method of separating isotopes from mixtures thereof and a 99mo / 99mtc generator

专利摘要:
PREPARATION OF MICROPOROUS COMPOSITE MATERIAL BASED ON CHITOSAN AND ITS APPLICATIONS. The present invention relates to cross-linked chitosan adsorbents with microporous glutaraldehyde, methods for producing and using them and a generator for the 99Mo radioisotope containing the adsorbents.
公开号:BR112013023711B1
申请号:R112013023711-2
申请日:2012-03-19
公开日:2020-11-03
发明作者:Shameem Hasan
申请人:Perma-Fix Environmental Services, Inc；
IPC主号:

专利说明:

This application claims benefit from United States Provisional Application Serial No. 61 / 453,772, filed on March 17, 2011, the content of which is incorporated herein by reference in its entirety. BACKGROUND Field
Described here are methods for modifying chitosan that increase its versatility as adsorbents, particularly as radioisotope adsorbents, as well as the ability of these materials to function in environments where radioactivity is present. Also described are the materials themselves, as well as methods for using them to separate and purify radioisotopes and to separate and purify contaminated materials, in particular those radioactive and non-radioactive currents contaminated by metal ions, especially those of heavy metals. Description of the Related Art
Radioactive isotopes are widely used, particularly in the field of nuclear medicine, both for therapy and imaging. However, these materials can present production, storage and disposal challenges due to their radioactivity, as well as their often significant half-life.
More particularly, in the radiopharmaceutical field, 99mTc (having a half-life ti / 2 = 6h), is one of the most widely used radioisotopes in diagnostic medicine, obtained from the decay product of "Mo (ti / 2 = 66 h) 99mTc is a pure gamma emitter (0.143 MeV) ideal for use in medical applications due to its short half-life (6 hours) .It is used in 80-85% of the approximately 25 million nuclear medicine diagnostic procedures performed each year. "Parental Mo can be produced by irradiating" Mo with thermal / epidermal neutrons in a nuclear reactor, but much of the worldwide supply of "Mo originates from the highly enriched uranium fission product (Highly Enriched Uranium - HEU) in a reactor. The HEU process generates large amounts of radioactive waste and does not allow reprocessing of unused uranium due to concerns about the proliferation of weapons.
Enriched uranium (LEU, 20 percent or less than 235U) could be used as a substitute, but it would produce large volumes of waste due to the large amounts of unusable 235U present. Currently, most of the worldwide supply of "Mo comes from sources outside the United States. Recent interruptions in the production of" Mo from these sources have disrupted medical procedures and demonstrated the unreliability of the supply chain. This highlights the need for alternative economically viable sources to produce "mTc from" Mo.
The main concerns with "Mo produced by neutron capture, when compared to the material produced by common fission described above, involve both the lower Curie yield and lower specific activity. The specific activity is significantly less and is of great concern because of impacts on the size of the "Mo /" mTc generator, efficiency and functionality. Therefore, the use of molybdate with less specific activity is only possible with a more efficient adsorbent to reduce the generator size and obtain a usable dose in terms of Several research works have been directed to the use of a molybdenum gel generator. See Marageh, MG et al., "Industrialscale production of" mTc generators for clinical use based on zirconium molybdate gel, "Nuclear Technology, 269, 279 -284 (2010); Monoroy- Guzman, F. et al., "99Mo / 99mTc generators performances prepared from zirconium molybdate gels" J. Braz. Chem. Soc., 19, 3, 380-388 (2008). Others focus on preparing a "Mo /" mTc generator based on polymeric or inorganic oxide as an adsorbent material for "Mo. See Masa-kazu, T. et al.," A "mTc generator using a new organic polymer absorbent for (n, y) "Mo", Appl. Radia. Isot., 48, 5, 607-711 (1997); Qazi, QM et al., "Preparation and evaluation of hydrous titanium oxide as a high affinity adsorbent for molybdenum ("Mo) and its potential for use in" mTc generator ", Radiochim. Acta, 99, 231-235 (2011).
However, such medical uses require that "mTc is produced in a highly purified form. For example, when" mTc is produced from the decay of "Mo, it is important to achieve a high degree of separation of the two elements in order to meet requirements regulatory requirements.
One approach to achieve this level of purity is to separate "mTc from" Mo using a selective, highly efficient adsorbent, for example, to adsorb "Mo and elute" mTc. Attempts have been made to use alumina as such an adsorbent. However, this alumina allows an efficiency for "Mo of about 25 mg / g of adsorbent. Consequently, there remains a need in the art for an absorbent that is efficient in adsorbing" Mo and resistant to the adverse effects of ionizing radiation. you. In addition, there remains a need for an adsorbent that is highly selective for "Mo, that is, that is able to adsorb" Mo while allowing good "mTc release.
More generally, there is still a need for an adsorbent that is readily available, that is, can be produced from readily available materials, and that is customized, through modification, to have one or more functional groups (which may be the same or different), allowing the material to remove constituents from a process stream that requires such purification and is resistant to degradation by ionizing radiation.
The ion exchange process, which has been used for decades to separate metal ions from an aqueous solution, is often compared to adsorption. The primary difference between these two processes is that ion exchange is a stoichiometric process that involves electrostatic forces within a solid matrix whereas, in adsorption separation, solute uptake on the solid surface involves both electrostatic forces and Van der Waals forces . In an attempt to find a suitable ion exchange resin for removing cesium and strontium from the effluent, several researchers have tried a series of inorganic and organic bio-adsorbent substances, with a varying degree of success. See Gu, D., Nguyen, L, Philip, C.V., Huckmen, M.E. and Anthony, R.G. "Cs + ion exchange kinetics in complex electrolyte solutions using hydrous crystalline silicotitanates", Ind. Eng. Chem. Res., 36, 5377-5383, 1997; Pawaskar, C.S., Mohapatra, P.K. and Manchanda, V.K. "Extraction of actinides fission products from salt solutions using polyethylene glycols (PEGs)", Journal of Radioanalytical and Nuclear Chemistry, 242 (3), 627-634, 1999; Dozol, J.F., Simon, N., Lamare, V., et al. "A solution for cesium removal from high salinity acidic or alkaline liquid waste: The Crown calyx [4] arenas", Sep. Sci. Technol., 34 (6 & 7), 877-909, 1999; Arena, G., Contino, A., Margi, A. et al. "Strategies based on calixcrowns for the detection and removal of cesium ions from alkali-containing solutions". Ind. Chem. Res., 39, 3605-3610, 2000.
However, the main disadvantages with the ion exchange process are the cost of the material and regeneration for repeated use when treating radioactive currents. See Hassan, N., Adu-Wusu, K. and Marra, J.C., "Resorcinol-formaldehyde adsorption of cesium (Cs +) from Hanford waste solutions-Part I: Batch equilibrium study", WSRC-MS-2004. The cost of disposal is also an important issue. The success of the adsorption process depends largely on the cost and capacity of the adsorbents and ease of regeneration.
Chitosan is a partially acetylated glucosamine polymer found in the cell walls of fungi. It results from the deacetylation of chitin, which is a primary component of crustacean shells and available in abundance in the wild. This biopolymer is very effective in adsorbing metal ions due to its ability to form a complex due to the high content of amino and hydroxyl functional groups. In its natural form, chitosan is soft and has a tendency to clump or form gels in an acidic medium. In addition, chitosan, in its natural form, is not porous and the specific binding sites of this biopolymer are not readily available for absorption. However, it is necessary to provide physical support and chemical modification to increase the accessibility of metal bonding sites for in-process applications. It is also essential that the metal bonding functional group is maintained after any modification.
It is well known that polysaccharides can be degraded due to splitting of glycosidic bonds by ionizing radiation. IAEA-TECDOC-1422, "Radiation processing of polysaccharides' International Atomic Energy Agency, November 2004. The hydrogel based on oligosaccharides and their derivatives has been extensively studied, but very limited work has been reported so far regarding the impact of radiation on microporous composite materials based on chitosan and its ability to absorb metal ions.
Chitosan is a non-toxic and biodegradable material. It has been investigated for several new applications due to its availability, polycationic character, membrane effect, etc. The amino group present in the chitosan structure is the active metal binding site, but it also takes the chitosan soluble in weak acid. In an acidic environment, chitosan tends to form a gel that is not suitable for the adsorption of metal ions in a continuous process.
Several reports indicate that the crosslinking of chitosan with glutaraldehyde produces chitosan resistant to acid or alkali. See Elwakeel, K.Z., Atia, A.A. and Donia, A.M. "Removal of Mo (VI) as oxoanions from aqueous solutions using chemically modified magnetic chitosan resins", Hydro-metallurgy, 97, 21-28, 2009; Chassary, P., Vincent, T. and Guibal, E. "Metal anion sorption on chitosan and derivative materials: a strategy for polymer modification and optimum use", Reactive and Functional Polymers, 60, 137- 149, 2004; Velmurugan, N., Kumar, G.G., Han, S.S., Nahm, K.S. and Lee, Y.S. "Synthesis and characterization of potential fungicidal silver nano-sized particles and chitosan membrane containing silver particles", Iranian Polymer Journal, 18 (5), 383-392, 2009. Glutaraldehyde is a five-carbon molecule terminated at both ends by aldehyde groups which are soluble in water and alcohol, as well as in organic solvents. It reacts quickly with chitosan amine groups during cross-linking through Schiff's reaction and generates thermally and chemically stable cross-links. See Migneault, I., Dartiguenave, C., Bertrand, M.J. and Waldron, K.C. "Gluteraldehyde: behavior in aqueous solution, reaction with proteins, and application to enzyme crosslinking", Bio Techniques, 37 (5), 790-802, 2004. Amine groups are also considered to be active metal binding sites for chitosan. Therefore, it is reported that, through crosslinking with glutaraldehyde, chitosan becomes resistant to acid or alkali, but the metal adsorption capacity will be reduced. Li and Bai (2005) proposed a method to coat the chitosan amino group by treatment with formaldehyde before crosslinking with glutaraldehyde which was then removed from the chitosan structure by washing carefully with a 0 HCI solution, 5 M. Li, Nan and Bai, R. "A novel amine-shielded surface cross-linking of chitosan hydrogel beads for enhanced metal adsorption performance", Ind. Eng. Chem. Res., 44, 6692-6700, 2005.
The crosslinking of chitosan with different functional groups is known to depend mainly on the crosslinking reaction conditions, such as pH, temperature, ionic concentration, and the surface charge of the materials.
Sing et al. (2006) showed that the swelling properties of crosslinked chitosan hydrogel with formaldehyde depend on the responsive behavior of pH, temperature and ionic resistance. Singh, A., Narvi, S.S., Dutta, P.K. and Pandey, N.D. "External stimuli response on a novel chitosan hydrogel crosslinked with formaldehyde", Bull. Mater. Sci., 29 (3), 233-238, 2006.
The chitosan surface charge that determines the type of bond that forms between the crosslinking agent and chitosan depends on the pH of the solution. Hasan, S., Krishnaiah, A., Ghosh, T.K., Viswanath, D.S., Boddu, V.M. and Smith, E. D. "Adsorption of divalent cadmium from aqueous solutions onto chitosan-coated perlite beads", Ind. Eng. Chem. Res., 45, 5066-5077, 2006. The point of zero charge (Point of Zero Charge - PZC) of pure chitosan is in the pH range 6.2-6.8. See Hasan, S., Ghosh, T.K., Viswanath, D.S., Loyalka, S.K. and Sengupta, B. "Preparation and evalua- tion of fullers earth for removal of cesium from waste streams", Separation Science and Technology, 42 (4), 717-738, 2007. Chitosan is not soluble in an alkaline pH but, at an acidic pH, the amine groups present in chitosan may undergo protonation to NH3 + or (NH2-H3O) +. Li et al. (2007) reported cross-linked chitosan globules / polyvinyl alcohol (PolyVinyl Alcohol - PVA) with high mechanical resistance. They observed that the H + ions in the solution can act as protection of amino groups of chitosan during the crosslinking reaction. Li, M., Cheng, S. and Yan, H. "Preparation of crosslinked chitosan / poly (vinyl alcohol) blend beads with high mechanical strength", Green Chemistry, 9, 894-898, 2007.
Farris et al. (2010) studied the reaction mechanism for crosslinking gelatin with glutaraldehyde. Farris, S., Song, J. and Huang, Q. "Alternative reaction mechanism for the cross-linking of gelatin with gluteraldehyde", J. Agric. Food Chem., 58, 998-1003, 2010. They suggested that, at higher pH values, the cross-linking reaction is regulated by the Schiff's base reaction whereas at a low pH, the reaction may also involve -OH groups hydroxyproline and hydroxylysine, leading to the formation of hemiacetals.
Hardy et al. (1969) proposed that, at an acidic pH, glutaraldehyde is in equilibrium with its cyclic hemiacetal and polymers of the cyclic hemiacetal and an increase in temperature produces the free aldehyde in acidic solution. Hardy, P.M., Nicholas, A.C. and Rydon, H.N. "The nature of gluteraldehyde in aqueous solution", Journal of the Chemical Society (D), 565-566, 1969.
Several studies have focused on crosslinking material based on chitosan for medical and radiopharmaceutical uses with some success. See, for example, Hoffman, B., Seitz, D., Mencke, A., Kokott, A. and Ziegler, G. "Gluteraldehyde and oxidized dextran as crosslinker reagents for chitosan-based scaffolds for cartilage tissue engineering", J. Mater Sci: Mater Med, 20 (7), 1495-1503, 2009; Salmawi, K.M. "Gamma radiation-induced crosslinked PVA / Chitosan blends for wound dressing", Journal of Macromolecular Science, Part A: Pure and Applied Chemistry, 44, 541-545, 2007; Desai, K. G. and Park, H.J. "Study of gamma-irradiation effects on chitosan microparticles", Drug Delivery, 13, 39-50, 2006; Silva, RM, Silva, GA, Coutinho, OP, Mano, JF e Reis, RL "Preparation and characterization in simulated body conditions of gluteraldehyde crosslinked chitosan membranes", Journal of Material Science: Materials in Medicine, 15 (10), 1105- 1112, 2004.
However, Sabharwal et al. (2004) reported that radiation processing of natural polymers has attracted less attention because natural polymers undergo a chain fission reaction when exposed to high energy radiation. Sabharwal, S., Varshney, L, Chaudhary, AD and Ramnani, SP "Radiation processing of natural polymers: Achievements & Trends" in Radiation processing of polysaccharides, 29-37, IAEA, November 2004. Chitosan irradiation is reported to confer lower viscosity and chitosan chain cleavage. See Kume, T. and Takehisa, M. "Effect of gamma-irradiation on sodium alginate and carrageenan powder", Agric. Biol. Chem. 47, 889-890, 1982; Ulanski, P. and Rosiak, J.M. "Preliminary studies on radiation induced changes in chitosan", Radiat. Phys. Chem. 39 (1), 53-57, 1992. The H + and OH' radicals formed by radiolysis during irradiation of water accelerate the cleavage of the chitosan molecular chain. The reaction between the free radical and the above chitosan molecules leads to a rapid degradation of the chitosan in aqueous solution. See IAEA-TECDOC- 1422, "Radiation processing of polysaccharides' International Atomic Energy Agency", November 2004. These studies suggest that the use of chitosan in environments where it will be exposed to irradiation and potential radiolysis is problematic.
However, current demands for bio-compatible polymeric materials in radiopharmaceutical and radioactive waste treatment have increased interest in the development of economically viable alternative sources of acidic, alkaline and radiation-resistant polymeric network structures. Recent development of chitosan-based materials in the area of medicine, radiopharmaceuticals and radioactive waste has attracted attention due to its availability and biocompatibility.
See Alves, N.M. and Mano, J.F. "Chitosan derivatives obtained by chemical modifications for biomedical and environmental applications", International Journal of Biological Macromolecules, 43, 401-414, 2008; Berger, J., Reist, M., Mayer, JM, Felt, O., Peppas, NA and Gurny, R. "Structure and interactions in covalently and ionically crosslinked chitosan hydrogels for biomedical applications", European Journal of Pharmaceutics and Biopharmaceutics, 57, 19-34, 2004. It is reported that chemical changes in chitosan occur due to irradiation and the degree of reaction induced by radiation depends on the structure of the polymeric network. See Zainol, I., Akil, H.M. and Master, A. "Effect of y-ray irradiation on the physical and mechanical properties of chitosan powder", Material Science and Engineering C, 29, 292-297, 2009; Chang, K.P., Cheng, C.H., Chiang, Y.C., Lee, S.C. et al., "Irradiation of synthesized magnetic nanoparticles and its application for hyperthermia", Advanced Materials Research, 47-50, 1298-1301, 2008; Casmiro, M.H., Botelho, M.L., Leal, J.P. and Gil, M.H. "Study on chemical, UV and gamma radiation-induced grafting of 2-hydroxyethyl methacrylate onto chitosan" Radiation Physics and Chemistry, 72, 731-735, 2005; Park et al. "Radioactive chitosan complex for radiation therapy", United States Patent 5,762,903, June 9, 1998; Wenwei, Z., Xiaoguang, Z., Li, Yu, Yuefang, Z. and Jiazhen, S. "Some chemical changes in chitosan induced by y-ray irradiation", Polymer Degradation and Stability, 41, 83-84, 1993; Lim, L. Y., Khor, E. and Koo, O. "y irradiation of chitosan", Journal of Biomedical Material Research, 43 (3), 282-290, 1998; Yoksan, R., Akashi, M., Miyata, M. and Chirachanchai, S. "Optimal y-ray dose and irradiation conditions for producing low molecular weight chitosan that retains its chemical structure", Radiation Research, 161, 471-480, 2004; Lu, Y.H., Wei, G.S. and Peng, J. "Radiation degradation of chitosan in the presence of H2O2", Chinese Journal of Polymer Science, 22 (5), 439-444, 2004. However, very little information is available regarding the effect of radiation on matrices composites of cross-linked chitosan. SUMMARY
One embodiment described here relates to a radiation resistant adsorbent comprising cross-linked chitosan with glutaraldehyde.
More particularly, microporous micronic porous particles based on chitosan and chitosan-titania microporous composite material which have been prepared by crosslinking chitosan with glutaraldehyde in the presence of a catalyst are described here.
Even more particularly, an adsorbent containing a microporous chitosan material which has been cross-linked with glutaraldehyde in the presence of a catalyst, such as an acid (for example, HCI) to a glutaraldehyde concentration of about 2 to 4% by weight, is described herein. and which is resistant to degradation by exposure to beta and gamma radiation and to degradation by exposure to acidic and alkaline solutions.
Without wishing to be bound by theory, it is believed that the cross-linked microporous chitosan matrix increases acid resistance and mechanical resistance of the chitosan particle. As a result, the ability to trap metal ions in acidic or alkaline radioactive solution of the crosslinked particles increases in comparison to available commercial resins and commercial alumines. This increased uptake can result in efficiencies, for molybdenum, as high as 500-700 mg / g of adsorbent, more particularly about 600 mg / g of adsorbent.
Modes of chitosan-based micro-porous composite materials which have been prepared using solution molding and a combination of solution molding and a sol-gel method are described here.
In one embodiment, chitosan was cross-linked with glutaraldehyde in the presence of an acid as a catalyst at temperatures of about 70 ° C under continuous agitation. Without wishing to be limited by theory, it is believed that amino groups present in the chitosan structure are protonated and, thus, protected against the reaction with glutaraldehyde. It is also believed that, at temperatures around 70 ° C, more aldehyde groups are available for reaction than available at room temperature. In this case, without pretending to be limited by theory, it is believed that glutaraldehyde undergoes aldol condensation and the free aldehyde group will react with the -OH groups of chitosan in the presence of an acid catalyst, so that the polymerization of chitosan with glutaraldehyde is a condensation polymerization. Reaction times generally range from about 4 hours to about 8 hours. In one embodiment, the molar ratio of chitosan hydroxyl group to glutaraldehyde is desirably maintained at around 4/1.
In a particular embodiment, the crosslinked material can be further processed by washing to remove excess glutaraldehyde, drying, wet or dry grinding and additional chemical processing. An example of this additional chemical processing that has been found to be particularly suitable is at least partial oxidation with an oxidizer. In particular, oxidation with a permanganate (for example, a potassium permanganate solution containing at least about 14 mg of Mn / L of solution) or other amphiphilic oxidant is especially suitable for increasing the selectivity of the adsorbent by Mo (VI) in relation to Tc (VII).
Desirably, the adsorbent has a surface area ranging from about 10 to about 100 m2 / g and, more particularly, is about 25 m2 / g. Also, desirably, the adsorbent has zero charge point values of about 7.5 to about 8.8 and, more particularly, it is about 8.8.
