JPH02501367A - ion exchange composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] ion exchange composition Technical field The present invention uses metal oxides such as high content silica or high content ruthenium or Glass compositions containing other Group 8 metal oxides and chemical adsorption, ion exchange or is a porous glass composition that is effective when a large surface area is required when using catalysts, etc. Concerning methods of manufacturing things.

Background technology Porous glass compositions containing high silica contents are well known; The type of metal oxide additive that can be used or the method of actually adding this additive. had considerable restrictions. Adding metal oxide to the surface or porous structure of the glass composition Additions can effectively change the properties of the composition.

The present invention also provides for extensive metal oxide addition to porous glass compositions. The present invention relates to a method in which agents can be added variably. This method involves the use of phase-separable glass compositions. , for example, the process of melting alkali silicate glass containing a predetermined amount of metal oxide additives. The degree is included. The glass composition is heat treated to form a soft, extractable phase and a hard, extractable phase. During the separation from the non-extractable phase, the considerable amount of metal oxide creates a solid phase, which When extracted with aqueous, usually acidic solutions, they remain within the porous glass structure.

The porous glass composition is then heat treated, e.g. with alkali metal ions or ammonia. Heat treatment with nium ions converts it into a highly effective ion exchange composition. present invention According to In the case of species such as alumina, which are separated into phases that can be extracted, metal oxide additives are added. method, e.g. adding this additive from the solution used when extracting the soft phase. A method may be implemented.

Applications of porous glass compositions include U.S. Pat. No. 4,469 by Simons et al. ．． No. 628, for example, after surface treatment with an ionic solution, cationic It is used as an ion exchanger such as an ion exchanger. On the other hand, for example, phase-separable gas Oxide additives are added by impregnating the solid phase of the glass and extracting it. Until now, it has not been possible to transform a porous glass composition into an ion exchange composition after adding Not proposed. U.S. Pat. No. 4,659,512 to Macedo et al. Preparation of an ion exchange composition comprising the step of treating interconnected porous supports In this case, the porous substrate is made of an organic amine, e.g. triethylene. Cylinders containing neutral or basic water-soluble alkylene amines such as tetraamines It is silicate glass or silica gel. Ions created by this creation method Exchange compositions are used to remove metal species such as cobalt from solutions, especially aqueous solutions. used. In addition, porous silicate glass containing metal oxide additives is used as a support. It is not suggested that this method be used.

The present invention further provides ion exchange separation of rare earth elements, actinides or mixtures thereof. It also relates to methods.

According to U.S. Patent No. 2.897.050 to Jaffee, the term "rare earth" Contains a group of elements from lanthanum with child number 57 to lutetium with atomic number 71, and its properties is almost the same as that of rare earths, and it is a group of 39 atoms that usually exist together in naturally deposited ore deposits. It is necessary to add thorium or scandium with atomic number 21 to these element groups. There is.

Furthermore, according to the Jaffee patent, rare earths are intimately mixed together in their natural state. , which differ very slightly from each other but have substantially similar scientific and physical properties. and cannot be easily separated. Various methods have been proposed to separate rare earths. example For example, fractional crystallization, fractional precipitation, solvent extraction, and ion exchange have been proposed; According to the national patent, all these methods are too time consuming and difficult to control.

Actinides are an important group of elements with similar scientific properties. These elements are When considering ions with the same oxidation state, they are similar to rare earths.

A commonly used method for rare earth separation is described by Peppard et al. in US Pat. No. 2.955. No. 913 and U.S. Pat. No. 3.59111.913 to Ciola et al. This is a solvent extraction method.

On the other hand, the ion exchange method requires an extremely small plate height and can be used for multi-element separation. It has considerable advantages over solvent extraction methods, such as high purity and high final purity. Kirk-Othmer, 3rd edition, Volume 19, Willie Interscience (11i2ey-1nterscjence), New York Encyclopedia of Che, 1982 (Vical Technology).

On the other hand, the ion exchange method relies only on the elution method when separating various rare earths; Theoretically, many plates are required to prevent the band from becoming wider. The operating conditions must be very precisely controlled, and the flow rates are low (and the influent concentration is limited). Because of this, it is not widely used. Other characteristics of the elution method include U.S. Pat. No. 2,798,789 by Taing et al. or Chaubin et al. As shown in National Patent No. 2.925.431, the degree of elution is always consistent with the complexation of various rare earths. determined by the relative magnitudes of the stability constants of the fields, or in all cases The heavier the lanthanide, the higher the stability constant and therefore the faster the desorption rate. Examples include.

One object of the present invention is to provide a porous material with a high silica content and a significant amount of metal oxide additives. An object of the present invention is to provide a glass composition.

Another object of the invention is to provide a porous material with a high silica content and a significant amount of metal oxide additives. An object of the present invention is to provide a method for making a quality glass composition.

Still another object of the present invention is to provide ion exchange compositions with high capacity, selectivity and chemical durability. Or to provide an absorbent.

Another object of the present invention is to produce an image based on a porous glass composition with a high content of silica. An object of the present invention is to provide a method for making an on-exchange composition.

A further object of the invention is to develop catalysts and chromatographs with high efficiency, selectivity and scientific durability. Our goal is to provide roughy wood.

Other objects of the invention are catalyst supports, enzyme supports, chromatography stationary phase supports, Or to provide a durable porous glass composition that can be used as a support for scientific reagents. There are many things.

Another object of the invention is to use the present invention as a support for dyes, enzymes or mixtures thereof in processor equipment. Corrosion resistance that can be used to measure the cost or physical properties of aqueous media over long periods of time. An object of the present invention is to provide a method for producing an edible porous glass composition.

Another object of the present invention is an ion exchange method that allows separation in large quantities without adding complexing agents. To provide a method for separating rare earths, actinides or mixtures thereof by .

Another object of the present invention is to combine strongly complexable rare earth ions with weakly complexable rare earth ions. An object of the present invention is to provide a method for selectively removing similar ions from a fluid containing them.

Another object of the invention is to use it for separating rare earths, actinides or mixtures thereof. An object of the present invention is to provide an ion exchange composition with high capacity selectivity.

Another object of the present invention is that it can be used in the optical field, has extremely low content of heavy rare earths, and has high purity. Our goal is to provide a method for creating high quality lanterns.

Another object of the present invention is to prepare rare earth elements of high purity individually or in groups. It is about providing law.

