CN105777101B - A kind of sodium zirconium phosphate-monazite glass ceramics firming body and preparation method thereof - Google Patents

Abstract

The invention discloses a sodium zirconium phosphate-monazite glass ceramic solidified body and a preparation method thereof, which are characterized in that: 30-60 parts by weight of P ₂ O ₅ , 10-35 parts by weight of Fe ₂ O ₃ , and B ₂ O ₃ 1 to 4 parts by weight, 3.5 to 14 parts by weight of CeO ₂ , 6 to 32 parts by weight of ZrO ₂ , 1.5 to 8 parts by weight of Na ₂ CO ₃ to obtain the raw materials for the base material after mixing, calcining and ball milling Powder; after mixing according to the ratio of 45-100 parts by weight of base material powder and 0-55 parts by weight of high-level radioactive waste or simulated high-level radioactive waste, the solidified body is obtained after ball milling, molding under pressure and sintering. According to the present invention, the sodium zirconium phosphate-monazite glass-ceramic solidified body has high containment capacity for high-level radioactive waste, large volume reduction ratio, good stability, simple preparation process, easy engineering application, and can be widely used for solidification of high-level radioactive waste deal with.

Description

Sodium zirconium phosphate-monazite glass ceramic solidified body and preparation method thereof

technical field

The invention belongs to the treatment and disposal of radioactive nuclear waste, and relates to a sodium zirconium phosphate-monazite glass ceramic solidified body and a preparation method thereof. It is especially suitable for solidification treatment of high-level waste containing plutonium and transuranic elements (ie high-level radioactive waste) discharged from nuclear industry and other fields.

Background technique

The peaceful use of nuclear energy has had a profound impact on the improvement of people's living standards and scientific and technological progress in my country and the world, and has become an indispensable part of human progress. However, the development of the nuclear industry will inevitably produce a large amount of radioactive waste, especially high-level radioactive waste. Once these radionuclides enter the biosphere, they will bring catastrophic radioactive pollution to the people of the world, which must be properly resolved. With the increasing amount of nuclear waste generated and the contradiction between the rapid development of the nuclear industry has become increasingly prominent, how to safely and effectively treat and dispose of it so that it can be isolated from the biosphere to the greatest extent has become an urgent problem to be solved in the development of the nuclear industry at home and abroad. one of the key issues.

In the prior art, an economically feasible treatment method for high-level radioactive waste is to select a solidified base material with high stability, "confine" radionuclides, and then conduct deep geological disposal to isolate it from the biosphere to the greatest extent. Among them, immobilization treatment is a step in direct contact with nuclides in high-level radioactive waste, and it is also a crucial step. The solidification treatment process and technology of low-level radioactive waste are relatively mature and have been applied in engineering. There are two main types of solidification of high-level radioactive waste: artificial rock solidification and vitrification. Although artificial rock solidification treatment has good chemical stability, thermal stability and radiation resistance, its solidification process is complicated, and its compatibility with high-concentration sodium salt and other wastes is poor. The selectivity of elements is very strong, and it is impossible to immobilize all components in high-level radioactive waste at one time. In addition, the equipment used in the solidification of artificial rocks is complex and expensive, and the consumption of materials and energy in the process is large. Therefore, vitrification is the preferred method for solidification of high-level radioactive waste in countries around the world. Vitrification treatment mainly includes borosilicate glass and phosphate vitrification. Borosilicate glass has very poor solubility to "harmful impurities" (such as: phosphate, molybdate, sulfate, iron oxide and some other heavy metal oxides) in waste, resulting in the prepared solidified body prone to " "Yellow phase" and the performance does not meet the requirements. In order to meet the performance requirements, the melting temperature has to be increased, or the content of such "impurities" in the solidified body has to be reduced at the expense of reducing the inclusion capacity. This is not desirable in terms of increasing the capacity reduction ratio and reducing costs. The iron phosphate system glass effectively solves the above problems. However, the irradiation stability and thermal stability of iron-phosphate vitrified body are poorer than that of borosilicate vitrified body, which limits its practical application. In addition, according to practical experience, whether it is a borosilicate system or a phosphate system glass solidified body, the containment capacity of high-level radioactive waste is relatively low, and it is easy to form uncontrollable crystallites in the solidified glass in actual operation. phase or produce uncontrollable phase separation, resulting in a sharp decrease in the stability of the cured body.