Modalities of the adsorbents described here have an excellent molybdenum retention capacity and can adsorb molybdenum in amounts of about 60% by weight, based on the dry weight of the adsorbent, or more. This retention capacity can be around 6.25 mmol / g of adsorbent or more. The adsorbents also have excellent selectivity for molybdenum over technetium and are able to retain molybdenum while allowing the passage of technetium ions in saline with an efficiency of at least about 80%. Modes of the adsorbents described here also allow excellent adsorption capacity of heavy metals including, for example, Hg adsorption capacity in amounts of 2.96 mmol / g of dry adsorbent or more from the aqueous solution at a pH of 6.
In another modality, titanium oxide was incorporated into the polymeric composite matrix of chitosan / glutaraldehyde. The development of crystalline silica titanate (Crystalline Silica Titanate - CST) and titanium-based oxide materials has been the basis for studies on the adsorption of metal ions on hydrated titanium oxide from radioactive and non-radioactive effluents. See Anthony, R. G., Dosch, R.G., Gu, D. and Philip, C.V. "Use of silicotitanates for removing cesium and strontium from defense waste", Ind. Eng. Chem. Res., 33, 2702-2705, 1994; Maria, P., Meng, X., Korfiatis, G.P. and Jing, C. "Adsorption mechanism of arsenic on nanocrystalline titanium dioxide", Environ. Sci. Technol, 40, 1257-1262, 2006; Meng et al., "Methods of preparing a surface-activated titanium oxide product and of using same in water treatment process", United States Patent 7,497,952 B2, March 3, 2009. Qazi and Ahmed (2011) reported that the hydrated titanium oxide as an adsorbent for "Mo and its potential for use in a generator" mTc Qazi, QM and Ahmed, M. "Preparation and evaluation of hydrous titanium oxide as a high affinity adsorbent for molybdenum (99Mo) and its potential for use in" mTc generators ", Radiochimica Acta, Doi: 10.1524 / ract.2011.18172011. It has been suggested that the oxide titanium can form complexes on the surface with metal ions resulting from a bidentified bonding mode to the oxygen atoms on the surface. Hasan, S., Ghosh, TK, Prelas, MA, Viswanath, DS and Boddu, VM "Adsorption of uranium on the novel bioadsorbent chitosan coated per-lite ", Nuclear Technology, 159, 59-71,2007.
However, none of these documents describes that TiO2, when dispersed over a chitosan matrix, improves the overall capacity for absorbing metal ions from the residual radioactive solution. In the method described here, hydrated titanium oxide gel was prepared using the sol-gel technique. The titanium oxide gel was incorporated into the chitosan and glutaraldehyde matrix in the presence of HCI as a catalyst.
Thus, one embodiment refers to a method for preparing a radiation-resistant adsorbent comprising:
Combination of chitosan with water in the presence of an acid to form a chitosan gel; adding glutaraldehyde to the gel to form a semi-solid mass in the presence of a 70 X} catalyst; washing the semi-solid mass to remove unreacted glutaraldehyde and forming a washed mass; suspension of the washed mass in an aqueous base to form a neutralized cross-linked mass; and drying the neutralized crosslinked mass to form the radiation resistant adsorbent.
Another method relates to such a method further comprising: formation of an amorphous titania gel by means of acid catalyzed hydrolysis and condensation of titanium isopropoxide; mixing the amorphous titania oxide gel with the chitosan gel under sufficient conditions for the gels to react before said addition of glutaraldehyde.
In one embodiment, the composite material based on microporous chitosan was then suspended in a solution with a pH of 3 and irradiated with 50,000 krad using a 60Co irradiator. The specific objectives of this work were 1) to prepare microporous composite particles based on chitosan to adsorb metal ions from highly acidic or alkaline radioactive waste solutions; and 2) optimize the crosslinking process to obtain the maximum metal bonding sites.
Thus, another embodiment relates to a method of separating isotopes from mixtures thereof, comprising: contacting a mixture of at least two isotopes with a radiation-resistant adsorbent according to claim 1 which preferably adsorbes at least one of said isotopes; adsorption of at least one of said isotopes on or in said adsorbent, while one or more of the remaining isotopes are not significantly adsorbed by the adsorbent; removing said one or more isotopes remaining from said adsorbent.
The crosslinked chitosan composite is an excellent low cost alternative adsorption material compared to the available resins and, therefore, a desirable adsorbent material for removing metal ions from aqueous radioactive and non-radioactive solutions. It was found that the success of the adsorption process in the "Mo /" mTc generating systems depends largely on the cost and capacity of the adsorbents and the ease of releasing "mTc from the generator. The main problem with this particular method from the point of view of radiation safety involves the "neutralization" or partial elution of the "parental Mo along with the" mTc of the generator, which must be kept within the standards of the Nuclear Regulatory Commission (NRC). Modalities of the materials and methods described here allow good release selective "generator mTc, thereby solving the problem and thus satisfying the need for such a generator.
In addition, modalities of the crosslinked chitosan composites described here can be used in a method for separation or concentration or both of one or more heavy metals in a liquid stream, such as an effluent or a process stream, by means of contacting the stream liquid containing one or more heavy metals with the crosslinked chitosan composite and adsorption of one or more of said heavy metals therein. BRIEF DESCRIPTION OF THE DRAWINGS
Various aspects of modalities described here can be understood more clearly with reference to the drawings, which should not be construed as limiting the claimed invention.
FIG. 1 is a photomicrophotography by scanning electron microscope that shows the chitosan and modified chitosan modalities (MPCM) described here. FIG. 1st shows unmodified chitosan; FIG. 1b shows a modality of the MPCM material.
FIG. 2 is a graph showing the results of a thermogravimetric analysis (ThermoGravimetric Analysis - TGA) of chitosan and an MPCM modality.
FIG. 3 is a graph showing a chitosan X-ray diffraction pattern and a modality of the MPCM material.
FIG. 4 is a graph showing Fourier Transform Infrared spectra (Fourier Transform jnfraRed - FTIR) and a modality of the MPCM material described here.
FIG. 5 is a graph showing research scans by X-ray photoelectron spectroscopy (X-ray Photoelectron Spectroscopy - XPS) for chitosan and an MPCM modality.
FIG. 6 is a graph showing research scans by X-ray photoelectron spectroscopy (X-ray Photoelectron Spectroscopy - XPS) for chitosan and an MPCM modality. FIGs. 6a, 6b and 6c show the positions C 1 s, O 1s and N 1 s, respectively.
FIG. 7 is a graph of microanalysis spectra by Energy-Dispersive X-ray Spectrometry (EDS) of an MPCM modality here. FIG. 7a shows chitosan spectra and an MPCM modality before and after irradiation. FIG. 7b shows a comparison of chitosan and an MPCM modality. FIG. 7c shows a comparison of an MPCM modality before and after irradiation.
FIG. 8 is a schematic diagram showing a reaction path for the preparation of an MPCM modality described here.
FIG. 9 is a graph showing FTIR spectra of a modified chitosan modality described here before and after irradiation.
FIG. 10 is a graph showing X-ray photoelectron spectroscopy (XPS) spectroscopy spectra for an MPCM modality before and after radiation. FIGs. 10a, 10b and 10c show the positions C 1 s, O 1s and N 1 s, respectively.
FIG. 11 is a graph showing the surface load of an MPCM modality with and without exposure to 1% Mo (VI) in solution in the presence of 1 M NaNOβ.
FIG. 12 is a graph showing the effect of pH on the adsorption of molybdate in an MPCM modality, with initial conditions of a concentration of 5.21 mmol / L and a temperature of 298 K
FIG. 13 is a schematic diagram showing the reaction mechanisms for adsorption of Mo (VI) in an MPCM modality from aqueous solution.
FIG. 14 is a graph showing the equilibrium adsorption isotherms for Mo (VI) uptake in an MPCM modality, showing the experimental data (•) correlated with the Langmuir isotherm model (continuous line) under conditions where the concentration of Mo (VI) in solution is in the range of 1 mmol / L to 94 mmol / L, temperature 298 X, pH ~ 3.
FIG. 15a is a graph showing an elution curve for the adsorption of Mo (VI) over a bed of MPCM, the inlet tributary concentration was 5.21 mmol of Mo (VI) / L at pH 3; FIG. 15b is a graph showing the effect of the pH of the affluent solution on the Mo (VI) elution curve from a column packed with an MPCM modality. The inlet tributary concentration was 5.21 mmol of Mo (VI) / L with 153.8 mmol of NaCI / L at pH 4 to 7, respectively. For both figures, the height of the column bed was 3.2 cm. The inflow inlet flow rate was 1 ml / min.
FIG. 16 is a graph showing elution curves for per- technate from a column packed with a non-oxidizing MPCM modality, which was loaded with 6.25 mM Mo (VI) / gram of MPCM. The column volume was 2.5 cm3. The inlet flow rate was 1 ml / min. The concentration in the incoming tributary was 0.25 mM / L pertechnetate in saline (0.9% NaCI).
FIG. 17 is a graph showing the surface load of oxidized and non-oxidized MPCM exposed to Mo (VI) in 1% aqueous solution in the presence of 1 N. NaNOa.
FIG. 18 is a graph showing an elution profile of "mTc from an MPCM modality loaded with Mo (VI) enriched with" Mo.
FIG. 19 is a graph showing the relationship between the number of elution (s) and the percentages of "mTc and Mo (VI) release from an MPCM modality as an adsorbent.
FIG. 20 is a flowchart of a process that uses "mTc /" Mo generating systems and a "Mo production using the neutron capture method with an MPCM modality as the adsorbent.
FIG. 21 is a graph showing the FTIR spectra of chitosan and another modality of modified chitosan described here. DETAILED DESCRIPTION OF SPECIFIC MODALITIES
The methods described here and the resulting modified chitosan materials, as well as methods for using them, can be better understood by reference to the following examples, which are intended to illustrate, not limit, the invention or appended claims.
Chitosan of average molecular weight (about 190,000 to about 310,000, as determined by viscosity data) that was 75-85% deacetylated was obtained from Sigma-Aldrich Chemical Corporation, WI, USA. All chemicals used in the examples were of analytical grade.
The modified chitosan described here can be prepared according to the reactions shown schematically in FIG. 7, through crosslinking with glutaraldehyde under acidic conditions at the temperature conditions set out below. Although the amount of glutaraldehyde used may vary slightly, it has been found to be effective to use from about 2 ml to about 10 ml, more particularly from about 2 ml to about 8 ml, even more particularly about 6 ml of glutaraldehyde for every 4 g of chitosan. The pH of the crosslinking reaction between glutaraldehyde and chitosan can also vary slightly, but it has been found to be effective to use a pH between about 0.7 and about 3, more particularly between about 0.7 and 2, still more particularly about 1.0. The temperature of the crosslinking reaction can also vary, but is desirably between about 50 ° C and about 80 ° C, more particularly about 70 ° C. EXAMPLE 1
The ionic capacity of chitosan used in this study was in the range of 9 to 19 milliequivalents / g, measured using a standard titrametric method. About 4 g of chitosan was added to 300 ml of Dl water with 1 ml of acetic acid and stirred for 2 hours at 70 ° C to form a gel. Approximately 5 ml of HCI / HNO3 was added to the chitosan gel and kept under continuous agitation for an additional 1 hour at 70 ° C to assist in the protonation of the amino substituent groups, which is beneficial for the reasons given below.
The reaction with glutaraldehyde was carried out by adding, dropwise, about 6 ml of glutaraldehyde solution, having a concentration of 50%, to the acid chitosan gel under continuous agitation (established based on trial and error but, in in general, from 200 rpm to 500 rpm) at 70 10. The final pH of the mixture was approximately 1.0. The amount of glutaraldehyde used in this study was established based on trial and error. The mixture was kept under continuous vigorous stirring (500 rpm) at 70 ° C for an additional 1 h to obtain a semi-solid gel. The amino groups present in chitosan are much more reactive with aldehyde through Schiff's reaction than the hydroxyl groups of chitosan. At 70 KD, it is considered that more free aldehyde groups will be present in the solution than at room temperature. In an acid solution, the protonation of the amine group will inhibit the formation of aldehyde complexes and amino groups. In addition, glutaraldehyde may undergo aldol condensation and the reaction of chitosan hydroxyl groups with free aldehyde can be catalyzed by acid at 70 13.
The resulting mass was then carefully washed with 2% monoethanol amine to remove any unreacted glutaraldehyde. The mass was then suspended in 0.1 M NaOH solution for 4 to 6 hours. The crosslinked mass was separated from the solution and washed with 0.1 Me HCI, then with deionized water (Dejonized - Dl) until the pH of the effluent solution was 7. The crosslinked mass was then dried in an oven at overnight vacuum at 70 ° C 13. The crosslinked chitosan / g lutaldehyde composite is referred to as "MPCM" or "microporous composite material" here.
The MPCM was ground using a laboratory grinder to a particle size in the range of about 50 to 200 pm. A quantity of these MPCM particles was suspended overnight in aqueous solution with pH = 3. The pH of the solution was maintained using 0.1 M HNO3. The suspended MPCM particles were irradiated using 60 O as the source of y. The characterizations of the MPCM sample were performed using SEM, EDS X-ray microanalysis, FTIR and XPS spectroscopic analysis.
A scanning electron micrograph (Scanning Electron Mi-crograph - SEM) of chitosan and MPCM material was taken to study the surface morphology and is shown in FIG. 1. The SEM secondary electron micrograph of the samples was obtained using electron re-dispersion with an acceleration potential of 10 KeV. SEM micrograph of the cross section of the chitosan and MPCM sample is shown in FIGs. 1a and 1b, respectively. It appears, from FIG. 1a, that chitosan is non-porous and, from FIG. 1b, it appears that the MPCM has a microporous nature.
TGA analysis of MPCM as prepared in the laboratory and pure chitosan, respectively, was performed using a TGA analyzer (TA Instruments) in a nitrogen flow atmosphere (200 mL / min.) For each experiment, approximately 20 mg of MPCM were heated to the temperature range of 30 to 600 ° C in an open alumina crucible at the predetermined heating rate. TGA measures the amount and rate of weight change of the sample as it is heated to a specified rate. Thermogravimetric analysis of MPCM and chitosan was obtained by providing supplementary information on changes in composition as heating progresses under controlled conditions. The heating rate in this analysis was adjusted to 5 ‘C / min. TGA profiles, as shown in FIG. 2, indicate a two-stage decomposition process for pure chitosan, while MPCM decomposes slowly with increasing temperature.
Thermogravimetric analysis (TGA) of chitosan at a heating rate of 5 12 / min in a nitrogen atmosphere (200 mL / min) indicates that complete dehydration occurs at 250 <C, with a weight loss of 8%. Anhydrous chitosan further decomposed in the second stage, with a weight loss of 32% at 360 TT. It was completely burned at 600 12, with an additional weight loss of 12%. The remaining 48% is the burnt chitosan residue at 600 V
In the case of MPCM, complete dehydration occurs at 230 'C, with a weight loss of 12%. Anhydrous MPCM burns completely at 600 ° C, with a weight loss of 36%. The remaining 52% is the burnt residue of MPCM at 600 1C. It can be noted that the combustion product of MPCM is 4% less compared to chitosan, which indicates that MPCM contains 4% crosslinking agent, such as glutaraldehyde, which has been completely burned in this heating range.
The swelling behavior and acid tolerance of the MPCM material were also evaluated. The swelling behavior of MPCM was assessed by immersion in deionized water and saline using a process described by Yazdani-Pedram et al., "Synthesis and unusual swelling behavior of combined cationic / non-ionic hydrogels based on chitosan", Macromol . Biosci., 3, 577-581 (2003).
The swelling behavior of chitosan was also studied with deionized water and saline solution.
The proportion of chitosan and MPCM swelling was calculated using the following equation:
Swelling ratio (%) = [(Vs - Vd) / Vd] * 100, where Vs is the MPCM swelling volume and Vd is the dry sample volume. In deionized water, it was observed that the chitosan swelled in approximately 105% of its original volume after an equilibrium time of 24 hours. MPCM shows very fast swelling behavior, reaching an increase of approximately 200% in five minutes and reaching equilibrium in 24 hours. Swelling studies with deionized water were carried out within the pH range of 3 to 6. In equilibrium, the maximum volume of MPCM was almost 219% more than its dry volume.
Similar MPCM swelling behavior was also observed for saline (0.9% NaCI). In equilibrium, the volume of MPCM increases up to 223% of its original dry volume in saline. The results of the swelling studies indicate that the hydrophilicity of MPCM is greater than that of chitosan. It has been reported that the swelling behavior of the chitosan hydrogel depends on the ionizable groups that are present within the gel structure. See Ray et al., "Development and Characterization of Chitosan Based Polymeric Hydrogel Membranes", Designed Monomers & Polymers, Vol. 13, 3, 193-206 (2010). Due to the protonation of MPCM -NH2 groups in the pH range of the solution between 3 and 6, the fast swelling behavior of MPCM in deionized water can be attributed to the high repulsion of groups - NH3 +. In saline, at a pH greater than 6, the carboxylic acid groups become ionized and the electrostatic repulsion forces between the charged sites (COO-) cause an increase in swelling. See Yazdani- Pedram et al., Supra; Radhakumari et al., "Biopolymer composite of Chitosan and Methyl Methacrylate for Medical Applications", Trends Biomater. Artif. Organs, 18, 2, (2005); Felinto et al., "The swelling behavior of chitosan hydrogel membranes obtained by UV- and y-radiation", Nuclear Instruments and Methods in Physics Research B, 265, 418-424 (2007).
The MPCM sample was immersed in different concentrations of HCI, HNO3 and H2SO4 for 24 hours. Chitosan tends to form a gel in an acidic medium, making it unsuitable for use in an adsorption column to separate metal ions from aqueous solutions. One of the main objectives of this work was to produce a material based on acid-resistant chitosan while exposing more groups -NH2, which are the active metal binding site for chitosan. Table 1 shows the results for MPCM acid tolerance. It was observed that the MPCM material shows better tolerance to HCI than tolerance to HNO3 and H2SO4. The physical size and shape of MPCM did not show any significant change in HCI solutions at 12M, H2SO4 at 12M and HNO3 at 3.9 M, but MPCM appeared to be completely dissolved in HNO3 solution at 7.8 M. It is evident that MPCM is more resistant to acid than chitosan. Table 1. Effect of different concentrations of acid on the physical properties of materials
V = undissolved x = tends to gel or dissolve completely
Figure 3 shows the XRD pattern for pure chitosan and MPCM globules. The chitosan sample showed a diffraction peak close to 20 ° indicative of relatively regular crystal networks (110,040) of chitosan. See Wan et al., "Biodegradable Polylactide / Chitosan Blend Membranes", Biomacromolecules 7 (4): 1362-1372 (2006). The peak observed for MPCM appeared to be widened, suggesting that the MPCM sample is amorphous in nature. It also indicates that chitosan and glutaraldehyde formed a complex in the presence of acid; therefore, the crystalline structure of chitosan was disrupted by the chemical bond between chitosan and glutaraldehyde. The Fourier Transform Infrared (Fourier Transform jnfraRed - FTIR) spectra of the MPCM sample prepared above were analyzed on a BRUKER FTIR spectrometer equipped with a mercury-cadmium-telluride detector (Mercury-Çadmium-Telluride - MCT) cooled with N2 broadband and a KCI beam splitter. FTIR spectra were collected in the absorbance mode with a resolution of 8 cm-1 using 128 scans ranging from 400-4000 cm'1. Intermolecular interactions between chitosan and glutaraldehyde in the presence of HCI acid are reflected by changes in the characteristics of peak IR. FIG. 4 shows the comparison of the IR spectra of chitosan with MPCM. In the 2900 cm'1 to 3500 cm'1 region of the spectrum, chitosan and MPCM exhibited peaks at 3498 cm'1 and 2950 cm'1, respectively, corresponding to the stretching of OH and NH groups and vibration by CH stretching in CH and -CH2-. The peaks at 1350 to 1450 cm'1 indicate flexion of C-H in alkane.
The complex nature of the absorption spectrum in the 1650-1500 cm'1 region suggests that aromatic ring vibration bands and double bond (C = C) overlap the C = O stretching vibration band and flexion vibration bands of OH. The peaks expected in this region of the IR spectrum include the protonated amine (-NH3 +), amine (-NH2) and carbonyl (-CONHR) bands. FIG. 4 shows a peak at 1600 cm’1 with a shoulder, as well as a peak centered around 1570 cm’1 and 1670 cm’1 representing NH2 and amide I, respectively, for chitosan. However, the presence of a relatively sharp peak at 1590 cm'1 in MPCM other than the observed peak for chitosan suggests the presence of the NH3 + band in the MPCM sample.
The XPS analysis of the sample of chitosan and MPCM prepared above was performed to obtain a better understanding of the inter-molecular interaction between chitosan and glutaraldehyde. In the XPS analysis, a scan scan was used to ensure that the energy range was adequate to detect all elements. The XPS data were obtained using a KRATOS spectrometer model AXIS 165 XPS with monochromatic Mg X-rays (hv = 1253.6 eV), which were used as the excitation source at a power of 240W. The spectrometer was equipped with an eight-channel hemispheric detector and a pass-through energy of 5-160 eV was used during the analysis of the samples. Each sample was exposed to X-rays for the same period of time and intensity. The XPS system was calibrated using UO2 peaks (4f7 / 2), whose binding energy was 379.2 eV. A probe angle of 0 ° was used for the analysis of the samples.
