• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    A molecular glass based upon a phosphate of aluminum, or other trivalent metal, provides significant improvement over prior art glasses for encapsulation of high level radioactive nuclear waste. When containing a controlled amount of those elemental oxides found in a typical nuclear waste, the waste-glass would not devitrify under conditions which produced devitrification in the non-nuclear-waste-containing glass, exhibited hydrolysis losses lower by an order of magnitude, had high solvency power for those elemental oxides, exhibited little tendency for internal crystallite formation, and possessed other desirable physical characteristics, all in direct antithesis to the properties of the best prior-known glasses used for this application.
    公开号:SU1087091A3
    申请号:SU802964750
    申请日:1980-08-13
    公开日:1984-04-15
    发明作者:Си Ропп Ричард
    申请人:Ричард Си Ропп (США)；
    IPC主号:
    专利说明:

    The invention relates to the treatment of radioactive waste, mainly to the technology of solidifying nuclear waste with a high level of radioactivity by incorporating them into poorly soluble materials to ensure long-term and reliable storage. The known method of radioactive radioactive waste curing by introducing a dry residue of radioactive waste into a phosphate glass melt 1. The disadvantage of this method is that the radioactive waste included in glass is a heat source due to naturally occurring processes of radioactive substances division. In the cured glass, temperature rises to the limit, after which the declassification process occurs, i.e. microcrystals are formed in the body, the mass becomes brittle, disintegrating and unsuitable for long-term storage. The closest to the invention in technical essence and the achieved result is a method of nuclear waste with a high level of radioactivity for long-term storage, including the preparation of a melt of phosphate glass, the introduction of solid high-level radioactive waste into it, the formation of blocks from the melt and their cooling glass has the formulas Na205 P, j Oj SiOj AljOj C2. The disadvantage of the known method is that the phosphate glass used does not dissolve the refractory oxides of highly radioactive waste, and the insoluble crystals of radioactive waste oxides recrystallize and grow. When the melt solidifies, they form centers of internal deformations, as a result of which cracks develop in the glass and it becomes brittle and unreliable for storage. The aim of the invention is to increase the reliability of storage of solidified waste. This goal is achieved in that the composition for solidifying phosphate glass-based radioactive waste contains a polymeric phosphate glass of the formula P. (70), where M is a trivalent metal selected from the group consisting of aluminum, indium and gallium. According to the proposed method of solidifying radioactive waste for their long-term storage, including the preparation of phosphate glass melt, the introduction of solid high-level radioactive waste into it, the formation of blocks from the melt and their cooling, they take polymeric phosphate glass precursor crystals having the formula MD0 (MRO), where M is trivalent the metal chosen from the group including aluminum, indium and gallium is shifted from 4-47% by weight of highly radioactive waste to 100% by weight of the mixture, the mixture is heated and contained in the vomited temperature 1200-1500 ° C to obtain the desired degree of polymerization, in the melt forming step used as precursor of the formula M () j. Before adding crystals to radioactive waste, the precursor crystals are additionally washed until complete removal of phosphoric acid. Before being mixed with radioactive waste, the precursor crystals are heated to form calcinate. In the melt forming stage, the precursor crystals are heated to initiate solid phase polymerization and form a first melt, the melt is cooled, milled to form a glass frit and the glass crystalline mixture is heated to form a second melt. The technology for the curing of highly radioactive waste consists of the following. The precursor compound), where M is a trivalent metal, is selected from the group consisting of aluminum, indium and gallium. The total content of impurities should not exceed 300 ppm. If required, the precursor crystals can be washed to eliminate excess phosphoric acid. Highly radioactive waste (BPO) is added to the crystals, then the mixture is heated at a controlled heating rate to initiate solid-state polymerization and form at 1350 ° C melt in which BPO oxides rapidly dissolve. 