According to the present invention, porous glass compositions containing transition metal oxide additives are Add oxidizing oxides or salts to the initial batch composition, e.g. Added to the silica-boron oxide-alkali oxide mixture used to make the composition Created by This mixture is melted and cooled to form a glass composition and further heat treated to form a soluble “soft” phase with considerably less silica than the rigid phase. Separate the ``hard'' phase that is extractable from the silica and has a high silica content. The flexible phase is an aqueous medium. body, usually removed by extraction with an acidic medium. Difficulties with this embodiment of the invention select a suitable transition metal additive and its suitable amount to include in the initial formulation. At the end of the extraction process, the final porosity consists of a solid phase in which most of the additives cannot be dissolved. The objective is to allow the glass to remain in the quality glass composition. The resulting porosity The quality glass composition can be used without further processing, e.g. as a chromatographic stationary phase, as an absorbent. , can be used as a catalyst, and can also be chemically treated to form ion exchangers, supporting reagents, catalysts, etc. It can be used as a medium, chromatography agent, enzyme, indicator dye. europe by bμ According to Patent Application No. 8511618L No. 5, Group 4J (not Group 8) of the periodic table (2) oxides can be held in a rigid phase. Create a catalyst with high specific activity transition metal oxidation with catalytic properties within a phase-separable batch glass composition to A method is adopted in which a material is added, followed by heat treatment to selectively extract the soft phase. child Transition metal oxides, such as ruthenium oxide, exhibit a rigid phase or solid phase during phase separation. A considerable amount of additive oxide remains in the interphase between the soft phase and the soft phase. remains on the surface of the final porous glass composition, thereby effectively carrying out the scientific catalytic process. I can. According to the production method of the present invention, the catalytic activity can be increased even when present at low concentrations. Ruthenium, rhodium, palladium, rhenium, osmium, iridium A porous glass composition containing a metal oxide additive that is an oxide with platinum and platinum was created. It will be done.

In some cases, porous glass compositions are required to have high corrosion resistance. for example Using chromatography supports for high pH or high temperature media, For example, small probes used for in vivo blood analysis, which are extremely difficult to dissolve due to their small dimensions. This highly corrosion-resistant strip is suitable for use as a support for indicator dyes in required. Metal oxides such as zirconium oxide before phase separation and extraction steps The chemical durability of porous glass compositions is greatly improved by adding additives can be done.

High content of transition metal oxides, reducing silica levels to 40 mole percent phosphorus oxide levels (both 20 mole percent). Porous glass composition according to U.S. Pat. No. 2.943.059 that requires Unlike the preparation method of , the preparation method of the present invention has a high silica content and can be applied to glass compositions In addition, there is no need to include phosphorus oxide.

According to another embodiment of the invention, the glass composition is phase separated in an aqueous solution, usually an acidic solution. Ion exchange is achieved by processing the material and simultaneously extracting the soft phase and impregnating it with metal additives. A method of making a replacement composition is provided.

Porous glass made by this method or by co-melting as described above The composition contains alkali metal ions, ammonia ions, ILB group ision amines, or combinations of these species to create highly effective ion exchangers. The pH can be activated using aqueous solutions, usually at relatively high levels.

By adding metal oxide additives, the ion exchange capacity or selectivity as well as Corrosion resistance is improved.

Corrosivity due to prolonged exposure to aqueous media, e.g. high Beha values or high temperatures In applications involving contact with media, corrosion resistance controls ion exchange performance. .

Further in accordance with the present invention, rare earths, actinides or By separating the mixture, rare earth ions, actinide ions, or A method is provided for separating a mixture of substances. The surface area of the ion exchange composition is approximately 5 to 1500+e"/g. The ion exchange composition contains from 0 to about 35 mole percent preferably 1 to 30 mole percent of metal oxide or hydrated metal oxide It is included. Metal oxides or hydrated metal oxides are group 38, group 4 of the periodic table. Group a, Group 58, Group 6a, Group 7a, Group 8, Group 1b and Group 2b transition metals genus, aluminum, gallium, indium, thallium, tin, lead, bismuth, berry titanium, actinides and mixtures thereof, preferably titanium oxide, zirconium acid selected from the group consisting of hafnium oxide, thorium oxide, and mixtures thereof. It will be done. The ion exchange composition includes an alkali metal cation, a Group 1b metal cation, Contains ammonium cations, organic amines, or mixtures thereof and has a Beha range of about 9 or higher. Impregnation in the above solution for a sufficient time to distribute these cations within the ion exchange composition. be done. Preferred cations are alkali metal cations, ammonium cations, Organic amines or mixtures thereof. The ion exchange composition contains from about 0.3 to about 10 moles. % alkali metal cations. complex in solution The components are collected as the solution is passed through the ion exchange composition, preferably in a column. I can't stand it. This method is preferred for separating rare earths, especially lanthanum or neodymium. Yes. This method separates lanthanum to 0.01 ppm or less. Particularly preferred when separating neodymium up to

Desirably, the ion exchange composition is a porous glass composition. This porous glass The composition contains 40 to 80 mole percent silica and elements 4a, 5a, and 5a of the periodic table. 6a, 0-3 selected from the group consisting of Ia group 18 transition metals and actinides and 5 mole percent of one or more transition metal oxides. The base glass composition is divided into at least a soluble phase and an insoluble phase by a process of creating a glass composition and a heat treatment. and extracting the soluble phase to a concentration of at least 50 mole percent. Porous glass containing 0.2 mole percent or less (both 0.2 mole percent) of transition metal oxides The method includes the step of creating a composition.

The porous glass composition also includes a base glass containing 40 to 80 mole percent silica. A process of melting the glass composition and making the base glass composition at least soluble by heat treatment. The step of separating into a phase and an insoluble phase, and periodic table Nos. 3a, 4a, 5a, 6a, 7 a, 8, Ib, 2b group transition metals, aluminum, gallium, indium, Contains one or more salts of thallium, tin, lead, bismuth, beryllium, and actinides. extracting the soluble phase with a solution containing It is created using the following method.

BEST MODE FOR CARRYING OUT THE INVENTION A borosilicate gas containing a considerable amount of transition metal oxides belonging to the bottom two rows of Group 8 of the periodic table. The final glass composition is obtained by melting the glass composition and heat treating it without causing crystallization. inducing a liquid/liquid phase within the silica to extract the soft phase with less soluble silica and extracting the silica-rich It is known from the above-mentioned known literature that a porous glass composition can remain. Unpredictable. Furthermore, during extraction, the silica-rich solid phase forming the porous glass composition is removed. It cannot be expected that large amounts of the virus will remain in the area.