FIG. 5 shows the peak positions of C 1s, O 1s and N 1s obtained by the verification study of the sample of chitosan and MPCM prepared above, respectively. FIG. 6 shows the peak positions in detail for C 1 s, O 1s and N 1s present in chitosan and MPCM. The observed C-1s peak showed two peaks in deconvolution, one for C-N at 284.3 eV and another for C-C at 283.5 eV (FIG. 6A). In the MPCM sample, the C-Cs peak appears to be doubled and slightly displaced, while the C-N peak showed greater intensity compared to chitosan (FIG. 6A). The peaks for the groups containing oxygen (O 1 s) were found at 530.5 eV and 531.1 eV for chitosan and MPCM, respectively (FIG. 6b).
Compared with the MPCM C 1s and O 1s peaks, it was observed that the chitosan CC peak at 283.5 eV doubled and the O 1s peak shifted from 530.5 eV to 531.1 eV due to the reaction of cross-linking with glutaraldehyde. This suggests that component 01 s can be uniquely linked, corresponding to the -OH or C-0 portion in the structure for different functional groups containing oxygen on the surface. See Wen et al., "Copper-based nanowire materials: Templated Syntheses, Characterizations, and Applications", Langmuir, 21, 10, 4729-4737 (2005). Chemical shifts are considered significant when they exceed 0.5 eV. See Hasan et al., "Adsorption of divalent cadmium from aqueous solutions onto chitosan-coated perlite beads", Ind. Eng. Chem. Res., 45, 5066-5077 (2006). As a result, the displacement of the O 1s peak in the MPCM sample also indicates that the glutaraldehyde reacted with functional groups containing chitosan oxygen. The XPS data suggest that the chemical bonding of glutaral-dehyde occurs with the -CH2OH or OH group on the chitosan structure, which is also in agreement with the data obtained from the FTIR analysis (FIG. 4).
The N 1s peak for chitosan was 397.5 eV (FWHM 1.87) for nitrogen in the chitosan group -NH2 (FIG. 5c); for MPCM, the peak of N 1s appeared at 397.7 eV. One of the objectives for investigating the N 1s peak was to identify whether the amine groups, which are active metal binding sites for chitosan, were involved in crosslinking reactions with glutaraldehyde. FIG. 6c shows a strong N 1s peak for MPCM at 397.7 eV, which can be attributed to -NH2 groups, suggesting that the chitosan amine groups were not affected by the crosslinking reaction with glutaraldehyde. This is also evident from the FTIR spectrum (FIG. 4).
Table 2 shows the XPS data for elemental surface analysis of the MPCM sample, as determined from the peak area after correction for the experimentally determined sensitivity factor (± 5%). It was found that, preparation of the porous material based on chitosan, in this case, the modality of MPCM described above, results in the exposure of more NH2 groups on the surface of the material. The nitrogen concentration, as determined from the N 1s peak in the MPCM sample, was almost twice as high as that calculated for chitosan (Table 2). It is believed that the nitrogen content in MPCM originated entirely from chitosan. The high nitrogen content in MPCM, as shown in Table 2, was due to the microporous nature of MPCM, which makes more amine groups available on the surface than in the case of non-porous chitosan. This is also consistent with the results reported by Hasan et al., Supra, obtained by dispersing chitosan over perlite. It is believed that the changes in the peak intensity of C 1s and peak binding energy O 1s at 531.0 eV of the MPCM sample compared to chitosan are due to the reaction with glutaraldehyde in the presence of an acid such as catalyst.
Table 2: Binding Energy (BE) absolute for the elements present in chitosan and MPCM obtained from X-ray Photoelectron Spectroscopy - XPS spectroscopy analysis
• MPCM-I sample after irradiation at 50,000 krad using 60Co y-source.
X-ray microanalysis by energy dispersion spectroscopy (Energy Dispersive Spectroscopy - EDS) was performed on the same MPCM sample as used for SEM micrograph. EDS microanalysis was used for elemental analysis of MPCM (FIG. 7). The peaks for carbon, oxygen and nitrogen are shown at 0.3 keV, 0.36 keV and 0.5 keV, respectively, which are the main components of chitosan (FIGs. 7a, 7b). Due to the reaction with glutaraldehyde, the peak carbon intensity for MPCM increases, while the peak oxygen intensity decreases compared to chitosan (FIG. 7b). FIG. 7b also shows that the nitrogen peak present in the MPCM sample has shifted due to the protonation of the amine groups (-NH2) compared to the nitrogen peak in chitosan. Based on FTIR, EDS and XPS analysis, and without wishing to be limited by theory, the possible mechanisms of reaction of glutaraldehyde with chitosan -OH groups by forming acetal bonds are provided in FIG. 8.
The MPCM sample described above was evaluated for radiation stability through irradiation with a 60Co source. The IR spectra of the MPCM composite sample before and after irradiation using a 60Co source are shown in FIG. 9. The results in FIG. 9 show that the MPCM sample suspended in water at a pH of 3.0 can tolerate radiation y around 50,000 krad without losing a substantial percentage of its identity.
FIG. 7C shows EDS spectra of chitosan and MPCM particles before and after irradiation at 50,000 krad with 60Co. FIG. 7c indicates that the intensity of the carbon, oxygen and nitrogen peaks do not change substantially after irradiation of the sample. FIG. 10 shows the peak positions of carbon, oxygen and nitrogen obtained by XPS analysis of the MPCM sample before and after irradiation. It was observed that the magnitude of the total C 1s peak binding energy changed after irradiation, as shown in Table 2. The C 1s peak for the MPCM sample was 283.5 eV whereas, for the MPCM sample after irradiation, two peaks were observed at 283.5 and 284.5 eV (FIG. 10a). The N1s peak present in the MPCM sample after irradiation around 397.5 eV can be attributed to NH2 groups in the MPCM structure. No changes were observed for the O-1 s peak of the irradiated MPCM sample. The magnitude of the deviation of binding energy depends on the concentration of different atoms, in particular on the surface of a material. In comparison with XPS (FIGs. 10a-c), the N 1s and O 1s pi of the MPCM sample did not deviate before and after irradiation (Table 2), indicating that the chemical state of N atoms was not much affected after irradiation. This is also reflected in the EDS and FTIR spectra, as shown in FIGs. 7 and 9.
The MPCM sample described above was evaluated for molybdenum adsorption using discontinuous techniques. About 1.0 gram of MPCM adsorbent was suspended in 100 ml of solution containing ammonium molybdate in the range of 1 mmol / L to 94 mmol / L. The initial pH values of the solutions were adjusted from 2.0 to 8.0 using 0.01 M NaOH or 0.1 M HCI solution. The solutions were then kept on a shaker (160 rpm) for 24 hours at 298 K After 24 hours, the final pH was recorded for each solution and the solutions were centrifuged for 5 minutes at 3000 rpm to separate the supernatant from the solution. The supernatant was then filtered through a 0.45 pm membrane filter and the filtrate was analyzed for molybdenum removal by an Inductively Coupled Plasma (ICP) (Agilent 7700X) which is equipped with mass spectroscopy for detecting molybdenum. The adsorption isotherm was obtained by varying the initial concentration of molybdenum in the solution. The amount of molybdenum adsorbed per unit mass of adsorbent (qe) was calculated using the equation:
where Ci and Ce represent the initial and equilibrium concentrations in mg / L, respectively, V is the volume of the solution in liters (L) and M is the mass of the adsorbent in grams (g).
The surface load of an MPCM sample globule was determined using a standard potentiometric titration method in the presence of a symmetrical electrolyte, sodium nitrate, according to Hasan et al., Supra. The magnitude and sign of the surface charge were measured in relation to the point of zero charge (Point of Zero Charge - PZC). The pH at which the net surface charge of the solid is zero at all electrolyte concentrations is referred to as the zero charge point. The pH of the PZC for a given surface depends on the basic and relative acidic properties of the solid and allows an estimate of the net uptake of H + and OH 'ions from the solution. The results are shown in FIG. 11.
The PZC value of the MPCM sample prepared as described above was found to be 8.8, which was similar to that reported by Hasan et al., Supra, for a perlite globule coated with chitosan. However, it is reported that the PZC value of pure chitosan is in the pH range of 6.2 to 6.8. See Hasan et al., Supra. It is seen from FIG. 11, that a positively charged surface prevailed over a relatively low pH range. The surface load of MPCM was almost zero in the pH range of 7.5 to 8.8. The protonation of MPCM increased sharply in the pH range of 7.5 to 2.5, making the surface positive. At a pH below 2.5, the difference between the initial pH and the pH after the equilibration time was not significant, suggesting complete protonation of the amine groups (-NH2) present in the MPCM. At a higher pH, from 7.5 to 8.8, the surface load of the MPCM decreased slowly, indicating a slow protonation of MPCM. In the case of chitosan, it is reported that the extent of protonation is as high as 97% at a pH of 4.3. However, it decreases as the pH increases. The protonation extent of the chitosan surface is reported to be 91%, 50% and 9% at a pH of 5.3, 6.3 and 7.3, respectively. See Hasan et al., "Dispersion of chitosan on perlite for enhancement of copper (II) adsorption capacity", Journal of Hazardous Materials, 52 2, 826- 837, 2008.
Without wishing to be limited by theory, it is believed that the PZC value of 8.8 and the surface load behavior of MPCM are due to the modification of chitosan when cross-linked with glutaraldehyde in the presence of an acid as a catalyst, which becomes amphoteric in the pH range of 7.5 to 8.8. The effect of pH on the adsorption of molybdenum by MPCM was studied by varying the pH of the solution between 2 and 8 (FIG. 12). The pH of the molybdenum solutions was first adjusted between 2 and 8 using 0.1 N H2SO4 or 0.1 Me NaOH, then MPCM was added. As the adsorption progressed, the pH of the solution slowly increased. No attempt was made to maintain a constant pH of the solution during the course of the experiment. The amount of molybdenum uptake in the equilibrium solution concentration is shown for each different starting pH of the solution in FIG. 12. MPCM uptake of molybdenum increased with a pH increase from 2 to 4. Although maximum uptake was observed at a pH of 3, as the pH of the solution increased to above 6, the uptake of molybdenum over the MPCM started to decline. Thus, experiments were not carried out at a pH higher than the PZC of the MPCM sample.
In order to adsorb a metal ion onto an adsorbent from a solution, the metal must form an ion in the solution. The types of ions formed in the solution and the degree of ionization depend on the pH of the solution. In the case of MPCM, the main functional group responsible for the adsorption of metal ions is the amine group (-NH2). Depending on the pH of the solution, these amine groups may undergo protonation to NH3 + or (NH2-H3O) + and the rate of protonation depends on the pH of the solution. Therefore, the surface charge on the MPCM will determine the type of bond formed between the metal ion and the adsorbent surface. Depending on the pH of the solution, molybdenum in an aqueous solution can be hydrolyzed, with the formation of several species. At relatively high and low pH values, MoO} ~ and various isopoly anions (mainly MogOf ~) predominate. The anion undergoes the formation of many different polyions in acidic solutions. See Guibal et al., "Molybdenum Sorption by Cross-linked Chitosa Beads: Dynamic Studies", Water Environment Research, 71, 1, 10-17, 1999; Mercê et al., "Molybdenum (VI) Binded to Humic and Nitrohumic Acid Models in Aqueous Solutions. Salicylic, 3-Nitrosaliculic, 5-Nitrosalicylic and 3,5 Dinitrosalicylic Acids, Part 2", J. Braz. Chem. Soc., 17, 3, 482-490, 2006. It is reported that, even if the polyanion is present in the solution, adsorption still occurs through the formation of MoCP ~. See Jezlorowski et al., "Raman and Ultraviolet Spectroscopic Characterization of Molybdena on Alumina", The Journal of Physical Chemistry, 83, 9, 1166-1173, 1979; El Shafei et al., "Association of Molybdenum Ionic Species with Alumina Surface", Journal of Colloid and Interface Science, 228, 105-113, 2000. The degradation of the polyanions in the solution occurs due to an increased local pH close to the adsorbent surface .
As mentioned above, it was observed that MPCM had a maximum adsorption capacity at a pH around 3 from a molybdenum ion solution. Without wishing to be bound by theory, it is believed that the MPCM amino group has an electron pair lost from nitrogen, which acts primarily as an active site for the formation of a complex with a metal ion. As previously mentioned, at lower pH values, the MPCM amino group undergoes protonation forming NH3 +, leading to an increase in the electrostatic attraction between NH3 + and the sorbate anion. Since the MPCM surface exhibits a positive charge in the pH range of 2.5 to 7.5, anionic molybdenum (Mo (VI)) is presumably the main species that is being adsorbed by Coulomb interactions. As mentioned earlier, it was found that the pH of the solution increases after adsorption, which can be attributed to the H + ions released from the surface of the MPCM as a result of adsorption of anions containing molybdenum from the solution. In the case of MPCM, protonation of NH2 groups occurs in a relatively low pH range. The fact that the pH of the solution increased as the adsorption progressed suggests that Mo (VI) formed a covalent bond with an NH2 group.
As the equilibrium pH increased from a lower pH to the pH in the PZC (pHPZc), the reduced percentage removal of Mo (VI) was attributed to the decrease in electrostatic attraction between the surface of MPCM and species of Mo (VI) anionic. It was found that the MPCM PZC is shifted to 4.5 in the presence of molybdenum ions when compared to the MPCM PZC without said ions (FIG. 11). The deviation of PZC from MPCM to a lower pH indicates strong specific adsorption and complex formation on the internal surface of the globule occurs due to the adsorption of molybdenum. Similar findings have been reported for adsorption of molybdenum on gibbsite. See Goldberg, S. "Competitive Adsorption of Molybdenum in the Presence of Phosphorus or Sulfur on Gibbsite", Soil Science, 175, 3, 10S- 110, 2010. Based on surface load analysis and pH studies, the mechanisms of reactions that occur between the surface of MPCM and molybdenum species in solution are provided in FIG. 13. The equilibrium adsorption isotherm of molybdenum uptake over MPCM was determined at a temperature of 298 ° K in the concentration range from 1 mmol / L to 94 mmol / L. As mentioned in the previous section, the maximum adsorption capacity of molybdenum over MPCM occurs at a pH of 3. Therefore, the equilibrium isotherm experiments were carried out at a pH of 3, unless otherwise indicated. The concentration profiles during MPCM uptake of molybdenum from the solution in various concentrations show that approximately 60% of molybdenum was adsorbed during the first 4 hours of an experimental test. Equilibrium was achieved monotonically at 24 hours in most experimental tests. The MPCM material contains amino groups that are available for characteristic coordination bonding with metal ions. Adsorption of metal ions, when dependent on pH, can be described by the Langmuir equation at a site below. The pH effect was incorporated by introducing a parameter "a" that is dependent on the pH of the solution. The expression is provided below:
qm = maximum amount of metal ion adsorption (mmole / g)
where q is the adsorption capacity corresponding to the concentration of metal ions [M], qm is the maximum amount of molybdenum ions adsorbed (mmol / g), [H +] the concentration of hydrogen ions, KH and KM are the concentration in balance. Equation 5 was used to correlate the adsorption capacity of MPCM. The equilibrium data for molybdenum could be correlated with the Langmuir equation within ± 5% of the experimental value. The constants in Equation 5 are obtained by means of nonlinear regression of the experimental data and are provided in Table 3.
It was observed that Equation 5 represented the adsorption behavior of molybdenum on MPCM properly (FIG. 14). The adsorption isotherm data obtained at a pH of 3 showed a Type I behavior.
This suggests an adsorption in molybdenum monolayer on MPCM. Table 3 shows the maximum MPCM adsorption capacity for Mo (VI) using the Langmuir equation (Equation 5). It was observed that the adsorption capacity of MPCM to molybdenum is approximately ~ 6.25 mmol Mo / g of MPCM at 298 X when the equilibrium concentration of Mo (VI) in the solution was 54.1 mmol / L and the initial pH of the solution was 3.0 (FIG. 14). The NH2 groups of MPCM are the main active sites for molybdenum adsorption. As can be seen from FIG. 13, two NH2 groups will be required for the adsorption of a molybdenum ion. Other sites on the surface, such as CH2OH or OH groups of MPCM, could be involved in adsorption of molybdenum in the solution at a pH of 3. The adsorption capacity of MPCM that was irradiated at 50,000 krad was also analyzed for the uptake of molybdenum from aqueous solution. It was observed that the adsorption capacity of irradiated MPCM did not change substantially, as shown in Table 3. Table 3. Estimated parameters for the Langmuir model
* MPCM-I: Sample after irradiation at 50,000 krad with 60Co y-source.
A column was used to study the adsorption of Mo (VI) with or without the presence of ions in solution under dynamic conditions. Approximately 1.125 grams of MPCM were used to make a 2.5 cm3 column with an internal diameter of 0.5 cm and a height of 3.2 cm. A flow rate of 1 ml / minute was used during an assay. The test was continued for 1500 minutes and samples exiting the bed were collected at regular intervals. The bed becomes saturated during this period of time, as indicated by the outlet concentration of Mo (VI). When the inlet concentration was 5.21 mmol of Mo (VI) / L at a pH of 3 and the flow rate was 1 mL / minute through the column, molybdenum left the column after 320 bed volumes (FIG. 15a). Complete column saturation occurred after 500 bed volumes. Output curves were also obtained from a mixed solution containing 5.21 mmole of Mo (VI) / L and NaCl at 153.8 mM / L at a pH of 6.86 and 4.0, respectively (FIG. 15 B). In both cases, the solution was passed through a column of similar size, as mentioned above, maintaining the same bed height and flow rate. It was observed that the column exit occurred quickly at 42 bed volumes for the mixed solution with a pH of 6.86, however, approximately 125 bed volumes were required to leave the column for the mixed solution with a pH of 4.0 . It is important to note that the exit time for the molybdenum solution with 153.8 mM / L NaCI can be delayed by using larger amounts of MPCM adsorbent and a longer column. The objective was to investigate the effect of the pH of the mixed inlet solution on the Mo (VI) outlet characteristic of the column, therefore, no attempt was made to determine the bed length to prolong the outlet time for the mixed solution.
The long-lived technetium ("Tc) was used to evaluate the performance of MPCM in adsorbing technetium with and without the presence of other ions from an aqueous solution in the pH range 3 to 11. Technetium is chemically inert and has multiple oxidation states ranging from I to VII. The most dominant technetium species that are found in aqueous effluents is pertechnetate (TcO, -). See Gu et al., "Development of Novel Bifunctional Anion-Exchange Resin with Improved Selectivity for Pertechnetate sorption from contaminated groundwater ", Environ. Sci. Techno /., 34, 1075-1080, 2000. Pertecnetate (TcO ^") adsorption from an aqueous solution over MPCM was studied under discontinuous equilibrium conditions following a described procedure somewhere else. The effect of pH on the adsorption of technetium in MPCM was evaluated over the pH range of 3 to 11 using a solution containing 0.11 pmole of technetium / L with and without the presence of 0.9% NaCI, respectively . When studying the effect of pH on the adsorption capacity, the initial pH of the solutions was adjusted to a desired value by adding 0.1 M HCI or 0.1 M NaOH. The solution's pH was not controlled during the adsorption process. After the adsorption tests, the solutions were filtered and the activity of "Tc in the filtrate, which was collected in a flask at a predetermined time, was evaluated using a liquid scintillation counter (Packard TriCarb 2900TR). The amount of technetium adsorbed on MPCM was determined following Equation 2.
Table 4 shows that the adsorption of technetium over MPCM is independent of the pH in the solution in the pH range of 3 to 11. It was observed that approximately 95% of technetium at 1 pM / L of solution were adsorbed on MPCM in the pH range 3 to 11, while technetium removal was reduced to 56% in the case of 0.9% NaCI over the pH range 3 to 11. As mentioned earlier, MPCM shows a positive charge in the pH range 3 to 7, 5. Spectrum of MPCM by FTIR confirms the presence of -NH2, CHOH and CH2OH groups on the MPCM surface (FIG. 4). The positive charge is assumed to occur due to protonation of the sites on the MPCM surface in the pH range of 3 to 7.5 and technetium undergoes covalent bonding with the positive sites on the MPCM surface. In the case of 0.9% NaCI in solution, the technetium adsorption capacity by MPCM was reduced, since pertechnetate ions had to compete with chloride ions in solution. In addition, the uptake of technetium in the pH range 9 to 11 in the presence of a 0.9% NaCI solution may correspond to an ion exchange reaction that occurs in this pH range. The result shown in Table 4 confirms that MPCM has a strong affinity for the pertechnetate ion in aqueous solutions. Table 4. Technetium adsorption to MPCM at different pHs