110 When using aluminum, the resulting BPO-polymerized aluminum phosphate (PAF) -glass has a hydrolytic leaching rate in boiling water approximately 15.8 times less than the CPO-borosilicate of zinc (BSC) -glass. The melt decomposes all the components of BPO, the formation of crystals in the melt or in the final glass product is not observed. The softening temperature of BPO-PAF-glass is 650 C. It has a high thermal conductivity, a low coefficient of thermal expansion, which becomes more negative at temperatures, has a low radiation absorption cross section, and does not require thermal annealing to relieve internal stresses during casting. melt to form glass, similar to other known glasses. In another embodiment, BPO may be mixed with the precursor crystals formed in combination with the phosphate form of the acid to form BPO-phosphate compounds before the precursor crystals melt and then the BPO glass composition is prepared. Another method, which makes it possible to obtain very stable BPO-glass, involves the preparation of a solid preburner substance by burning the precursor crystals to form calcinate, to which BPO is added. Then, at 1350 ° C, a melt is formed, which is subsequently cast to produce a stable BPO glass block for long-term storage. Another option is to form a polymerized melt from the precursor crystals, followed by pouring the melt and forming glass to form a glass frit. The frit softens at 850 ° C and BPO quickly dissolves in the melt with the formation of solidified BPO-glass block, intended for long-term or permanent storage. The glass composition used to validate nuclear waste according to the invention has the formula or M (PO-).,. The glass can be soee e „.., the dinyn of one of the formulas or a mixture of two compounds. 1 Connection. M (POj) is obtained by a bundle of solid-state polymerization, examined above, for a longer time or by precipitation of soluble salt and metaphosphoric acid from purified solutions. - A high degree of chemical durability of non-silicate glasses like phosphates, sulphates etc. is not achieved unless first forming the precursor as a separate phase, which is heated to initiate solid phase polymerization of the said phase to form a melt to form a polymerized glass. For the curing of nuclear waste with a high level of activity, polymerized aluminum phosphate with a high degree of purity is required. The precursor compound is prepared by dissolving the aluminum compound in an excess of phosphoric acid. A (OH) j is preferred as the source of aluminum, although other aluminum compounds may be used. It is important to maintain a certain molar ratio of H, PO in the solution; The minimum ratio is 6: 1, the maximum ratio is 9: 1. Best results are obtained at a ratio of 7: 1. Higher ratios contribute to the accelerated dissolution of A2 (pH) j, which can last 3-5 days at a 6: 1 ratio. After purification of the resulting solution, controlled evaporation is used to obtain the precursor crystals (A (H2P (), Crystals with high crystallinity and regular morphology), then washed with an organic solvent, for example methyl ethyl ketone or ethyl acetate (but not only these solvents), to remove excess HjPO with obtaining monobasic crystals not contaminated by impurities. A large excess of NARO during evaporation affects the formation of precursor crystals, preventing the appearance of aluminum phosphates that are not subjected to solid phase polymerization when heated to temperatures below. Table 1 shows the composition of the precursor crystals used to obtain the proposed polymer glass.
    Impurity
    million
    Table 1
    million 1 Impurity 1 ml
    Impurity
    The glass product obtained by heating the precursor crystals and em is a new stoichiometry. The washed and dried crystals contain,%: A "() 3 98.33; H PO 0.05; 1.62. When the precursor crystals are heated in the container, by the time the temperature reaches 175 ° C, all absorbed water is lost. At 210C, the removal of three constitutional water molecules begins, which stops at, in accordance with the reaction scheme inAI (H2PO) (P03) 3H20f, H where m is the initial degree of polymerization, m 1-4. At a temperature of about 870 ° C, a small amount of excess phosphoric acid in the form of 7HjPO x X3H20 is lost. If a prebaked substance or calcinate is required, the temperature of 1100-1150 ° C is maintained for several hours. When the temperature is higher than IZOO C, a loss is observed according to the reaction scheme, H "ez tzP7 ° 22 -P2 ° 5-2. Loss of P205 Accelerates at temperatures above the melting point of 1325-1350 and ends to. If the temperature is maintained at the melting point, the loss continues until the final stoichiometry is reached, given in reaction (2). With a polymerization time of 30 hours or more, the stoichiometry starts to change and crystals appear in the melt in accordance with the reaction scheme / i.e. (POjy tnAepo. (3), 0.2 Thus, the composition of glass suitable for use can be represented by compound A (POj), as well as their mixtures, depending on the duration of polymerization. The precursor containing about 4,000 million with esey, analyzed by thermogravimetric method comprises,%: At (H2P04) a 98,14; H20 1.84, when heated it gives steklosostav polymerization for 16 hours Kristallpredshestvennika of unwashed batch contains,%: AfCHjPO).. 