This book involves melting the initial glass composition in the presence of additive oxides, further phase separation and extraction. According to the method of the invention, at least 50 mole percent, preferably less than Mo60%/l/・% of 5jOz, and groups 42, 5a and 5a of the periodic table. Group consisting of oxides of the elements of group 68, group 8 and the lower two rows of group 7a, and actinides 0.01 to 35 mole percent of a transition metal oxide selected from (family nomenclature is Cotton and Wilkin). Advanced Inorganic Science by Wilkinson (Wilkinson) (Wiley Interseience), New York, 1980, 4th edition ). The oxides include Tieos, Tl0tsZr0y, H rO,, TbO,, l1bO,, TatOs, Cry’s, ReO3, RuQ, , Rh*Os, Rho, , PdO, 0stDss DsDtlrOt, pto and and PLOl. The glass composition contains 0 oxides of elements of group 48. ．． 2-25 mole percent of the elements of the bottom two rows of Group VIII and rhenium dioxide Preferably, 0.01-10 mole percent of hydrogen dioxide is included. . Optimal glass compositions include those belonging to the group consisting of Tiny, Zr0t and BfOy. 1 to 25 mole percent of the oxide.

Surface treatment proposed to create porous glass compositions modified with metal additives For example, U.S. Pat. No. 2.34 (by NOrdherg) Borosilicate glass phase-separated in a strong mineral acid solution as shown in No. 0.013. Extract the composition, cold rinse the glass composition, and then add the glass composition to the desired metal salt solution. immerse inside. In all of the above cases, the addition of additives is done in a separate step. This is done after the preparation of the porous glass composition by extraction and washing. A fruit of the present invention According to the examples, the phase-separated glass composition can be processed in a solution of the desired additive salts. It is Noh. Additive salts used in the present invention, such as AI(No, )5, Zr0( Many solutions containing NOs)y or Zr(NOs) are acidic.

If necessary, the acidity of this solution can also be increased by adding a suitable mineral acid such as HNOs. It is also possible to increase By treating with this metal salt solution, additive salt solution A single process in which the extraction process and additive addition process are mixed without separation after processing. Extracted porous high silica glass set containing desired additives e.g. A1 or Zr A composition is created. This single process can be employed even at relatively low temperatures such as room temperature. be.

Furthermore, the ionization of porous glass modified with metal oxides produced by the method of the present invention The properties of the exchange compositions are completely unpredictable from the conventional ones. Tran ) et al., U.S. Pat. No. 4,333.847 and Fojita et al. with a metal additive solution as described in U.S. Pat. No. 4,1711°270. The purpose of modifying porous silicate glass compositions and silica gel is to simple anions of transition elements such as cobalt that can form complexes or The objective is to improve the ion exchange capacity of the silica material for ions. This is oxidized Silica is the only effective cation compared to tan, zirconium oxide, alumina, etc. It is based on the technical fact that it is an exchange body. For example, ion exchange compositions (Amphlett, Elsevie) r), 1964), hydrated silica shows only cation exchange, and tetravalent silica Con ions have a high electron affinity, so the basicity of the hydroxyl group is extremely low. The hydrogen atom of the roxyl group is easily substituted with a cation even in an acidic solution: 5not s Other tetravalent oxides such as TzOt and Zr0t vary depending on the Beha value of the solution. Has both on-exchange and anion-exchange properties; amphoteric oxides like hydrated alumina can adsorb either cations or anions depending on the P/S value of the solution. It is stated as. Furthermore, according to U.S. Pat. No. 4,178,270, silica The zeta potential is extremely negative, at least in the power-of-magnitude range of 3-10. On the other hand, the zeta potential of alumina and dilleffnium oxide is the pH value. It is positive up to 8, and the zeta potential of titanium oxide is up to P71 value 4.5-5. It is correctness. Accordingly, the Amphlett reference cited above and U.S. Pat. No. 4,333. No. 847 and U.S. Pat. No. 4,178,270, adsorbing anionic species Titanium oxide, zirconium oxide and alumina are thought to increase its effectiveness. It will be done. On the other hand, certain metal species always appear in aqueous solutions in the cationic state. this metal The seeds contain alkali metal ions, especially cesium, which is used in the nuclear industry. is one of the many radioactive contaminants commonly found in wastewater produced by of this ion In this case, from the above it can be seen that vesilica is better as an ion exchanger than supported zirconium. It is considered to be effective. Of course, untreated silica has a very neutral level of At this value, the surface protons are strongly bound to the silica structure, so the cesium ion Reacts very slowly with cations. On the other hand, U.S. Patent No. 4.4 by Simons et al. According to No. 69.628 and U.S. Pat. No. 4.659.512 to Macedo et al. The drawbacks mentioned above are the non-radioactive group 1b metal ions, ammonium, in medium basic media. This problem can be solved by pretreating the silica surface with cations or organic amines. In fact, the glass composition is not so much dissolved. Siri activated in this way Kate glass compositions have surfaces partially covered with alumina, titanium oxide or zirconium. or a fully coated composition with the same surface/1iffi ratio. More effective as a cation exchanger for, for example, cesium in liquids it is conceivable that.

On the other hand, the porous glass composition created by the method described above is made of zirconium oxide. Alternatively, an oxide additive such as alumina can be used to form a porous glass according to one method of the present invention. When added to the composition, i.e. before converting the porous glass composition to an ion exchange composition. When an unsaturated solution is introduced into the first melt, the neutral liquid stream becomes separated. The capacity for removing sium is significantly increased.

Furthermore, titanium oxide or zirconium oxide added by the production method of the present invention Porous glass compositions containing oxide additives such as and transition metals, such as cobalt, as well as water in its cationic and anionic state. to adsorb actinides, such as uranium or plutonium, that may be present in the neutral medium. It can be used to

The production method of the present invention allows high silica, porous ion exchange compositions to contain zirconium oxide and The advantage of adding oxide additives such as alumina is that it improves corrosion resistance in aqueous media. It can be said that it will be significantly improved. This advantage is that in the next process, porous glass The composition may be a catalyst, a chromatographic or chemical reagent support, an enzyme, or It becomes important when used as an indicator dye. Other advantages of the production method of the present invention are , in which the oxide additive is highly dispersed within or on the surface of the porous glass composition. This is obtained because it can be added in This means that individual oxide molecules are of the same type. bound by other molecules and forced into contact with the surrounding medium rather than being sorted out. For example, the catalytic activity of the oxide additive can be improved.

