Method for the capture and storage of waste

Abstract

Systems and methods for capturing waste are disclosed. The systems and methods provide for a high level of confinement and long term stability. The systems and methods include adsorbing waste into a metal-organic framework (MOF), and applying pressure to the MOF material's framework to crystallize or make amorphous the MOF material thereby changing the MOF's pore structure and sorption characteristics without collapsing the MOF framework.

Claims

1. A method of remediating waste, comprising: adsorbing a waste material onto a metal-organic framework material; and applying pressure to the metal-organic framework material to convert the crystalline structure of the metal-organic framework to an amorphous structure.

2. The method of claim 1, wherein the pressure is between 7,350 psi and 18,000 psi.

3. The method of claim 1, wherein the waste material is a gas.

4. The method of claim 1, wherein the waste material is radioactive iodine.

5. The method of claim 1, wherein the metal-organic framework material is treated with a metal ion.

6. The method of claim 1, further comprising: encapsulating the metal-organic framework material is a glass material.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 shows representative synchrotron high energy X-ray pair distribution functions (PDFs) data sets, G(r), for the crystalline and amorphous materials (a), and differential PDFs (b) corresponding to I-I and I-framework interactions in the pressure-amorphized as-loaded series (120 wt % loading) of the MOF commonly named ZIF-8. The intensity and position of features in differential PDFs for crystalline and amorphous, and as-loaded and annealed samples are compared (c).

(2) FIG. 2 are graphs showing the mass loss associated with I.sub.2 release from the crystalline and amorphized ZIF-8 based on TGA of the as-loaded (left) and annealed (right) samples. The mass losses for the vacant ZIF-8 materials have been subtracted.

(3) Wherever possible, the same reference numbers will be used throughout the drawings to represent the same parts.

DETAILED DESCRIPTION

(4) The present invention now will be described more fully hereinafter with reference to the accompanying drawings, in which preferred embodiments of the invention are shown. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein; rather, these embodiments are provided so that this disclosure will be thorough and complete and will fully convey the scope of the invention to those skilled in the art.

(5) The present invention is directed to systems and methods for capturing waste, including gases and elements, ions or molecules in solution. The systems and methods provide for a high level of confinement and long term stability. The systems and methods include adsorbing waste into a metal-organic framework (MOF), and applying pressure to the MOF material's crystalline framework to change the framework to an amorphous MOF. This change or modification of the MOF material changes the sorption characteristics without collapsing the MOF cage framework. In such a manner, the modified MOF has improved adsorption retention, reduced desorption kinetics. The modification results in a more compacted, less porous, MOF material with lowered possibility of desorption of guest material. Additionally, modified MOF material, for example modified MOF adsorbed radioactive contaminated I.sub.2 are less powdery and have higher resistance to flow compared to unmodified MOFs. The modified MOF may then be further treated/and or contained.

(6) The waste may be a gas or an element or molecule in aqueous solution. The captured waste may be referred to as a guest. In an embodiment, the waste may be stable or radioactive isotope form of a light gas. In an embodiment, the light gas may be a stable or radioactive isotope form of I, H, CO, CO.sub.2, Kr, Xe, Ra, Cs, Ba, Y, Sr, and Rb; also including CH.sub.4 and H.sub.2O. In an embodiment, the radioactive gas is selected from the group including .sup.129I, .sup.131I, .sup.3H, .sup.14CO.sub.2, .sup.85Kr, .sup.133Xe, .sup.90Sr, .sup.135Cs and .sup.137Cs, plus the other isotopes of each of these radioelements.

(7) In an embodiment, the waste may be an element or molecule in solution. In an embodiment, the waste may be radioactive cesium in seawater. In another embodiment, the waste may be radioactive uranyl-containing ions in seawater.

