PROCESS FOR REMOVING COBALT, LEAD, CADMIUM, AND CHROMIUM IONS FROM BODY FLUIDS USING METALATE ION EXCHANGE COMPOSITIONS

Abstract

A process for removing CO2+, Pb2+, Cd2+, and Cr3+ toxins from body fluids is described. The process involves contacting the body fluid with an ion-exchange composition to remove the metallic toxins from the body fluid, which includes blood and gastrointestinal fluid. Alternatively, blood can be contacted with a dialysis solution, which is then contacted with the ion-exchange composition. The ion-exchange compositions are represented by the following empirical formula: AmZraTibSncMdSixOy. A composition comprising the above ion-exchange compositions in combination with body fluids or dialysis solution is also described. The ion-exchange compositions can be supported by porous networks of biocompatible polymers such as carbohydrates or proteins.

Description

This invention relates to extracorporeal or intracorporeal processes for removing Co2+, Pb2+, Cd2+, and Cr3+ ions from body fluids. The blood or other body fluid is brought into direct contact with a metallate ion-exchange composition capable of selectively removing the toxins, or the blood or other body fluid is first brought into contact with a dialysis solution, which is then brought into contact with the metallate ion-exchange composition. Background of the Invention In mammals, such as humans, when the kidneys and / or liver fail to remove metabolic waste products from the body, most other organs will soon fail as well. Therefore, extensive efforts have been made to discover safe and effective methods for removing toxins from patients' blood through extracorporeal blood therapy. Many methods have been proposed for removing small molecular toxins, protein-bound molecules, or larger molecules believed to be responsible for coma and liver failure. Some of these toxic compounds are... Ref. 330498 has identified urea, creatine, ammonia, phenols, mercaptans, short-chain fatty acids, aromatic amino acids, false neurotransmitters (octopamine), neural inhibitors (glutamate), and bile salts. Among these, phenols and mercaptans, along with bilirubin and bacterial endotoxins, also occur as potent protein-bound toxins and are therefore more difficult to remove effectively from the blood. Medium-molecular-weight toxins, ranging from 300 to 10,000, may also be present and are difficult to remove effectively. The technique shows several ways to treat blood containing such toxins. The classic method is, of course, dialysis. Dialysis is defined as the removal of substances from one fluid by diffusion through a semipermeable membrane into a second fluid. Blood dialysis outside the body (hemodialysis) is the basis of the artificial kidney.The artificial kidney treatment procedure generally used today is similar to that developed by Kolff in the early 1940s. Since the 1940s, there have been several descriptions of improvements to artificial kidneys or artificial livers. U.S. Patent No. 4,261,828 describes an apparatus for blood detoxification. The apparatus comprises a housing loaded with an adsorbent, such as carbon or a resin, and optionally, an enzyme carrier. To prevent direct contact between the blood and the adsorbent, the adsorbent may be coated with a lining that is permeable to allow substances to be adsorbed but prevents direct contact between the corpuscular blood components and the adsorbents. U.S. Patent No.US Patent 4,581,141 describes a dialysis composition containing a surface adsorbent, water, a suspending agent, urease, a calcium-charged cation exchanger, an aliphatic carboxylic acid resin, and a metabolizable organic acid regulator. The calcium-charged cation exchanger may be a calcium-exchanged zeolite. EP 0046971 A1 describes that zeolite W can be used in hemodialysis to remove ammonia. Finally, US Patent 5,536,412 describes plasma filtration and hemofiltration devices in which blood flows through the interior of a hollow fiber membrane, and during blood flow, a sorbent suspension is circulated against the outer surfaces of the hollow fiber membrane.Another stage involves the alternating exit and re-entry of the plasma fraction of the blood into the membrane, thus eliminating toxins. The sorbent can be activated carbon along with an ion exchanger such as a zeolite or a cation exchange resin. There are problems associated with the adsorbents described in the previous patents. For example, carbon does not remove water, phosphate, sodium, or other ions. Zeolites have the disadvantage that they can partially dissolve in the dialysis solution, allowing aluminum and / or silicon to enter the bloodstream. Furthermore, zeolites can adsorb sodium, calcium, and potassium ions from the blood, thus requiring these ions to be added back into the blood. More recently, examples of microporous ion exchangers that are essentially insoluble in fluids, such as body fluids (especially blood), have been developed, namely the zirconium-based silicates and titanium-based silicates of U.S. Patent No. 5,888,472; U.S. Patent No. 5,891,417; and U.S. Patent No. 6,579,460. The use of these zirconium-based silicate or titanium-based silicate microporous ion exchangers for removing toxic ammonium cations from blood or dialysate is described in U.S. Patent Nos. 6,814,871, 6,099,737, and 6,332,985. In addition, some of these compositions were found to be selective with respect to potassium ion exchange and could remove potassium ions from body fluids to treat hyperkalemia, as described in U.S. patents 8,802,152 and 8,802,152. 8,808,750; US 8,877,255; US 9,457,050; US 9,662,352; US 9,707,255; US 9,844,567; US 9,861,658; US 2015 / 0225249; US 20016 / 0000825; US 2016 / 0038538; US 2016 / 0271174 and US 2018 / 0214479. Ex vivo applications of these materials, for example, in dialysis, are described in US Patent No. 9,943,437. Blood-compatible polymers have also been incorporated into devices for treating bodily fluids. U.S. Patent No. 9033908 describes small desktop and portable devices for removing toxins from the blood. The device features a sorption filter that uses nanoparticles embedded in a porous, blood-compatible polymer matrix. Toxic materials targeted by this device and filter system include potassium, ammonia, phosphate, urea, and uric acid. Similarly, a 3D-printed hydrogel matrix consisting of crosslinked poly(ethylene glycol) diacrylate to which polydiacetylene-based nanoparticles are attached has been shown to be successful in removing the toxin melittin (Nature Communications, 2014, DOI: 10.1038 / ncomms4774). In addition to toxins derived from metabolic waste, humans are susceptible to environmental toxins that can enter the body, for example, through ingestion, absorption through the skin, or inhalation. In 1997, the U.S. Environmental Protection Agency's Toxic Release Inventory (TRI) monitoring of 3,391 large chromium processing facilities reported the release of nearly 33 million pounds of chromium into the environment. The majority of this waste, 94.1%, was released into the soil, including waste chromium slag containing potentially toxic levels of Cr6+ that was used as landfill at more than 160 residential, industrial, and recreational sites. Exposure routes include leaching into groundwater, windborne dust, and direct contact. Airborne chromium compounds accounted for 2.Two percent of environmental releases include emissions from the metals industry, emissions from chromium plating facilities (almost exclusively Cr6+ compounds), and emissions from the combustion of fuels, coal, and oil. The galvanizing, leather tanning, and textile industries release chromium into surface waters, accounting for 0.3% of total chromium releases. While the tanning industry primarily uses the less toxic Cr3+, the chromium plating industry uses almost exclusively Cr6+. Exposure to Cr6+ has been associated with lung cancer, whereas Cr3+, a necessary nutrient, is toxic in large doses and has been associated with respiratory problems (see Agency for Toxic Substances and Disease Registry, Case Studies in Environmental Medicine (CSEM), Chromium Toxicity, Dianil Yu, 2008). Cr6+ is a powerful oxidant and is frequently reduced to Cr3+.Inhaled Cr6+ is reduced to Cr3+ in the lower respiratory tract, while a large portion of ingested Cr6+ is reduced to Cr3+ by gastrointestinal fluids. Airborne Cr6+ can be similarly reduced to Cr3+ by contaminants, and Cr6+ released into environmental waters can be reduced to Cr3+ by airborne organic materials. Therefore, such exposures can result in elevated levels of Cr3+ in body fluids. Patients who have undergone hip replacement surgery sometimes experience toxic levels of Cr3+ and CO2+ in their blood. Another well-known toxic metal is lead. For many years, lead was a key component of gasoline in the form of tetraethyllead and a key component of paints. Lead is no longer used or is used only rarely in these industries today, but environmental hazards remain. Remodeling activities in older homes painted with lead-containing paints produce dust that can be inhaled or end up in nearby soils, where the lead leaches into groundwater or is taken up by plants. Unreliable or unregulated water supplies represent a dangerous exposure to Pb2+ toxicity, most notably the recent case in Flint, Michigan, USA, where some residents were found to have dangerously high levels of Pb2+ in their blood after exposure to a new drinking water supply.Lead contamination is associated with many harmful health effects, including affecting the nervous and urinary systems and inducing learning and developmental disabilities in exposed children. Removing lead from the blood of affected patients would reduce further exposure and damage. Cadmium occurs naturally in association with zinc and is released into the environment during zinc mining and smelting operations, the latter of which releases airborne particles containing cadmium. Another source of airborne cadmium comes from the incineration of municipal waste containing plastics and Ni-Cd batteries. Industrial processes that use and can release cadmium into the environment include the manufacture of Ni-Cd batteries, cadmium-stabilized plastics, metal plating, and pigments. Zinc mining operations can contaminate local water sources with cadmium. In one such case, the use of contaminated water to irrigate fields led to contamination of rice crops and the poisoning of a portion of the population (see Agency for Toxic Substances and Disease Registry, Case Studies in Environmental Medicine (CSEM) Chromium Toxicity, Pamela G. Tucker, 2008).The primary source of cadmium exposure for the general public is food, while those with occupational exposure to cadmium, which is mainly through inhalation, have a higher risk of experiencing adverse effects. Chronic cadmium exposure primarily affects the kidneys and, secondarily, the bones. Treatments for cadmium exposure largely involve removing the patient from exposure. Like many other metals, cobalt is released into the environment during mining and smelting operations. The application of cobalt-containing slurries or phosphate fertilizers also leads to the spread of cobalt through the environment. Cobalt exposure is more likely to occur through diet than through drinking water or inhalation. Cobalt is necessary for human health, especially as a component of vitamin B12, and has been used to stimulate red blood cell production in pregnant women. However, workers exposed to higher levels of cobalt have developed respiratory problems. Cardiomyopathy has been reported in humans and animals following cobalt exposure. Workers at nuclear facilities and nuclear waste storage sites may be exposed to potentially high levels of radioactive cobalt.