68.80-, 10.19; NzR0421,01. Its behavior during thermal decomposition is identical to the above. Thus, the reaction is not affected by the level of impurities or the presence of excess phosphoric acid. Glass composition can be obtained by precipitating AtCPO) from a soluble salt and metaphosphoric acid, followed by calcining the product. The following precipitation reactivity scheme (NO lj + SKPOj (POj) j4 -3HNO ,. (4) Salt solutions tAt (NOJ), j and metaphosphoric acid must be dbiTb purified, with impurity levels not exceeding 300 ppmX Although HPO is well soluble in water, prone to hydrolysis to HjPO, it is very difficult to regulate the reaction (4) without introducing other undesirable aluminum phosphates into the melt. In addition, contamination with an anion, in this case nitric ion NOj, interferes with subsequent reactions during the separation, drying At (PC) j and heating. The worst possible methods to use are combining and H, P into a solid mass, burning of the mass of fusion and its rapid cooling. The resulting glass is subject to nucleation of recrystallization and is a very slowly water-soluble dehydrated phosphate, suitable for water purification. If the intermediate is not isolated and if it is not of high purity , the improved product according to the invention cannot be obtained. The products obtained according to the known inventions are not sufficiently stable in terms of recrystallization and not sufficiently resistant to hydrolytic pickling with boiling water. It is advisable to isolate the monobasic precursor, burn it to the pre-calcined calcinate and then form a glass melt. And it is known to use 3.00 mol H, PO, per mole of aluminum salt, but even at the proposed ratio (7.00 mol mol of aluminum salt) and roasting the mixture, the quality of the glass product is not improved. The glass obtained by melting the separated precipitated product, A1 (PO3) 3, is of lower quality than the invention. The physical properties of the proposed glass, AtaP-CL-, are as follows: glass transition temperature, Td, s 790 Softening temperature, Tdr, ° C 820 Deglaring temperature, T, 1050 Melting point, Td. An endothermic peak is observed, which is conjugated to Tgp, which corresponds to the warmth of softening. For Nlr is 200 cal / mol. Its thermal conductivity is high and is 0.53 cap cm / S / cm / s at 100 ° C, 1.28 cal / cm / C / ctf / s at 250 ° C and 2.57 cal / cm / S / cm / s at 500 ° C. At 750 ° C (the expected internal temperature for BPO is glass), the proposed glass dissipates about 13.8 kcal / cm / h of energy, or almost 14.9 kW per square foot of surface per hour. The expansion coefficient of the proposed glass is low compared to the known and more closely matches the similar coefficients for the metal containers used for storage. When a frit melt is obtained in a metal crucible, the expansion coefficient is estimated by carefully observing the glass produced at a particular temperature and determining the effect of temperature change on it. Above the rapid cooling temperature (eacalki), the expansion coefficient becomes negative (to), which is confirmed by an increase in the gap between the crucible wall and the glass block. Below 275 ° C, glass has a positive expansion coefficient, from 30x10 to 45x10 inch / inch / s. The negative expansion ratio is from -7x10 to -11x10 inches / inch. Thermal expansion can be controlled to some extent by changing the polymerization time. A negative expansion factor is a valuable property of glass that is reheated with nuclear waste. As the metal container expands, this glass is compressed, resulting in the elimination of external stresses that can cause cracking of the glass block. Adding a synthetic mixture of chemical oxides to the melt A. quantities, modeling additives -BRO, revealed the following. BPO-PAF-glass is not subject to devitrification of B to any conditions (this is detected. It has been visually and repeatedly confirmed by differential thermal analysis methods — an analytical method for studying the thermal behavior of glasses), which is due to two factors — the chemical composition of BPO and the amount added. (minimum). The presence of molybdenum appears to be one of the factors influencing the characterization of the BRO-PAF typeglass combination. The compounds listed in Table 2 are oxides or decompose to oxides when heated. The overall composition is similar to that of standard synthetic waste, i.e. FW-7a I (instead of actinides, K20 (KOH) instead of Cs and Pb and MpO, instead of Hot, this mixture of Tc, O, and RuO.) Is non-radioactive in nature, and its chemical properties are identical to those of the radioactive mixture resulting from division processes in a nuclear power plant. . When added to the PAF glass, BPO-PAF-glass conductor does not de-tarnish at a ratio of 20 wt.% BPO-80 wt.% PAF glass. At a content of less than 10 wt.% BPO, the de vitrification takes place in the form of a slow process with the formation of microscopic flakes on the surface of a glass rod heated to within 36 hours. Minimal. is about 5% BPO, i.e. 5% BPO, 95% PAF glass to form a non-glassy BPO glass composition. If a rod of 20% BPO - 80% PAF is heated in an alumina bath for 96 hours at 1500 ° C, it sags and de-vitrification does not occur, although heat treatment should accelerate the kinetics of the solid-phase de-vitrification about 2.1 million times.