Contents of the invention

The purpose of the present invention is to overcome the deficiencies in the prior art, using glass-ceramic materials as the solidified base material, which has the advantages of large waste storage capacity of pure amorphous glass materials, many types of wastes, large compositional adjustability and long-term durability of pure crystal ceramic materials. The advantage of stabilizing the long-lived nuclide of "imprisonment" is to provide a simple and effective sodium zirconium phosphate-monazite glass-ceramic solidified body that can solidify all components in high-level radioactive waste. and its preparation method, thereby providing a new and effective treatment and disposal method for solidification and radioactive nuclear waste for high-level radioactive waste solidification treatment.

The content of the present invention is: a sodium zirconium phosphate-monazite glass ceramic solidified body, which is characterized in that: 30-60 parts by weight of P ₂ O ₅ , 10-35 parts by weight of Fe ₂ O ₃ , 1-35 parts by weight of B ₂ O ₃ 4 parts by weight, 3.5 to 14 parts by weight of CeO ₂ , 6 to 32 parts by weight of ZrO ₂ , 1.5 to 8 parts by weight of Na ₂ CO ₃ The base material raw material powder obtained by mixing, calcining and ball milling each raw material material; after mixing according to the ratio of 45-100 parts by weight of base material powder and 0-55 parts by weight of high-level radioactive waste or simulated high-level radioactive waste, the solidified body obtained after ball milling, molding under pressure and sintering.

In the content of the present invention: said P ₂ O ₅ 30-60 parts by weight, Fe ₂ O ₃ 10-35 parts by weight, B ₂ O ₃ 1-4 parts by weight, CeO ₂ 3.5-14 parts by weight, ZrO ₂ 6 ~ 32 parts by weight, Na ₂ CO ₃ 1.5 ~ 8 parts by weight of the raw materials, can be replaced by: (NH ₄ ) H ₂ PO ₄ 30 ~ 62 parts by weight, Fe ₂ O ₃ 7 ~ 29 parts by weight, The proportions of H ₃ BO ₃ 1.5-4.5 parts by weight, CeO ₂ 3-11 parts by weight, ZrO ₂ 5-26 parts by weight, and Na ₂ CO ₃ 1.3-9 parts by weight are the raw materials.

In the content of the present invention: the high-level waste is high-level waste containing plutonium and/or transuranic elements.

In the content of the present invention: the simulated high-level radioactive waste is radioactive waste or non-radioactive waste similar in chemical properties to elements containing Ce and/or Zr.

Another content of the present invention is: a kind of preparation method of sodium zirconium phosphate-monazite glass ceramic solidified body, it is characterized in that the steps are:

(1) Preparation of sodium zirconium phosphate-monazite glass-ceramic substrate raw material powder:

a. Ingredients: Using _P2O5 , _Fe2O3 , _B2O3 , _{CeO2 , ZrO2} , _{Na2CO3 as} raw _materials , according to _{P2O5 30 ~} 60 parts by weight, _{Fe2O3 10} ~ 35 parts by weight, 1-4 parts by weight of B ₂ O ₃ , 3.5-14 parts by weight of CeO ₂ , 6-32 parts by weight of ZrO ₂ , 1.5-8 parts by weight of Na ₂ CO ₃ ;

b. Mixing: Put the raw materials into the ball mill and mill for 3-5 hours (mix well);

c. Pre-burning: Pre-burning the ball-milled material at a temperature of 550-700°C for 2-6 hours (hours);

d. Ball milling: mill the pre-fired material in a ball mill for 3 to 5 hours to obtain sodium zirconium phosphate-monazite glass ceramic substrate raw material powder;