Alkali ions, Group 1b ions, ammonia ions, organic Zirconium, aluminum, titanium, etc. treated with amines or combinations thereof Porous glass compositions containing metal additives are produced by the addition of metal additives and the following main ion exchange process: For porous sisocate compositions that were not created by a single process with a combination of treatments. Compared to other ion exchange compositions, it was found that the overall performance was significantly superior. Ta.

The present invention creates porous, high silica glass compositions with transition metal oxide additives. In summary, the method includes the following steps.

(a) Melting of glass composition (b) Phase separation (cl) Extraction or (cl) Single step extraction/additive impregnation (d) Surface treatment (e) Chemical or heat treatment A transition metal additive species is added in step (a), (cl), or both steps.

Steps (d) and (e) are optional steps.

(a) Melting of glass composition In the preferred embodiment of the invention described above, the untreated base glass initially used is The blending range of the gas composition is shown in Table 1 below.

5ins 30-80 40-70 44-59Btus 15-50 24- 42 24-37R204-114-106-10 (as Nano) A]yOs　O-50-30-2 MxOy　0.2(0)-350,5(0)-301(0)-25NuOt　O ,01(0)-250,05(0)-100,2(0)-25In this table , 5iOy is replaced in whole or in part with the corresponding amount of Gene. R and O are Al Indicates a combination of potassium metal or alkaline rare earth oxide. l! ,0. is the period selected from the group consisting of oxides and actinides of Groups 4a, 5a and 6a of the Table of Contents Indicates one or more oxidic additives. Also, N and O are from group 8.7a of the periodic table. or more selected from the group consisting of oxides of table 1 shows two lower limit values (one of which is zero) for the three compounding ranges. It is understood that there is. The lower limit value of M, O, is only N and O in the glass composition. and when M, O, is added only in the step (cl). Ru. On the other hand, the zero lower limit of N1 even is M, 0. and when only N is added to the glass composition , 07 is added only to step (cl). Actually, M, O, and N, 0. The amount used is based on the molten carbon in the alkali borosilicate melt and the resulting It is limited by the crystallization resistance of the resulting glass composition in the subsequent cooling step. basic The glass composition is a homogeneous glass composition that can be easily made at a temperature below about 1500°C. In other words, f & suitability should be selected so that the viscosity at 1500°C is 1000 poise or less. It is. Well known glass composition melting processes may be used here.

(b) Phase separation (cl) Extraction (cl) Extraction/Additive Impregnation in a Single Step According to one embodiment of the invention, the flexible phase is Heat treated and phase separated to extract and add additives to the porous glass composition surface. Glass compositions are treated with solutions of additives such as aluminum and zirconium . This example applies when no additive is included in the initial melt, i.e. in step (a). M, 0. and N10. used when not intentionally added. used.

On the other hand, this example also shows that, if necessary, the melt made from the melt made in step (a) Also used when added to porous glass compositions in the same or separate additive solutions It is possible.

The additive used in step (cl) is an oxide of an alkaline earth metal, 3a of the periodic table. , 4a, 5a, 6a, 7a, 8, lb, oxidation of transition metals consisting of 2b groups aluminum, gallium, indium, thallium, tin, lead, bismuth, Selected from the group consisting of oxides of rare earth elements and actinides. of these oxides Aluminum, gallium, tin, lead, alkaline earth metals, lanthanum, rare earth elements element, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, titanium Preferred are ion, zirconium, hafnium, thorium, and ruthenium. In particular, Al Minium, iron and zirconium are most suitable. Treated with additive solution in step (cl) The processed and altered porous glass composition contains at least 60 mole percent dry weight. silica, preferably at least 75 mole dry weight percent 5i02, is the most Suitably contains a small amount (also dry) of 75 mol percent 5iOy. The amount of additive added in (cl) ranges from 0.005-25 mole percent, preferably preferably in the range of 0.1-10 mole percent, optimally -10 mole percent. This is the range of events. Solutions used in a single extraction/impregnation step preferably contain (both 0.02 g/l, but optimally at least 2 g/l) metal oxide additives. The Beha value of the solution is preferably below 4, optimally 3 or less. Many metal additives such as aluminum or zirconium In this case, saline solutions sufficiently containing high S degree metal ions are generally highly acidic. melt For neutral or near-neutral salts that can be dissolved, add acid to the solution to facilitate extraction. can be added. According to a preferred method, the concentration of the metal species exceeds the solubility limit. A solution is used that does not exceed or exceed significantly. Glass composition and solution Contacting can occur at relatively low temperatures, such as room temperature, or at elevated temperatures. temperature of solution To prevent excessive evaporation loss or thermal precipitation in the added solution as it approaches the boiling point. It is necessary to keep this in mind.

(d) Surface treatment After the glass composition is treated with extraction/additive impregnation media, absorbent, anionic heat exchanger Alternatively, it can be used as a cationic heat exchanger. This explanation is also used in step (a). Created by melting or a combination of this melting and extraction/additive impregnation This also applies to porous glass compositions that are According to a preferred embodiment, the click The performance of the glass composition as a heat exchanger on alkali metal cations, Group 1b Contains metal cations, ammonium cations, organic cations, or mixtures thereof can be improved by further treatment with a solution, in which case this solution is a neutral alkali Maintained at pH level.

(e) Additional chemical or heat treatment The ion-exchange composition is created by porous glass compositions containing oxide additives as previously described. Porous glass compositions containing metal oxide additives in addition to creating compositions or absorption media Objects can also be used in other fields. Porous glass compositions containing oxide additives are suitable for applications Therefore, it is necessary to dry it. If the glass composition is washed before drying, this The resulting dried glass composition is more homogeneous. This dry porous glass The gas composition should not be further processed (as is, as a catalyst or chromatographic support). It can be used as Additionally, porous glass compositions can be The organic stationary phase, enzymes, catalysts, reagents or Desired species, such as indicator dyes, may be deposited to make it applicable to chemical sensor devices. Furthermore, this Porous glass compositions can be heat treated to create solid glass or glass foam.

This heat treatment is described, for example, in U.S. Pat. No. 4.110.096 by Macedo et al. This is done after further impregnation with a doping agent, as shown in FIG. The solid obtained in this way The shaped glass composition can be used, for example, as a leading wave tube with a predetermined refractive index or a predetermined thermal Used for applications that require expansion coefficient, thermal conductivity, and electrical conductivity. Has a low coefficient of thermal expansion Glass foams are used, for example, where lightweight construction or thermal insulation is required.