    Table 2 shows the typical BPO composition (composite mixture) used to model typical waste with a high level of radioactivity.
    Table 2 The loss of VRO-PAF glass as a result of hydrolysis depends on the duration of polymerization. This dependence is linear and satisfies the equation Wi 0.0473t -0.799, (5 where Wt is the mass change, 10 t is the polymerization time, h. At a polymerization time of 4 h, a loss of 0.61x10 is observed in boiling water, while for the polymerization time 24 h, an increment of 0.33 x 10 was determined.According to the equation given, a polymerization time of 17 h should give a zero mass change, the result of checking the loss is 1.91 x 10 g / cm / h (4.6 x X 10 g / cm / day), which is approximately 15 times lower than that of VRO-BSC-glass. These results are obtained by measuring the physical dimensions of the glass rod when immersed in boiling water for 96 hours. These data were obtained for a BRO-PAF-glass rod in which the glass was polymerized for 17 hours at 1350 s before the melt was opened. Table 3 shows the effect of the drying time on the mass changes observed for BRO-PAF glass polymerized for 17 hours. Table 3 The surface of the BPO-PAF glass becomes hydroxylated and the actual weight loss (or gain) is actually zero (at a polymerization time of 17 hours). The data of Table 3 agrees with the exponential decay equation, starting with a drying time of 1 hour. The statistical agreement is 97% and the resulting equation has the form Wt 0.370 exp - 0.0233 t. (6 Extrapolating the increase from 72 hours to one week gives 7.4 x 10G g / cm / h, t for 2 weeks - 1, and for 4 weeks - Wt 5.9 x 10 g / cm / h (final weight loss). Thus, the change in the increase observed for the glass rod is reversible and caused by boiling water. The change in mass is then balanced, eventually returning to its original value, i.e. the wife is only on the surface of the glass, but it returns to its original state after being removed from the boiling water. This proves that the change in the glass matrix is actually zero according to the experimental equation (5) for a polymerization time of 17 hours. It is also a function of the polymerization time. The data obtained were obtained at 350 ° C. It is also possible to melt the BPO-precursor mixture with a subsequent change in the temperature of the melt in order to accelerate or reduce the polymerization process. To obtain a glass surface free from the effects of hydrolytic etching, it is necessary to melt the melt for 17 hours at 13 SOС at 1450 ° С, this only takes 4 hours, and at 1250 ° С 44 hours. When the temperature of the melt drops to 1200 ° C the required degree of polymerization of the melt in the presence of BPO increases to 153 hours (about 6 days). Thus, to achieve the required degree of polymerization in order to increase the resistance of the glass surface to hydrolytic etching, higher temperatures are preferable. Below are the experimental equations related to other temperatures: 1200 ° С 0.0052 t - 0.797 (7) 1250С 0.0183 t - 0.798 (В) 1450 ° С 0.188 t - 0.800, (9) wt where t is time. In another embodiment of the method, the preparation of glass is carried out separately from BPO and provides polymerization in the course of the required time. The resulting glass frit is mixed with BPO in the required proportion. The mixture is then heated, whereby the glass softens at 850 ° C and starts dissolving BPO. The melt is kept until the dissolution process is completed, and then cooled. BRO-PAF glass is formed for long-term storage. The weight, changes attributable to the hydroxylation of the glass surface are affected by specific methods of preparing BRO-PAF-glass. Table 4 presents the results of the influence of the method of preparation of BROTPAF glass (96 h in boiling water) on the resistance to surface hydroxylation ().