(8) The MOF material has an open structure through which the target molecules can diffuse and be adsorbed for capture and storage. MOFs are crystalline framework structures with metal clusters interconnected by organic linker groups, a design that endows the materials with large pores, open channels, and huge internal surface areas for adsorbing molecules. A particular MOF may be selected based on the size of the pore required to receive the target species or guest. The pore size may be selected by the smallest dimension of the molecule that can fit into the pore opening of the MOF and may be aided by temperature and pressure of operating system. In this invention, MOFs can be 3D (cage) or 2D (layered) framework types. MOFs are highly porous crystalline materials, with a very diverse structural and chemical profile. A large set of metal and organic linkers are available. As such, MOFs which can be used in this invention can be categorized following several criteria, including topology (ex. MOFs with zeolitic topologies: zeolitic imidazolate frameworks (ZIFs), zeolite-like metal-organic frameworks (ZMOFs), or based on the organic linkers they include: carboxylate-based MOFs, phosphonate-based MOFs, N-based linker MOFs, NO-heterofunctional linkers based MOFs. In an embodiment, the MOF may be selected from the group including, but not limited to IRMOFs series (MOF-5), MOF-74 series, Sandia Metal-Organic Frameworks (SMOFs) series, and ZIFs series.

(9) ZIFs are a type of MOF framework. They are generally built from tetrahedral metal nodes and imidazolate ligands and form analogs to zeolite mineral structures. In an embodiment, the ZIF may be selected from the group including, but not limited to ZIF-6, ZIF-8, ZIF-10, ZIF-11. The framework of ZIF-8 has a chemical composition of ZnL2 (wherein L=2-Methylimidazolate, i.e., the anion of 2-Methylimidazole) and a topology defined by the Zn cations that is identical to the zeolitic framework type SOD. SOD is a three letter framework type code for a sodalite structure type, as defined by the International Zeolite Association (IZA) in the Atlas of Zeolite Framework Types (Ch. Baerlocher, L. B. McCusker, D. H. Olson, Sixth Revised Edition, Elsevier Amsterdam, 2007). In an embodiment, the MOF may be ZIF-4, ZIF-5, or ZIF-8.

(10) In another embodiment, the crystalline MOF may be a highly porous coordination polymer, HKUST-1. The framework of HKUST-1 is [Cu.sub.3(benzene-1,3,5-carboxylate).sub.2. It has interconnected [Cu.sub.2(O.sub.2CR).sub.4] units (where R is an aromatic ring), which create a three-dimensional system of channels with a pore size of 1 nanometer and an accessible porosity of about 40 percent in the solid.

(11) In an embodiment the MOF material may be treated by the addition of a metal ion or gas that reacts to form nanoparticles within the pores of the MOF. Those nanoparticles will participate in gas recovery by reaction with the gas as it enters the MOF pore. In an embodiment, the reactive substance may be silver or palladium. Silver provides a reactive nanoparticle component to selectively adsorb I.sub.2 gas molecules, resulting in containment of the radioactive iodine. The iodine loaded silver containing MOF is then treated to for a long term storage waste form.

(12) In another embodiment, the reactive particle may be Pd, which may be used to enhance the selectivity and storage capacity of neutral and radioactive forms of hydrogen. Palladium can either impregnate the MOF pore from solution with a Pd precursor, followed by hydrogen reduction (reference: M. Sabo, A. Henschel, H. Frode, E. Klemm, S. Kaskel, J. Mater. Chem. 2007, 17, 3827-3832); another method to impregnate the MOF pore is by vapor deposition, again followed by hydrogen reduction (reference: S. Hermes, M. K. Schroter, R. Schmid, L. Khodeir, M. Muhler, A. Tissler, R. W. Fischer, R. A. Fischer, Angew. Chem. 2005, 117, 6394-6397; Angew. Chem. Int. Ed. 2005, 44, 6237-6241.) Yet another method of impregnating the MOF pore is via solution route, by an autoredox reaction between the organic ligand incorporated in the MOF solid and palladium(II) ions (reference: Cheon, Y. E.; Suh, M. P. Angew. Chem. Int. Ed. 2009, 48, 2899-2903).

