Patent Publication Number: US-8974675-B2

Title: Porous solids, selective separations, removal of sulfur compounds, adsorption

Description:
RELATED APPLICATIONS 
     This application is a divisional of U.S. patent application Ser. No. 12/376,804, filed 9 Feb. 2009, now U.S. Pat. No. 8,293,133 issued 23 Oct. 2012, which claims priority to and the benefit of PCT Application Serial No. PCT/US07/17729, filed 9 Aug. 2007, which claims priority to and the benefit of U.S. Provisional Patent Application Ser. No. 60/836,806 filed 10 Aug. 2006. 
    
    
     BACKGROUND OF THE INVENTION 
     1. Field of the Invention 
     The present invention relates to a class of porous metal organic materials has novel selective adsorption characteristics and for methods of making and using same. 
     More particularly, the present invention relates to a class of porous metal organic materials has novel selective adsorption characteristics, where materials are based on trans linked chains of metal oxygen octahedra that are cross-linked by aromatic dicarboxylic acids and for methods of making and using same. 
     2. Description of the Related Art 
     Many applications of nanoporous materials such as molecular sieving, ion exchange and functional nanocomposites are based on specific interactions between the host frameworks and removable guest species. The capacity and selectivity of nanoporous materials in absorption and in separation of molecular mixtures depend on specific interactions between the host frameworks and removable guest species and in some cases the degree to which the structure of the host lattice can relax as molecular species are intercalated. Detailed structural data are critical to understand these interactions. 
     The classical zeolite frameworks are relatively rigid and exhibit little deformation upon loading and unloading of various guest species. 1  On the other hand, intercalation into layered structures leads to expansion of the interlayer separation because of the very weak interlayer bonding, and can lead to complete exfoliation of the layers. 2    
     Variable flexibilities without loss of crystallinity are expected for structures containing rigid building blocks linked by relatively deformable hinge-like units. Examples of framework flexibility have been found in a number of metal-organic frameworks (MOFs). 3  Among them, a group of compounds first reported by Férey and coworkers, 4  based on chains of trans corner-sharing octahedra MO 6  (M=V, 4  Cr, 5  Al, 6  Fe, 7  In 8 ) cross-linked by 1,4-benzene dicarboxylate (BDC) upon removal or absorption of guest species show remarkable framework flexibility. The first member of the group [V(OH)BDC](H 2 BDC) x  was designated as MIL-47as. 4  The guest H 2 BDC molecules are removed on heating in air and the V 3+  ions are oxidized to V 4+  without changing the framework topology. The product, VOBDC (designated MIL-47) was observed to absorb different small guest molecules. No structural information on the absorbed guest molecules is available although the structure of MIL-47 was solved from single crystal data. 4    
     Sorption studies of these metal organic frameworks have focused on H 2  adsorption, 9  but some studies of the absorption of CO 2   10  and CH 4   11  have been reported. Of particular relevance to this work is the paper by Férey and coworkers on the adsorption of CH 4  and CO 2  by MOHBDC (M=Cr, Al) and VOBDC. 11a  The V(IV) phase VOBDC shows some differences in the absorption isotherms compared with the trivalent compounds, but the amounts of CO 2  adsorbed above 10 bar are comparable. The relatively weak enthalpy of adsorption suggested that VOBDC has no specific adsorption sites for CO 2 . 11a    
     Thus, there is a need in the art for improved absorbants or absorbents, especially for sulfur containing compounds. 
     SUMMARY OF THE INVENTION 
     The present invention provides a class of porous metal organic materials has novel selective and reversible adsorption characteristics. The materials are based on trans linked chains of metal oxygen octahedra that are cross-linked by aromatic dicarboxylic acids. The materials contain diamond shaped channels that permit access of aromatic and other molecules. The general composition can be written as MOADA, where M is a tetravalent metal or a mixture of tetravalent metals, O is an oxygen atom, and ADA is an aromatic dicarboxylic acid dianion (H 2 ADA). The inventors have found that MOADA compounds selectively and reversibly adsorb sulfur-containing components of fluids (gases or liquids), such as hydrocarbon fluids, resulting in the selective reduction of a concentration of sulfur-containing components in the hydrocarbon fluids. In the case of gaseous fluids, the inventors have found that the absorbents operate effectively at a total pressure of 1 atmosphere at ambient temperature. The absorbents, therefore, are suitable for desulfurizing any fluid, gas or liquid, especially hydrocarbon fluids. The inventors believe that the absorbents are better suited for hydrocarbon fluids having relatively low viscosity as use of the absorbents with higher viscosity fluids may result in unacceptable fluid losses. 
     A specific example is the compound VOBDC, where V is vanadium, O is an oxygen atom, and BDC is benzenedicarboxylate, the dianion of benzene dicarboxylic acid (H 2 BDC). VOBDC has been found to selectively and reversibly adsorb thiophene from octane, a separation that indicates potential use for sulfur removal from hydrocarbon fluid such as diesel, gasoline or the like. VOBDC also been found to selectively and reversibly adsorb sulfur compounds such as dimethyl sulfide and thiophene from methane or ethane at a total pressure of 1 atmosphere at ambient temperature. 
     The present invention provides a method for removing sulfur from a fluid, including the step of contacting the fluid with an effective amount of at least one absorbent of the general formula MOADA, where M is a tetravalent metal or a mixture of tetravalent metals, O is an oxygen atom and ADA is an aromatic dicarboxylic acid dianion, where the effective amount is sufficient to reduce a concentration of sulfur-containing components in the fluid or to reduce a concentration of sulfur-containing components in the fluid to desired lower concentrations. The process can also include the step of removing the absorbent from the fluid and heating the absorbent to recover the absorbed sulfur-containing components regenerating the absorbent. The process can include repeating the steps of contacting, removing and regenerating on intermittent, periodical, semi-continuous or continuous basis. 
     The present invention provides a system including at least one vessel containing at least one absorbent of this invention. The system also includes a source of a fluid including sulfur-containing components. The system also includes piping and valves sufficient to connect the vessel to the source of the fluid. The system is adapted to remove the sulfur-containing components in the fluid or reduce concentration of the sulfur-containing components in the fluid, when the fluid is brought into contact with the absorbent. If the absorbent is in a column, then a residence time of the fluid in the column, a temperature of the column and a pressure of the column can be adjusted to achieve a given reduction in sulfur-containing components in the fluid. 
    