MPCM was also used to adsorb Mo (VI) and Tc (VII) simultaneously from a mixed solution containing 1 mmole of Mo (VI) / L and 0.11pmole of pertechnetate / L, with or without the presence of NaCI at 0 , 9%. MPCM was found to adsorb molybdenum and technetium simultaneously from the solution to a pH of the solution of 3. It was observed that approximately 95% of 0.11pmole of pertechnetate was adsorbed on the surface of MPCM, while 99% of molybdenum to 1 mmole were adsorbed from the mixed solution. In the presence of molybdenum in the solution, pertechnetate (rcO4 ") had to compete for positive sites on the surface of MPCM. In another attempt, the adsorption of technetium from a mixed solution on MPCM was studied, containing NaCI at 153.8 mmol / L, 1 mmol of Mo (VI) / L and 0.11 pmole of pertechnetate / L. Table 5 shows that molybdenum (AfoO | “) was preferentially adsorbed on the surface of MPCM, whereas the adsorption of pertechnetate (TcO * -) was reduced to 55% of technetium at 0.11pmole / L in mixed solution, it is assumed that, in the presence of 0.9% NaCI, the adsorption of pertechnetate (TcO4 ~) on the MPCM surface was reduced by due to competition for sites on the surface with chloride ions in solution at a pH of 3. In another attempt, a column with an internal diameter of 1 cm was used to study the adsorption of pertechnetate on MPCM, the column was prepared with MPCM which was initially loaded with Mo (VI). Discontinuous equilibration process was used to adsorb 6.25 mmole Mo (VI) / g MPCM at 298 * K when the Mo (VI) equilibrium concentration in the solution was 54 mmol / L and the initial pH of the solution was 3.0. Approximately 1.125 g of Mo (VI) loaded into the MPCM was used to prepare a 2.5 cm3 bed. A saline solution (0.9% NaCI) with 0.25 mM / L pertechnetate was passed through the column using a peristaltic pump at a flow rate of 1 mL / min during the test.
Table 5. Adsorption of pertechnetate and molybdenum in MPCM from a mixed solution