(See Toxicological Profile for Cobalt, Department of Health and Human Services, Agency for Toxic Substances and Disease Registry, April 2004). μλ / t / ζυζζ / υυοζυυ Chelation therapy has been used to try to remove some of these metallic toxins from the blood. Chelation therapy targeting the removal of Co2+, Cr3+, and Cd2+ yielded uninterpretable results or provided no benefit (J Med Toxicol., (2013) 9, 355-369). Chelation therapy has also been used for Pb2+ poisoning. The chelating agent CaNa2EDTA has been used to remove Pb2+ from the blood, but this complex is not well adsorbed by the gastrointestinal tract and frequently must be administered intravenously. This chelate was observed to mobilize Pb2+, transferring it to other tissues, including the brain (Int. J. Environ. Res. Public Health, (2010), 7, 2745-2788). Dimercaptosuccinic acid (DMSA) was recognized as an antidote for heavy metal poisoning and has been used to treat poisoning with Co2+, Cd2+ and Pb2+ (See U.S. Patent No. 5519058).Concerns about chelation therapy include toxic side effects, non-selective metal binding, and spread of toxins throughout the body. Supported chelating agents, i.e., chelating agents bound to resins, have been used for heavy metal removal in a dialysis mode, where blood is on one side of a semipermeable membrane and the resin-supported chelates on the other (see U.S. Patent No. 4612122). Zeolites have been proposed to treat chronic lead poisoning, taken in pill form in U.S. patent no. US 2018036279A1, but zeolites have limited stability, especially in the gastrointestinal tract. The applicants have developed a process that uses metalate ion exchangers that are essentially insoluble in fluids, such as body fluids (especially blood) or dialysis solutions. These ion exchangers have an empirical formula on an anhydrous basis of: AmZraTibSncMdSixOy where A is an exchangeable cation selected from the group consisting of potassium ion, sodium ion, rubidium ion, cesium ion, calcium ion, magnesium ion, hydronium ion or mixtures thereof, M is at least one framework metal selected from the group consisting of hafnium (4+) or niobium (5+), m is the molar ratio of A to total metal (total metal = Zr + Ti + Sn + M) and has a value of 0.10 to 15, a is the mole fraction of total metal being Zr and has a value of zero to 1, b is the mole fraction of total metal being Ti and has a value of zero to 1, c is the mole fraction of total metal being Sn and has a value of zero to 1, d is the mole fraction of total metal being M and has a value of zero to less than 1, where a + b + c + d = l and a + b + c > 0, x is The molar ratio of Si to the total metal has a value from 0 to 12, and the molar ratio of O to the total metal has a value from 2.1 to 33.Since these compositions are essentially insoluble in body fluids (at neutral and slightly acidic or basic pH) they can be ingested orally to eliminate toxins in the gastrointestinal system as well as be used to remove toxins from the blood, specifically, Co2+, Pb2+, Cd2+ and Cr3+. Brief Description of the Invention As mentioned, this invention relates to a process for removing Co2+, Pb2+, Cd2+, Cr3+, or combinations thereof from fluids selected from the group consisting of a body fluid, a dialysate solution, and mixtures thereof. The process comprises contacting the toxin-containing fluid with an ion exchanger, resulting in the exchange of ions and the removal of the toxins from the fluid. The metalate ion exchanger is selected from zirconium metalate, titanium metalate, tin metalate, a multi-metalate containing at least two or more zirconium, titanium, or tin elements, or mixtures thereof. The composite metalate has an empirical formula on an anhydrous basis of: AmZ raTibSncMdS ixOy where A is an exchangeable cation selected from the group consisting of potassium ion, sodium ion, rubidium ion, cesium ion, calcium ion, magnesium ion, hydronium ion or mixtures thereof, M is at least one framework metal selected from hafnium (4+) or niobium (5+), m is the molar ratio of A to total metal (total metal = Zr + Ti + Sn + M) and has a value of 0.10 to 15, a is the mole fraction of the total metal being Zr and has a value of zero to 1, b is the mole fraction of the total metal being Ti and has a value of zero to 1, c is the mole fraction of the total metal being Sn and has a value of zero to 1, d is the mole fraction of the total metal being M and has a value of zero to less than 1, where a+b+c+d=l and a+b+c > 0, x is the ratio molar ratio of Si to total metal and has a value of 0 to 12, and is the molar ratio of O to total metal and has a value of 2.1 to 33. The body fluids treated by the present invention include blood and gastrointestinal fluids.Blood may include whole blood, blood plasma, or other blood components as known to an expert in the technique. Another embodiment of the invention is a combination of a body fluid or dialysate solution and a metalate ion exchanger selected from zirconium metalate, titanium metalate, tin metalate, a multi-metalate containing at least two or more zirconium, titanium, or tin, or mixtures thereof, the composite metalate having an empirical formula on an anhydrous basis of: AmZ raT itS ncMdS ixOy where A is an exchangeable cation selected from the group consisting of potassium ion, sodium ion, rubidium ion, cesium ion, calcium ion, magnesium ion, hydronium ion or mixtures thereof, M is at least one framework metal selected from the group consisting of hafnium (4+) or niobium (5+), m is the molar ratio of A to total metal (total metal = Zr + Ti + Sn + M) and has a value of 0.10 to 15, a is the mole fraction of the total metal being Zr and has a value of zero to 1, b is the mole fraction of the total metal being Ti and has a value of zero to 1, c is the mole fraction of the total metal being Sn and has a value of zero to 1, d is the mole fraction of the total metal being M and has a value from zero to less than 1, where a + b + c + d = l and a + b + c > 0, x is the molar ratio of Si to the total metal and has a value from 0 to 12, and y is the molar ratio of O to the total metal and has a value from 2.1 to 33. Another embodiment of the invention is an apparatus incorporating an ion exchanger metalate selected from zirconium metalate, titanium metalate, tin metalate, a multi-metalate containing at least two or more zirconium, titanium or tin, or mixtures thereof, the composite metalate having an empirical formula on an anhydrous basis of: AmZ raTibSncMdS ixOy where A is an exchangeable cation selected from the group consisting of potassium ion, sodium ion, rubidium ion, cesium ion, calcium ion, magnesium ion, hydronium ion or mixtures thereof, M is at least one framework metal selected from the group consisting of hafnium (4+) or niobium (5+), m is the molar ratio of A to total metal (total metal = Zr + Ti + Sn + M) and has a value of 0.10 to 15, a is the mole fraction of total metal being Zr and has a value of zero to 1, b is the mole fraction of total metal being Ti and has a value of zero to 1, c is the mole fraction of total metal being Sn and has a value of zero to 1, d is the mole fraction of total metal being M and has a value of zero to less than 1, where a + b + c+d=lya+b+c>0, x is the molar ratio of Si to the total metal and has a value from 0 to 12, yy is the molar ratio of O to the total metal and has a value from 2.1 to 33.The apparatus is configured to come into contact with a body fluid or dialysate solution to remove selected ions of Co2+, Pb2+, Cd2+, and Cr3+. The apparatus of the present invention, containing the metalate ion exchanger described above, may be a sorption filter in a portable device or a device located away from the individual. The metalate ion exchanger may be supported or embedded in a porous, biocompatible matrix, including polymers, metal oxides, and porous and mesoporous silicates. For the purposes of the present invention, the useful polymers considered in particular are natural or biological polymers such as carbohydrates or cross-linked proteins. This and other objects and modalities will become clearer after a detailed description of the invention. Detailed Description of the Invention As mentioned, the applicants have developed a novel process for removing toxins from selected body fluids and dialysate solution. An essential element of the present process is an ion exchanger with high capacity and strong affinity, i.e., selectivity for at least one or more of Co2+, Pb2+, Cd2+, or Cr3+. These compositions are identified as zirconium metalate, titanium metalate, tin metalate, multi-ion metalate containing at least two or more of zirconium, titanium, or tin, or mixtures thereof. They are further identified by their compound empirical formula (on an anhydrous basis), which is: AmZ r aT itS ncMdS ixOy The composition has one or more frame structures composed of at least one octahedral unit of ZrOg / n, TiOg / n or SnOg / n where n = 2 or 3 or both, optionally octahedral units of NbOg / n or HfOg / n where n = 2 or 3 or both, and optionally tetrahedral units of SiO2. A is an exchangeable cation selected from the group consisting of potassium ion, sodium ion, rubidium ion, cesium ion, calcium ion, magnesium ion, hydronium ion or mixtures of these, M is an optional octahedrally coordinated framework metal selected from the group consisting of hafnium (4 + ) or niobium (5 + ) or both, m is the molar ratio of A to total metal (total metal = Zr + Ti μλ / t / ζυζζ / υυοζυυ + Sn + M) and has a value of 0.10 to 15, a is the mole fraction of the total metal which is Zr and has a value from zero to 1, b is the mole fraction of the total metal which is Ti and has a value from zero to 1, c is the mole fraction of the total metal which is Sn and has a value from zero to 1, d is the mole fraction of the total metal which is M and has a value from zero to less than 1, where a + b + c + d = 1 and a + b + c > 0, x is the molar ratio of Si to the total metal and has a value from 0 to 12, and y is the molar ratio of O to the total metal and has a value from 2.1 to 33. Zirconium metalates, titanium metalates, tin metalates, multi-metalates containing two or more zirconium, titanium, or tin elements, and mixtures thereof are prepared by hydrothermal crystallization of a reaction mixture prepared by combining a reactive source of at