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
       The invention can be better understood with reference to the following detailed description together with the appended illustrative drawings in which like elements are numbered the same. 
         FIGS. 1A-H  depict the structures of: (A) [VOBDC]0.7(C 8 H 6 O 4 ), 1; (B,C) [VOBDC](aniline), 3; (D,E) [VOBDC](thiophene) 0.91 , 4; (F,G) [VOBDC](acetone), 5, and (H) a collection of images of 1, 2, 3 and 4 for comparison purposes. 
         FIG. 2  is a plot of thiophene uptake by VOBDC from methane saturated with thiophene at ambient temperature. The temperature profile is shown in the top panel and the corresponding weight change in the bottom panel. The inset shows an expanded view of the thiophene uptake kinetics. The right panel shows a second experiment in which a sample saturated with thiophene at ambient is heated to 150° C. (blue data). 
         FIG. 3  depicts the structure of Al(OH)(C 8 H 4 O 4 )0.7(C 8 H 6 O 4 ), 1. 
         FIG. 4  is a plot of dimethyl sulfide absorption data. 
         FIG. 5  is a plot of thiophene absorption data. 
         FIG. 6  is a plot of thiophene absorption data. 
         FIG. 7  is a plot of toluene absorption data. 
         FIG. 8  is a plot of octane absorption data. 
         FIG. 9  is a plot of thiophene absorption data from octane. 
         FIG. 10  is a plot of thiophene absorption data from octane. 
         FIG. 11  depicts an embodiment of a batch system for desulfurizing a fluid using an absorbent of this invention. 
         FIG. 12  depicts an embodiment of a semi-continuous or continuous system for desulfurizing a fluid using an absorbent of this invention. 
         FIG. 13  depicts an embodiment of a fluid bed system for desulfurizing a fluid using an absorbent of this invention. 
         FIG. 14  depicts an embodiment of a moving bed system for desulfurizing a fluid using an absorbent of this invention. 
         FIG. 15A  depicts an embodiment of a gas cartridge for desulfurizing a gas using an absorbent of this invention. 
         FIG. 15B  depicts an embodiment of a fuel cartridge for desulfurizing a fuel using an absorbent of this invention. 
     