    13
    20 20 20 20 20
    High
    High 72
    20 The data in Table 4 show that pre-stage calcination gives the best material for melt production; the conversion of BPO to phosphates helps to approach zero weight loss, and cleaning the precursor crystals gives BPO-PAF glass with essentially no weight change, i.e. 1.6 x 10 g / cm / h or 3.8 x 10 / cm 2 / day as an increment (as the surface continues to dehydroxylate, the increment returns to zero). The properties of molecular glass are manifested by the encapsulation of BPO. The melt dissolves all metals, including noble metals (Pt), very medically, but Rh and Pd dissolve quickly. All oxides or compounds that decompose are dissolved.
    1087091
    1A Table 4
    0.61
    0.14
    0.10 by the development of oxides, including refractory oxides CeOj, Zr02 and EiOd. Formation of crystals has not been observed for some time due to the addition of BROB additives if the polymerization time does not exceed 36 hours when AtPO crystals are formed. The melt has a low viscosity (about 180 mP). The amount of BPO additives can vary from 4 to 96 wt.% Of the glass weight, the upper limit is about 47 wt.% Of BPO and 53 wt.% Of glass. It is preferable to use about 20-25 wt.% VRO additives. The present invention consists in using a novel polymerized molecular phosphate glass for solidifying nuclear waste with a high level of radioactivity in order to bury it. The data and results reported relate mainly to an aluminum-cationic type of glass. Two tervalent cations that can replace aluminum, I AM ;. indium and gallium, however, these materials are more expensive than one and also have a larger neutron capture cross section than aluminum. The aluminum used also has a lower nuclear capture and absorption cross section compared with indium and gallium and with known zinc glass: Icate (BSC) glasses. The transparency of the nuclear particles reduces the likelihood of radiation damage to the molecular structure and reduces the increase in thermal energy. Example 1 In order to prepare the precursor compound is measured. 970 ml of 85% .JUD. weight 1,689 g / s. f chemically pure (lower grades are possible), and added to 1000 ml of water. Dilute to a total volume of 200 ml. Weigh out 156, O g AE (OH) j and dissolve it in a solution of HjPO. In order to obtain a clear solution, heating may be required. 5.0-10.0 g of 1 -pyrrole din-dithiocarbamate ammonium (APC) is weighed out, dissolved in 50 ml of water and added to the solution. Dark gray precipitate is filtered off using a 0.45 μm filter. Adjust the electrolytic apparatus with the mercury bath and conduct the electrolysis of the solution in a nitrogen atmosphere at 2.90 V (at a constant current) on the mercury bath for several hours to remove residual impurities. To remove most of the impurities, a minimum of 2 hours is required. Slowly evaporate the purified solution using a heating source to obtain precursor crystals in combination with a liquid. Liquid contains excess naro. The crystals are washed using methyl ethyl ketone as a washing agent. The washed and dried crystals are collected. Add 20.0 g of BPO additives per 96.5 g of crystals (estimated yield of 83.0%); all the mass used must fill the container for heating. Heating at a speed of 10-12 C / min. causes initial dehydration and polymerisation. As the temperature rises to 1350 ° C, a melt is formed, the bale of 10 116 ka of which is about 80%. A larger amount of the VROcrystals mixture is added until the container is filled with melt (this takes about 1 hour). The melt is agitated for another 16 hours to achieve a suitable degree of polymerization, and then it is poured into a suitable form with the formation of the final BPO-CFA glass container for long-term storage. Burning is not required, but for large pieces, minimum burning may be required. The firing of molecular glasses is performed at a temperature of 8-18 ° C above the softening point. EXAMPLE 2 A precursor compound was prepared analogously to example 1, however, BPO was added at the time the firing started. The precursor crystals are heated separately (speed l f, about 10 ° C / min) to 1100 ° C, and then incubated for several hours with the formation of calcinate in the form of powder. The partially polymerized powder is cooled and mixed with BPO in a ratio of 80.0 g of powder and 20.0 g of BPO additives, heated to form a melt that is kept at this temperature for 17 hours to complete polymerization, and then poured into a final form for a long-term storage. . Froze Another variant of the process is that the precursor crystals are heated to initiate polymerization and then to obtain a melt. Then the melt is poured and cooled. The glass is ground to obtain a glass frit, which is then used to solidify the BPO additive according to the procedure of Example 2. In this