FIG. 16 shows that the pertechnetate anion has affinity for sites available on the MPCM surface in the presence of the molybdenum anion (AfoO | -). It was observed that, in 10 bed volumes, approximately 15% of the input concentration of pertechnetate was eluted with a saline solution (0.9% NaCI). It can be noted that approximately 60% of the input concentration of pertechnetate was obtained in the eluent that was collected in 20 bed volumes (FIG. 15). The column reaches saturation very quickly for technetium, while another 40 bed volumes of saline with technetium were passed through the column. After the column reached its saturation for technetium, more than 95% of the technetium fed to the column was collected at the column outlet as an eluent. The aim of this study was to investigate the maximum amount of pertechnetate uptake (TCO4 ") over MPCM loaded with Mo (VI) at 6.25 mM / gram of MPCM. No attempts were made to determine the bed length to reproduce the release of pertechnetate from the MPCM bed loaded with Mo (VI).
Although discontinuous and column studies have shown that MPCM exhibited excellent adsorption capacity for Tc (VII), its removal from the bed was a challenge. A bed of MPCM loaded with technetium was prepared in a column to study the technetium desorption of the MPCM sample. The adsorption of technetium over MPCM was carried out under conditions in batch equilibrium. It was observed that approximately 0.12 pM of "Tc were adsorbed per gram of MPCM from a concentration of" Tc of 0.48 pM / L of solution at a temperature of 298 K. For studies of desorption of "Tc, about 1.125 grams of MPCM containing 0.12 pM "Tc / gram of MPCM were used to prepare the column. Pertecnetate is soluble in water and therefore deionized water was used to regenerate technetium from the column. It was observed that only 1% of the technetium was absorbed from the MPCM bed using 10 volumes of water bed. Preliminary studies show that complete recovery of technetium from MPCM is a challenge, even when using different concentrations of NaCI. It was observed that about 50 bed volumes of 1.5% NaCI were needed to regenerate 10% of "Tc from the column. Similar amounts of low concentration (<1M) acidic solutions of HCI, H2SO4 and HNO3, also were used without any significant regeneration In another attempt, the MPCM adsorbent was oxidized with different concentrations of potassium permanganate or hydrogen peroxide to study the effect of oxidation on the adsorption / desorption of technetium on the oxidized MPCM adsorbent. EXAMPLE 2
In another modality, MPCM was oxidized with different concentrations of hydrogen peroxide with or without the presence of transition metal catalysts. The temperature was also varied. Oxidation studies of MPCM with hydrogen peroxide were carried out to determine whether controlled oxidation alone could improve technetium recovery from technetium-loaded MPCM. The concentration of hydrogen peroxide was varied from 1% to 5%. Discontinuous technique was used to adsorb the technetium on oxidized MPCM. Technetium regeneration of oxidized MPCM was carried out in a column. The column was prepared with 0.12 nmole of "Tc / gram of oxidized MPCM. The column was regenerated to desorb the technetium from the oxidized MPCM using 0.9% NaCI solution. It was observed that the technetium recovery was not as high as desired, since 10 to 17% of the available technetium were recovered from the bed of oxidized MPCM (Table 6) .In addition, the adsorption of Mo (VI) in peroxide-oxidized MPCM reduced to 4.6 mmole / g in compared to 6.25 mmole / g adsorbed by unoxidized MPCM. Table 6. Desorption of "Tc from oxidized MPCM using 0.9% NaCIa solution
EXAMPLE 3
MPCM was also oxidized using potassium permanganate in solution. The concentration of potassium permanganate in solution and the oxidation time were determined based on trial and error. The concentrations of potassium permanganate and the pH of the solution were varied between 0.1% and 5% and 3 to 11, respectively. The oxidation time was varied from 30 minutes to 24 hours. The surface load analysis of oxidized and non-oxidized MPCM loaded with Mo (VI) was also performed to elucidate the pertechnetate (7cO4 ") adsorption pattern in oxidized MPCM.
It was observed that the permanganate solution containing 0.04 mmole of Mn / L of solution in the pH range of 3 to 4.5 and a time period of 12 hours was sufficient to partially oxidize MPCM to facilitate maximum uptake of molybdenum and simultaneous release technetium of the MPCM adsorbent. The performance of oxidized MPCM was evaluated for adsorption of molybdenum from aqueous solutions using the batch technique. It was observed that oxidized MPCM can adsorb 6.25 mmole of Mo (VI) / g of MPCM at 298 X when the equilibrium concentration of Mo (VI) in the solution was 54 mmol / L at a pH of 3.0.
In another attempt, two separate columns were prepared using oxidized MPCM and oxidized MPCM which was loaded with 6.25 mmol of Mo (VI) / g, respectively. A 0.9% NaCI solution with about 0.11 pmole of Pertecnetate (rcO4 ~) / L solution was passed through both columns at a flow rate of 1 ml / min. It was interesting to note that pertechnetate (TcO ^ -) does not adsorb on oxidized MPCM with or without Mo (VI) loading and about 90% of pertechnetate (TcO4 ~) in the solution passed through both types of columns as an eluent. The results confirm that pertechnetate (rcO4_) does not adsorb on oxidized MPCM and MPCM loaded with Mo (VI). The objective of this work was to maximize the capture of Mo (VI) and increase the release of technetium simultaneously from sites on the surface of MPCM.
MPCM shows a great affinity for Mo (VI) and Tc (VII) from the aqueous solution. The surface charge of MPCM loaded with Mo (VI) revealed (FIG. 11) that Mo (VI) was adsorbed on MPCM through a complex formation reaction on the inner surface of the sphere. It can be noted that the MPCM loaded with Mo (VI) exhibited positive charge in the pH range of 3 to 4.5 and, therefore, anionic pertechnetate presumably formed covalent bonds with the positive sites available on the surface. Interestingly, pertechnetate adsorption on MPCM is approximately 55% from a solution containing 0.9% NaCI in the pH range 3 to 8 (Table 4). Almost 95% of pertechnetate at 1 mmole were adsorbed on MPCM in the presence of Mo (VI) at 1 mmole in solution. This confirms that pertechnetate (Tcü4 “) was adsorbed to sites on the surface of MPCM. The permanganate ion is amphiphilic in nature. In an acid solution, Mn (VII) ions of the potassium permanganate change to possible intermediate products, such as Mn (VI), Mn (V), Mn (IV) and Mn (lll), which are finally reduced to Mn (ll). See Dash et al., "Oxidation by Permanganate: Synthetic and mechanistic aspects", Tetrahedron, 65, 707-739, 2009. The content of permanganate (MnO ~) in potassium permanganate is reported to be the reactive oxidative species for oxidation of chitosan with acid-catalyzed permanganate. See Ahmed et al., "Kinetics of Oxidation of Chitosan polysaccharide by Permanganate Ion in Aqueous Per-chlorate solutions", Journal of Chemical Research, v 2003, n 4, pages 182 - 183, 2003. In an acidic environment, possible reactions between the ion ofA7 // C>; and H + are as follows:

Due to the protonation of MnO ~ ions in the acidic solution, the HMnO4 species can be formed, which is also a powerful oxidizer. See Sayyed et al., "Kinetic and Mechanistic Study of Oxidation of Ester by KMnO4", International Journal of ChemTech Research, v 2, n 1, pages 242- 249, 2010. The formation of colloidal Mnθ2 is possible due to the MnO reaction ~ with H + and, depending on the acidity of the solution, it can also undergo reaction with H + to produce Mn2 + in solution. Ahmed et al., 2002, reported oxidation with chitosan permanganate as an acid-catalyzed reaction that led to the formation of chitosan diceto-acid derivatives. See Ahmed et al., "Kinetics of Oxidation of Chitosan polysaccharide by Permanganate Ion in Aqueous Perchlorate solutions", Journal of Chemical Research, v 2003, n 4, pages 182 - 183, 2003.
In oxidation of MPCM with acid catalyzed permanganate, the permanganate ion (Mnθ4-) can be considered as the reactive oxidation agent. The oxidation effect with MPCM permanganate for the adsorption and release of Mo (VI) and Tc (VII) simultaneously from the oxidized MPCM surface was evaluated by analyzing the surface load of the MPCM sample. The oxidation of MPCM by potassium permanganate alters its adsorption selectivity from the aqueous solution. FIG. 17 shows the surface loading pattern for MPCM loaded with Mo (VI) with or without oxidation. In the case of the non-oxidized MPCM sample loaded with Mo (VI), the protonation of the surface appeared to be progressively increased in the pH range of 4.5 to 3. Therefore, in this pH range, the formation of covalent bond through pertechnetate with positive sites on the surface of Mo-loaded MPCM are possible. At a pH <2.9, the difference between the initial pH and the pH after equilibration time for MPCM loaded with the Mo (VI) sample was not significant, suggesting a complete protonation of the MPCM sample.
The surface charge of oxidized Mo (VI) loaded MPCM shows almost zero charge in the pH range of 3 to 4.5, compared to that of the unoxidized Mo (VI) loaded MPCM sample (FIG. 17). In the acidic pH range of 3 to 4.5, the functional groups on the surface of unoxidized MPCM show positive charge, which can still undergo a reaction with MnO ~ during the oxidation reaction. It is assumed that the manganese ion (MnO ~) entered the porous matrix of MPCM and partially oxidized the functional groups on the positive surface when donating electrons, followed by reduction to A7 / 2 + ions in the solution. In addition, the formation of colloidal manganese in the solution was controlled by controlling the pH of the solution in the range of 3 to 4.5, more specifically at a pH of 4. In addition, the proportion of Mn2 + ions for positive sites on the MPCM surface favors further adsorption of Mn2 + on the MPCM surface. It was observed, from discontinuous and column studies, that technetium does not adsorb on oxidized MPCM loaded with Mo (VI), although it shows a strong affinity for non-oxidized MPCM loaded with Mo (VI). This indicates that the lack of positive charge on the surface of the oxidized MPCM loaded with Mo (VI) does not attract technetium to form a covalent bond compared to the surface of unoxidized MPCM loaded with Mo (VI). It is interesting to note that technetium does not adsorb on oxidized MPCM, while almost 95% of the 1 mmole technetium solution was adsorbed on unoxidized MPCM. This confirms that the technetium adsorbed on the surface of the unoxidized MPCM and was not adsorbed on the oxidized MPCM through covalent bonding.
Balanced batch adsorption studies were performed by exposing the oxidized MPCM to the 1% Mo (VI) solution which was enriched with 5.0 mL of "Mo (2 mCi / ml). Initially, 1% molybdenum was prepared by dissolving 4, 5 ml of ammonium hydroxide and 1.5 g of MoOs in 95 ml of deionized water. The mixture was kept under stirring until the MoOs completely dissolved in solution. A solution containing 5.0 ml of "Mo (2 mCi 99Mo / ml ) was mixed with 97.5 mL of 1% molybdenum solution. The pH of the solution was adjusted to 3 using 0.1 N HCI or NaOH solution. The final specific activity of Mo (VI) in the solution was 78.12 pCi / mL.
About 0.5 grams of oxidized MPCM were added to a 125 ml plastic bottle containing 50 ml of enriched solution. The solution was then kept on the shaker (160 rpm) for 3 hours at 25 ± 1 “C. Another set of similar experiments was also carried out to duplicate the data. After 3 hours, the final pH was recorded for the solution and the solution was centrifuged for 5 minutes at 3000 rpm in order to separate the MPCM from the supernatant solution. The MPCM loaded with Mo (VI) was then rinsed with deionized water twice to remove any Mo (VI) adhered from its surface. Mo (VI) loaded MPCM and supernatant and rinse solutions were analyzed for molybdenum uptake using a dose calibrator and an ICP-MS. It was observed that, in the steady state, the oxidized MPCM had a capacity of 2.47 mmoles of Mo / g of MPCM, where 1300 pCi of activity are of the enriched "Mo.
The activity for "Mo e" mTc was assessed using a dose calibrator and a gamma spectrometer. The dose calibrator (Atomlab 400) is equipped with a small container for samples of lead shielded against "mTc gamma, while most of the 99Mo gamma passes through the shield and into the detector. Therefore, the readings taken while the sample is contained in the armored container are attributed exclusively to the activity of "Mo. Readings taken without protection are the sum of "Mo e" mTc activities.
After the batch adsorption test, the MPCM loaded with 98MO and "Mo was transferred to a column (0.5 cm x 3.2 cm, with polytetrafluoroethylene (PTFE) frit at the bottom). Two ends of the column were closed with silicone rubber stopper The column was thoroughly washed with deionized water to remove any molybdenum solution on the surface of the MPCM The washed sample was collected from the column using evacuated flasks The column was eluted with saline (0.9 NaCI) %) after allowing the maximum time necessary to develop the product derived from "mTc from the decay of" Mo remaining in the column. The column was eluted with 9 ml of saline which was subsequently collected in 3 individual evacuated vials of 3 ml each The fluid was obtained from the column at predetermined time intervals The eluate of each set was analyzed for molybdenum and manganese released from the column using inductive plasma mass spectrometry quadruple (ICP-MS) with an external calibrator. Pertecnetate-related activity or "Mo was assessed using a dose calibrator and gamma spectroscopy.
FIG. 18 shows the elution profile of the column consisting of 0.5 grams of MPCM loaded with 2.47 mmol of Mo (VI) / gram of oxidized MPCM, where the activity is 1300 pCi of "adsorbed Mo. The column started to elution with saline (0.9% NaCI) on the day after the column was prepared and elution was continued for the period of 8 days. One observation is that the first set of elution (Elution 1) was performed on 8 hours after the column was prepared in order to verify the "mTc desorption behavior of the MPCM column. The rest of the elutions, numbers 2 to 8, were performed at 24-hour intervals, except for elution number 5, which was performed at least 45 hours after elution number 4. It was found that the elution efficiency for the product derived from "mTc of the column was within the range of 75 to 90% (FIG. 18). In elution 1, as shown in FIG. 18, more than 80% of the activity due to" mTc is obtained at about 9 ml of solution saline (0.9% NaCI), where 62% of the "available mTc activity eluted in the first 3 mL of normal saline volume. The second elution was collected within 24 hours after the first elution and shows that the" mTc in the column ranged from 70% to 90% and can be recovered using 3 to 9 mL of saline. In all cases, the eluate was clear and the pH was in the range 6 to 7. The column was eluted continuously over the 8 day period, with an average of ~ 82% of all "mTc eluted from the column.
FIG. 19 shows the percentage of "mTc and Mo (VI) released from the column during the 8-day period. The concentration of Mo (VI) in the eluates was within the range of 1% to 3% of the 6.25 mmole of Mo (VI ) / gram of MPCM in the column The process of capturing any leakage of molybdenum from the column by passing it through the acid-catalyzed MPCM is possible, as shown in FIG. 15, thereby reducing the concentrations of Mo (VI ) and Mn (VII) in the eluent for extremely low levels Another way to control molybdenum leakage from the column can be obtained by controlling the pH of the saline solution (0.9% NaCI) within the range of 4 to 4.5 (FIG In this case, an additional protection column will not be necessary to control the leakage of Mo (VI) from the column. EXAMPLE 4
Production of "Mo via the neutron capture method draws attention as an alternative to" Mo derived by fission due to non-proliferation problems. The "Mo produced by the activation of natural molybdenum neutrons would provide a less complex, cheaper and more practical route for the production and use of" mTc. However, it is evident that the specific activities produced by the neutron capture method are not high enough to prepare small chromatographic generators. This limitation, however, can be overcome by using MPCM as an adsorbent, which has the ability to adsorb molybdenum. It is shown that MPCM is able to adsorb more than 6.25 mmole of Mo (VI) / gram (600 mg of Mo (VI) / g of MPCM) from an aqueous solution at pH 3, which is also applicable to "Mo obtained easily by the reaction (n, y) of natural molybdenum. The generator, in this case, consists of MPCM loaded with" Mo, which thus combines the performance of the chromatographic generator and the use of (n, y) " Mo. If used as an adsorbent in a "mTc /" Mo generator, MPCM is capable of storing up to 60% by weight of its body weight, compared to only 0.2% by weight of alumina. The potential of MPCM as an adsorbent for the preparation of the "Mo /" mTc generator was explored using a 1% solution of Mo (VI) enriched with "Mo (2 pCi / ml). It was observed that MPCM adsorbed Mo (VI) enriched with "Mo according to its capacity demonstrated from an aqueous solution at a pH of 3. It was also observed that" mTc, which was the decay product of "Mo, was eluted with normal saline (0.9%) to obtain more than 80% elution. A typical "CMTc /" Mo generator preparation flowchart based on MPCM as an adsorbent is provided in FIG. 20. EXAMPLE 5
About 4 g of chitosan was added to 300 ml of deionized water (Dl) with 1 ml of acetic acid and stirred for 2 hours at 70 “C to form a gel. About 4 ml of HCI was added to the chitosan gel and kept under continuous stirring for an additional 1 hour at 70 ° C.
In this example, an amorphous titania gel was prepared by means of acid-catalyzed controlled hydrolysis and condensation of titanium isopropoxide. See Hasan, S., Ghosh, T.K., Prelas, M.A., Viswanath, D.S. and Boddu, V.M. "Adsorption of uranium on a novel bioadsorbent chitosan coated perlite", Nuclear Technology, 159, 59-71, 2007; Schattka, JH, Wong, EH-M., Antonietti, M. and Caruso, RA "Sol-gel templatingof membranes to form thick, porous titania, titania / zirconia and titania / silica films", Journal of Materials Chemistry, 16, 1414 -1420, 2006; Agoudjil, N. and Benkacem, T. "Synthesis of porous titanium dioxide membranes", Desalination, 206, 531-537, 2007. Equal volumes of isopropanol (IP) and Dl water were mixed in a certain amount of titanium isopropoxide under agitation continuous at 70 'C. Dropwise addition of HCI under continuous stirring and heating to 70 ° C produced a clear solution. The hydrolysis and the condensation reaction were controlled by the proportion of water and titanium and H + and titanium in the mixture, respectively. The final pH of the mixture was approximately 2.0 and the final reagent stoichiometry was Ti: IP: H2O: H + = 0.0132: 0.39: 1.67: 0.01. Based on the proportion of concentration of the reagents, the gel time was varied between 25 and 45 minutes.
In about 75% of the total gel time, an amorphous titania sol-gel solution was mixed with the chitosan gel. The mixture was kept under stirring at 70 “C for an additional 1 h to complete the reaction of chitosan and amorphous titanium oxide. The reaction with glutaraldehyde was carried out by adding dropwise about 6 ml of 50% glutaraldehyde solution to the titania / chitosan acid gel under continuous stirring at 70 ‘C. The pH of the final mixture was approximately 1.0. The mixture was kept under vigorous stirring at 70 ° C for more than 1 h to obtain a semi-solid gel.
The resulting mass was carefully washed with 2% monoethanol amine to remove any unreacted glutaraldehyde. The mass was then suspended in 0.1 M NaOH solution for 4 to 6 hours. The crosslinked mass was separated from the solution and washed with 0.1 M HCI, then with deionized water (Dl), until the pH of the washed solution was 7. The crosslinked mass was then dried in a vacuum oven. overnight at 70 ° C 13. The crosslinked chitosan / glutaraldehyde composite prepared in this process is referred to as "CGST" here.
In the case of the CGST sample, it was found that the peak at 1590 cm'1 is weakened, indicating that the amide groups may be involved in crosslinking reactions with titanium. The carbonyl spectra (- CONHR) around 1650 cm'1 are observed for all three samples. For primary aromatic amines, C-N elongation vibrations fall between 1350 and 1150 cm'1.
There is a peak observed at 1170 cm'1 (FIG. 21) for chitosan and CGST samples, respectively. In comparison with chitosan, it was found that the peak at 1170 cm'1 is weakened and a new peak appears at 1090 cm'1 for CGST samples.
The peak that appears at 1090 cm'1 shows prominent deviations due to C = O stretching vibrations of an ether bond.
In the region of 1000 cm'1 to 1200 cm'1, chitosan shows two peaks at 1157 cm'1 and 1070 cm'1, which correspond to the elongation of a C-0 bond of C3 of chitosan (secondary OH) and elongation of C -0 of C6 of chitosan (primary OH), respectively.
In comparison to the C-0 spectrum of chitosan obtained at 1070 cm -1, the absorption peaks of the secondary hydroxyl group of the CGST samples are doubled, as indicated in FIG. 21, and the O-H band was reduced and moved from 3498.0 to 3450.0 cm'1, suggesting that the chitosan O-H groups may be involved in the reaction with glutaraldehyde by forming hemiacetal in the presence of an acid catalyst. Evidence of decreased C-0 chemical bonding constant and significant decline in peak elongation intensities for OH (1000 to 1200 cm cm'1) support the presence of a glutaraldehyde complex formation reaction with the functional groups surface oxygen, such as the secondary hydroxyl group in chitosan. In the case of the CGST sample, titanium oxide appears to be involved in a reaction with the chitosan amine group (FIG. 21).
Several modalities of the microporous composite material based on chitosan (MPCM) were prepared by crosslinking glutaraldehyde at 70 13 in the presence of catalyst. MPCM was prepared in the laboratory via phase inversion of chitosan slurry dissolved in acetic acid and condensation of glutaraldehyde aldol for better exposure of amine groups (NH2). The MPCM was characterized by scanning electron microscopy (SEM), which revealed its porous nature. Two MPCM-based derivatives, such as oxidized MPCM and acid-catalyzed MPCM were also prepared. The stabilization study for MPCM was carried out at 50,000 krad using a 60Co radiator as a y source. Microanalysis spectra by FTIR, XPS and EDS X-rays revealed that the peak intensity of C, O and N for MPCM does not change substantially after irradiation. In the case of adsorption of Mo (VI) from aqueous solution at 298 X, MPCM can contain up to 60% of its own body weight. MPCM and its derivatives demonstrate the ability to adsorb "Mo and release the derived product" mTc simultaneously under equilibrium and discontinuous conditions. It was also observed that "mTc, which was the decay product of" Mo, was eluted with normal saline (0.9%) to obtain more than 80% elution. The data show that the high elution yield of "mTc and the leakage of Mo (VI) from the continuous column was minimal, so MPCM and its derivatives can be used as an adsorbent in the" mTc / "Mo generator without using any protection column.
As used here, the terms "around", "approximately" and "about" in relation to a numerical value denote that some variations in relation to the numerical value may be possible up to a maximum of ± 10% of the numerical value. The terms "one", "one", "o" and "a" and the like, which denote a single occurrence, should also be understood as including a plurality of occurrences, unless expressly stated otherwise.
The present invention has been described with reference to certain specific embodiments and examples; it will be understood that these are illustrative and do not limit the scope of the appended claims.