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
     The inventors have found that a new class of absorbant or absorbent molecules can be constructed and that the new absorbants or absorbents can be used to reduce the content of sulfur-containing compounds in a fluid such as hydrocarbon fluids, e.g., chemicals, refinery streams, fuels, oils, lubricants, natural gas, crude natural gas (sour gas), or other hydrocarbon fluids including such components. 
     The present invention broadly relates to absorbents of the general formula MOADA, where M is a tetravalent metal or a mixture of tetravalent metals, O is an oxygen atom and ADA is an aromatic dicarboxylic acid dianion. 
     The present invention broadly relates to a method for removing sulfur from a fluid, including the step of contacting the fluid with an effective amount of at least one absorbent of the general formula MOADA, where M is a tetravalent metal or a mixture of tetravalent metals, O is an oxygen atom and ADA is an aromatic dicarboxylic acid dianion, where the effective amount is sufficient to reduce a concentration of sulfur-containing components in the fluid or to reduce a concentration of sulfur-containing components in the fluid to desired lower concentrations. The process can also include the step of removing the absorbent from the fluid and heating the absorbent to recover the absorbed sulfur-containing components regenerating the absorbent. The process can include repeating the steps of contacting, removing and regenerating on intermittent, periodical, semi-continuous or continuous basis. 
     The present invention broadly relates to a system including at least one vessel containing at least one absorbent of this invention. The system also includes a source of a fluid including sulfur-containing components. The system also includes piping and valves sufficient to connect the vessel to the source of the fluid. The system is adapted to remove the sulfur-containing components in the fluid or reduce concentration of the sulfur-containing components in the fluid, when the fluid is brought into contact with the absorbent. If the absorbent is in a column, then a residence time of the fluid in the column, a temperature of the column and a pressure of the column can be adjusted to achieve a given reduction in sulfur-containing components in the fluid. Generally, when a column is used, there are at least two columns. While one column is desulfurizing the other column is regenerating. Of course, the system can include a number of columns with appropriate piping and valves to permit desulfurization and regeneration on a continuous or semi-continuous basis. If the system is batch, then a batch of fluid is contact with an amount of absorbent in an appropriate vessel under conditions to reduce the sulfur-containing components to a desired lower value. The conditions include at least residence time of the fluid in the vessel, the temperature of the vessel and the pressure of the vessel. For continuous system, the absorbent is fed into a fluid bed vessel or a moving bed vessel, where absorbent is continuously removed, regenerated and supplied to the vessel. 
     The present invention broadly relates to a disposable sulfur absorbent for purifying case including an inline cartridge including at least one absorbent of this invention, where the cartridge is adapted to be placed in a transfer line between a fluid source and the fluid destination. The cartridge can also includes a means for identifying when the absorbent must be regenerated. 
     Suitable Reagents 
     Suitable metals for use in the MOADA absorbents of this invention include, without limitation, aluminum (Al), vanadium (V), chromium (Cr), iron (Fe), titanium (Ti), zirconium (Zr), hafnium (Hf), cerium (Ce), or mixtures thereof. 
     Suitable dicarboxylic acids include, without limitation, any aryl or alkaryl dicarboxylic acid. Exemplary examples include, without limitation, 1,4-benzene dicarboxylic acid (terephthalic acid), 1,3-benzene dicarboxylic acid (isophthalic acid), 4,4′-diphenyl dicarboxylic acid, 2,5-pyridine dicarboxylic acid, 1,4-naphthylene dicarboxylic acid, 1,5-naphthylene dicarboxylic acid, other rigid aryl dicarboxylic acids or mixtures thereof. 
     Suitable fluids include, without limitation, any gas, liquid or mixtures or combinations thereof including undesirable levels of sulfur-containing components. Exemplary fluids include, without limitations, water, sewer gas, hydrogen gas, syngas, chemical gases and/or liquids, hydrocarbon gases and/or liquids, biological gases and/or liquids, biochemical gases and/or liquids, any other gas and/or liquid containing undesirable levels of sulfur-containing components or mixtures or combinations thereof. Exemplary hydrocarbon fluids include, without limitation, natural gas (sweet or sour), diesel fuel, gasoline, kerosene, jet fuel, refinery cuts, alkanes containing 1 to 20 carbon atoms, alkenes containing 1 to 20 carbon atoms, alkynes containing 1 to 20 carbon atoms, or mixtures or combinations thereof or mixtures or combinations thereof, where one or more carbon atoms can be replaced by a main group element selected from the group consisting of B, N, O, Si, P, S, Ga and Ge and one or more of the hydrogen atoms can be replaced by F, Cl, Br, I, OR, SR, COOR, CHO, C(O)R, C(O)NH2, C(O)NHR, C(O)NRR′, or other similar monovalent groups, where R and R′ are the same or different and are carbyl group having between about 1 to about 16 carbon atoms and where one or more of the carbon atoms and hydrogen atoms can be replaced as set forth immediately above. 
     Suitable sulfur-containing components include, without limitation, hydrogen sulfide, alkyl, aryl, alkaryl, and aralkyl sulfide, disulfide and undesirable other sulfur-containing compounds generally found in fluid. 
     Preparation and Characterization of the Absorbents and Absorbent/Absorbed Species Interaction 
     Single crystals of [VOBDC](H 2 BDC) 0.71  1 were synthesized directly, where V is vanadium, O is oxygen, BDC is 1,4-benzene dicarboxylate (the dianion of 1,4-benzene dicarboxylic acid), and H 2 BDC is 1,4-benzene dicarboxylic acid. [VOBDC](H 2 BDC) 0.71  (1), is the V 4+ -analog of the previously compound MIL-47as. 9  After removal of the guest acid molecules by heating 1 in air, the resulting VOBDC structure showed sufficient flexibility to undergo single-crystal-to-single-crystal transformations upon absorption of aniline, thiophene, and acetone from the liquid phase. After absorption, we were able to characterize the resulting structure detailing the guest structure, framework-guest interactions, and framework deformations from single crystal X-ray diffraction data. 
     We have also observed rapid and highly selective gas phase absorption of thiophene from methane by VOBDC, a process relevant to desulfurization of fluids including sulfur-containing components such as hydrocarbon gases, e.g., natural gas to produce so call sweet natural gas. This and other applications of MOFs were described in a recent review. 12    
     The octahedral chain in the structure of [VOBDC](H 2 BDC) 0.71  1 contains a —V═O—V═— backbone with alternating short and long V—O apical bonds of the VO 6  octahedra. The equatorial corners of the VO 6  octahedra are shared with the BDC ligands that cross-link the octahedral chains to form 1D rhomb-shape tunnels which are each filled by two columns of guest H 2 BDC. Assuming that the H 2 BDC molecules in each column are linked by hydrogen bonds similar as to the bonding in In(OH)BDC.(H 2 BDC) 0.75 , 8  and that a H 2 BDC molecule has a length of 9.6 Å, a theoretical number of 0.71 guest H 2 BDC per vanadium atom can be derived from the lattice constants. This guest acid content has been confirmed by chemical analysis and structure refinements. 13    
     The [M(OH)BDC](H 2 BDC) x , phases have the same space group symmetry as M(OH)BDC with the guest H 2 BDC molecules in neighboring tunnels oriented perpendicular to each other. The same arrangement of the guest molecules is found in the compound 1, probably because this pattern allows all columns of the guest H 2 BDC molecules to have favorable π-π interactions with the framework BDC. The columns of the H 2 BDC molecules in different tunnels of the compound 1 are found disordered over positions shifted relative to each other along the tunnel axis in steps of ca. 1.4 Å. If viewed along the tunnel axis, the H 2 BDC molecules in neighboring tunnels are oriented perpendicular to each other so that all columns of guest H 2 BDC molecules have favorable π-π interactions with the framework BDC. This arrangement of the guest molecules is not compatible, however, with the symmetry Pnma of the compound 2 that has a mirror plane running through the —O═V—O═V— backbone. The space group symmetry of the compound 1 is lowered to the non-centrosymmetric P2 1 2 1 2 1 , which was confirmed by SHG (second harmonic generation) measurements. The SHG efficiency measured on a powder sample of the compound 1 is comparable to that of quartz. 
     Although the structures of the compound 2 and M(OH)BDC, M=Al 3+ , Cr 3+  and V 3+ , have the same topology and the same space group Pnma, they show important differences in local symmetry. In the compound 1, the metal atom is located at an inversion center while the symmetry mirror planes are perpendicular to the octahedral chain and pass through the centers of the BDC ligands. In the compound 2, the inversion symmetry center is shifted to the center of the BDC ligand, because the V 4+  ion is displaced from the center of a VO 6  octahedron to form a V═O double bond. The mirror plane is parallel to the octahedral chain and runs through the —V═O—V═O— backbone. This symmetry difference between the frameworks naturally leads to different space group symmetries of the corresponding compounds intercalated by the guest H 2 BDC molecules. 
     By heating the compound 1 in air to remove the guest acid, high quality single crystals of VOBDC 2 identical to MIL-47 were obtained and were observed to show single-crystal-to-single-crystal transformations upon absorption of various guest molecules. Accurate structural data of the guest molecules and framework deformations obtained from single crystal X-ray diffraction data are reported here. The thermal removal of the guest H 2 BDC led to crystals of VOBDC 2 suitable for single crystal X-ray measurement. 14  Our determination of the structure of VOBDC 2 is in agreement with that reported earlier by Férey. 4    
     Upon immersing in liquid aniline, thiophene and acetone, the crystals of the compound VOBDC 2 as shown in  FIG. 1A , are transformed into an intercalation compound [VOBDC](aniline) 3 as shown in  FIGS. 1B&amp;C , into an intercalation compound [VOBDC](thiophene) 0.91  4 as shown  FIGS. 1D&amp;E  and into an intercalation compound [VOBDC](acetone) 5 as shown in  FIGS. 1D&amp;G , respectively. The compounds 3, 4, and 5 are transformed from the compound 2, without losing their crystallinity of the single crystal part of each structure.  FIG. 1H  shows all four compounds 2, 3, 4, and 5, where compounds 3, 4 and 5 are shown with their guest molecule in their proper orientations. 15    
     The aniline molecule (ca. 7.5 Å long) is much shorter than H 2 BDC, but still longer than the period (6.8 Å) of the VOBDC framework along the tunnel axis. The intercalated aniline molecules in the compound 3 form angles of ±17° to the tunnel axis, which can be considered as a compromise between adapting to the framework period, maximizing packing efficiency, and facilitating π-π interactions with the framework BDC ligands. The shortest distance between the benzene ring center of aniline and the carbon atoms of the BDC benzene ring is 3.507(1) Å, and the distance between their benzene ring centers is 4.43(1) Å, which indicates a π-π interaction with substantial ring-ring offset. 15  The π-π interactions are complemented by weak C—H . . . π and N—H . . . π interactions between the aniline molecules and the BDC ligands. 12    
     The packing of thiophene molecules in the compound 4 is similar to aniline in the compound 3, but the angles between the thiophene molecules and the tunnel axis are changed to ±26°, probably due to the smaller molecular size of thiophene relative to aniline. A clear C—H . . . π interaction between the thiophene molecules and the framework BDC seems to play a major rule in dictating the thiophene orientation. 16  The occupancy of the thiophene position was refined to 0.91(1) in agreement with the absorption measurements as described below. Similar to the compound 1, the guest molecule packing in the compounds 3 and 4, which result from the weak interactions between the guest molecules and the host framework, is not compatible with the space group symmetry of VOBDC. The centrosymmetric space group Pnma of VOBDC changes to the chiral space group P2 1 2 1 2 1  upon loading of the guest aniline or thiophene molecules. 
     Unlike the aniline and thiophene molecules that form two columns in each tunnel, the acetone molecules in the compound 5 are stacked into one column along the tunnel axis with an antiparallel packing pattern. The intermolecular C═O . . . C═O distances between about 3.506(1) Å and about 3.510(1) Å within the column indicate weak dipolar carbonyl-carbonyl interactions between the acetone molecules, which probably dictate the packing pattern. 17  The VOBDC tunnel is too small to host two columns of the antiparallel-packed acetone molecules. With only one column of acetone molecules in each tunnel the framework deforms so that the rhomb-shaped tunnel section flattens substantially. The flattening not only improves packing efficiency of the whole structure but also facilitates dipolar interactions between the carbonyl group of acetone and the carboxylate groups of the framework BDC ligands (C═O . . . CO 2 : 3.267(1) Å). The packing of the acetone molecules is compatible with the symmetry of the VOBDC framework, therefore, the compound 5 has the same space group symmetry as VOBDC, represent by the compound 2. 
     The VOBDC structure 2 has the most open tunnels. Upon intercalation of guest molecules, the tunnel opening systematically shrinks, because of the interactions between the guest molecules and the host framework. This is illustrated by the ratio of the two diagonals of the tunnel section which changes from 13.99/16.06 (0.87) in the compound 2 to 13.03/16.85 (0.77) in the compound 3, to 12.74/16.88 (0.75) in the compound 4, to 12.62/17.09 (0.74) in the compound 1, and to 10.21/18.41 (0.55) in the compound 5. For comparison, the shrinkage in going from Al(OH)BDC.H 2 BDC to Al(OH)BDC.H 2 O is even larger, 19.05/7.78 (0.41). The deformations are realized mainly through changes of the torsion angle V—O═C—C, which is the most flexible component of the framework. The packing density calculated for the guest molecule column of the compound 5 is 122.2 Å 3  per acetone molecule, which is almost identical to that of liquid acetone. In contrast, the guest packing densities calculated for the compound 3 and the compound 4 are both ca. 21% lower than the corresponding liquid densities of the guest molecules assuming a full occupancy, probably because the oriented interactions between the guest molecules and the framework BDC ligands also dictate the stoichiometry of the intercalated compounds. 
     Thiophene is also absorbed by VOBDC directly from the gas phase as shown in  FIG. 2 . Single crystals of VOBDC×0.71H 2 BDC were heated on a thermo-balance in flowing air to 350° C. to remove the H 2 BDC guest molecules as shown in the top, left plot. After cooling to room temperature the gas stream was switched to a 5% CH 4 /He stream. The data in  FIG. 2  show that methane is not absorbed under these conditions as shown in the bottom, left plot. The gas stream was switched to a 5% CH 4 /He stream saturated with thiophene at ambient temperature and a pressure of 1 atm (10 kPa at 20° C.). Rapid absorption occurs on exposure to methane/thiophene/He corresponding to the uptake of 0.88 molecules of thiophene per VOBDC in agreement with the liquid phase uptake as shown in the inset plot of  FIG. 2 . Similar results were obtained for the uptake of dimethyl sulfide, and thiophene at 1 kPa as tabulated in Table 1. 
     