case, the frit softens at 850 ° C and becomes liquid at. The melt is used to cure BPO additives. When the final molding container used for long-term storage fails to withstand the effects of elevated temperatures that are necessary to obtain a direct melt, lower temperatures can be used according to the proposed method. Example 4 The procedure is similar to that described in Example 1, however, to remove the excess. the crystals are not washed. A part of the crystals are analyzed to calculate their weight in combination with phosphoric acid, necessary to obtain a ratio of 0.20% BPO-0.80% PFA glass by weight. BPO added before heating forms phosphates. When heated, the formation of phosphates is accelerated and completed by the time the temperature of the melt is reached. The formation of BPO-phosphates accelerates the dissolution of BPO in the melt and promotes their dispersion. EXAMPLE 5 The procedure for the preparation of each calcite is similar to that described in Example 2. BPO supplement and H.RO are added in a ratio of 207 ml of 85% BPO supplement per 100 g. The BPO-HzP04 mixture is thoroughly mixed before adding to the calcinate and then the final mixture is heated according to the procedure of Example 2 to form a melt to obtain a composite of a glass of 0.20% BPO - 0.80% PAF glass intended for storage. EXAMPLE 6 If glass frit is used, the technique is similar. described in examples 3 and 5. The difference is that they are mixed with BPO additives before adding to the glass former and carefully heated to 100-150 ° C to initiate foaming and phosphate formation. After the formation of phosphate BPO-phosphates is added to FFA-glass frit with the formation of the composition about, 20% BPO - 0.80% PAF-glass. The mass is heated at a rate of 8-10 C / min until the frit size rushes. Heating is continued until IIOO-IISO C, after which the melt is released for several hours until the BPO additive is dissolved and dispersed. Then the melt is cast and the procedures indicated in the described examples are repeated. Example7. The examples described cure using the static or single-container method. There are several options for ensuring a continuous process. A glass melting furnace, continuously operating at 1400, is used. These furnaces typically consist of a preheating chamber, a melt chamber and a storage tank. The inner surface of each chamber is lined with impermeable alumina (high density), which is the only material sufficiently resistant to extremely corrosive melts. A mixture of BPO-add1. and the precursor crystals are introduced into the preheating chamber to form a melt. As the volume increases, the melt moves to the melt chamber, and then to the holding chamber. BPO-phosphates are added simultaneously with PAF-calcinate, increasing the amount of melt until a ratio of 0.20% BPO to 0.80% PAF-glass in the final product is obtained. The transit time of BRO-PAF glass should ensure a sufficient degree of polymerization before the glass casting is formed. The rate of addition of the BPO calcinate powder is controlled according to the dimensions of the furnace used, according to a polymerization time of 8-9 hours. The CPO additives are introduced in the form of oxides obtained by drying or calcining liquid highly radioactive waste, or in the form of phosphates obtained by adding HjPO to liquid waste, followed by separation of the deposited radioactive waste in the form of phosphates. The melt can be formed from precursor crystals (unwashed or washed precursor crystals) or PAF-calcium calcium powder. When using BPO-calcinate, it is better to use non-washed crystals containing an excess to convert BPO oxides to phosphates in the preheating chamber of the furnace. If BPO-phosphates are used, then PAF-calcined may be used, which is added simultaneously to the preheating chamber. The BPO-PAF melt glass is continuously drained from the holding chamber of a glass-melting furnace, and the melt stays in the furnace before pouring into a suitable container for long-term storage is 8-9 hours. EXAMPLE 8 When using glass frit under conditions x continuous spreading method is used, which differs from that described in Example 7. VRO is taken in combination with glass frit or. BPO-phosphates in combination with glassfritte mixed in the ratio of 0.20% BPO
    19108709t20
    0.80% PAF-glass frit, but no more, higher than 0.45-0.55 oxide tanks and directly added, which gives a smaller skimmer in the heated container, withstand heat transfer from the furnace. After boiling at 1150 C. The addition of pro-filling of the melt is slowed down so that it is kept at (the total soak time for the formation of the melt melt was about 17 h). It is enough. For a stainless steel container, the capacity is slowly cooled and the speed of addition of steel with steel can be added to long-term storage.