权利要求:
Claims (6)
[0001]
1. Method of separating isotopes from mixtures thereof, characterized by the fact that it comprises contact of a mixture of two or more isotopes with a radiation-resistant sorbent comprising a microporous material comprising chitosan, which has been cross-linked with glutaraldehyde in the presence of a catalyst for a concentration of glutaraldehyde of about 2 to about 4% by weight and which is resistant to degradation by exposure to beta and gamma radiation and exposure to acids, which adsorb one or more of said isotopes; adsorption of one or more of said isotopes on or within said adsorbent, while one or more of the remaining isotopes are not significantly adsorbed by the adsorbent; removing said one or more isotopes remaining from said adsorbent.
[0002]
Method according to claim 1, characterized by the fact that said two or more isotopes comprise 99Mo and 99mTc.
[0003]
Method according to claim 2, characterized by the fact that said adsorbent adsorbes said 99Mo and in which said20 99mTc is not significantly adsorbed by said adsorbent.
[0004]
Method according to claim 1, characterized by the fact that one of said isotopes is a cesium isotope.
[0005]
Method according to claim 4, characterized by the fact that said one or more remaining isotopes comprise one or more isotopes present in a radioactive effluent.
[0006]
6. 99Mo / 99mTc generator, characterized by the fact that it comprises the adsorbent as defined in claim 1.