The ion exchange compositions prepared according to the present invention are extremely useful in separating rare earths from each other. It has been found to be effective. According to one feature of the ion exchange composition of the present invention, Earths can be extracted from this composition without adding complexing agents to solutions in which some of them are present. are effectively separated from each other by passing through the bed. Next elution step (Since the absorption process is highly selective, this feature simplifies operation.) The effectiveness of this separation operation is increased. The ion exchange operation partially described above and the present invention The other big difference is that the more strongly complexable rare earth ions like Nd" be retained in the bed in advance of weaker complexable rare earth ions such as It is in. This feature is important when removing contaminants by ion exchange. Absorbing small amounts of pollutants from the body is the preferred method, so many of the weaker Removes a small amount of more strongly complexable rare earth ions from the more strongly complexable rare earth ions. For example, if it is necessary to remove a small amount of Nd from La used in the optical transmission field, This is a big advantage when you have to leave your home.

The literature also states that when processed to contain suitable counterfeit transition metal oxide additives, The method of making silica gel compositions that can be employed in the invention is fully explained. This silikage For example, E.I. Denibont des Nemose & Company ():, 1. Sold by DuPont de Nemours & Co. 0, 08-0., which is thought to exist as a silicon-bonded NaO group. f4 As LUDOX silica gel containing fi percent NayO Available.

Other types of silica gel compositions that can be employed in the present invention include Single component (especially high silica) or multi-component (e.g. Nut -Btus 5iOy, 5iOt-TiOz) fully or partially polymerizable (Yoldas, Journal of Materials Chemistry, Dan, 1) 943. (3979); Magazine by Joldas, Non-crystalline Solids (Non-c) ryst.

5olids), 38.81.1943 (1977)); Maharaja ( Mukberjee, Material Processing in the Space Environment with Small Gravity (Mukberjee) materials Processing in the Reduced G ravity Environment or Space), Esepia (El Sevier), 1982)).

The inclusion of metal oxide or hydrous metal oxide additives can improve the performance of rare earth separation operations. It has been found that the effectiveness of porous glass compositions is significantly improved. rare earth ions In order to create a highly separable composition, the porous glass composition can be alkalised. Metal ions, Group 1b metal cations, ammonium cations, organic amines, and must be treated with the mixture. At this time, low levels of metal oxides or For glass compositions containing water metal oxide additives, the performance of rare earth ion separation is The improvement increases as the additive content 9 increases, but this tendency does not change until the additive content reaches a certain level. It turns out that it will stop when it reaches that point. The performance of glass compositions containing high amounts of additives is , with moderate levels of additives, e.g., about 10 to about 15 weight percent ZrO, It appears that the performance is not as good as that of glass compositions containing .

The present invention will be explained along with the following experimental examples, but the present invention is not limited to such specific experimental examples. It is understood that this is not possible.

Experimental example J This example experiment includes an untreated sample prior to creating a porous glass composition containing metal oxide additives. The first method of melt preparation of glass compositions was adopted.

The initial glass composition melt shown in Table 2 contains oxides or (in the case of boron) water. oxides or (in the case of alkali metals) oxide precursors such as carbonates It was made by mixing and melting a batch of: These batch compositions are the best It was melted in a platinum crucible at humidity up to about 1450°C. pulled out of this melt The glass composition rods were pulverized and dissolved in aqueous hydrofluoric acid, and plasma The ingredients were determined by photophotometric analysis.

Table 2 Siot Btu3NatOtwo Altos Tl0t ZrO, Hro? Rus, Cry’s157.133.9 9.0 25g, 931.0 6J 3.0 355.233.7 3.8 4.0 3.3452.130.9 9.0 g ,0 549.830.2 4.0 5.0 1.010.0645.22B, 8 4 ．． 0 8.0 1.015.0? 55.633.8 6.0 2.5 2.1 11! 54.233.7 9.4 0.6 2.1953.1! 32.4 9.6 4.21047.632.810.0 9.6+151.325.71 0.0 13.01250.935.8 5.7 3.6 4.01357.0 33.7 9.0 0.31458.430,7 6.7 3.2 1.015 55.135.7 B, 6 0.6 Experimental Example 2 In this experimental example, the batch composition obtained in Experimental Example 1 was heat-treated to undergo phase separation. The soft phase was then extracted and washed to create a high silica porous glass composition.

The rod obtained in Experimental Example 1 was crushed, sieved, and separated into 120+80 mesh pieces. The glass composition powder, and in some cases the rod itself, are placed in a heat-resistant furnace and exposed to heat. They were treated to separate into a hard phase and a soft phase, respectively. Then add this powder or rod When immersed in heated solutions of mineral acids or acid salts, the soft phase is extracted and dissolved in water. Washed to remove residue. Extraction time and temperature ensure that the flexible phase is fully selected to be removed. Generally, heat treatment is carried out at a temperature range of 500-650°C. Extract for 17 hours and then at a temperature range of 90-100°C for 1-72 hours. Processed. In some cases, for an aqueous solution of the acid salt AI(NOs)a (17%) Details of the heat treatment and extraction treatment methods are shown in Table 3.

Entoko Sou Concave 1 Maro Sake Extraction time 1 71F @ (Hr) (''C) (Hr ) (”C) 1 2 550 3MHCl 3 1001a 2 550 IT %AI(NO3)s 24 251b 2 550 17%^1(NO3)i 24 25 + 3M! lR, oII (pH 3) 2 2 550 3MHCl 2 953 15 500 3M HCl 3 1004 17 500 3M I] C14100525703M) IC13100 6175203MHCl 3 100 7 3 550 3MHCl 2.5 95Il! 2 550 3MHCl 3 1009 2 550 3MHCl 3 10010 17 540 1. 5) ILso, 3 +00II 17 620 1.5MB, So, 3 1 0012 17 555 3M HCl 3 10013 17 556' 3M HCl 1 10014 1 650 3MHCl 18 90151°7 5 55 3M) IcI 3 100 porous glass composition ] 3, ] 4 color is dark gray , Porous Glass Composition 15 was green, and the rest were all colorless.

Experimental example 3 In this example experiment, alkali metal cations, ammonium cations, or a mixture thereof improved cationic properties by treating porous glass compositions with solutions containing compounds. An exchange porous glass composition was prepared.

Table 4 shows various conditions for the main ion exchange treatments. One volume of glass composition powder is usually Treated with 4 volumes of ion exchange solution.