(13) The MOF is modified post capture by the application of pressure. The pressure is in an amount sufficient to mechanically modify the MOF to trap the waste gas inside the MOF phase for longer periods of time and to higher temperatures than in the original unmodified MOF. In an embodiment, the amount of pressure is sufficient to create pressure-induced amorphization of the MOF, which alters the pore structure and sorption characteristics of the MOF without collapsing the MOF. In an embodiment, the amount of pressure to amorphized ZIF-8 may be up to 9 tons per square inch (18,000 psi).

(14) Pressure may be applied to the MOF by a variety of applications, such as, but not limited to pressing, grinding, ball milling, sonication, and hot isostatic pressing (HIPping) below the volitization temperature of the waste.

(15) In an embodiment, pressure may be applied by HIPping, at a temperature below the volitization temperature of the waste, of ZIF-8 between pressures of between about 7,350 psi and 18,000 psi. In another embodiment, pressure may be applied by HIPping between pressures of between about 10,000 psi and 18,000 psi. In another embodiment, pressure may be applied by HIPping at a pressure of about 15,000 psi.

(16) The modified MOF containing the stored waste may then be further processed by encapsulating in glass, stored in containers, or forming a core/shell waste form in which formed pellets (the core) are stacked in a low temperature sintered BiSi Glass tube (shell) and sealed by a sintered cap of the same composition as the shell, for example by the method disclosed in U.S. Pat. No. 8,262,950, which is herein incorporated by reference in its entirety.

(17) Detailed analysis of the local structure of I.sub.2 guests, using a PDF method which can probe both crystalline and amorphous materials, indicates that the MOF crystallographic cage and gas trapping ability remains unaffected by the framework amorphization. In contrast to chemical post synthetic modification of MOFs, mechanical modification through pressure can be applied at an intermediate point in a sorption or sequestration process, rather than simply being used to generate the initial sorbent and sorption characteristics. Consequently, when employed after guest-sorption, mechanical modification alters desorption properties to physically trap guests. This approach decouples guest sorption process from the guest trapping process; the process changes the bulk porosity of the MOF, and the gas sorption pathway into MOF. This is unique and distinct from instances in which adsorption of a molecule into a pore causes the MOF pore to either constrict or expand (sometimes named guest-triggered switching of pores). Whatever affects the adsorption of a molecule into the MOF pore on the resultant shape of the pore, the overall resulting MOF-guest molecule can be treated with this amorphization process to form an interim waste form.

(18) ZIF-8, Zn(2-methylimidazole).sub.2, is part of a broad family of MOFs with expanded zeolite topologieszeolitic imidazolate frameworks (ZIFs)where the Zn-imidazolate-Zn link replicates the characteristic T-O-T angle of zeolites. The sodalite-type topology of the cubic ZIF-8 framework defines 12.0 diameter pores connected via 3.5 diameter apertures (6-rings). The unmatched I.sub.2 sorption capacity, retention, and selectivity of the ZIF-8 pore network benefits from the close correspondence of these 6-ring apertures to the I.sub.2 molecular dimensions.

(19) Activated (which means desolvated) ZIF-8 (approx. 1.5 g, Sigma-Aldrich) was loaded with iodine at approx. 75 C. to different final concentrations (20, 40, 60, 80, 100, and 120 wt % I.sub.2). A portion of each sample was annealed at 125 C. for 6 h to remove I.sub.2 from the external surface. While the as-loaded samples were brown, with the color intensity increasing for higher loadings, all samples faded to a pale brown or tan shade upon annealing, independent of I.sub.2 loading. This suggests that the color of the bulk sample is correlated to external surface-sorbed I.sub.2.

(20) Variable pressure X-ray diffraction measurements, for a 40 wt % I.sub.2 sample, indicate that the I.sub.2-containing sample can be amorphized at the same pressure as the vacant framework (approx. 0.34 GPa). Bulk powders of I.sub.2-loaded ZIF-8 (as-loaded and annealed) were amorphized within a pellet press (9 ton, 10-mm-diameter die, approx. 1.2 GPa average pressure), and redispersed as powders for subsequent analysis. The structure of the crystalline and amorphized materials were compared using PDF analysis of high energy X-ray scattering data collected at beamline 11-ID-B at the Advanced Photon Source at Argonne National Laboratory. The PDF provides local structure information, independent of crystallinity, as a weighted histogram of all atom-atom distances within a material. Not only can the PDF provide insight into the structural features that are retained in the amorphous ZIF-8 framework, but using a differential approach, and subtracting the contribution associated with the framework, the local I-I and I-framework interactions in the crystalline and amorphized materials can be directly compared.