least one zirconium, titanium, or tin element, optionally one or more M metals, optionally a silicon source, and at least one alkali metal with water. The alkali metal acts as an annealing agent. Any zirconium compound that can be hydrolyzed to zirconium oxide or zirconium hydroxide may be used. Specific examples of such compounds include zirconium alkoxide, e.g., zirconium n-propoxide, zirconium hydroxide, zirconium acetate, zirconium oxychloride, zirconium chloride, zirconium phosphate, and zirconium oxynitrate.Specific examples of titanium metal sources include, but are not limited to, titanium alkoxides, titanium tetrachloride, titanium trichloride, and titanium dioxide. Specific examples of tin metal sources include tin tetrachloride and tin isopropoxide. Sources of silica include colloidal silica, fumed silica, tetraethyl orthosilicate, and sodium silicate. Alkaline sources include potassium hydroxide, sodium hydroxide, rubidium hydroxide, cesium hydroxide, sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate, sodium halide, potassium halide, rubidium halide, and cesium halide. Sources of M-metals include oxides, alkoxides, halide salts, acetate salts, nitrate salts, and sulfate salts of M-metals. Specific examples of M-metal sources include niobium isopropoxide, hydronic niobium oxide, hafnium isopropoxide, hafnium chloride, and hafnium oxychloride.Sources of hydroxide include quaternary ammonium hydroxides (ROH), specific examples of which are tetramethylammonium hydroxide, hexamethonium dihydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide. Generally, the hydrothermal process used to prepare the ion-exchange compositions of zirconium metalate, titanium metalate, tin metalate, multinary metalate, or mixtures thereof of this invention involves forming a reaction mixture which, in terms of molar ratios of the oxides, is expressed by the formula: r Fd / sO : p A2O : a ZrO2 : b TiO2 : o SnO2 : d MOq / 2 : e S1O2 : f H2O where R is one or more quaternary ammonium cations, s is the charge on the quaternary ammonium cation and is 1 to 2, r has a value from 0 to 40, p has a value from 0.25 to 40, a has a value from 0 to 1, b has a value from 0 to 1, c has a value from 0 to 1, a + b + c > 0, d has a value from 0 to less than 1, a+b+c+d=1, e has a value from 0 to 25 and f has a value from 10 to 3000. The reaction mixture is prepared by mixing the desired sources of zirconium, titanium or tin, optionally ammonium hydroxide quaternary ammonium hydroxide, optionally silicon, and optionally metal M and alkali metal in any order to give the desired mixture. The mixture must also have a basic pH and, preferably, a pH of at least 8. The basicity of the mixture is controlled by adding an excess of alkali hydroxide, quaternary ammonium hydroxide, and / or basic compounds of the other constituents of the mixture.Having formed the reaction mixture, it is then reacted at a temperature of 100 °C to 200 °C for a period of 1 to 30 days in a sealed, pressure-controlled reaction vessel. After the allotted time, the mixture is filtered to isolate the solid product, which is washed with deionized water and air-dried. As mentioned, the compositions of this invention have a framework structure of octahedral ZrOg / n units, TiOg / n units, SnOg / n units, or combinations thereof, optionally octahedral MOg / n units, n = 2 or 3, and optionally tetrahedral SiCb units. This framework frequently results in a microporous structure having an intracrystalline pore system with uniform pore diameters; that is, the pore sizes are crystallographically regular. The pore diameter can vary considerably, from 3 Å and larger. Furthermore, the framework of this composition can be stratified or amorphous. As synthesized, the compositions of this invention will contain a portion of the alkali metal quenching agent in the pores, between layers, or in other charge-equilibrium positions. These metals are described as exchangeable cations, meaning they can be exchanged with other (secondary) A' cations. Generally, the exchangeable A cations can be exchanged with A' cations selected from other alkali metal cations (K+, Na+, Rb+, Cs+), alkaline earth metal cations (Mg2+, Ca2+), hydronium ions, or mixtures thereof. It is understood that the A' cation is distinct from the A cation. The methods used to exchange one cation for another are well known in the art and involve contacting the compositions with a solution containing the desired cation (in molar excess) under exchange conditions. The exchange conditions include a temperature of 100°C to 100°C and a time of 20 minutes to 2 hours.The specific cation (or mixture thereof) present in the final product will depend on the particular use of the composition and the specific composition used. A specific composition is an ion exchanger where the A' cation is a mixture of Na+, Ca2+, and H+ ions. In certain cases, when a quaternary ammonium cation is used in the synthesis, usually as a hydroxide source, the quaternary ammonium cation may be incorporated into the product. Usually, this will not be the case because quaternary ammonium cations will frequently be displaced by alkali metal cations, which have a greater affinity for incorporation into the product. However, the quaternary ammonium ion must be removed from the product. This can often be achieved by the ion-exchange processes mentioned in the previous paragraph. Sometimes, the quaternary ammonium ion may become trapped in a pore, and it may not be possible to remove the quaternary ammonium cation by ion exchange; calcination will be required. Typically, calcination consists of heating the sample to a temperature of 500–600 °C for 2–24 hours under a stream of air or under a stream of nitrogen followed by a stream of air.In this process, the quaternary ammonium cation decomposes and is replaced by a residual proton. Once calcination is complete, the sample can be exchanged with ions until the desired A' cation composition is achieved, as described above. It is also within the scope of the invention that these ion-exchange compositions can be used in powder form or shaped into various forms by means well known in the art. Examples of these various forms include pills, extruded products, spheres, granules, and irregularly shaped particles. This was previously demonstrated in U.S. Patent Nos. 6579460B1 and 6814871B1. The ion-exchange compositions of this invention can also be supported, ideally, on a porous network, including insertion into or bonding to a blood-compatible porous network, such as in a sorption filter as described in U.S. Patent No. 9033908B2. The porous network can consist of natural or synthetic polymers, biopolymers, and mesoporous metal oxides and silicates.Suitable natural polymers (biopolymers) may comprise a crosslinked carbohydrate or protein, made of oligomeric and polymeric carbohydrates or proteins. The biopolymer is preferably a polysaccharide. Examples of polysaccharides include α-glucans having 1,3, 1,4, and / or 1,6 linkages. Among these, the starch family, including amylose, amylopectin, and dextrins, is particularly preferred, but pullulan, elsinan, reuteran, and other α-glucans are also suitable, although the proportion of 1,6 linkages is preferably less than 70%, and more preferably less than 60%. Other suitable polysaccharides include β-l,4-glucans (cellulose), β-l,3-glucans, xyloglucans, glucomannans, galactans and galactomannans (guar gum and locust bean gum), other gums including heterogeneous gums such as xanthan, ghatti, carrageenans, alginates, pectin, β-2,1 and β-2,6 fructans (inulin and levan), etc.A preferred cellulose is carboxymethylcellulose (CMC, e.g., AKUCELL from AKZO Nobel). The carbohydrates that can be used are therefore carbohydrates consisting only of C, H, and O atoms, such as glucose, fructose, sucrose, maltose, arabinose, mannose, galactose, lactose, and oligomers and polymers of these sugars, cellulose, dextrins such as maltodextrin, agarose, amylose, amylopectin, and gums such as guar gum. Preferably, oligomeric carbohydrates with a degree of polymerization (DP) of DP2 and above, or polymeric carbohydrates of DP50 and above, are used. These can be naturally occurring polymers such as starch (amylose, amylopectin), cellulose, and gums, or derivatives thereof, which can be formed by phosphorylation or oxidation. Starch can be cationic or anionic modified starch.Examples of suitable (modified) starches that can be modified include corn starch, potato starch, rice starch, tapioca starch, banana starch, and cassava starch. Other polymers (e.g., caprolactone) can also be used. In certain embodiments, the biopolymer is preferably a cationic starch, with the highest preference being an oxidized starch (e.g., C6 oxidized with hypochlorite). The level of oxidation can be freely chosen to suit the application of the sorbent material. Ideally, the oxidation level is between 5 and 55%, with the highest preference between 25 and 35%, and even more ideally between 28% and 32%. Ideally, the oxidized starch is crosslinked. A preferred crosslinking agent is diepoxide. The level of crosslinking can be freely chosen to suit the application of the sorbent material. Ideally, the level of crosslinking is between 0.The protein content ranges from 1% to 25%, with a higher preference between 1% and 5%, and a higher preference between 2.5% and 3.5%. Proteins that may be used include albumin, ovalbumin, casein, myosin, actin, globulin, hemoglobin, myoglobin, gelatin, and small peptides. Proteins obtained from hydrolysates of plant or animal material may also be used. The particularly preferred protein polymers are gelatin or a gelatin derivative. As mentioned, these compositions are particularly useful for adsorbing various metallic toxins, including Co2+, Pb2+, Cd2+, and Cr3+, from selected body fluids, dialysate solutions, and mixtures thereof. As used herein and in the claims, body fluids shall include, but not be limited to, blood, blood plasma, and gastrointestinal fluids. The compositions are also intended for use in treating the body fluids of any mammal, including, but not limited to, humans, cows, pigs, sheep, monkeys, gorillas, horses, dogs, etc. The present process is particularly suitable for removing toxins from the human body. There are several means of bringing the fluids into direct or indirect contact with the desired ion exchanger and thereby removing the toxins.One technique is hemoperfusion, which involves packaging the ion-exchange composition described above in a column through which blood flows. Such a system is described in U.S. Patent No. 4,261,828. As stated in patent '828, the ion-exchange composition is preferably formed into desired shapes such as spheres. Furthermore, the particles of the ion-exchange composition may be coated with compounds, such as cellulose derivatives, that are compatible with blood but not permeable to corpuscular blood components. In one specific case, the spheres of the desired ion-exchange compositions described above may be packaged