1 method S^3M NH4OH+3M Na1tOs, 17 hrs, 25℃^ 3M NIi, OB, 17 hrs, 25℃N no treatment Experimental example 4 This example experiment uses several polygons created according to the method described in Examples 1-3. 2 shows the chemical components of the porous glass composition.

After each porous glass composition is prepared, it is washed with deionized water, dried, and aqueous fluoridated water. It was dissolved in a basic acid solution and analyzed by DC plasma spectrophotometry. Display the results of this analysis. 5.

IN 95.0 5.0 <0.1 <0.11a N 94.2 1.7 1.1 1.6 1.4Ia S^92.0 2.1 3.7 0.3 1.9 1b A90.3 2.0 5.8 0.2 1.73 N89.0 54 < 0.1 <0.1 5.24 N g4.3 3.0 <(1,112,74N a4.2 2.7 0.1 <0.1 13.05 N83.3 0.7 0. 1 <0.1 16.06 N75.8 <0.1 <1.1 <01 24. 27 N93.9 2.80, l <O, 13,222Na5.3 0.6 0 ．． 7 (1,512,823N90.4 3.2 (1,090,056゜32 4 N g6.0 3.1 0.02 1111.925 N78.4 8.0 1.4 0.11 12.126 N 74.3 6. (10,0519,4 271166,71,50,1631,628N89.8 3.1 0.0g <0.1 0.06 6.3 In this example, the basic gas was The glass compositions are melted together, the phases are separated at high temperature, the soft phase is extracted, and the phase is washed with water. A corresponding amount of metal oxide additive is added into the glass composition (e.g. in the case of Trot). up to at least 24 mole percent, at least 18 mole percent for Zr0t -cent). Furthermore, in contrast to Experimental Example 1, metal oxides within the porous glass composition The concentration of the additive is related to the amount of corresponding metal oxide added in the initial melt and This allows control.

Significant agitation of metal oxide additives (e.g. 1 to at least 4 mol. combination of additive impregnation and extraction with acidic solutions of metal salts corresponding to can be added to porous, cation exchange glass compositions. Amount of additive added is used in conjunction with the concentration of metal salt in the doping solution.

In particular, concentrated ionic solutions (aqueous sodium nitrate, sodium anhydride) after doping Additives can be removed from porous glass compositions even when immersed in ammonia or ammonia alone. It cannot be removed.

Glass compositions containing large nail metal additives, such as high titanium oxide glass compositions 5.6 It was found that the residual boron oxide levels were extremely low (less than 1 percent).

Experimental example 5 In this example, Example 1 is used as an ion exchange medium in a synthetic non-radioactive test solution. -3 Performance of some porous glass compositions prepared according to the method explained in 3. Explain.

The test procedure used for each glass composition included a 10 hm'' cross section. 1 volume of 5 mL of glass composition powder in a column (colu+mn) of remethyl methacrylate The test solution is passed through the column and sampled from the column at regular intervals. sample, analyze the chemical composition of this sample, and compare the analysis with the influent.

The definitions explained below are based on the ion exchange test conditions and conditions in this experimental example and the following experimental examples. Used to specify test results.

If 1 cV is the volume of solution equal to the volume of the ion exchange composition forming the column, then The volume of solution that has passed through the column at a particular point is expressed in cv number. A solution of lCv passes through the column. The residual time RT taken to flow is inversely proportional to the flow rate. What is the pollutant removal factor DF? The concentration of a particular species in the solution flowing into the column, i.e., the inflow, and the solution flowing out of the column, i.e., the flow It is the ratio of the concentration of the same species in the exudate. As the amount of solution passing through the column increases, the column The adsorption capacity of the specific species further approaches the saturated state, and the DF decreases accordingly. Special The adsorption capacity of a column for a fixed species is the cv when DF decreases to a predetermined value, for example 1o or 2 Defined as a value.

In the case of this experimental example, the test solution was 3000 mg/1. Poron (ttsB os), 11,100 mg/I, of sodium (Naoll and 20 mg/L cesium (introduced as CsN0.), and introduced as cobalt (Co(No-)t, 68-0) at 9rng/L An aqueous solution containing The Beha value of this test solution was 8.0. . Residence time in the test was approximately 1 minute. The species examined in the test were cesisomum (determined by flame) and cobalt (determined by DC plasma spectroscopy) Met. Table 6 shows the test results for each porous glass composition.

Ja SA 800 903 1b A 650 790 7N337432 7 SA 845 t]2 8 SA > 900 274 9 SA 769 329 10 SA 762 675 II SA 874 F7 According to these results, sodium nitrate, sodium ammonia, or ammonia Of the glass compositions treated solely with zirconium oxide or Glass compositions containing additives such as alumina should not be melted together or exposed to acidic additives. Added by extraction in solution, the ion exchange capacity of this glass composition is significantly higher than similarly treated glass compositions that were not previously added with additives. It turned out that something was wrong.

Furthermore, according to these results, additives were added and then alkali metal salts and alkali metal anhydrides were added. When treated with a main ion exchange solution containing monia or ammonia alone, the ion exchange The conversion capacity is improved, and the favorable effects of the two treatments do not suppress each other. I can see that we strengthen each other. Finally, when comparing the results of Experimental Example 4, we find that porous gas Control the formulation of the glass composition (by controlling the ionization of the glass composition for various ions). It was found that it was possible to control the exchange capacity.

Experimental example In this experimental example, an actual radioactive water flow and the chemical composition of this water flow were simulated. Porous ion exchange compositions used in removing cesium from simulated water streams In order to express and compare the performance of various porous glass compositions, the tests An organic ion exchange resin was also used. This resin is Dowex HC R-S strongly acidic cation exchanger (nuclear grade, hydrogen form, 8% crosslinked, -20+50 dry Sigma Chemical Co., Missouri, St. Louis (published by Rikitae et al.).

Table 7 shows the formulation of the solutions used in these tests.

Solution pu concentration (mg/1.) 6.4 6.2 9.4 Na 0.023 0. 068 2.097K O, 0020, 0?7 0.005Ca 08001 0.024 0.004CI O,0020,0292,586So, 0,0 14 0.002 0.05 ONOs < 0.001 0.007 0.10 0BOs 0.480 5.387 5.818Cs-137,! 34 Activity uci/L 0.50 0.55 1.05 Solution l is a pressurized water power reactor (P WR) Created by simulating typical blended components contained in wastewater from nuclear factories. Ta. This Solution 1 was doped at the actual level of Cs-137 activity.