    权利要求:
    Claims (7)
    [1]
    1. Composition for curing radioactive waste based on phosphate glass, characterized in that, in order to increase the reliability of storage of cured waste, it contains polymer phosphate glass.
    [2]
    2. The composition of pop. 1, characterized in that the polymer phosphate glass take the formula or M (PO ^) ^, where M is a trivalent metal selected from the group consisting of aluminum, indium and gallium.
    •
    [3]
    3. A method of curing radioactive waste with a high level of radioactivity for their long-term storage, including the preparation of a phosphate glass melt, the introduction of solid highly radioactive waste into it, the formation of blocks from the melt and their cooling, characterized in that in order to increase the reliability of storage of solidified waste, the predecessor crystals polymer phosphate glass take the formula M ^ P ^ O ^ or M (P.O ^) ^, where M is a trivalent metal selected from the group including aluminum. indium and gallium, mixed with 4-47 wt.% highly radioactive waste per 100 wt.% of the mixture, the mixture is heated and kept in the temperature range 1200-1500 ° C until the desired degree of polymerization is obtained.
    [4]
    4. The method according to claim 3, characterized in that at the stage of melt formation using the precursor of the formula M (H 2 PO 4 ) j.
    [5]
    5. The method of pop. 4, characterized in that at the stage of melt formation before adding crystals to the radioactive waste, the crystals of the precursor are additionally washed until phosphoric acid is completely removed.
    [6]
    6. The method according to claims 3 and 4, characterized in that the crystals of the precursor are heated before mixing with the radioactive waste until calcification is formed.
    [7]
    7. The method according to claims 3 and 4, characterized in that, at the stage of melt formation, the crystals of the precursor are heated to induce solid phase polymerization and the formation of the first melt, the melt is cooled, ground to form a glass frit and the glass crystal mixture is heated to form a second melt.
    类似技术:
    公开号 | 公开日 | 专利标题
    SU1087091A3|1984-04-15|Composition for solidifying radioactive wastes and method for solidifying radioactive wastes
    US4514329A|1985-04-30|Process for vitrifying liquid radioactive waste
    KR850000461B1|1985-04-05|Containment of nuclear waste
    US4464294A|1984-08-07|Process for the stabilization of radioactive wastes
    EP0046085B1|1984-06-27|Method of encapsulating nuclear waste
    US4097401A|1978-06-27|Thermodynamically stable product for permanent storage and disposal of highly radioactive liquid wastes
    Metcalfe et al.2004|Candidate wasteforms for the immobilization of chloride-containing radioactive waste
    WO2010150823A1|2010-12-29|Filtration material
    US4126665A|1978-11-21|Preparation of polymeric alkaline earth metaphosphate glasses
    US4049779A|1977-09-20|Crystalline salt monomers for stable phosphate glasses
    JP2989508B2|1999-12-13|Vitrification of high-level radioactive liquid waste
    US4083728A|1978-04-11|Method for making glass
    Hasdemir et al.1998|Crystallisation of lithium di‐and metasilicate solid solutions from Li2O–SiO2 glasses
    EP2717270B1|2017-01-04|Matrix for immobilising radioactive waste including at least alkaline salts and method for immobilising said radioactive waste in order to obtain the immobilisation matrix
    CA1131004A|1982-09-07|Molecular glasses for nuclear waste encapsulation
    RU2566084C1|2015-10-20|Gadolinium oxide and samarium oxide co-doped aluminoborosilicate glass with high radiation resistance
    Ropp1982|Molecular glasses for nuclear waste encapsulation
    Krak1929|VOLATILITY OF SELENIUM AND ITS COMPOUNDS IN THEMANUFACTURE OF RUBY GLASS 1
    US3694179A|1972-09-26|Method for producing phosphate optical glasses
    SU1597936A1|1990-10-07|Method of neutralizing radioactive waste of variable composition