in hollow fibers, thereby providing a semipermeable membrane. It should also be noted that more than one type of ion-exchange composition may be mixed and used in the process to enhance its efficiency. Another way to carry out the process is to prepare a suspension or slurry of the molecular sieve adsorbent using methods known in the art, such as those described in U.S. Patent No. 5,536,412. The apparatus described in patent '412 can also be used to carry out the process. The process basically involves passing a fluid, e.g., blood, containing the metal toxins through the interior of a hollow fiber and, during the passage, circulating a suspension of the sorbent against the outer surfaces of the hollow fiber membrane. At the same time, intermittent pulses of positive pressure are applied to the sorbent solution so that the fluid alternately flows out and re-enters the interior of the hollow fiber membrane, thereby removing the toxins from the fluid. Another type of dialysis is peritoneal dialysis. In peritoneal dialysis, the peritoneal cavity, or abdominal cavity, is filled with a dialysate fluid or solution through a catheter inserted into the peritoneal cavity. This fluid comes into contact with the peritoneum. Toxins and excess water flow from the blood through the peritoneum, a membrane that lines the outside of the organs in the abdomen, into the dialysate fluid. The dialysate remains in the body for a sufficient time (dwell time) to remove the toxins. After the required dwell time, the dialysate is removed from the peritoneal cavity through the catheter. There are two types of peritoneal dialysis. In continuous ambulatory peritoneal dialysis (CAPD), dialysis is performed throughout the day.The process involves maintaining the dialysate solution in the peritoneal cavity and periodically removing the used dialysate (which contains toxins) and refilling the cavity with fresh dialysate. This is done several times a day. The second type is automated peritoneal dialysis, or APD. In APD, a dialysate solution is exchanged by a device overnight while the patient sleeps. In both types of dialysis, fresh dialysate solution must be used for each exchange. The zirconium metalates, titanium metalates, tin metalates, or multimetalates of the present invention can be used to regenerate dialysate solutions used in peritoneal dialysis, thereby further reducing the amount of dialysate required to cleanse the blood and / or the amount of time needed to perform the exchange. This regeneration is carried out by any of the means described above for conventional dialysis. For example, in an indirect contact process, the dialysate from the peritoneal cavity—that is, the first dialysate that has captured metal toxins transferred through the peritoneum—is brought into contact with a membrane, and a second dialysate solution and metal toxins are transferred through a membrane, thereby purifying the first dialysate solution, resulting in a purified dialysate solution.The second dialysate solution containing the metal toxins is circulated through at least one adsorption bed containing at least one of the ion exchangers described above, thereby removing the metal toxins and producing a second, purified dialysate solution. It is usually preferred to continuously circulate the second dialysate solution through the adsorption bed until the toxic metal ions—Co2+, Pb2+, Cd2+, and Cr3+—have been removed. It is also preferred to circulate the first dialysate solution through the peritoneal cavity, thereby increasing the efficiency of toxic metal removal and decreasing the total residence time. A direct contact dialysis (DCD) process can also be performed, in which the initial dialysate solution is introduced into the peritoneal cavity and then flowed through at least one bed containing at least one ion exchanger. As described above, this can be carried out as either CAPD or APD. The composition of the dialysate solution can vary to ensure an adequate electrolyte balance in the body. This is well understood in the art, along with the various devices used to perform dialysis. Zirconium metalates, titanium metalates, tin metalates, and multi-metalates can also be formed into pills or other forms that can be ingested orally and collect toxins in the gastrointestinal fluid as the ion exchanger passes through the intestines and is eventually excreted. To protect the ion exchangers from the high acidity of the stomach, the formed articles can be coated with various coatings that will not dissolve in the stomach but will dissolve in the intestines. As also indicated, although the present compositions are synthesized with a variety of exchangeable cations (A), it is preferred to exchange the cation with secondary cations (A') that are more compatible with blood or do not adversely affect it. For this reason, the preferred cations are sodium, calcium, hydronium, and magnesium. The preferred compositions are those containing sodium and calcium ions or sodium, calcium, and hydronium ions. The relative amounts of sodium and calcium can vary considerably and depend on the composition and concentration of these ions in the blood. The X-ray patterns presented in the following examples were obtained using standard X-ray powder diffraction techniques. The radiation source was a high-intensity X-ray tube operating at 45 kV and 35 mA. The copper K-alpha diffraction pattern was obtained using appropriate computational techniques. Flat compressed powder samples were continuously scanned at 2oa 56° (2Θ). Interplane separations (d) in Angstrom units were obtained from the position of the diffraction peaks, expressed as θ, where Θ is the Bragg angle as observed from digitized data. Intensities were determined from the integrated area of ​​diffraction peaks after subtracting the background, where Io is the intensity of the strongest line or peak and I is the intensity of each of the other peaks. As those skilled in the art will understand, the determination of the parameter 2Θ is subject to both human and mechanical error, which, in combination, can impose an uncertainty of ±0.4° on each reported value of 2Θ. This uncertainty is also evidently apparent in the reported values ​​of the d separations, which are calculated from the 2Θ values. This imprecision is general throughout the art and is not sufficient to prevent the differentiation of the crystalline materials present from one another and from the compositions of the prior art. In the reported X-ray patterns, the relative intensities of the d separations are indicated by the notations vs, s, and myw, which stand for very strong, strong, medium, and weak, respectively. In terms of 100 × I / Io, the above designations are defined as: w > 0-15; m > 15-60: s > 60-80 and vs > 80-100 In certain cases, the purity of a synthesized product can be assessed by reference to its powder X-ray diffraction pattern. Therefore, for example, if a sample is stated to be pure, it is only intended that the sample's X-ray pattern is free of lines attributable to crystalline impurities, not that amorphous materials are not present. To more fully illustrate the present invention, the following examples are set forth. It should be understood that the examples are for illustrative purposes only and are not intended to excessively limit the broad scope of the invention as set forth in the appended claims. EXAMPLES Na+ ion exchange procedure The products described in the following examples, not synthesized in the Na+ form, were sodium ion exchange products prior to testing. Typically, a three-stage ion exchange with NaCl was employed. The ion exchange procedure consisted of exposing 5–10 g of the product to be tested to 500 mL of 1–2 M NaCl exchange solution. Three ion exchanges were performed at 75 °C, stirring for 1.5 hours for each exchange stage. The exchanged solids were isolated by filtration or centrifugation. Acid treatment procedure Several of the test candidates were selected for acid treatment. A 5 wt% nitric acid solution was used, directed at 2–3 g of test material in 100 g of ion exchange solution. Acid washing was performed in a three-stage exchange procedure at 75 °C for 1.5 hours per stage. The exchanged materials were isolated by filtration, thoroughly washed with deionized water, and dried at 80 °C. Example 1 In a Teflon beaker equipped with a high-speed stirrer, 101.64 g of KOH (87.8%) was dissolved in 191.03 g of deionized water. To this solution, 79.64 g of colloidal silica (Ludox AS-40, 40% SiO₂) was added in a single pour with vigorous stirring, forming a translucent solution that became clear after 2 hours of homogenization. To the clear solution, 77.69 g of Ti(OiPr)₄ (97%) was added dropwise for 6 minutes. The reaction mixture became an opaque white colloidal suspension after an additional 20 minutes of stirring. The reaction mixture was then transferred to a 600 mL stirred autoclave and digested for 120 hours at 175 °C with stirring at 250 rpm. The solid products were isolated by centrifugation, washed with deionized water (µl / t / ζυζζ / υυοζυ΅), and dried at room temperature. The product was identified as titanium silicate pharmacosiderite by X-ray powder diffraction, accompanied by a slight impurity of K₂TiSi₃O₉.Representative X-ray diffraction lines for the product are shown in Table 1, with asterisks indicating peaks associated with the K₂TiSi₃O₉ impurity. Elemental analysis yielded the empirical formula K₁.75TiSi₁.06O₅. An ion exchange of a portion of this product with NaCl was performed prior to testing. Table 1 ma / t / ζυζζ / υυοζυυ 2-Θ d (Á) I / Io % 11.68 7.57 vs 15.70 5.64 w* 16.42 5.39 w 20.08 4.42 w 23.18 3.83 m 26.18 3.40 w* 28.40 3.14 vs 30.73 2.91 w 32.06 2.79 w* 32.92 2.72 m 34.83 2.57 w 36.84 2.44 m 38.81 2.32 w 40.38 2.23 w* 40.56 2.22 w 47.08 1.93 w 48.43 1.88 m 50.03 1.82 w * Impurity K2TÍSÍ3O9 Example 2 In a Teflon beaker equipped with a high-speed stirrer, 73.34 g of KOH (87.7%) was dissolved in 254.43 g of deionized water. To this solution, 68.27 g of colloidal silica (Ludox AS-40, 40% SiO2) was added and stirred vigorously for 10 minutes, forming a white suspension. After 20 minutes of homogenization, 45.61 g of zirconium acetate solution (22.1% ZrO2) was added rapidly and dropwise. After another 10 minutes of homogenization, 5.35 g of hydrous Nb2Os (62.5%) was added, and the reaction mixture was stirred for an additional 5 minutes. The reaction mixture was loaded into a 600 mL stirred autoclave and digested for 24 hours at 200 °C with stirring at 250 RPM. The solid product was isolated by centrifugation, washed with deionized water, and air-dried. X-ray powder diffraction revealed that the product had the umbite structure.Representative diffraction lines for the product are shown below in Table 2. Elemental analysis yielded the empirical formula K2.15Zro.8iNbo.19Si3.34O9.5. Ion exchange was performed on a portion of the product with NaCl before use for testing. μλ / t / ζυζζ / υυοζυυ Table 2 2-Θ d (Á) I / Io % 10.82 8.17 m 13.32 6.64 m 14.90 5.94 s 