Solutions ■ and ■ were actual samples of wastewater from a nuclear factory.

Descriptions of test column operation, influent and effluent analysis, and data processing are as described in the previous example experiment. It is almost the same as Ming. The volume of the ion exchange composition used for the pillar is 0.3-15mL was within the range. Cesium levels can be measured using sodium iodide detectors and multichannel Determined by Nell analyzer. The test results for the pillars are shown in Table 8.

Table 8 Re 1 last 1 ion exchange! Law 1Qtill S-Sufu customer P cv (minutes) DF】ODF2 +2 SA　O,64,00010,0007SA　O,619,00024 ,000n HCR-S 2.7 150 2S＾　4. +1010 7 SA 3.4 >1370 IHCR-S 6.0 10 2 SA 8.5 100 ? SA 8.4 340 According to these results, in all cases sodium with zirconium oxide additive The Cs capacity of the exchanged porous glass composition was determined by sodium exchange without additives. It is considerably higher than that of porous glass compositions and is widely used for cesium removal in the nuclear industry. It was found that the Cs capacity was even higher than that of the nuclear grade strongly acidic cation exchanger used. did.

Suitable for drying porous ion exchange compositions used in removing radioactive species from fluids dried, incorporated into various solid base compositions, melted again in the presence of additives, or compressed By uniting, radioactive species can be immobilized and sealed.

Experimental example 7 In this example, a porous glass composition co-fused with ruthenium oxide as a catalyst. performance is shown.

Glass composition 2 without additives, with additives co-fused with ruthenium oxide Each sample of the glass composition was crushed according to the method described in Experimental Example 1-3. d. Sieved, heat treated, extracted, washed and dried. Then each glass composition The catalytic activity test of 1 volume of O, saturated with argon for 24-30 minutes j　M　20-30mg of glass composition in Ce(NB+)t(NOs)s aqueous solution is stirred and a Parian nirograph (Varfan Aero graph) ・Using gas chromatography and thermal conductivity detector, catalytic acid This was done by measuring the amount of hydrogen generated by an aqueous compound solution. Kiwi vi), by Gratzel and Chj*ia According to U.S. Patent 1 each, 2g9-292 (1979), Rub, to Ce'° It is known that aqueous oxide solutions are effective catalysts. Glass composition 14 The amount of hydrogen generated in the case is 8.0 micromol per duram of glass composition. I observed something. On the other hand, the amount of hydrogen generated in the case of glass composition 2 is It did not exceed 0.6 micromol per duram of the composition. Based on these results For example, the active Ru5 of a porous glass composition made from a melt containing ruthenium oxide The catalytic activity properties of t were significantly improved, while porous gas containing no ruthenium oxide The catalytic activity of the lath composition is not significantly improved.

Experimental example 8 In this experimental example, a porous glass fabricated according to the method described in Experimental Examples 1-3 was used. Performance of compositions and transition metal oxides as ion exchange media when separating rare earth mixtures Compare the performance with and without additives.

The separation method chosen when testing the glass compositions yields a highly transparent lanter. Optical fibers containing oxides as main components and optical fibers containing fluorides as main components Neodymium, which is strongly light-absorbing and undesirable, was removed. Lanthanum also contains oxides It is more effective than neodymium in the main superconducting material.

The contaminant removal coefficient DF is the La:Jid ratio of the solution flowing into the column, that is, the inflow liquid from the column. It is obtained by multiplying by the corresponding ratio of the effluent solution or effluent.

In the case of this experimental example, the test solution was about 1c+omg/l of La and 10hg/l. An aqueous solution containing L of Nd was employed. Both La and Nd are rare earth elements, and an aqueous solution of nitrate Added as. This aqueous solution was acidified with nitrate to a Beha value of 1.3. Te The remaining time at the stop was approximately 30 minutes. Testing of two glass compositions shown in Table 1 The results are given in Table 2.

Porous ion exchange composition 3-SA containing zirconium oxide additives is composed of La to Nd (10CV with a DF of at least 2), and is also effective in removing transition metals. Glass composition containing no oxide additive]-3A has a large separation capacity for rare earth separation. It can be concluded that the amount is not indicated.

8 0.20 0.25 0,9 0.05 (0,05>110 5.0 9 ．． 1 0.6 <0.05 0.05 <112 156 121 1.4 0 ．． 2 <(1,1>2I4 173 205 0,9 0.5 <0.1)5 16 166 180 1.0 2.6 <1) 3Ht 169 163 1 ．． 2 216 50.1 4.822 134 129 1.2 213 24 3 1.0 Influent 95.9 IO2,595,9107,5 Experimental example 9 In this experimental example, the method explained in Experimental Examples 1-3 was followed when separating the rare earth mixture. The performance of some porous glass compositions containing metal oxide additives was Contrast.

As in Example 8, this test procedure was designed to separate neodymium from lanthanum. It is. In this case the influent is chosen more practically with respect to lanthanum purification, i.e. contains a low concentration of Fld of about 50 mg/L in the presence of a high concentration of La of about 2/+mL. It was This influent is not oxidized and has a pH value of 3.8±0.3 in both cases. Met. Residence times were 49 and 7 in all but one case. test results is given in Table 10. Separation capacity is defined as the cV value when the DP value is 10 or less. It will be done.

The main conclusions based on these results are as follows.

a. Rare earth of compositions without ion exchange treatment (glass compositions 2-N and 3-N) The separation capacity for class separation was not very good.

b, Separation capacity of glass composition containing ZrO and additives for La/Nd is ZrO , increases as the content approaches about 12%. ZrO, increases further However, the separation capacity will not increase any further.

Separation capacity and 1 contaminant removal of glass composition containing 13 percent c, Tie, The coefficients are not significantly different compared to glass compositions containing the same amount of ZrO. H The separation capacity and contaminant removal factor of a glass composition containing 6 percent r-islands is 6 percent. It is almost the same as the glass composition containing ZrO.

d. As expected, the contaminant removal coefficient increases significantly as the residence time increases. be done.

22-5A 15 23-N Q 23-SA + 2 24-SA 13 25-SA 22 26-8^〉24 27-SA 20 28-8＾　1゜ Although the present invention has been described in detail with reference to particularly preferred embodiments, the present invention is not limited to the following claims. Technically, Ii! ! It will be understood that this includes design changes included in the concept.