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KR102232786B1|2021-03-26|Process and device for removing iodine using gold particles

---

Weng et al.2021|Efficient and Ultrafast Adsorption of Rhenium by Functionalized Hierarchically Mesoporous Silica: A Combined Strategy of Topological Construction and Chemical Modification

---

Hamed et al.2022|Utilization of modified polymeric composite supported crown ether for selective sorption and separation of various Beta emitting radionuclides in simulated waste

---

Dall’Orto et al.2016|Design, characterization, and environmental applications of hydrogels with metal ion coordination properties

---

Abdellah et al.2020|Removal of Technetium | from Aqueous Waste by Manganese Oxide Nanoparticles Loaded into Activated Carbon

同族专利:

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公开号 | 公开日

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WO2012125994A9|2013-06-13|

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KR20140035351A|2014-03-21|

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EA201301039A1|2014-04-30|

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CA2830434A1|2012-09-20|

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BR112013023711A2|2016-12-13|

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EP2686101A2|2014-01-22|

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CA2830434C|2019-08-27|

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KR101967005B1|2019-04-08|

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US20130039822A1|2013-02-14|

---

US8911695B2|2014-12-16|

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WO2012125994A3|2013-04-04|

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EA023546B1|2016-06-30|

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WO2012125994A2|2012-09-20|

引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

---

DE4318094B4|1993-06-01|2004-03-04|Stockhausen Gmbh & Co. Kg|Superabsorbents, processes for their preparation and their use|

---

US5599916A|1994-12-22|1997-02-04|Kimberly-Clark Corporation|Chitosan salts having improved absorbent properties and process for the preparation thereof|

---

US5762903A|1995-03-10|1998-06-09|Korea Atomic Energy Research Institute|Radioactive chitosan complex for radiation therapy|

---

US7497952B2|2002-02-14|2009-03-03|The Trustees Of Stevens Institute Of Technology|Methods of preparing a surface-activated titanium oxide product and of using same in water treatment processes|

---

US7007752B2|2003-03-21|2006-03-07|Halliburton Energy Services, Inc.|Well treatment fluid and methods with oxidized polysaccharide-based polymers|US20150139870A1|2011-03-17|2015-05-21|Perma-Fix Environmental Services, Inc.|Preparation of chitosan-based microporous composite material and its applications|

---

AU2015349895B2|2014-11-19|2019-08-29|Perma-Fix Environmental Services, Inc.|Preparation of chitosan-based microporous composite material and its applications|

---

WO2019190791A1|2018-03-26|2019-10-03|Perma-Fix Environmental Services, Inc.|Preparation of chitosan-based microporous composite material and its applications|

---

US10500564B2|2011-03-17|2019-12-10|Perma-Fix Environmental Services, Inc.|Preparation of chitosan-based microporous composite material and its applications|

---

SG10201610469QA|2011-11-13|2017-02-27|Cresilon Inc|In-situ cross-linkable polymeric compositions and methods thereof|

---

US9368241B2|2012-06-29|2016-06-14|Ge-Hitachi Nuclear Energy Americas Llc|System and method for processing and storing post-accident coolant|

---

US9406407B2|2012-12-11|2016-08-02|Ge-Hitachi Nuclear Energy Americas Llc|Radioactive capture system for severe accident containment of light water reactors , and method thereof|

---

FR2999777A1|2012-12-14|2014-06-20|Commissariat Energie Atomique|Use of composite material to eliminate radioactive element e.g. strontium of aqueous effluent, where the material comprises inorganic compound to capture radioactive element, and porous polymeric matrix entrapping the inorganic compound|

---

TW201439011A|2013-04-10|2014-10-16|Ya-Chung Wei|Stabilization of activated sludge for water treatment|

---

WO2016057603A1|2014-10-08|2016-04-14|Therakine|Cross-linked biopolymer macroscopic systems and method of making same|

---

KR20180053636A|2015-06-22|2018-05-23|크레실론, 인코퍼레이티드|High Efficiency Hemostatic Binding Adhesive Composition Scaffold|

---

RU2645131C1|2017-07-18|2018-02-15|Андрей Александрович Нестеренко|Production process of a sorption material|

---

CN109652649B|2017-10-10|2021-08-03|中国石油化工股份有限公司|Method for improving recovery rate of cobalt and molybdenum of waste catalyst|

---

KR102218075B1|2018-06-04|2021-02-19|동국대학교 경주캠퍼스 산학협력단|Chitosan immobilized metal oxide for the adsorption materials of radioisotope generator and method for fabricating the same and radioisotope generating method|

---

CN110215913B|2019-07-05|2021-10-29|南京师范大学|Nano molybdate-loaded resin composite adsorbent, preparation method and application|

---

US11008425B1|2019-11-13|2021-05-18|King Abdulaziz University|Method of producing metal nanoparticle-loaded biopolymer microgels|

---

KR20210152232A|2020-06-08|2021-12-15|한국원자력연구원|Chitosan-titanium composite, method for preparing and use thereof|

---

CN111807630A|2020-07-17|2020-10-23|安徽工业大学|High-efficient molybdenum-removing vertical subsurface flow constructed wetland purification device|

---

RU2750034C1|2020-09-03|2021-06-21|Федеральное государственное бюджетное образовательное учреждение высшего образования "Ивановский государственный химико-технологический университет"|Method for producing composite sorbent for extraction of heavy metal ions from aqueous solutions|

法律状态:
2019-01-29| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|

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2019-11-19| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|

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2020-06-09| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2020-11-03| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 19/03/2012, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US201161453772P| true| 2011-03-17|2011-03-17|

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US61/453,772|2011-03-17|

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PCT/US2012/029629|WO2012125994A2|2011-03-17|2012-03-19|Preparation of chitosan-based microporous composite material and its applications|

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