       
         
           
               
             
               
                 TABLE 1 
               
             
            
               
                   
               
               
                 Gas Phase Adsorption by VOBDC 
               
            
           
           
               
               
               
               
               
            
               
                   
                 Formula 
                 +Δw % 
                 Molecules/fu a   
                 P b  (kPa) 
               
               
                   
                   
               
            
           
           
               
               
               
               
               
            
               
                   
                 (CH 3 ) 2 S 
                 34 
                 1.12 
                 66.9 
               
               
                   
                 C 4 H 4 S 
                 31.9 
                 0.88 
                 10 
               
               
                   
                 C 4 H 4 S c   
                 23.4 
                 0.65 
                 1 
               
               
                   
                   
               
               
                   
                   a formula unit; 
               
               
                   
                   b partial pressure, 
               
               
                   
                   c thiophene at 1 kPa. 
               
            
           
         
       
     
     The reversibility of thiophene uptake was investigated thermo-gravimetrically and by X-ray diffraction. A sample was saturated with thiophene on a thermobalance following the procedure described above. When the sample reached constant weight at ambient temperature, the temperature was raised to 150° C. Thiophene desorbed and the sample weight returned to its initial value as shown in the top, right and bottom, right plots of  FIG. 2 . An X-ray powder pattern of the final sample indicated complete retention of crystallinity. 
     A single crystal of [VOBDC](thiophene) was heated to 200° C. for 30 minutes to remove the thiophene. The results shows that the structure reverted back to space group Pnma and the complete absence of any electron density in the channels indicates complete desorption of thiophene. The lattice parameters are a=6.813(2) Å, b=16.248(4) Å, c=13.749(3) Å indicating a 1% smaller cell volume than of the compound 2 suggesting that annealing at &gt;200° C. is necessary to allow the framework to completely relax. 
     The structural details of the four intercalated compounds presented here and the selective and reversible removal of sulfur-containing molecules from methane show the importance of non-covalent oriented weak interactions in the packing of organic molecules within channels of a specific metal-organic framework. Such interactions, although relatively weak, can readily cause remarkable deformation and symmetry changes in the framework, which point to effective ways of manipulating known materials or designing new materials with targeted properties through intercalation chemistry. 
     Preparation and Characterization of the Generalized Absorbents and Absorbent/Absorbed Species Interaction 
     The metal oxide organic frameworks with the general composition M(OH)BDC×H 2 BDC where BDC=1,4-benzenedicarboxylate (C 8 H 4 O 4 ) and H 2 BDC is the corresponding acid (C 8 H 6 O 4 ) were first synthesized by Férey and co-workers who described in a series of papers the synthesis of compounds where M=Al, V, Cr, Fe. All of the compounds with the exception of V(III)OHBDC were obtained in polycrystalline form. 4,5,6,9a,18  In recent work, we have extended the class to include single crystals of Al(OH)BDC×0.7H 2 BDC, 7  In(OH)BDC×0.75H 2 BDC, 9  Fe(OH)BDC pyridine, 8  Fe(DMF)BDC, 8  and M(III)VO[Fe 0.28 V 0.72 OH 0.8 (NH 4 ) 0.2 (C 8 H 4 O 4 )]×0.53(C 8 H 6 O 4 ). 10  The synthesis of the Fe,V compound and Férey&#39;s observation 4  that the V(III) compound can be oxidized to V(IV) suggest the possibility of making V(IV)OBDC, directly, which we described above. 
     Referring now to  FIG. 3 , the structure of Al(OH)(C 8 H 4 O 4 )×0.7(C 8 H 6 O 4 )  6 , which was recently determined by single crystal X-ray diffraction is shown. The Al 3+  is coordinated to six oxygen atoms in distorted octahedral geometry and the octahedral Al—O centers are linked by sharing trans hydroxyl groups forming Al—OH—Al chains. The Al—OH—Al chains are bent with an angle of ˜129°. The oxygen atoms of the BDC groups occupy the equatorial positions of the octahedra. The BDC ligands bridge the chains to form a three dimensional framework with large diamond shaped channels parallel to the b axis as shown in  FIG. 3 . 
     As synthesized, the channels of Al(OH)(C 8 H 4 O 4 )×0.7(C 8 H 6 O 4 ) 6 are filled with H 2 BDC guest molecules that can be removed by heating to a temperature between about 380° C. and about 400° C. After removal of the guest molecules, one water molecule is absorbed on exposure to atmosphere at room temperature to give Al(OH)(C 8 H 4 O 4 )×H 2 O 7; the water molecules are located at the center of the channels. 
     Sorption Chemistry 
     The sorption behavior of the M(OH)BDC compounds has not been studied in detail for applications and is presently not well understood. The sorption chemistry of these materials is unusual and falls between the behavior of rigid three-dimensional host lattices and layer structures that can expand infinitely in a direction perpendicular to the layers. In the BDC compounds, the expansion is constrained so that the maximum area for a guest molecule is proportional to the square of the distance between metal oxide chains and decreases as the angle of the diamond decreases of the structure shown in  FIG. 3 . 
     The table summarizes some of the known sorbates based on our work and on literature data. The first thing to note is the paucity of data and the second is that insufficient data is available to discern systematic trends; there are no sorption isotherms available. The known sorbates include hydrogen bond acceptors, aromatics, and others. The energetics of sorption are determined by the guest-host interactions, mainly hydrogen bonding with the framework OH groups and π-π or C—H π interactions with the bridging ligands, and by guest-guest interactions which may similarly be due to hydrogen bond or π-π interactions. The framework Al—OH groups are only weakly (if at all) acidic. The strongest acceptors like water and DMF form hydrogen bonds, but because of π-π interactions M(OH)BDC readily absorb mesitylene, thiophene, and pyridine as shown in the data tabulated in Table 2. 
     