16.34 5.42 w 17.00 5.21 wm 18.08 4.90 w 20.02 4.43 wm 21.78 4.08 m 24.54 3.63 w 25.03 3.56 w 26.40 3.37 m 28.38 3.14 m 28.96 3.08 m 29.50 3.03 vs 29.96 2.98 s 30.76 2.90 m 31.84 2.81 w 32.96 2.72 w 34.14 2.62 w 34.94 2.57 wm 37.62 2.39 w 38.10 2.36 w 41.52 2.17 w 42.56 2.12w 43.22 2.09 w 45.58 1.99 w 46.06 1.97 w 48.74 1.87 w 49.74 1.83 w 50.22 1.82 m Example 3 A Teflon beaker was loaded with 650.00 g of TEAOH (35%) and stirred with a high-speed stirrer. μλ / t / ζυζζ / υυοζυυ Next, 53.05 g of TEOS (98%) was added rapidly dropwise with stirring. The reaction mixture was stirred for one hour to hydrolyze the TEOS, producing a clear solution. Then, 12.76 g of SnC14*5 H2O was dissolved in 25.00 g of deionized water. This solution was added slowly dropwise to the reaction mixture over a period of 40 minutes. The reaction mixture was stirred vigorously for an additional 20 minutes and then placed in a Teflon bottle and shaken overnight. The following day, Na+ was added; 4.17 g of NaCl was dissolved in 15.00 g of deionized water and added dropwise to the reaction mixture. As the addition continued, the previously clear solution became a cloudy suspension. The reaction mixture was transferred to a Teflon bottle and digested at 100 °C for 4 days. The solid product was isolated by centrifugation, washed with deionized water, and dried at room temperature.X-ray powder diffraction characterization showed that the Na-Sn-silicate was amorphous. Ion exchange of a portion of the product with NaCl was performed before its use in the test. Example 4 Sodium nonatinate, Na₂IgCPo, obtained from Honeywell, was used. Characterization of the sample by X-ray powder diffraction was consistent with sodium nonatinate. Representative X-ray diffraction lines for the sample are provided in Table 3 below. Table 3 2-Θ d (Á) I / Io % 9.00 9.81 vs 18.08 4.90 w 24.38 3.65 w 24.40 3.65 w 28.12 3.17 w 29.01 3.08 w 33.83 2.65 w 34.70 2.58 w 39.94 2.26 w 44.33 2.04 w 44.63 2.03 w 47.70 1.91 wm 48.34 1.88 wm Example 5 A solution was prepared by dissolving 40.69 g of NaOH granules (Fisher) in 1141.37 g of deionized water. With vigorous top stirring using a high-speed mechanical stirrer (600 rpm), 68.79 g of colloidal silica (Ludox™ AS-40; 40% SiO₂) was added slowly in a single pour. After approximately one hour of mixing, 149.15 g of Ti(OiPr)₄ (97%) was rapidly added in a single pour to the translucent colloidal suspension, immediately causing precipitate formation. The reaction mixture was homogenized for an additional 5 minutes and The sample was loaded into a 2 L Parr stirred autoclave. The reaction mixture was digested for 24 hours at 200 °C while stirring at 300 rpm, including a 4-hour warm-up from room temperature to 200 °C. The product was isolated and washed three times with deionized water using centrifugation and dried in an oven at 100 °C overnight. The product was characterized by X-ray powder diffraction, which exhibited both components, zorite and sitinakite. Representative diffraction lines for the product are shown in Table 4, Example 5A. The described procedure was repeated to produce a duplicate sample; representative diffraction lines for this material are shown in Table 4, Example 5B. Table 4 Example 5A Example 5B 2-Θ d(A) I / Io % 2-Θ d(A) I / To % 7.66 11.54 m 7 . 72 11.44 s 11.26 7.85 vs 11.38 7.77 vs 12.72 6.95 m 12.88 6.87 m 16.85 5.26 w 16.96 5.22 m 19.90 4.46 w 17.74 5.00 w 25.94 3.43 m 18.28 4.85 m 26.38 3.38 m 20.05 4.43 w 28.98 3.08 wm 24.85 3.58 w 29.20 3.06 m 26.11 3.41 w 29.96 2.98 m 26.54 3.36 m 32.37 2.76 w 28.09 3.18 w 34.64 2.59 m 29.14 3.06 m. m λ / t / ζυζζ / υυοζυ 29.34 3.04 ms 30.06 2.97 m 30.91 2.89 m 32.54 2.75 m 34.18 2.62 m 34.56 2.59 m 34.74 2.58 s-vs 37.10 2.42 w 48.12 1.89 m ml / t / zvzv / vvzv Example 6 A solution was prepared by dissolving 29.07 g of NaOH granules (Fisher) in 815.27 g of deionized water. With vigorous top stirring using a high-speed mechanical stirrer, 49.13 g of colloidal silica (Ludox™ AS-40, 40% SiO₂) was added slowly in a single pour. After approximately one hour of mixing, 106.53 g of Ti(OiPr)₄ (97%) was rapidly added in a single pour to the translucent colloidal suspension, immediately forming a precipitate. The reaction mixture was homogenized for an additional 5 minutes and loaded into a 2 L autoclave. The material was digested for 24 hours at 200 °C under static conditions. The product was isolated by centrifugation, washed three times with deionized water, and dried overnight in an oven at 100 °C. The product was characterized by X-ray diffraction, which identified the product as titanium silicate sitinakite.The representative X-ray diffusion lines for the product are shown in Table 5. μλ / t / ζυζζ / υυοζυυ 2-Θ Tabla 5 I / Io % d (Á) 11.30 7.82 vs 17.85 4.97 w 26.68 3.34 w 27.25 3.27 m 27.68 3.22 ms 32.30 2.77 w 34.50 2.60 m Example 7 A series of sodium tin silicates was prepared as follows. 36.16 g of colloidal silica (Ludox AS-40, 40% SiCh) was added to a Teflon beaker and placed under a high-speed stirrer. A solution was then prepared by dissolving 19.26 g of NaOH granules in 90.00 g of deionized water. This solution was added to the colloidal silica with vigorous stirring. The white reaction mixture was homogenized for 20 minutes after the addition. Separately, 21.10 g of SnC14*5H2O was dissolved in 83.48 g of deionized water. This solution was added to the reaction mixture and mixed for an additional 20 minutes. The white, fluid reaction mixture was divided among four 125 ml Teflon-lined autoclaves and digested under static conditions at 200 °C for 3, 7, 14, and 21 days at autogenous pressures. Solid products were isolated by centrifugation, washed with deionized water, and dried at room temperature.X-ray powder diffraction was used to characterize the products. Representative X-ray diffraction lines are shown for the products in Table 6. Table 6 μλ / t / ζυζζ / υυοζυυ Example 7A, 3 days Example 7B, 7 days Example 7C, 14 days Example 7D, 21 days 2-0 d(A) l / lo % 2-0 d(A) l / lo % 2-0 d(A) l / lo % 2-0 d(A) l / lo % 7.42 11.91 s-vs 7.46 11.84 w 7.52 11.74 m 7.58 11.65 w-m 11.12 7.95 w-m 14.10 6.28 m 14.04 6.30 m 14.06 6.29 m 18.88 4.70 m 15.25 5.81 m 15.22 5.82 m-s 15.26 5.80 m 32.21 2.78 vs 16.04 5.52 m 16.00 5.54 m 16.02 5.53 m 34.35 2.61 m 17.19 5.15 w 17.16 5.16 w-m 17.17 5.16 m 43.02 2.10 m 18.82 4.71 w 18.78 4.72 w 18.82 4.71 w 20.84 4.26 w 20.78 4.27 w-m 20.80 4.27 m 22.46 3.96 w 22.36 3.97 w 22.38 3.97 w 27.02 3.30 w 23.66 3.76 w 27.00 3.30 m 27.19 3.28 w 27.04 3.30 m 28.22 3.16 w 29.38 3.04 vs 28.20 3.16 w 29.36 3.04 vs 30.76 2.90 m 29.34 3.04 vs 30.76 2.90 m 32.32 2.77 m 30.74 2.91 m 32.32 2.77 m 32.67 2.74 w 32.28 2.77 m 34.00 2.63 w 34.76 2.58 w 33.92 2.64 m 34.70 2.58 w 36.77 2.44 m 34.68 2.58 m 36.74 2.44 m 38.14 2.36 w-m 36.74 2.44 w-m 38.34 2.35 w-m 38.34 2.35 w-m 38.07 2.36 m 41.66 2.17 w 43.84 2.06 w 38.36 2.34 w-m 43.77 2.07 m 48.66 1.87 m 41.35 2.18 w 45.64 1.99 w 41.66 2.17 w 46.88 1.94 w 43.76 2.07 w 48.06 1.89 w 48.60 1.87 m 48.66 1.87 m 49.24 1.85 w 49.34 1.85 w 49.72 1.83 w 49.78 1.83 w. Ejemplo 8 A Teflon beaker equipped with a high-speed stirrer was filled with 42.61 g of colloidal silica (Ludox AS-40, 40% SiCt). A solution was prepared by dissolving 29.28 g of NaOH granules in 163.38 g of deionized water. This solution was rapidly added dropwise to the colloidal silica with vigorous stirring, forming a creamy, bright white reaction mixture. Separately, a solution was prepared by dissolving 14.73 g of SnC₁₄·5H₂O in 200 g of deionized water. This solution was added in a single pour with vigorous stirring. The bright white reaction mixture was stirred for an additional 20 minutes. The homogeneous white gel was loaded into a 600 mL shaken autoclave and digested for 72 hours at 200 °C, shaken at 250 rpm. The solid products were isolated by centrifugation, washed with deionized water, and dried at room temperature. X-ray powder diffraction identified the product as SnSi-1.The representative Tabla 7 μλ / t / ζυζζ / υυοζυυ 2-Θ d (Á) I / Io % 7.04 12.55 S-VS 7.72 11.44 m 10.88 8.12 w 14.16 6.25 w 16.27 5.44 w 18.97 4.68 wm 21.21 4.19 w 23.46 3.79 w 24.50 3.63 w 31.86 2.81 s 32.54 2.75 vs 42.99 2.10 w 43.25 2.09 w μλ / t / ζυζζ / υυοζυυ Example 9 In a Teflon beaker, 19.54 g of KOH (85.22%) was dissolved in 115.86 g of deionized water using a Heidolph stirrer. Then, 46.14 g of colloidal silica (LUDOX AS-40, 40% SiO₂) was added in a single pour and stirred for 10 minutes. This was followed by the addition of 30.0 g of Ti(OiPr)₄ (97%). A bright white gel was produced and allowed to homogenize further. The homogeneous gel was distributed among three Teflon-lined Parr reactors and digested at rest at 200 °C for 46 hours under autogenous pressure. The solid products were isolated by centrifugation, washed with deionized water, and dried at room temperature. The product was identified as Ti-umbite by X-ray powder diffraction. Representative diffraction lines are shown in Table 8 below. Elemental analysis yielded the empirical composition K1.79TiSi2.60O8.1. Sodium ion exchange was performed on the products prior to testing. Tabla 8 2-Θ d (A) I / Io % 11.26 7.85 m 13.72 6.45 m 14.20 6.23 w 15.33 5.77 m 17.92 4.95 w 19.21 4.62 w 20.60 4.31 w 21.83 4.07 w 22.49 3.95 w 22.90 3.88 w 24.96 3.57 w 25.76 3.46 m 26.51 3.36 w 27.44 3.25 w 27.89 3.20 m 28.54 3.13 m 29.80 3.00 m 30.34 2.94 s 30.62 2.92 m 30.88 2.89 m 31.66 2.82 s 32.56 2.75 w 32.94 2.72 m 33.82 2.65 w 35.42 2.53 w 35.84 2.50 w 36.50 2.46 w 37.74 2.38 w 38.44 2.34 w 38.64 2.33 w 38.92 2.31 w 39.10 2.30 m 39.58 2.28 w 41.32 2.18 w 42.12 2.14 w 42.72 2.11 w 44.50 2.03 w 45.05 2.01 w 45.86 1.98 w 46.32 1.96 w 47.07 1.93 w 47.71 1.90 w 50.27 1.81 w 51.06 1.79 w 51.84 1.76 w 52.38 1.75 w 52.68 1.74 w 53.30 1.72 w 54.62 1.68 w 55.40 1.66 w 55.58 1.65 w ma / t / ζυζζ / υυοζυυ Ejemplo 10 A Teflon beaker was placed on a high-speed stirrer and filled with 69.15 g of colloidal silica (Ludox AS-40, 40% SiO₂). A solution was prepared by dissolving 74.25 g of KOH (87.7%) in 257.16 g of deionized water. This solution was added to the colloidal silica in a single pour with vigorous stirring, forming a white suspension that became clear after 20 minutes of homogenization. To the clear solution, 49.45 g of zirconium acetate solution (22.1 wt% ZrO₂) was added rapidly dropwise, and the reaction mixture was allowed to homogenize. The reaction mixture was then placed in a 600 mL stirred autoclave and digested for 36 hours at 200 °C with stirring at 250 rpm. The solid product was isolated by centrifugation, washed with water, and dried at room temperature. The product was identified as Zrumbite by X-ray powder diffraction. Representative X-ray diffraction lines are shown in Table 9.Elemental analysis yielded the empirical composition K2.33ZrSi3.47O1 o. 1 · Ion exchange of a portion of product with NaCl was done before the test. Table 9 μλ / t / ζυζζ / υυοζυυ 2-Θ d (A) I / Io % 10.92 8.10 m 13.40 6.60 m 15.02 5.89 vs 16.49 5.37 w 17.14 5.17 m 18.18 4.88 w 20.20 4.39 wm 21.90 4.06 m 24.74 3.60 w 