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Claims (20)

[Claims] (1) Allow the solution to pass through an ion exchange composition to remove rare earth ions and actinides in the solution. separating the ions or mixture thereof and passing the solution through an ion exchange composition; of the ion exchange composition. The ion exchange composition has a surface area of about 5-1500 m2/g and a pH value of about 9 or higher. In the above range, an alkali metal cation, a Group 1b metal cation, an ammonium cation; pre-impregnated with a liquid containing organic amines, organic amines, or mixtures thereof. A method for separating rare earth ions, actinide ions, or their mixtures from liquids. (2) at least about 0.2 mole percent of a metal oxide or metal oxides or hydrated metal oxides, metal oxides or hydrated metal oxides are Group 3a, Group 4a, Group 5a, Group 6a, Group 7a, Group 8, Group 1b, Group 2b Group transition metals, aluminum, gallium, indium, thallium, tin, lead, bis gold selected from the group consisting of mass, beryllium, actinides, and mixtures thereof; 2. The separation method according to claim 1, wherein the oxide is an oxide of the genus oxide. (3) A patent application in which the ion exchange composition is a porous glass or silica gel composition. The separation method described in item 1 of the scope of the request. (4) Metal oxides or hydrated metal oxides include titanium oxide, zirconium oxide, a patent claimant comprising a material selected from the group consisting of hafnium, thorium oxide or mixtures thereof; The separation method described in item 3 of the scope of the request. (5) about 2 to about 35% of the metal oxide or hydrated metal oxide in the porous glass composition; 2. The method of separation according to claim 2, which comprises molar percent. (6) Ion-exchange a solution containing rare earth ions, actinide ions, or a mixture thereof. 2. The separation method according to claim 1, wherein the separation composition is passed through a column containing a deconcentrating composition. (7) Rare earth ions contain lanthanum and neodymium, and these two rare earth Any of claims 1 to 3, at least one of which is substantially separated from each other. The separation method described in item 1. (8) In the patent claim, the lanthanum is purified to contain about 0.1 ppm of neodymium. The separation method according to scope item 11. (9) 40-80 mole percent silica and the lower two rows of Group 8 of the periodic table; Up to 10 mole percent transition of one or more selected from the group of rhenium base glass from melts containing metal oxide additives or precursors of oxide additives. The process of creating a base glass composition and heat treating the base glass composition to at least melt the base glass composition. The process of separating the soluble coffin and the non-dissolvable phase, and extracting the soluble phase to form a porous glass. at least 50 moles of porous glass composition. per cent silica and a sufficient amount of oxide additives to form a porous glass assembly. at least one transition metal acid whose composition exhibits a catalytic activity indicative of the presence of the additive; A method for making porous silicate glass compositions containing chemical additives. (10) The process according to claim 9, wherein the oxide additive is ruthenium oxide. Enacted law. (11) Groups 3a, 4a, 5a, 68, 7a, and 8 of the periodic table Group 1b, group 2b transition metals, aluminum, gallium, indium, tantalum lium, tin, lead, bismuth, beryllium, actinides, and mixtures thereof. The metal oxide or hydrated metal oxide selected from the first group containing at least about 0. 2 mole percent and alkali metal cations, Group 1b metal cations, ammonia at least about 0.3 mole per centium cation, organic amine, or mixture thereof. - a porous ion exchanger with a surface area of approximately 5-1500 m2/8 Glass or silica gel composition. (12) The porous glass composition contains 40-80 mole percent silica and a second group consisting of transition metals of groups 4a, 5a, 6a, 7a, 8 and actinides; 0.2-35 mole percent of one or more transition metal oxides selected from A process of creating a base glass composition from the melt, and a process of forming the base glass composition by heat treatment. separating the soluble phase into at least a soluble phase and an insoluble phase; 0 mole percent and preferably at least 0.2 mole percent transition metal By a production method comprising a step of producing a porous glass composition containing an oxide. An ion exchange composition as claimed in claim H. (13) The porous glass composition contains 40-80 mole percent silica. A step of melting the present glass composition and a heat treatment to reduce the base glass composition to at least A step of separating into a soluble phase and an insoluble phase, periodic table Nos. 3a, 4a, 5a, 6a, 7a, Transition metals of groups 8, 1b, 2b, aluminum, gallium, indium, thallium , tin, lead, bismuth, beryllium, and a solution containing one or more salts of actinides. and extracting the soluble phase and processing the phase-separated glass composition. The ion exchange composition according to claim 11, which is prepared by a method. (14) The porous glass composition contains 40-80 mole percent silica. The step of melting the present glass composition and the step of heat treating the base glass composition to at least melt the base glass composition. The process of separation into solvable and insoluble phases, alkaline earth metals, periodic table Group 3a, Group 4a, Group 58, Group 6a, Group 7a, Group 8, Group 1b, Group Group 2b transition metals, aluminum, gallium, indium, thallium, tin, lead, one or more selected from the group consisting of bismuth, rare earth metals and actinides; Even in solutions containing the above additive elemental salts and having a pH lower than about 4, the phase-separated glass remains. a treatment step for treating the base composition, the treatment step extracting the soluble phase from the soluble phase; The patented method involves introducing additive elements into the porous glass composition at the same time as the porous glass composition. The ion exchange composition according to claim 11. (15) The base glass composition includes oxide additives from the first group or from the first and second groups. 0.5 mole percent and 40-70 when selected from the group of mole percent silica and the oxide additive is selected from the second group. 0.05 mole percent and 40-70 mole percent silica. A unique ion exchange composition. (16) The transition metal is titanium, zirconium, hafnium, aluminum or 12. The ion exchange composition according to claim 11, comprising a mixture of. (17) treated with one or more surfactants such as organosilanes; It is then treated with one or more species and obtained from groups 3a and 4a of the periodic table. Group 5a, Group 63, Group 7a, Group 8, Group 1b, Group 2b transition metals, Aluminum, gallium, indium, thallium, tin, lead, bismuth, beryllium a metal oxide selected from the first group consisting of actinides, actinides, and mixtures thereof; or containing at least about 0.2 mole percent hydrated metal oxide and having a surface area of about 5-1500 m2/g of organic stationary phase, enzymes, catalysts, chemical reagents or indicator dyes. Porous active ion exchange glass or silica gel compositions that can be used as materials. (18) A porous ion exchange composition containing the additive according to claim 11 is brought into contact with a liquid. Desired ions are removed from the liquid by ion exchange on the surface of the porous ion exchange composition. A treatment method that removes the minerals. (19) The treatment method according to claim 18, wherein the ions are toxic ions. (20) The treatment method according to claim 18, wherein the ions are radioactive ions.