       
         
           
               
             
               
                 TABLE 2 
               
             
            
               
                   
               
               
                 Adsorption by M(OH)BDC of Various Compounds 
               
            
           
           
               
               
            
               
                 Compound 
                 Sorbate 
               
               
                   
               
            
           
           
               
               
               
               
               
               
               
            
               
                 Al(OH)BDC 
                 H 2 BDC 
                 H 2 O 
                 pyridine 
                 thiophene 
                 n-octane 
                 H 2   
               
               
                 V(OH)BDC 
                 H 2 BDC 
                 H 2 O 
                 diethylether 
                 mesitylene 
                 2-Me-1- 
               
               
                   
                   
                   
                   
                   
                 propanol 
               
               
                 Cr(OH)BDC 
                 H 2 BDC 
                 H 2 O 
                 DMF 
                   
                   
                 H 2   
               
               
                 Fe(OH)NDC 
                   
                   
                 pyridine 
               
               
                 Al(OH)NDC 
                   
                 H 2 O 
                 DMF 
               
               
                   
               
            
           
         
       
     
     EXPERIMENTS OF THE INVENTION 
     Examples 
     The following examples are included for the sake of the completeness of the disclosure and to illustrate the present invention, but in no way are these examples included for the sake of limiting the scope or teaching of this invention. 
     Example 1 
     The compound 1 was synthesized by hydrothermal reaction from a mixture of VO 2 , HCl, 1,4-benzene dicarboxylic acid (H 2 BDC) and H 2 O with molar ratios of 1:2:0.5:770. The mixture was heated at 220° C. in a sealed Teflon vessel for 3 days. Red brown prisms of the compound 1 were recovered as a major phase by vacuum filtering and drying in air, together with dark green impurities that were easily removed by washing with methanol. For the absorption measurements, red prism crystals of VOBDC×0.71H 2 BDC represented by the compound 1 were heated in air to 350° C. using a 3° C. min −1  heat-up rate to form VOBDC represented by the compound 2. Intercalation experiments were carried out by immersing crystals of the compound 2 in liquid aniline, thiophene and acetone. For gas phase absorption, crystals of the compound 1 were heated on a thermobalance to 350° C. in air to remove H 2 BDC. The sample was maintained at constant temperature for 30 minutes and then cooled to 28° C. When the weight was constant at 28° C., the air flow was switched to 5% methane in He. After the weight became constant, the flow of 5% methane in He was passed through a bubbler containing liquid (CH 3 ) 2 S. After a short time, the weight of VOBDC increased dramatically. 
     Example 2 
     This example illustrates the synthesis of VOBDC by three different methods. 
     A mixture of VO 2 , HCl, H 2 BDC, and H 2 O in the molar ratios 1:2:0.86:32 were placed in a Teflon lined steel autoclave. The mixture was heated at 220° C. in the sealed vessel for 6 d and then cooled to ambient temperature. Red brown prism-shaped crystals of VOBDC bigger than 500μ are obtained in &gt;60% yield, together with a dark green vanadium compound, which can be washed out easily by methanol. 
     A second synthesis used the same reaction conditions, but different starting reagents namely VOSO 4 ×3H 2 O, (NH 4 ) 2 BDC and H 2 O in the ratios 1:1:65. The product in the form of brown needles, is obtained in more than 95% yield. 
     In both of the syntheses described above the product is obtained in the form of VOBDC×H 2 BDC. The free acid is then removed by heating to 340° C. in air to obtain VOBDC. 
     A third synthesis was developed at lower reaction temperature and at 1 atmosphere pressure to eliminate the need for pressure vessels in scale up. The reactants VOSO 4 ×3H 2 O (2 mmol), (NH 4 ) 2 BDC (2 mmol), and DMF 20 mL were transferred into a round bottomed flask, which was fitted with a condenser. The mixture was heated with stirring at 160° C. for 3 days using an oil bath. A yellow brown powder was precipitated from the solution, filtered and washed with methanol. The product was confirmed to be VOBDC without extra acid molecules and requires no further treatment before use. 
     Example 3 
     This example illustrates the adsorption of thiophene from the gas phase by VOBDC. 
     Red prism crystals of VOBDC×H 2 BDC were heated on a thermobalance in air to 350° C. using a 3° C. min −1  heat-up rate. The temperature was maintained at constant temperature for 30 minutes and then cooled to room temperature, 28° C. When the weight was constant at 28° C., the air flow was switched to 5% methane in He. After the weight became constant, the flow of 5% methane in He was passed through a bubbler containing liquid (CH 3 ) 2 S. After a short time, the weight of VOBDC increased dramatically. After 1.5 minutes, the weight change saturated. The increase of 34%, corresponds to the adsorption of 1.25 molecules of (CH 3 ) 2 S. These results are shown graphically in  FIG. 4 . 
     Example 4 
     The same procedure was used as in Example 3 except that dimethyl sulfide replaced thiophene. These results are shown graphically in  FIG. 5 . 
     Example 5 
     This example illustrates the adsorption of thiophene from the gas phase by VOBDC. 
     A 5 cc/min flow of 5% methane in He balance flow was passed through a bubbler containing thiophene. The exit stream was mixed with 90 cc/min 5% methane in He and then passed into the thermobalance. At the lower thiophene partial pressure compare to that used in Example 3, a longer time (26 min) was needed to reach constant weight and a smaller weight uptake was observed. A-6(R-30). These results are shown graphically in  FIG. 6 . 
     Example 6 
     The same procedure was used as in Example 4 except that toluene replaced dimethyl sulfide. P-59-1-2(27). These results are shown graphically in  FIG. 7 . 
     Example 7 
     The same procedure was used as in Example 4 except that octane replaced dimethyl sulfide. A-4-1(R-27). These results are shown graphically in  FIG. 8 . 
     Example 8 
     The table summarizes the weight changes and time to equilibrium for Examples 3-7. Data for hexadecane are also given in the Table 3 obtained using conditions of Example 3. In this case the time to reach saturation is much longer (&gt;13 h). 
     
       
         
           
               
             
               
                 TABLE 3 
               
             
            
               
                   
               
               
                 Gas Phase Adsorption using VOBDC 
               
            
           
           
               
               
               
               
               
            
               
                 Example # 
                 Adsorbate 
                 Formula 
                 +Δw % 
                 Time (min) 
               
               
                   
               
            
           
           
               
               
               
               
               
            
               
                 3 
                 Dimethyl Sulfide 
                 (CH 3 ) 2 S 
                 34 
                 1.5 
               
               
                 4 
                 Thiophene 
                 C 4 H 4 S 
                 31.9 
                 3 
               
               
                 5 
                 Thiophene 
                 C 4 H 4 S 
                 23.4 
                 26 
               
               
                 6 
                 Toluene 
                 C 6 H 5 CH 3   
                 26 
                 14 
               
               
                 7 
                 Octane 
                 C 8 H 8   
                 21 
                 34 
               
               
                 8 
                 Hexadecane 
                 C 16 H 34   
                 12.5 
                 &gt;13 h 
               
               
                   
               
            
           
         
       
     
     Example 9 
     This example illustrates the liquid phase adsorption of thiophene from an octane sample. 
     VOBDC.xH 2 BDC red crystals were ground and heated at 400° C. for 10 h in air to remove the guest H 2 BDC molecules. A sample of VOBDC (0.5 g) was placed in a flask, and 15 mL of a solution of 2000 ppm of thiophene in octane added. The mixture was stirred and heated to 60° C. using an oil bath. Samples of the supernatant liquid were remove at regular intervals and analyzed using gas chromatography. A Shimadzu (SSI) Gas Chromatograph 2010 used to measure the thiophene contents of the samples was calibrated by standard solutions of thiophene in octane as tabulated in Table 4. These results are also shown graphically in  FIG. 9 . 
     