25.10 3.55 w 26.70 3.34 m 28.24 3.16 w 28.66 3.11 m 29.14 3.06 m 29.20 vs 3.20 3.06 m 2.95 s 30.98 2.88 m 32.08 2.79 w 34.38 2.61 w 34.90 2.57 wm 35.32 2.54 w 41.72 2.16 w 43.52 2.08 w μλ / t / ζυζζ / υυοζυυ Example 11 In a Teflon beaker placed under a high-speed stirrer, 15.39 g of KOH (87.8%) was dissolved in 26.01 g of deionized water. Then, 14.47 g of colloidal silica (Ludox AS-40, 40% SiO₂) was added in a single pour with vigorous stirring. An initially translucent solution became clear after 2 hours of homogenization. To the clear solution, 14.12 g of Ti(OiPr)₄ (97%) was added dropwise for 7 minutes. The reaction mixture became an opaque, beige, colloidal-type suspension after an additional 20 minutes of stirring. The reaction mixture was loaded into a 125 mL Parr reactor and digested under rest for 5 days at 150 °C under autogenous pressure. The solid product was isolated by centrifugation, washed with deionized water, and dried at room temperature. X-ray powder diffraction identified the product as titanium silicate pharmacosiderite.Representative diffraction lines for the product are shown in Table 10. Elemental analysis yielded the empirical composition K1.45TiSi1.13Ox. Ion exchange was performed on a portion of the product with NaCl prior to testing. Table 10 μλ / t / ζυζζ / υυοζυυ 2-Θ d(Á) I / Io 11.32 7.81 vs 16.00 5.53 w 19.82 4.48 w 22.61 3.93 w 27.58 3.23 m 28.16 3.17 m 32.67 2.74 w 34.50 2.60 w 36.30 2.47w 38.42 2.34w 46.46 1.95w Example 12 The alkoxides TEOS (98%), 38.00 g and Ti(OiPr)4 (97%), 10.48 g were mixed in a Teflon beaker placed under a high-speed stirrer. Separately, 5.89 g of NaOH (99%) was dissolved in 85.00 g of deionized water. This solution was added rapidly to the stirred reaction mixture, dropwise, using a 23 mL dropper. After adding a few dropperfuls of the NaOH solution, the addition was stopped, and the reaction mixture was allowed to stir for a few minutes since a gel had formed. The addition was then continued until complete. The thick gel was then stirred for 2 hours to facilitate homogenization. The reaction mixture was transferred to two Teflon-lined Parr reactors and digested at 200 °C for 140 h under autogenous pressure. The products were isolated by centrifugation, washed with deionized water, and dried at room temperature.Characterization of the solid by X-ray powder diffraction showed that the material had the zorite topology. Representative X-ray diffraction lines for the product are provided in Table 11 below. Table 11 μλ / t / ζυζζ / υυοζυυ 2-Θ d (Á) I / Io % 7.62 11.59 m 12.72 6.95 s-vs 12.92 6.85 ms 16.87 5.25 m 19.91 4.46 wm 24.84 3.58 m 26.02 3.42 m 26.36 3.38 m 29.06 3.07 ms 29.28 3.05 vs 2.76 m 34.08 2.63 m 34.66 2.59 m 35.94 2.50 w 36.79 2.44 w 37.03 2.43 w 39.26 2.29 w 39.58 2.28 w 41.62 2.17 w 4.18 w 2.68 w 42.52 2.12 w 43.10 2.10 w 44.74 2.02 w 46.97 1.93 w 48.04 1.89 w 48.50 1.88 w 50.89 1.79 w 51.52 1.77 w 52.76 w 52.56 1.74 m 53.90 1.70 m μ λ / t / ζυζζ / υυοζυυ Example 13 This manufactured sample, received from UOP, has the structure of sitinake with the anhydrous composition Na3.24Ti2.67Nb1.i8Si2O13.9- Representative X-ray diffraction lines for this material are shown in Table 12 below. Table 12 2-Θ d (Á) I / Io 8.76 10.08 w* 10.00 8.84 w* 11.28 7.84 vs 14.71 6.02 m 15.90 5.55 w 17.60 5.03 m 18.00 4.92 w* 14.75 w* 4.75. 22.67 3.92 w 23.64 3.76 w* 25.26 3.52 w 2 6.46 3.37 m 27.42 3.25 m 29.63 3.01 w 30.25 2.95 w* 31.80 2.81 w 3.272 w 23.72. 2.64 m 34.26 2.62 m 36.19 2.48 w 36.99 2.43 w 37.63 2.39 w 42.87 2.11 w 44.39 2.04 w 45.15 2.01 w 45.97 1.97 w 46.23 1.96 w 46.76 1.94 w 47.74 1.90 w *impurity μλ / t / ζυζζ / υυοζυυ Example 14 This sample is the one from Example 13, but it has been further washed with acid, leading to some ion exchange and removing some of the sodium. The anhydrous composition is HxNai.56Nbi.i4TÍ2.6oSÍ20y. X-ray powder diffraction of this sample identified it as having the sitinakite structure. Representative diffraction lines for the material are shown in Table 13 below. Table 13 2-Θ d (Á) I / Io 11.26 7.85 vs 14.76 6.00 m 15.94 5.56 w 17.62 5.03 m 18.56 4.78 w 21.81 4.07 w 25.29 3.52 w 26.44 3.37 m 27.14 3.28 m 27.48 3.24 m 29.76 3.00 w 31.94 2.80 m 32.19 2.78 w 33.10 2.70 w 33.94 2.64 m 34.22 2.62 m 36.14 2.48 w 36.88 2.44 w 37.44 2.40 w 45.32 2.00 w 45.94 1.97 w 46.18 1.96 m 46.82 1.94 w 47.64 1.91 w 48.38 1.88 w ma / t / ζυζζ / υυοζυυ Example 15 This sample has the structure of sitinakite with the anhydrous composition Na3.16Ti2.77Nb1.05Si2O13.74. Large batches of this material were prepared using the formulation: 0.95 Na2O:0.15 Nb2O5: 0.75 TiO2: 0.85 SiO2: 129 H2O: 3.0 i-PrOH : 3.4 EtOH A typical preparation used 50% NaOH solution, hydrous niobium pentoxide, titanium isopropoxide, Ti(OiPr)4, tetraethyl orthosilicate (TEOS), and deionized water. The NaOH solution was diluted with water in which the hydrous niobium pentoxide was suspended. TEOS was then added slowly with vigorous stirring, and the reaction mixture was homogenized for an additional 15 minutes after the addition. Ti(OiPr)4 was then added slowly, and the reaction mixture was further homogenized. The reaction mixture was transferred to a reactor and digested at 200 °C for 24 h under autogenous pressure. The product was isolated by filtration, washed with deionized water, and dried. Representative X-ray diffraction lines for the product are shown in Table 14 below. Tabla 14 2-Θ d (Á) I / Io % 8.75 10.10 w* 9.99 8.85 w* 11.2 7.85 vs 14.69 6.03 m 15.93 5.56 w 17.58 5.04 m 18.58 4.77 w 22.68 3.92 w 25.30 3.52 w 25.98 3.43 w 26.42 3.37 m 27.10 3.29 w 27.0 3.25 m 29.59 3.02 w 30.21 2.96 w 31.79 2.81 w 32.24 2.77 w 33.84 2.65 m 34.24 2.62 m 36.15 2.48 w 36.93 2.43 w 37.49 2.40 w 42.81 2.11 w 44.37 2.04 w 45.15 2.01 w 45.95 1.97 w 46.28 1.96 w 4 6.66 1.94 w 47.74 1.90 w * impureza μλ / t / ζυζζ / υυοζυυ Ejemplo 16 A solution was prepared by dissolving 11.31 g of NaOH granules in 20 g of deionized water. To this solution, 3.59 g of LiOH*H2O (Aldrich) was added with vigorous stirring. After 20 minutes of homogenization, 27.84 g of colloidal silica (Ludox AS-40, 40% SiO2) was added dropwise over 10 minutes. Separately, a solution was prepared by dissolving 16.25 g of SnC14*5H2O in 20.7 g of H2O. After 1 hour of homogenization, this solution was added to the white suspension and mixed for an additional 20 minutes. The creamy reaction mixture was loaded into a 125 mL autoclave and digested for 16 days at 200 °C under autogenous pressure. The solid product was isolated by centrifugation, washed with deionized water, and dried at room temperature. The product was analyzed by X-ray powder diffraction, and representative X-ray diffraction lines for the product are listed in Table 15 below.Sodium ion exchange was performed on a portion of this material prior to testing. Table 15 μλ / t / ζυζζ / υυοζυυ 2-Θ d (Á) I / Io % 14.50 6.10 m 16.22 5.46 m 19.14 4.63 wm 20.44 4.34 w 24.99 3.56 w 27.06 3.29 m 29.82 2.99 vs 33.22 2.69 m 35.62 2.52 w 37.10 2.42 m 38.82 2.32 w 41.90 2.15 w 44.54 2.03 m 46.98 1.93 w 47.56 1.91 m 49.46 1.84 w 49.83 1.83 w 51.56 1.77 w 53.86 1.70 w 54.36 1.69 w Example 17 In this study, a potassium titanate sample received from Honeywell was used. This compound consists primarily of potassium octatitanate, K₂Ti₈O₇, along with some potassium hexatitanate, K₂Ti₆O₇, and some anatase, TiO₂. The sample was characterized by powder X-ray diffraction. Representative X-ray diffraction lines are shown in Table 16. Sodium ion exchange of the sample was performed prior to testing. Table 16 μλ / t / ζυζζ / υυοζυυ 2-Θ d (Á) I / Io % 11.14 7.94 s 11.46 7.72 m-s 12.04 7.34 w 13.82 6.40 w 19.77 4.49 w 24.10 3.69 w 25.30 3.52 vs 28.91 3.09 m 29.25 3.05 m 29.93 2.98 w 31.99 2.80 w 33.13 2.70 w 34.70 2.58 w 36.93 2.43 w 37.79 2.38 m 38.57 2.33 w 43.02 2.10 w 43.51 2.08 w 47.68 1.91 m 48.04 1.89 m 49.17 1.85 w 53.87 1.70 w-m 55.06 1.67 w-m μλ / t / ζυζζ / υυοζυυ Ejemplos 18A y 18B A Teflon beaker was filled with 150.00 g of TEAOH (35%) and stirred using a high-speed stirrer. Then, 53.05 g of TEOS (98%) was added dropwise and stirred for 2 h to hydrolyze the TEOS. Separately, 11.72 g of ZrOC₁₂·8H₂O was dissolved in 2.00 g of deionized water. This solution was added to the reaction mixture dropwise, intermittently. During the addition, a white gel formed. This was further homogenized for 2 h. A solution was prepared by dissolving 14.40 g of CsOAc (98%) in 2.00 g of deionized water. This solution was rapidly added to the reaction mixture. The reaction mixture was transferred to Teflon-lined Parr reactors and digested at 175 °C for 48 (Example 18A) and 96 h (Example 18B). The products were isolated by centrifugation, washed with deionized water, and air-dried. X-ray powder diffraction showed that the products are amorphous.Sodium ion exchange was performed on a portion of the products before testing. Example 19 In a Teflon beaker under a high-speed stirrer, 22.76 g of NaOH granules were dissolved in 357.45 g of deionized water. To this solution, 41.38 g of colloidal silica (Ludox AS-40, 40% SiO₂) was added and stirred vigorously for 10 minutes, forming a white suspension. After 20 minutes of homogenization, 28.44 g of zirconium acetate solution (22.1 wt% ZrO₂) was added, and the mixture was stirred for an additional 3 minutes. The reaction mixture was loaded into a 600 mL stirred autoclave and digested for 72 hours at 200 °C while stirring at 250 rpm. The solid products were isolated by centrifugation, washed with deionized water, and dried at room temperature. The product was identified as Zr-gaidonnayite by X-ray diffraction. Representative diffraction lines for the product are shown in Table 17 below. Elemental analysis yielded the empirical composition Na2.19ZrSi3.28O9.66. Table 17 μλ / t / ζυζζ / υυοζυυ 2-Θ d (Á) I / Io % 13.88 6.37 m 15.12 5.86 vs 15.80 5.60 ms 20.58 4.31 w 26.72 3.33 w 27.65 3.22 w 28.68 3.11 vs 30.54 2.93 ms 31.18 2.87 wm 31.81 2.81 wm 34.10 2.63 w 36.12 2.48 w 37.46 2.40 w 41.14 2.19 w 4.19 4.19 2.03 w 48.00 1.89 wm Example 20 Removal of metal ions from the μλ / t / ζυζζ / υυοζυυ solution The samples described in Examples 1-19 were tested to determine their ability to adsorb Co2+, Pb2+, Cd2+, and Cr3+ ions from a test solution by determining the distributions (Kd) for each metal between adsorption on the solid versus remnant in the solution state. The test solutions were prepared by dissolving cobalt acetate, lead acetate, cadmium acetate, and chromium nitrate in tap water. These test solutions were analyzed by ICP, with the first test solution containing 23.5 ppm Co2+, 13.5 ppm Pb2+, 22.4 ppm Cd2+, and 13.6 ppm Cr3+, while a second test solution contained 26.7 ppm Co2+, 21.6 ppm Pb2+, 24.9 ppm Cd2+, and 19.2 ppm Cr3+. For the test, 200 mg of ion exchanger is placed in a 30 ml borosilicate vial to which 20 ml of test solution containing metals is added using a 20 ml syringe.The loaded vial was sealed with a cap and placed in a Bohdan shaker and vigorously shaken for 24 hours at room temperature. Once the ion exchanger was in