(2) Preparation of sodium zirconium phosphate-monazite glass-ceramic solidified body:

a. Ingredients: Sodium zirconium phosphate-monazite glass-ceramic substrate is obtained according to the ratio of 45-100 parts by weight of raw material powder of sodium zirconium phosphate-monazite glass ceramics, and 0-55 parts by weight of high-level radioactive waste or simulated high-level radioactive waste. Raw material powder and high-level radioactive waste or simulated high-level radioactive waste;

b. Mixing materials: Put the sodium zirconium phosphate-monazite glass ceramic base material powder and high-level radioactive waste or simulated high-level radioactive waste into a ball mill for ball milling for 3 to 5 hours (fully mixed evenly);

c. Forming: Take the powder after ball milling (take a certain amount according to the need), and form it into a green body under a pressure of 40-60 MPa;

d. Sintering: put the green body in a high-temperature furnace to raise the temperature to 850-1400°C at a rate of 1-4°C/min and keep it warm for 6-16 hours, and then cool in the natural furnace to obtain sodium zirconium phosphate-monazite glass ceramics and solidify body.

In another content of the present invention: said P ₂ O ₅ 30-60 parts by weight, Fe ₂ O ₃ 10-35 parts by weight, B ₂ O ₃ 1-4 parts by weight, CeO ₂ 3.5-14 parts by weight, ZrO ₂ 6-32 parts by weight, Na ₂ CO ₃ 1.5-8 parts by weight The raw materials can be replaced by: (NH ₄ )H ₂ PO ₄ 30-62 parts by weight, Fe ₂ O ₃ 7-29 parts by weight parts, H ₃ BO ₃ 1.5-4.5 parts by weight, CeO ₂ 3-11 parts by weight, ZrO ₂ 5-26 parts by weight, and Na ₂ CO ₃ 1.3-9 parts by weight.

In another content of the present invention: the high-level waste is high-level waste containing plutonium and/or transuranic elements.

In another content of the present invention: the simulated high-level radioactive waste is radioactive waste or non-radioactive waste whose chemical properties are similar to elements containing Ce and/or Zr.

In another content of the present invention: the ball mill is preferably a planetary ball mill, or other existing ball mill equipment.

In another content of the present invention: the raw material described in step (1) a can also be decomposed into P ₂ O ₅ , Fe ₂ O ₃ , B ₂ O ₃ , CeO ₂ , ZrO ₂ and /or other raw materials of Na ₂ O.

Compared with the prior art, the present invention has the following characteristics and beneficial effects:

(1) The present invention uses sodium zirconium phosphate-monazite glass ceramics as the solidified base material, and adjusts the ratio of sodium zirconium phosphate, monazite, Fe ₂ O _{3 -B 2} O ₃ -P ₂ O ₅ glass and high-level radioactive waste to design The formula composition of the glass ceramic solidified body, adjusting the melting process, and combining the scanning electron microscope (SEM) test, X-ray diffraction (XRD) test and chemical stability test methods for analysis, to select and determine a sodium zirconium phosphate-solitary The formula composition and curing treatment method of the high-level waste glass-ceramic solidified body that solidifies all the components in the high-level radioactive waste; the solidification treatment method is: pre-fire the raw materials of sodium zirconium phosphate-monazite glass ceramics After ball milling, add high-level radioactive waste or simulated high-level radioactive waste containing plutonium and transuranic elements, ball mill and mix again, and sinter in a high-temperature furnace after molding to obtain a solidified body of zirconium phosphate-monazite glass ceramics;

(2) Adopt the present invention, in sodium zirconium phosphate-monazite glass-ceramics, the zirconium position of sodium zirconium phosphate is easily replaced by tetravalent or trivalent actinide elements, and the sodium position is easily replaced by monovalent or divalent metal elements, The cerium site of monazite CePO ₄ is easily substituted by trivalent actinide elements, and the crystal structure remains unchanged after substitution; therefore, sodium zirconium phosphate can stably "imprison" the monovalent alkali metal and divalent alkaline earth metal elements in the waste in the crystal The Na position of the structure "confines" radionuclides or high-valence metal elements in the Zr position of the crystal structure, and more radionuclides or high-valence metal elements can also be "confine" in the monazite crystal structure, and other elements can enter Glass phase, so the selected glass-ceramic system can effectively solidify (simulate) all components in high-level waste containing plutonium and transuranic elements;