       
         
           
               
             
               
                 TABLE 4 
               
             
            
               
                   
               
               
                 VOBDC Adsorption in 2000 ppm of Thiophene/Octane Solution 
               
            
           
           
               
               
               
            
               
                   
                 Time (min) 
                   
               
               
                 Sample number 
                 samples taken 
                 GC measurement (ppmw) 
               
               
                   
               
            
           
           
               
               
               
            
               
                 0 
                 0 
                 2000 
               
               
                 1 
                 40 
                 1506 
               
               
                 2 
                 75 
                 821 
               
               
                 3 
                 132 
                 640 
               
               
                 4 
                 220 
                 574 
               
               
                 5 
                 280 
                 375 
               
               
                   
               
            
           
         
       
     
     Example 10 
     A 0.5 g sample of VOBDC was added to 60 ml of octane containing 100 ppm of thiophene. Samples of the supernatant liquid were remove at regular intervals and analyzed using gas chromatography. A Shimadzu (SSI) Gas Chromatograph 2010 used to measure the thiophene contents of the samples was calibrated by standard solutions of thiophene in octane as tabulated in Table 5. 
                     TABLE 5                  VOBDC Adsorption in 2000 ppm of Thiophene/Octane Solution                         Sample number   Time (min)   GC measurement (ppm)                                 0   0   93       1   10   85       2   40   83       3   100   81       4   160   77                    
These results are also shown graphically in  FIG. 10 .
 