contact with the metal solution for the desired amount of time, the solution / solid suspension was withdrawn from the vial using a syringe. The solids were separated from the solution by pushing the syringe contents through a 0.45 µm nylon filter. The solution was collected in a plastic vial and sent for chemical analysis by TCP or ICP / mass spectrometry. The detection level for Co2+, Cd2+, and Cr3+ was 80 ppb, while the detection level for Pb2+ was 0.2 ppm or 200 ppb. The disappearance of the metals from the solution was assumed to be due to adsorption by the solid. The Kd value for the distribution of metals between the solution and the solid was calculated using the following formula: Kd(mL / g) = (V) (Ac) (W) (Se) where: V = volume of the waste simulator (mi) Ac = concentration of cation absorbed in the ion exchanger (g / ml) W = mass of the ion exchanger evaluated (g) Se = cation concentration in supernatant after reaction (g / ml) Table 18 below summarizes the results of the recruitment studies. Table 18 Distribution of Co2+, Pb2+, Cd2+ and Cr3+ expressed as Kd values. Example Co2+ Kd (mg / ml) Pb2+ Kd (mg / ml) Cd2+ Kd (mg / ml) Cr3+ Kd (mg / ml) 1 >29275 >6650 >27900 15011 2 >29275 >6650 >27900 >16900 3 12268 >6650 14833 >16900 4 >29275 >6650 >27900 3575 5A >29275 >6650 >27900 >16900 5B >29275 >6650 >27900 >16900 6 >29275 4400 15900 5566 7A >29275 >6650 >27900 >16900 7B >29275 >6650 >27900 >16900 7C >29275 >6650 >27900 >16900 7D >29275 >6650 >27900 >16900 8 8003 6650 4877 >16900 9 16686 >6650 >27900 >16900 10 10169 >10700 >31025 >23900 11 >33275 3500 22536 3210 12 >29275 >6650 >27900 >16900 13 >33275 >10700 >31025 >23900 14 10580 >10700 >31025 >23900 15 >33275 >10700 >31025 >23900 16 >29275 >6650 >27900 >16900 17 >29275 >6650 >27900 >16900 18A 3356 >6650 4048 >16900 18B >6650 >16900 19 11508 >10700 16500 >23900 Of these, the metalates respectively have an empirical formula on an anhydrous basis of: AmZ raTibSncMdS ixOy where A is an exchangeable cation comprising potassium ion, sodium ion, rubidium ion, cesium ion, calcium ion, magnesium ion, hydronium ion or mixtures thereof, M is at least one framework metal selected from the group consisting of hafnium (4+) or niobium (5+), m is a molar ratio of A to total metal (total metal = Zr + Ti + Sn + M) and has a value of 0.10 to 15, a is a mole fraction of the total metal being Zr and has a value of zero to 1, b is a mole fraction of the total metal being Ti and has a value of zero to 1, c is a mole fraction of the total metal being Sn and has a value of zero to 1, where a + b + c > 0, d is a mole fraction of the total metal being M and has a value of zero to less than 1, where a + b + c + d = ly, x is a molar ratio of Si to total metal and has a value from 0 to 12, yy is a molar ratio of O to total metal and has a value from 2.1 to 33.An embodiment of the invention is any one or all of the embodiments in this paragraph up to and including the first embodiment in this paragraph, wherein the body fluid is selected from the group consisting of whole blood, blood plasma or other blood component, gastrointestinal fluids, and dialysate solution containing blood, blood plasma, other blood component, or gastrointestinal fluids. An embodiment of the invention is any one or all of the embodiments in this paragraph up to and including the first embodiment in this paragraph, wherein M is hafnium(+4) or niobium. An embodiment of the invention is any one or all of the embodiments in this paragraph up to and including the first embodiment in this paragraph, wherein x = 0. An embodiment of the invention is any one or all of the embodiments in this paragraph up to and including the first embodiment in this paragraph, wherein a + c + d = 0.One embodiment of the invention is any one or all of the embodiments in this paragraph up to and including the first embodiment in this paragraph, wherein A is a mixture of calcium and sodium. Another embodiment of the invention is any one or all of the embodiments in this paragraph up to and including the first embodiment in this paragraph, wherein the ion exchanger is compacted into hollow fibers incorporated into a membrane. A third embodiment of the invention is any one or all of the embodiments in this paragraph up to and including the first embodiment in this paragraph, wherein the ion exchanger is contained in particles coated with a coating comprising a cellulose-derived composition.One embodiment of the invention is any one or all of the embodiments in this paragraph up to and including the first embodiment in this paragraph, wherein the process is a hemoperfusion process in which body fluid is passed through a column containing the ion exchanger. Another embodiment of the invention is any one or all of the embodiments in this paragraph up to and including the first embodiment in this paragraph, wherein a dialysate solution is introduced into a peritoneal cavity and then passed through at least one adsorbent bed containing at least one ion exchanger.One embodiment of the invention is any one or all of the embodiments in this paragraph up to and including the first embodiment in this paragraph, wherein the ion exchanger is formed in an article for oral ingestion, followed by ion exchange between the ion exchanger and the toxins Co2+, Pb2+, Cd2+, and Cr3+ contained in gastrointestinal fluid in the intestines of a mammal, and subsequently by excretion of the ion exchanger containing the toxins. Another embodiment of the invention is any one or all of the embodiments in this paragraph up to and including the first embodiment in this paragraph, wherein the formed article is coated with a coating that does not dissolve under the conditions within a stomach. A second embodiment of the invention is a composition comprising a combination of a body fluid, a dialysate solution, or a mixture of the body fluid and the dialysate solution; the combination further comprising an ion exchanger selected from zirconium metalate, titanium metalate, tin metalate, multi-ion metalate containing more than one of zirconium, titanium, and tin, and mixtures thereof; the metalates respectively having an empirical formula on an anhydrous basis of AmZ raTibSncMdSixOy where A is an exchangeable cation comprising potassium ion, sodium ion, rubidium ion, cesium ion, calcium ion, magnesium ion, hydronium ion or mixtures thereof, M is at least one framework metal selected from the group consisting of hafnium (4+) or niobium (5+), m is a molar ratio of A to total metal (total metal = Zr + Ti + Sn + M) and has a value of 0.10 to 15, a is a mole fraction of the total metal being Zr and has a value of zero to 1, b is a mole fraction of the total metal being Ti and has a value of zero to 1, c is a mole fraction of the total metal being Sn and has a value of zero to 1, where a + b + c > 0, d is a mole fraction of the total metal being M and has a value of zero to less than 1, where a+b+c+d=ly, x is a molar ratio of Si to the total metal and has a value from 0 to 12, yy is a molar ratio of O to the total metal and has a value from 2.1 to 33.An embodiment of the invention is any one or all of the embodiments in this paragraph up to and including the second embodiment in this paragraph, where the body fluid is whole blood, blood plasma, another blood component, or gastrointestinal fluid. A third embodiment of the invention is an apparatus comprising a matrix containing a support material for an ion exchanger selected from zirconium metalate, titanium metalate, tin metalate, multi-metalate containing more than one of zirconium, titanium, and tin, and mixtures thereof, the metalates respectively having an empirical formula on an anhydrous basis of AmZ raTibSncMdS ixOy where A is an exchangeable cation comprising potassium ion, sodium ion, rubidium ion, cesium ion, calcium ion, magnesium ion, hydronium ion, or mixtures thereof, M is at least one framework metal selected from the group consisting of hafnium(4+) or niobium(5+), m is a molar ratio of A to total metal (total metal = Zr + Ti + Sn + M) and has a value from 0.10 to 15, a is a mole fraction of the total metal, which is Zr, and has a value from zero to 1, b is a mole fraction of the total metal, which is Ti, and has a value from zero to 1, c is a mole fraction of the total metal, which is Sn, and has a value from zero to 1, where a + b + c > 0, d is a mole fraction of the total metal, which is M, and has a value from zero to less than 1, where a + b + c + d = y, x is a mole ratio of Si to the total metal and has a value from 0 to 12, y is a mole ratio of O to the total metal and has a value from 2.1 to 33. An embodiment of the invention is any one or all of the embodiments in this paragraph up to the third embodiment in this paragraph, wherein the matrix comprises a porous network comprising biocompatible polymers and oxides and metallic silicates.One embodiment of the invention is any one or all of the embodiments in this paragraph up to and including the third embodiment in this paragraph, wherein the biocompatible polymers comprise carbohydrates or crosslinked proteins. Another embodiment of the invention is any one or all of the embodiments in this paragraph up to and including the third embodiment in this paragraph, wherein the biocompatible polymer is a polysaccharide selected from α-glucans having 1,3, 1,4, or 1,6 linkages. A further embodiment of the invention is any one or all of the embodiments in this paragraph up to and including the third embodiment in this paragraph, wherein the biocompatible polymer is a carbohydrate selected from glucose, fructose, sucrose, maltose, arabinose, mannose, galactose, lactose, and oligomers and polymers comprising one or more of these carbohydrates.One embodiment of the invention is any one or all of the embodiments in this paragraph up to and including the third embodiment in this paragraph, wherein the biocompatible polymer comprises a protein selected from albumin, ovalbumin, casein, myosin, achin, globulin, hemoglobin, myoglobin, gelatin, and small peptides. Without further detail, it is believed that, by using the foregoing description, a person skilled in the art can utilize the present invention to its fullest extent and readily determine its essential features, without departing from its spirit and scope, to make various changes and modifications to the invention and adapt it to various uses and conditions. The specific preferred embodiments described above should therefore be considered merely illustrative and not limiting in any way the remainder of the description, which is intended to encompass various equivalent modifications and arrangements included within the scope of the appended claims. In the above, all temperatures are stated in degrees Celsius and all parts and percentages are by weight, unless otherwise stated. It is hereby stated that, as of this date, the best method known to the applicant for putting the aforementioned invention into practice is the one that is clear from the present description of the invention.