    Rudolph et al.1972|Lab-scale R+ D work on fission product solidification by vitrification and thermite processes
    KR20180126820A|2018-11-28|Borate glass wasteform to immobilize rare-earth oxides from pyro-processing and manufacturing method thereof
    CN109721242A|2019-05-07|A kind of low-melting glass and its preparation, application method for solidifying volatile nucleic Tc/Re
    Nishi et al.1996|Applicability of V2O5-P2O5 glass system for low-temperature vitrification
    GB2371542A|2002-07-31|Immobilising waste metals in glass
    同族专利:
    公开号 | 公开日
    US4351749A|1982-09-28|
    CA1131005A|1982-09-07|
    EP0043397A1|1982-01-13|
    JPS56169151A|1981-12-25|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US3365578A|1962-08-10|1968-01-23|Atomic Energy Authority Uk|Glass composition comprising radioactive waste oxide material contained within a steel vessel|
    DE2240928A1|1972-08-19|1974-03-14|Gelsenberg Ag|Radioactive waste bonding in phosphate glasses - carried out with recycling of waste gases from vitrification to concn denitration step|
    NL176659B|1972-09-14|Wiederaufarbeitung Von Kernbre|PROCEDURE FOR FORMING PHOSPHATE GLASS, AS WELL AS MOLDED PHOSPHATE GLASS OBTAINED BY APPLICATION OF THE PROCEDURE.|
    US4087511A|1975-11-20|1978-05-02|Allied Chemical Corporation|Glasses prepared by the melting of stoichiometric compounds|
    US4049779A|1975-12-24|1977-09-20|Allied Chemical Corporation|Crystalline salt monomers for stable phosphate glasses|DE3238962C2|1982-10-21|1985-01-17|Nukem Gmbh, 6450 Hanau|Process for the solidification of aqueous radioactive waste solutions containing alkali nitrate|
    US4847008A|1984-04-11|1989-07-11|The United States Of America As Represented By The Department Of Energy|Lead iron phosphate glass as a containment medium for disposal of high-level nuclear waste|
    AT167951T|1992-08-18|1998-07-15|Tech Resources Pty Ltd|STABILIZATION OF RADIONUCLIDES IN WASTE|
    US5461185A|1994-04-19|1995-10-24|Forsberg; Charles W.|Radioactive waste material disposal|
    US5645518A|1995-01-31|1997-07-08|The University Of Chicago|Method for stabilizing low-level mixed wastes at room temperature|
    US5840638A|1996-12-23|1998-11-24|Brookhaven Science Associates|Phosphate glasses for radioactive, hazardous and mixed waste immobilization|
    US5960368A|1997-05-22|1999-09-28|Westinghouse Savannah River Company|Method for acid oxidation of radioactive, hazardous, and mixed organic waste materials|
    AU6831501A|2000-06-12|2001-12-24|Geomatrix Solutions Inc|Processes for immobilizing radioactive and hazardous wastes|
    IL136685D0|2000-06-12|2001-06-14|Gribbitz Arthur|Process for treatment of radioactive waste|
    BR0211833A|2001-08-10|2004-09-21|Ceratech Inc|Composite materials and methods for the manufacture and use of such composite materials|
    US8742195B2|2004-02-26|2014-06-03|Ch2M Hill, Inc.|Aluminum phosphate ceramics for waste storage|
    EP1603641A4|2003-02-26|2010-05-19|Ch2M Hill Inc|Method of waste stabilization with dewatered chemically bonded phosphate ceramics|
    WO2005084756A1|2004-02-23|2005-09-15|Geomatrix Solutions, Inc.|Process and composition for immobilization wastes in borosilicate glass|
    US7550645B2|2004-02-23|2009-06-23|Geomatrix Solutions, Inc.|Process and composition for the immobilization of radioactive and hazardous wastes in borosilicate glass|
    US8115044B2|2006-03-20|2012-02-14|Geomatrix Solutions, Inc.|Process and composition for the immobilization of high alkaline radioactive and hazardous wastes in silicate-based glasses|
    RU2524930C1|2013-03-15|2014-08-10|Федеральное государственное унитарное предприятие "Научно-производственное объединение "Радиевый институт имени В.Г. Хлопина"|Composition for long-term storage of transuranium elements|
    JP6126031B2|2014-03-14|2017-05-10|日立Ｇｅニュークリア・エナジー株式会社|Solidification method for radioactive waste|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US06/146,302|US4351749A|1978-11-18|1980-05-05|Molecular glasses for nuclear waste encapsulation|
    [返回顶部]