 14 weight percent, respectively, for the two compounds (Figure 6) at 1 atmosphere partial pressure of carbon dioxide. As with the compounds of Examples 1 and 2, the amine functionalized material (USO-2-Ni-A) shows significantly higher • CO2 adsorption capacity than the unfunctionalized material despite the fact that the' functionalized material has a lower specific surface area. The results are shown in Figure 6.

Claims

Claims :
1. A process for oxide gas capture which process comprises contacting a gas comprising an oxide with a metal-organic framework wherein a metal-coordinating organic component carries a non-metal-coordinating electron pair donor group, and optionally releasing captured gas from said metal-organic framework by- raising temperature and/or reducing pressure.
2. A process as claimed in claim 1 wherein said donor group is selected from the group consisting of amine, thiol and hydroxy groups .
3. A process as claimed in either of claims 1 and 2 wherein said organic component coordinates a metal selected from the group consisting of Al, Zn and Ni.
4. A process as claimed in any one of claims 1 to 3 wherein said organic component is a polycarboxylate .
5. A process as claimed in any one of claims 1 to 4 wherein said organic component comprises at . least one cyclic group.
6. A process as claimed in any one of claims 1 to 5 wherein said gas comprising an oxide is a carbon dioxide-containing gas .
7. A process as claimed in any one of claims 1 to 6 comprising contacting said metal-organic framework with a gas produced by hydrocarbon combustion.
8. A process as claimed in any one of claims 1 to 6 comprising contacting said metal-organic framework with a gas produced by a shift reactor.
9. A process as claimed in any one of claims 1 to 8 wherein gas captured by said metal-organic framework is released therefrom by increasing the temperature thereof to a temperature below 400° C.
10. A process as claimed in any one of claims 1 to 9 wherein gas captured by said metal-organic framework is released therefrom by reducing the surrounding pressure by 1 to 4 MPa.
11. An oxide gas capture apparatus comprising a conduit containing a metal-organic framework wherein a metal- coordinating organic component carries a non-metal- coordinating electron pair donor group.
12. An apparatus as claimed in claim 11 wherein said donor group is selected from the group consisting of amine, thiol and hydroxy groups.
13. An apparatus as claimed in either of claims 11 and 12 being an exhaust gas treatment apparatus for a hydrocarbon-fuelled engine.
14. A shift reactor incorporating an apparatus according to either of claims 11 and 12.
PCT/GB2007/001330 2006-04-10 2007-04-10 Mof-compounds as gas adsorbers WO2007128994A1 (en)

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