Claims

1. A process for removing toxins of Co2+, Pb2+, Cd2+, Cr3+ or mixtures thereof from body fluids, characterized in that it comprises contacting the toxin-containing fluid with an ion exchanger to remove the toxins from the fluid by ion exchange between the ion exchanger and the body fluid, the ion exchanger being selected from zirconium metalate, titanium metalate, tin metalate, multi-ion metalate containing more than one of zirconium, titanium and tin, and mixtures thereof, the metalates respectively having an empirical formula on an anhydrous basis of: AmZ raTibSncMdS ixOy where A is an exchangeable cation comprising potassium ion, sodium ion, rubidium ion, cesium ion, calcium ion, magnesium ion, hydronium ion or mixtures thereof, M is at least one framework metal selected from the group consisting of hafnium (4+) or niobium (5+) ) ,m is a molar ratio of A to total metal (total metal = Zr + Ti + Sn + M) and has a value from 0.10 to 15, a is a mole fraction of the total metal which is Zr and has a value from zero to 1, b is a mole fraction of the total metal which is Ti and has a value from zero to 1, c is a mole fraction of the total metal which is Sn and has a value from zero to 1, where a + b + c > 0, d is a mole fraction of the total metal which is M and has a value from zero to less than 1, where a+b+c+d=ly, x is a molar ratio of Si to total metal and has a value from 0 to 12, ey is a molar ratio of O to total metal and has a value from 2.1 to 33.

2. The process according to claim 1, characterized in that the body fluid is selected from the group consisting of whole blood, blood plasma, or other blood component, gastrointestinal fluids, and dialysate solution containing blood, blood plasma, other blood component, or gastrointestinal fluids.

3. The process according to claim 1, characterized in that the ion exchanger is compacted into hollow fibers incorporated in a membrane.

4. The process according to claim 1, characterized in that it is a hemoperfusion process in which the body fluid is passed through a column containing the ion exchanger.

5. The process according to claim 1, characterized in that a dialysate solution is introduced into a peritoneal cavity and then flowed through at least one adsorbent bed containing at least one μλ / t / ζυζζ / υυοζυυ ion exchanger.

6. The process according to claim 1, characterized in that the ion exchanger is formed in an article formed to be ingested orally, followed by an ion exchange between the ion exchanger and the toxins Co2+, Pb2+, Cd2+, Cr3+ contained in a gastrointestinal fluid in the intestines of a mammal and then by excretion of the ion exchanger containing the toxins.

7. A composition characterized in that it comprises a combination of a body fluid, a dialysate solution or a mixture of the body fluid and the dialysate solution; the combination further comprises an ion exchanger selected from zirconium metalate, titanium metalate, tin metalate, multi-ion metalate containing more than one of zirconium, titanium and tin, and mixtures thereof, the metalates respectively having an empirical formula on an anhydrous basis of: AmZ raTibSncMdSixOy where A is an exchangeable cation comprising potassium ion, sodium ion, rubidium ion, cesium ion, calcium ion, magnesium ion, hydronium ion or mixtures thereof, M is at least one framework metal selected from the group consisting of hafnium (4+) or niobium (5+), m is a molar ratio of A to total metal (total metal = Zr + Ti + Sn + M) and has a value of 0.10 to 15, a is a mole fraction of the total metal which is Zr and ma / t / ζυζζ / υυοζυυ has a value from zero to 1, b is a mole fraction of the total metal which is Ti and has a value from zero to 1, c is a mole fraction of the total metal which is Sn and has a value from zero to 1, where a + b + c > 0, d is a mole fraction of the total metal which is M and has a value from zero to less than 1, where a+b+c+d=ly, x is a molar ratio of Si to the total metal and has a value from 0 to 12, ey is a molar ratio of O to the total metal and has a value from 2.1 to 33.

8. The composition according to claim 7, characterized in that the body fluid is whole blood, blood plasma, another blood component, or gastrointestinal fluid.

9. An apparatus characterized in that it comprises a matrix containing a support material for an ion exchanger selected from zirconium metalate, titanium metalate, tin metalate, multinary metalate containing more than one of zirconium, titanium and tin, and mixtures thereof, the metalates respectively having an empirical formula on an anhydrous basis of: AZ raTibSncMdS ίχOγ where A is an exchangeable cation comprising potassium ion, sodium ion, rubidium ion, cesium ion, calcium ion, magnesium ion, hydronium ion or mixtures thereof, M is at least one framework metal selected from the group consisting of hafnium (4+) or niobium (5+), m is a molar ratio of A to total metal (total metal = Zr + Ti + Sn + M) and has a value of 0.10 to 15, a is a mole fraction of the total metal which is Zr and has a value from zero to 1, b is a mole fraction of the total metal which is Ti and has a value from zero to 1, c is a mole fraction of the total metal which is Sn and has a value from zero to 1, where a + b + c > 0, d is a mole fraction of the total metal which is M and has a value from zero to less than 1, where a+b+c+d=ly, x is a molar ratio of Si to the total metal and has a value from 0 to 12, ey is a molar ratio of O to the total metal and has a value from 2.1 to 33.

10. The apparatus according to claim 9, characterized in that the matrix comprises a porous network comprising biocompatible polymers and metal oxides and silicates.