(3) In the sodium zirconium phosphate-monazite glass ceramic solidified body prepared by the present invention, the sodium zirconium phosphate phase and the monazite phase are alternately dispersed in the Fe ₂ O ₃ -B ₂ O ₃ -P ₂ O ₅ glass phase, and the zirconium phosphate Both sodium and monazite are ceramic materials with excellent chemical stability, and the stability of the Fe ₂ O ₃ -B ₂ O ₃ -P ₂ O ₅ glass phase is also excellent. High inclusion capacity, large volume reduction ratio, and good stability. The mass loss rate in 90°C deionized water for 14 days is <10 ^-9 g·cm ^-2 ·min ^-1 ;

(4) Adopt the present invention, the element or the radionuclide of the similar property with Ce or Zr in the high-level radioactive waste enters the zirconium position of sodium zirconium phosphate crystal phase or monazite crystal phase selectively, and the similar property of alkali metal and alkaline earth metal Elements enter the sodium position of the sodium zirconium phosphate crystal phase, and other elements are "confine" in the Fe ₂ O ₃ -B ₂ O ₃ -P ₂ O ₅ glass phase. The package capacity is high, the capacity reduction ratio is large, and the stability is good;

(5) By adopting the present invention, only the sodium zirconium phosphate-monazite ceramic base material is pretreated, and the synthesis of the sodium zirconium phosphate-monazite ceramic solidified body is completed in one step. The preparation process is simple, easy for engineering application, and can be widely used in The solidification treatment of high-level radioactive waste has strong practicability.

Description of drawings

Fig. 1 is the XRD pattern of the sodium zirconium phosphate-monazite glass-ceramic solidified body that embodiment 1 or embodiment 2 of the present invention makes;

Fig. 2 is the SEM image of the sodium zirconium phosphate-monazite glass-ceramic solidified body prepared in Example 1 of the present invention (the glass phase was etched away with HF solution before the test).

Detailed ways

The embodiment given below intends to further illustrate the present invention, but can not be interpreted as limiting the protection scope of the present invention, those skilled in the art make some non-essential improvements and adjustments to the present invention according to the content of the above-mentioned present invention, still belong to protection scope of the present invention.

Example 1:

A preparation method of sodium zirconium phosphate-monazite glass-ceramic solidified body, the steps are as follows:

(1) Preparation of sodium zirconium phosphate-monazite glass-ceramic substrate raw material powder:

a. Ingredients: using _P2O5 , _Fe2O3 , _{B2O3 , CeO2 , ZrO2} , _Na2CO3 as raw materials, according _{to P2O5 41.64} parts by _weight , _{Fe2O3 28.11} parts by weight, 2.01 parts by weight of B ₂ O ₃ , 10.10 parts by weight of CeO ₂ , 14.49 parts by weight of ZrO ₂ , and 3.62 parts by weight of Na ₂ CO ₃ take each raw material;

b. Mixing: put each raw material into a planetary ball mill and ball mill for 2 hours and mix well;

c. Pre-burning: Pre-burning the uniformly mixed materials at a temperature of 650°C for 4 hours;

d. Ball milling: mill the pre-fired material for 4 hours in a planetary ball mill to obtain sodium zirconium phosphate-monazite glass ceramic substrate raw material powder;

(2) Preparation of sodium zirconium phosphate-monazite glass-ceramic solidified body:

a. Ingredients: 95 parts by weight of sodium zirconium phosphate-monazite glass ceramic substrate raw material powder, 10 parts by weight of high-level radioactive waste containing plutonium and transuranium elements or simulated high-level radioactive waste;

b. Mixing: Put the weighed raw materials in a planetary ball mill for 4 hours and fully mix them evenly;

c. Forming: Form the uniformly mixed powder into a green body under a pressure of 60MPa;

d. Sintering: Heat the molded body in a high-temperature furnace at a rate of 3°C/min to 1000°C for 10 hours, then cool in a natural furnace to obtain a sodium zirconium phosphate-monazite glass-ceramic solidified body.