     APPARATUS OF THE INVENTION 
     Referring now the  FIG. 11 , an embodiment of an apparatus for reducing sulfur in a fluid, generally  100 , is shown to include a fluid source reservoir  102  having an outlet  104  and filled with an input fluid  106 , where the input fluid  106  includes sulfur-containing components. The apparatus  100  also includes a treating vessel  108  having an inlet  110 , an interior section  112  filled with a MOADA absorbent  114  of this invention and two outlets  116   a &amp; b . The source reservoir outlet  104  is connected to the treating vessel inlet  110  via a conduit  118  including a first inline valve  120 . The first inline valve  120  is adapted to start or stop the flow of the input fluid  106  from the source reservoir  102  to the treating vessel  108 . The apparatus  100  also includes an output reservoir  122  including an inlet  124 , where the output reservoir  122  is adapted to receive an output fluid  126 , where the output fluid includes lower concentrations of the sulfur-containing components. The treating vessel outlet  116   a  is connected to the output reservoir inlet  124  via a conduit  128  including a second inline valve  130 . The second inline valve  130  is adapted to start or stop the flow of the output fluid  126  from the treating vessel  108  to the output reservoir  122 . The apparatus  100  also includes a sulfur-containing component collection vessel  132  including an inlet  134  and adapted to be filled with the absorbed sulfur-containing components  136 , where the sulfur-containing component collection vessel  132  is adapted to receive the sulfur-containing components  136  absorbed by the MOADA  114  during regeneration of the absorbent  114 . The treating vessel outlet  116   b  is connected to the collection vessel inlet  134  via conduits  138  including a third inline valve  140 . The third inline valve  140  is adapted to start or stop the flow of the sulfur-containing components  136  from the treating vessel  108  to the collection vessel  132  during absorbent  114  regeneration. It should be recognized that the input and output reservoirs  102  and  122  can be vessels that have an outlet (not shown), a tank car, a pipeline, or any other type of fluid supply system or transport system. It should also be recognized that the collection vessel  132  can be a vessel that has an outlet, or any other type of vessel such as a tank car, a pipeline or any other type of fluid transport system. 
     The apparatus  100  operates by closing the third valve  140  and opening the first and second valves  120  and  130  to allow the input fluid  106  to flow through the absorbent  114  in the interior  112  of the treating vessel  108 . As the fluid  106  passes through the interior  112  of the vessel  108 , a portion of the sulfur-containing components  136  in the fluid  106  are absorbed by the absorbent  114  to produce the output fluid  126 . The output fluid  126  is then stored in the output reservoir  122 . The size of the interior  112 , the fluid flow rate, the temperature and the pressure in the interior  112  of the vessel  108  are adjusted to achieve a desired reduction in the sulfur-containing components  136  in the output fluid  126 . The input fluid  106  is processes until the absorbent is near or at its saturation level, at which point the valves  120  is closed and remaining fluid is drained from the vessel  108  into the output reservoir  122 . Alternatively, the fluid remaining in the vessel  108  can be forced out by a gas. Once the remaining fluid has been removed from the vessel  108 , the valve  130  is closed and the valve  140  is opened and the vessel  108  is heated to a release temperature. At the release temperature, the absorbed sulfur-containing components are released and flow into the collection reservoir  132 . The regeneration process can include the use of a gas such as air or an inert gas such as nitrogen to aid in the regeneration process. After the sulfur-containing components have been desorbed, the valve  140  is closed and the valves  120  and  130  are opened and more input fluid  106  is processed. Processing is continued until the absorbent is no longer active. However, the inventors believe that the absorbent should work indefinitely if it is not fouled by materials that are not reversible absorbed. In most embodiments, the absorbents can be regenerated at least 10 times. In certain embodiments, the absorbents can be regenerated at least 20. In other embodiments, the absorbents can be regenerated at least 50. In other embodiments, the absorbents can be regenerated at least 100. In other embodiments, the absorbents can be regenerated at least 500. In other embodiments, the absorbents can be regenerated at least 1000. 
     Referring now the  FIG. 12 , an embodiment of an apparatus for reducing sulfur in a fluid, generally  200 , is shown to include a fluid source reservoir  202  having an outlet  204  and filled with an input fluid  206 , where the input fluid  206  includes sulfur-containing components. The apparatus  200  also includes four treating vessel  208   a - d , each vessel  208   a - d  have an inlet  210   a - d , an interior section  212   a - d  filled with a MOADA absorbent  214   a - d  of this invention and two outlets  216   a - d  and  217   a - d . The source reservoir outlet  204  is connected to the treating vessel inlets  210   a - d  via conduits  218   a - d  including first inline valves  220   a - d . The first inline valves  220   a - d  are adapted to start or stop the flow of the input fluid from the source reservoir  202  to the treating vessel  208   a - d . The apparatus  200  also includes an output reservoir  222  including an inlet  224 , where the output reservoir  222  is adapted to receive an output fluid  226 , where the output fluid includes lower concentrations of the sulfur-containing components. The treating vessel outlets  216   a - d  are connected to the output reservoir inlet  224  via conduit  228   a - d  including second inline valves  230   a - d . The second inline valves  230   a - d  is adapted to start or stop the flow of the output fluid from the treating vessels  208   a - d  to the output reservoir  222 . The apparatus  200  also includes a sulfur-containing component collection vessel  232  including an inlet  234  and filled with the absorbed sulfur-containing components  236 , where the sulfur-containing component collection vessel  232  is adapted to receive the sulfur-containing components  236  absorbed by the MOADA absorbents  214   a - d  during regeneration of the absorbent  214   a - d . The treating vessel outlets  217   a - d  are connected to the collection vessel inlet  234  via conduits  238   a - d  including third inline valves  240   a - d . The third inline valves  240   a - d  are adapted to start or stop the flow of the sulfur-containing components  236  from the treating vessels  208   a - d  to the collection vessel  232  during absorbent  214   a - d  regeneration. It should be recognized that the input and output reservoirs  202  and  222  can be vessels that have an outlet (not shown), a tank car, a pipe-line, or any other type of fluid supply system. It should also be recognized that the collection vessel  232  can be a vessel that has an outlet, or any other type of vessel. It should also be recognized that the absorbents, although generally the same, can be different so that different fluids can be treated. It should also be recognized that the four vessels can also be configured so that the input fluid flows through each vessel consecutively and each vessel can include a different absorbent of this invention, where the absorbents can be tailored to remove specific sulfur-containing components. 
     The apparatus  200  operates by closing the valves  240   a - d  and opening some or all of the first and second valves  220   a - d  and  230   a - d  to allow the input fluid  206  to flow through some of all of the absorbent  214   a - d  in the interiors  212   a - d  of the treating vessels  208   a - d . As the fluid  206  passes through the interiors  212   a - d  of the vessels  208   a - d , a portion of the sulfur-containing components  236  in the fluid  206  are absorbed by the absorbents  214   a - d  to produce the output fluid  226 . The output fluid  226  is then stored in the output reservoir  222 . The fluid flow rate, the temperature and pressure in the interiors  212   a - d  of the vessels  208   a - d  are adjusted to achieve a desired reduction in the sulfur-containing components  236  in the input fluid  206 . The input fluid  206  is processes until the absorbent is near or at its saturation level, at which point some or all of the valves  220   a - d  are closed and remaining fluid is drained from the vessels  208   a - d  into the output reservoir  222 . Alternatively, the fluid remaining in the vessels  208   a - d  can be forced out by a gas. Once the remaining fluid has been removed from the vessels  208   a - d , some of all of the valves  240   a - d  are opened and the vessel is heated to a release temperature. At the release temperature, the absorbed sulfur-containing components are released and flow into the collection reservoir  232 . The regeneration process can include the use of a gas such as air or an inert gas such as nitrogen to aid in the regeneration process. After the sulfur-containing components have been desorbed, some or all of the valve  240   a - d  are closed and some or all of the valves  220   a - d  and  230   a - d  are opened and more input fluid  206  is processed. Processing is continued until the absorbent is longer active. However, the inventors believe that the absorbent should work definitely if it is not fouled by materials that are not reversible absorbed. The absorbents can be regenerated at least 10 times. In certain embodiments, the absorbents can be regenerated at least 20. In other embodiments, the absorbents can be regenerated at least 50. In other embodiments, the absorbents can be regenerated at least 100. In other embodiments, the absorbents can be regenerated at least 500. In other embodiments, the absorbents can be regenerated at least 1000. 
     The system  200  is designed to run on a semi-continuous and/or continuous because one or more of the vessels  208   a - d  can be processing fluid, while one or more of the vessels  208   a - d  are being regenerated. The method operates by causing valves to switch the flow of the input fluid between vessels so that fluid can be processed on essentially a continuous basis. 