(21) The well-defined long-range correlations, evident in PDFs for the crystalline materials, are eliminated for the amorphized ZIF-8 systems (FIG. 1). However, the shorter range features, including those up to 6 , which correspond to the Zn-imidazolate-Zn links, are entirely preserved in the amorphous materials. The combined retention of guests, porosity, and the Zn . . . Zn connectivity in the pressure-amorphized materials suggests that the sodalite topology of ZIF-8 is preserved, despite the local structural changes that destroy the long-range order, that is, the crystallinity. These structural changes are likely to involve symmetryreducing distortions of the 6-ring apertures, eliminating the well-defined features in the PDF beyond approx. 6 and impeding diffusion of guest molecules through the framework. This displacive amorphization contrasts with the reconstructive transition to a dense amorphous phase induced thermally in ZIFs containing unsubstituted imidazole.

(22) While the long-range framework order is eliminated upon amorphization, the short-range I-I and I-framework interactions remain unchanged. Indeed, a larger change in local structure is associated with the annealing and surface-desorption compared to the amorphization itself (FIG. 1). Specifically, the nearest neighbor I-I peak shifts from 2.8 to 2.6 while simultaneously narrowing, indicating less disorder (dynamic or static). This is accompanied by an increase in the relative intensity of the second and third peaks at 3.85 and 4.3-4.4 , associated with intermolecular interactions within pores. These changes may reflect a refinement of the I.sub.2 arrangement within the pores upon annealing. The retention of I.sub.2 is enhanced in the amorphized relative to the crystalline ZIF-8, as evidenced from thermogravimetric analysis (TGA). The mass losses upon heating (10 C./min, N.sub.2 flow, see FIG. 2) were shifted to higher temperatures for the amorphized materials, by up to 150 C. These gains were most pronounced for the intermediate I.sub.2 loadings. At the highest loadings, there appeared to be some destabilization of the framework, with a greater overall mass loss for the I.sub.2-containing framework than for the vacant ZIF-8. This is consistent with the reduced crystallinity observed at high loadings. For the as-loaded samples, the TGA showed mass loss associated with surface desorption starting at 100-120 C., with a further loss at 170-240 C. associated with release of I.sub.2 from within the pores. For the surface-desorbed samples, the mass loss occurred at 170-240 C., starting at lower temperatures for higher loadings.

(23) The improvement in I.sub.2 retention was quantified by comparing the I.sub.2 mass loss from ZIF-8 samples (annealed 80 wt %) at constant temperature in the TGA apparatus (200 C., N.sub.2 flow). The I.sub.2 loss is retarded by a factor of approximately I.sub.2 in the amorphized ZIF-8 (see FIG. 2).

(24) The enhanced guest retention of the amorphized material is associated with a kinetic trapping mechanism, rather than a change in binding energy, with identical host-guest interactions in the crystalline and amorphous materials. Leach testing, which evaluates the long-term durability of a final waste form, by heating in deionized water for 7 days at 90 C., showed minor differences in I.sub.2 retention upon amorphization. As such, the amorphized pellets are most suitable for applications as an interim waste-form. These can be incorporated into core-shell structured final waste form that combines excellent long-term stability with potentially unmatched I.sub.2 densities.

(25) The ZIF-8 framework can be amorphized at the same mild pressure and temperature conditions as empty ZIF-8. This is particularly striking considering the extremely high I.sub.2 loading (up to approx. 6 I.sub.2 molecules per sodalite cage). This is generally consistent with the relative independence of certain MOFs' compressibility to different guest loadings. The structural changes to the framework associated with this amorphization improve the I.sub.2 retention upon heating, by up to 150 C., retaining the local structure of the captive I.sub.2 despite the changes to the framework crystallinity.