Example 2:

A preparation method of sodium zirconium phosphate-monazite glass-ceramic solidified body, the steps are as follows:

(1) Preparation of sodium zirconium phosphate-monazite glass-ceramic substrate raw material powder:

a. Ingredients: using _P2O5 , _Fe2O3 , _B2O3 , _{CeO2 , ZrO2} , _Na2CO3 as _{raw materials} , according to _{P2O5 41.07} parts by _weight , _{Fe2O3 22.01} parts by weight, B ₂ O ₃ 1.92 parts by weight, CeO ₂ 9.49 parts by weight, ZrO ₂ 20.41 parts by weight, and Na ₂ CO ₃ 5.09 parts by weight are all raw materials;

b. Mixing: put each raw material into a planetary ball mill and ball mill for 2 hours and mix well;

c. Pre-burning: Pre-burning the uniformly mixed materials at a temperature of 700°C for 6 hours;

d. Ball milling: mill the pre-fired material in a planetary ball mill for 5 hours to obtain sodium zirconium phosphate-monazite glass ceramic substrate raw material powder.

(2) Preparation of sodium zirconium phosphate-monazite composite glass-ceramic solidified body:

a, batching: take each raw material according to the batching ratio of 50 parts by weight of sodium zirconium phosphate-monazite glass ceramic substrate raw material powder, and 50 parts by weight of high-level radioactive waste containing plutonium and transuranium elements or simulated high-level radioactive waste;

b. Mixing: Put the weighed raw materials in a planetary ball mill for 4 hours and fully mix them evenly;

c. Forming: Form the uniformly mixed powder into a green body under a pressure of 60MPa;

d. Sintering: Heat the molded body in a high-temperature furnace at a rate of 2°C/min to 1100°C for 15 hours, and then cool it in a natural furnace to obtain a sodium zirconium phosphate-monazite glass-ceramic solidified body.

Example 3:

A preparation method of sodium zirconium phosphate-monazite glass-ceramic solidified body, the steps are as follows:

(1) preparing sodium zirconium phosphate-monazite glass-ceramic substrate raw material powder;

a, ingredients: with (NH ₄ )H ₂ PO ₄ , Fe ₂ O ₃ , CeO ₂ , ZrO ₂ , H ₃ BO ₃ , Na ₂ CO ₃ as raw materials, according to (NH ₄ )H ₂ PO ₄ 52.43 parts by weight, 17.33 parts by weight of Fe ₂ O ₃ , 2.68 parts by weight of H ₃ BO ₃ , 7.47 parts by weight of CeO ₂ , 16.07 parts by weight of ZrO ₂ , and 4.01 parts by weight of Na ₂ CO ₃ are taken from each raw material.

Others are the same as in Embodiment 2, omitted.

Example 4:

A preparation method of sodium zirconium phosphate-monazite glass-ceramic solidified body, the steps are as follows:

(1) preparing sodium zirconium phosphate-monazite glass-ceramic substrate raw material powder;

a, ingredients: with (NH ₄ )H ₂ PO ₄ , Fe ₂ O ₃ , CeO ₂ , ZrO ₂ , H ₃ BO ₃ , Na ₂ CO ₃ as raw materials, according to (NH ₄ )H ₂ PO ₄ 35.10 parts by weight, 14.62 parts by weight of Fe ₂ O ₃ , 1.03 parts by weight of H ₃ BO ₃ , 5.25 parts by weight of CeO ₂ , 7.52 parts by weight of ZrO ₂ , and 1.63 parts by weight of Na ₂ CO ₃ are taken from the respective raw materials.

Others are the same as embodiment 1, omitted.

Example 5:

A preparation method of sodium zirconium phosphate-monazite glass-ceramic solidified body, the steps are as follows:

(1) preparing sodium zirconium phosphate-monazite glass-ceramic substrate raw material powder;

a, ingredients: with (NH ₄ )H ₂ PO ₄ , Fe ₂ O ₃ , CeO ₂ , ZrO ₂ , H ₃ BO ₃ , Na ₂ CO ₃ as raw materials, according to (NH ₄ )H ₂ PO ₄ 34.85 parts by weight, 11.52 parts by weight of Fe ₂ O ₃ , 1.68 parts by weight of H ₃ BO ₃ , 4.97 parts by weight of CeO ₂ , 10.67 parts by weight of ZrO ₂ , and 2.32 parts by weight of Na ₂ CO ₃ are taken from the respective raw materials.