     Referring now the  FIG. 13 , an embodiment of a fluid bed apparatus for reducing sulfur in a fluid, generally  300 , is shown to include a fluid bed treating column  302 . The column  302  includes a fluid inlet  304 , a fluid outlet  306 , an absorbent inlet  308 , an absorbent outlet  310  and a screen  312 . The screen  312  is adapted to prevent the absorbent particles  318  from falling into a lower section  314  of the column  302 . The column  302  also includes a fluidized absorbent section  316  including the fluidized absorbent particles  318  and a top section  320 , where treated fluid free of the absorbent particles  318  proceeds upward and out of the column  302  via the fluid outlet  306 . The fluid inlet  304  is connected to an inlet fluid handling system (not shown) and the fluid outlet  306  is connected to an output fluid handling system (not shown). The absorbent outlet  310  is connected to a regenerator  322  via a first conduit  324  and the regenerator  322  is connected to the absorbent inlet  308  via a second conduit  326 . As the absorbent particles  318  are circulated from the treating column  302  to the regenerator  322 , where the absorbed sulfur-containing components absorbed by the absorbent particles  318  in the fluidized absorbent section  316  of the column  302  are desorbed. The flow rate of the absorbent, its size and shape, the flow rate of the fluid, the size, temperature and pressure of the treating column and the size, temperature and pressure of the regenerator are adjusted so that a desired reduction in sulfur-containing components can be achieved. The regenerator  322  is connected to a sulfur-containing component collection vessel  328  via a conduit  330 . The apparatus  300  is designed to be operated on a continuous basis with absorbent being added and withdrawn as needed. 
     Inlet fluid enters the apparatus  300  on a continuous basis through the inlet fluid inlet  304 . The fluid travels up the column  302  as indicated by the heavy grey arrows. As the fluid flow up, it passes through the screen  312 , with sufficient velocity or flow rate to suspend the absorbent particles  318  in the fluid. Generally, the fluid is a gas, but the fluid can be a gas liquid mixture provided that the particle fluidization is achieved. In the absorbent fluidized section, sulfur-containing components in the inlet fluid are absorbed by the absorbent, producing an output fluid with lower concentrations of the sulfur-containing components. The output fluid then flows upward into the upper section  320  of the column which due to column conditions is substantially fee of absorbent particles  318  and exits the column  302  via the fluid outlet  306 . Simultaneously, regenerated or fresh absorbent particles  318  are being fed into the column  302  via the absorbent inlet  308  and spent absorbent is withdrawn via the absorbent outlet  310  as shown by the heavy black arrows. The spent absorbent  318  is regenerated in the regenerator  322 , where it is heated to desorb the absorbed sulfur-containing components, which are collected in the collector  328 . The regenerated absorbent  318  is then fed back into the column  302  as shown by the heavy black arrows. 
     Referring now the  FIG. 14 , an embodiment of a moving bed apparatus for reducing sulfur in a fluid, generally  400 , is shown to include a moving bed treating column  402 . The column  402  includes a fluid inlet  404 , a fluid outlet  406 , an absorbent inlet  408 , an absorbent outlet  410  having a collector  412  and screens  414 . The screens  414  are adapted to prevent an absorbent  416  from falling into a lower section  418  of the column  402 . The column  402  also includes a moving absorbent section  420  including the absorbent  416 . The fluid inlet  404  is connected to an input fluid handling system (not shown) and the fluid outlet  406  is connected to an output fluid handling system (not shown). The absorbent outlet  410  is connected to a regenerator  422  via a first conduit  424  and the regenerator  422  is connected to the absorbent inlet  408  via a second conduit  426 . As the absorbent  416  is circulated from the treating column  402  to the regenerator  422  as shown by the heavy black arrows, the absorbed sulfur-containing components absorbed by the absorbent  416  in the moving absorbent section  420  of the column  402  are desorbed in the regenerator  422 . The flow rate of the absorbent, its size and shape, the flow rate of the fluid, the size, temperature and pressure of the treating column and the size, temperature and pressure of the regenerator are adjusted so that a desired reduction in sulfur-containing components can be achieved. The regenerator  422  is connected to a sulfur-containing component collection column  428  via a conduit  430 . The apparatus  400  is designed to be operated on a continuous basis with absorbent being added and withdrawn as needed. The moving bed apparatus  400  operates in a manner analogous to the fluid bed apparatus  300 . 
     Referring now the  FIG. 15A , an embodiment of a gas treating apparatus for reducing sulfur in a gas, generally  500 , is shown to include a gas cylinder  502 . The cylinder  502  includes a valve  504 . The apparatus  500  also includes a cartridge  506  including an inlet  508 , an outlet  510 , an absorbent  512  and an indicator  514 . The cylinder valve  504  is connected to the cartridge inlet  508  via a first conduit  516 . The cartridge outlet  510  is connected to a system  518  at an inlet  520  via a second conduit  522 , where the system  518  adapted to use the gas after is passes through absorbent  512  in the cartridge  506 . 
     Referring now the  FIG. 15B , an embodiment of a fuel treating apparatus for reducing sulfur in a fuel, generally  550 , is shown to include a fuel reservoir or tank  552 . The tank  552  includes an outlet  554 . The apparatus  550  also includes a cartridge  556  including an inlet  558 , an outlet  560 , an absorbent  562  and an indicator  564 . The reservoir or tank outlet  554  is connected to the cartridge inlet  558  via a first conduit  566 . The cartridge outlet  560  is connected to a fuel consuming system  568  at an inlet  570  via a second conduit  572 , where the system  568  adapted to use the fuel after is passes through absorbent  562  in the cartridge  556 . The fuel consuming system  568  can be an internal combustion engine, a fuel power generator, or any other system that consumes a fuel that can include various levels of undesirable sulfur-containing components. 
     REFERENCES CITED IN THE INVENTION 
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Loiseau, C. Serre, C. Huguenard, G. Fink, F. Taulelle, M. Henry, T. Bataille, G. Férey,  Chem .- Eur. J.  2004, 10, 1373.   7 a) T. R. Whitfield, X. Wang, L. Liu, A. J. Jacobson, Solid State Sci. 2004, 7, 1096; b) T. R. Whitfield, X. Wang, A. J. Jacobson,  Mater. Res. Soc. Symp. Proc.  2003, 755, 191.   8 E. V. Anokhina, M. Vougo-Zanda, X. Wang, A. J. Jacobson,  J. Am. Chem. Soc.  2005, 127, 15001.   9 a) G. Férey, M. Latroche, C. Serre, F. Millange, T. Loiseau, A. Percheron-Guégan,  Chem. Commun.  2003, 2976; b) N. L. Rosi, J. Eckert, M. Eddaoudi, D. T. Vodak, J. Kim, M. O&#39;Keeffe, O. M. Yaghi,  Science  2003, 300, 1127.   10 a) D. N. Dybtsev, H. Chun, S. H. Yoon, D. Kim, K. Kim,  J. Am. Chem. Soc.  2004, 126, 32; b) A. C. Sudik, A. R. Millward, N. W. Ockwig, A. P. Cöte, J. Kim, O. M. Yaghi,  J. Am. Chem. Soc.  2005, 127, 7110; c) L. Pan, K. M. Adams, H.; X. Wang, C. Zheng, Y. Hattori, K. Kaneko,  J. Am. Chem. Soc.  2003, 125, 3062.   11 a) S. Bourrelly, P. L. Llewellyn, C. Serre, F. Millange, T. Loiseau, G. Férey,  J. Am. Chem. Soc.  2005, 127, 13519; b) K. Seki,  Phys. Chem. Chem. Phys.  2002, 4, 1968; c) T. Düren, L. Sarkisov, O. M. Yaghi, R. Q. Snurr,  Langmuir  2004, 20, 2683.   12 U. Mueller, M. Schubert, F. Teich, H. Puetter, K. Schierle-Arndt, J. Pastre  J. Mater. Chem.  2006, 16, 626.   13 Elemental analysis results for 1: V, 14.8% obs. (14.6% calc.); C, 47.10% obs. (47.08% calc.); H, 2.68% obs. (2.37% calc.). Crystal data for 1: space group P2 1 2 1 2 1 , a=6.8094(3), b=12.4220(6), c=17.1733(8) Å, V=1452.6(1) Å 3 , Z=4, T=223 K, d calc =1.593 g cm −3 . Single crystal data were collected on a Siemens SMART/CCD diffractometer (14526 reflections total, 3498 unique, R int =0.0478). The structure was solved and refined with the SHELXTL software package. Final refinements converged at R1=0.0394 for all 3498 reflections and 188 parameters.   14 Thermogravimetric analyses of 1 carried out in air at 3° C./min showed two weight-loss events. The first between 320 and 400° C. corresponds to the loss of the guest H 2 BDC. The second between 440 and 480° C. corresponds to the loss of framework BDC. A sample heated at 390° C. for 10 h was confirmed to be identical to MIL-47 by IR (disappearance of the band at ca. 1700 cm −1  characteristic of free —C═O species) and single crystal X-ray diffraction (VOBDC, 2: space group Pnma, a=6.8249(8), b=16.073(2), c=13.995(2), T=293 K, d calc =1.000 g cm −3 , R1=0.0443 for all 1904 unique reflections and 67 parameters).   14 After immersing the VOBDC crystals in the corresponding guest liquid in air at room temperature for ca. 1 h, a suitable crystal for each intercalation phase was selected and sealed in a capillary together with the guest liquid in air and mounted on a Siemens SMART/CCD diffractometer for X-ray data collection. Crystal data for 3: space group P2 1 2 1 2 1 , a=6.785(1), b=13.031(2), c=16.851(2) Å, V=1489.8(4) Å 3 , Z=4, T=223 K, d calc =1.445 g cm 3 . 12940 reflections total, 3511 unique, R int =0.0698. R1=0.0394 for all 3511 unique reflections and 180 parameters. Crystal data for 4: space group P2 1 2 1 2 1 , a=6.786(1), b=12.618(2), c=17.086(3) Å, V=1463.0(4) Å 3 , Z=4, T=223 K, d calc =1.503 g cm −3 . 8691 reflections total, 3368 unique, R int =0.0641. R1=0.0695 for all 3368 unique reflections and 174 parameters. Crystal data for 5: space group Pnma, a=6.796(3), b=18.410(8), c=10.214(4) Å, V=1278.0(9) Å 3 , Z=4, T=223 K, d calc =1.431 g cm 3 . 7544 reflections total, 1006 unique, R int =0.2022. R1=0.134 for all 1006 unique reflections and 43 parameters. The crystal quality of 5 is comparatively poor probably because of the large unit cell changes during intercalation.   15 C. Janiak,  Dalton Trans.  2000, 3885.   16 H. Suezawa, T. Yoshida, Y. Umezawa, S. Tsuboyama, M. Nishio,  Eur. J. Inorg. Chem.  2002, 3148.   17 a) D. R. Allan, S. J. Clark, R. M. Ibberson, S. Parsons, C. R. Pulham, Sawyer, L.  Chem. Commun.  1999, 751; b) F. H. Allan, C. A. Baalham, J. P. M. Lommerse, P. R. Raithby,  Acta Cryst.  1998, B54, 320.   18 Barthelet, K.; Marrot, J.; F ey, G.; Riou, D.  VIII ( OH ){ O   2   C—C   6   H   4   —CO   2 }.( HO   2   C—C   6   H   4   —CO   2   H ) x ( DMF ) y ( H   2   O ) z  ( or MIL -68),  a new vanadocarboxylate with a large pore hybrid topology: reticular synthesis with infinite inorganic building blocks?  Chem. Commun. 2004, 520-521.       

     All references cited herein are incorporated by reference. Although the invention has been disclosed with reference to its preferred embodiments, from reading this description those of skill in the art may appreciate changes and modification that may be made which do not depart from the scope and spirit of the invention as described above and claimed hereafter.