(26) An efficient radioactive waste capture process, in reprocessing nuclear fuel or cleanup following inadvertent environmental release, is perhaps one of the highest impact (in terms of cost savings per unit quantity) potential sorption applications for MOFs. In this field, there are overwhelming economic drivers that dictate that contamination, and accordingly, processing steps and materials, must be minimized, with the same storage requirements applied to any component used as part of the waste capture as for the waste itself. The amorphization of I.sub.2-loaded ZIF-8 provides for secure interim storage before incorporation into a long-term waste form, ensuring non-contamination of the environment. The unmatched I.sub.2 uptake capacity for ZIF-8, relative to existing zeolite getters, and the possibility to minimize subsequent release through amorphization, makes this a promising I.sub.2 capture method.

(27) Furthermore, the invariance of the host-guest interactions to pressure treatment, answers an important question in materials for radioactive waste storage. Here, an optional technology to densify radioactive waste to a monolithic form that is suitable for transport is hot isostatic pressing (HIPping). The modified MOFs of the present invention provide a route to an interim waste form based on amorphized ZIF-8, but more generally, it provides insight into the behavior of other I.sub.2 containing MOFs under HIPping conditions, showing that the pore structure can retain iodine under pressure.

(28) More generally, in contrast to chemical post synthetic modification of MOF structure and sorption-desorption behaviors which must be applied before guest-loading, this mechanical modification through pressure can be applied at any point in a sorption-sequestration process. Consequently, pressure-induced structural changes can be used as a macro-scale handle with which to control the nanoscale sorption properties. Specifically, they can be used for increasing hysteresis in the sorption-desorption kinetics, at will, to kinetically trap I.sub.2.

(29) In another embodiment, modified MOFs may be used for the controlled release of agrochemicals (insecticides, herbicides, and fungicides). This could reduce the harmful effects on the environment and have a targeted release on as needed basis. A similar concept is also valid for the targeted release of various drugs.

(30) In an example, .sup.129I in the form of I.sub.2 gas, which may be from spent nuclear fuel reprocessing or from nuclear reactor accidents, which is of particular concern due to its very long half-life, its potential mobility in the environment and its deleterious effect on human health, may be treated to remove and store .sup.129I. .sup.129I is separated from spent fuel during fuel reprocessing as .sup.129I.sub.2 vapor. The gas containing .sup.129I.sub.2 vapor is passed through a bed of ZIF-8, such that the ZIF-8 selectively captures the .sup.129I. the ZIF-8 is then modified by pressure to form a stable storage media.

(31) In another example, radiological Cs.sup.+ ion in aqueous solutions, for example in seawater, from nuclear reactor accidents or from spent nuclear fuel reprocessing is captured by a charged framework MOF material, and the MOF is modified by pressure treatment.

(32) In another example, radiological Uranyl (e.g., UO.sub.2.sup.2+, (UO.sub.2)CO.sub.3(OH).sub.3.sup., UO.sub.2(CO.sub.3).sub.2.sup.2, UO.sub.2(CO.sub.3).sub.3.sup.4) ion in aqueous solutions, for example seawater, is captured by a charged framework (2D) MOF material, and the MOF is modified by pressure treatment.

(33) The invention being thus described, it will be obvious that the same may be varied in many ways. Such variations are not to be regarded as a departure from the spirit and scope of the invention, and all such modifications as would be obvious to one skilled in the art are intended to be included within the scope of the appended claims. It is intended that the scope of the invention be defined by the claims appended hereto. The entire disclosures of all references, applications, patents and publications cited above are hereby incorporated by reference.

(34) In addition, many modifications may be made to adapt a particular situation or material to the teachings of the disclosure without departing from the essential scope thereof. Therefore, it is intended that the disclosure not be limited to the particular embodiment disclosed as the best mode contemplated for carrying out this disclosure, but that the disclosure will include all embodiments falling within the scope of the appended claims.