Others are the same as in Embodiment 2, omitted.

Embodiment 6～12:

A method for preparing a sodium zirconium phosphate-monazite glass-ceramic solidified body. Except for the ratio of raw materials, the amount of simulated waste added and the melting temperature, the preparation steps and process conditions are the same as those in Embodiment 1 or 2, and omitted. Concrete weight portion consumption, sintering (or claiming melting) temperature of each raw material in each embodiment are shown in the following table:

Example 13:

A sodium zirconium phosphate-monazite glass ceramic solidified body is: 30 parts by weight of _P2O5 , ₁₀ parts by weight _{of Fe2O3} , 1 part by weight _{of B2O3} , 3.5 parts by weight of _CeO2 , and 6 parts by weight of _ZrO2 1.5 parts by weight, Na ₂ CO ₃ 1.5 parts by weight of each raw material, the substrate raw material powder obtained after mixing, pre-calcination and ball milling; A solidified body obtained after mixing 55 parts by weight of waste, ball milling, forming under pressure and sintering.

Example 14:

A sodium zirconium phosphate-monazite glass ceramic solidified body is: 60 parts by weight of _P2O5 , 35 parts by weight _{of Fe2O3} , ₄ parts by weight of _B2O3 , 14 parts _by weight of _CeO2 , and 32 parts by weight _{of ZrO2} 100 parts by weight, Na ₂ CO ₃ 8 parts by weight of each raw material, the substrate raw material powder obtained after mixing, pre-calcination and ball milling; The solidified body obtained by ball milling, forming under pressure and sintering after mixing the waste at a ratio of 0 parts by weight.

Example 15:

A sodium zirconium phosphate-monazite glass ceramic solidified body is: ₅₄₅ parts by weight of _P2O , 23 parts by weight of _Fe2O3 , _2.5 parts by weight of _B2O3 , ₉ parts by weight _of CeO2, and 19 parts by weight _{of ZrO2} , Na ₂ CO ₃ 5 parts by weight of each raw material, the base material powder obtained after mixing, pre-burning and ball milling; 23 parts by weight are mixed, and the solidified body is obtained after ball milling, molding under pressure and sintering.

Embodiment 16～21:

A sodium zirconium phosphate-monazite glass-ceramic solidified body, comprising: 30-60 parts by weight of P ₂ O ₅ , 10-35 parts by weight of Fe ₂ O ₃ , 1-4 parts by weight of B ₂ O ₃ , 3.5-4 parts by weight of CeO ₂ 14 parts by weight, ZrO ₂ 6-32 parts by weight, Na ₂ CO ₃ 1.5-8 parts by weight, the base material powder obtained after mixing, pre-calcining and ball milling; 45 to 100 parts by weight of materials, 0 to 55 parts by weight of high-level radioactive waste or simulated high-level radioactive waste are mixed, and the solidified body obtained after ball milling, molding and sintering under pressure; the specific weight parts of each raw material in each embodiment See the table below for dosage:

Example 23:

A sodium zirconium phosphate-monazite glass-ceramic solidified body is: 30 parts by weight of (NH ₄ )H ₂ PO ₄ , 7 parts by weight of Fe ₂ O ₃ , 1.5 parts by weight of H ₃ BO ₃ , 3 parts by weight of CeO ₂ , The proportions of ZrO ₂ 5 parts by weight and Na ₂ CO ₃ 1.3 parts by weight are the raw materials; others are the same as any of Examples 13-22, and omitted.

Example 24:

A sodium zirconium phosphate-monazite glass ceramic solidified body is: (NH ₄ )H ₂ PO ₄ 62 parts by weight, Fe ₂ O ₃ 29 parts by weight, H ₃ BO ₃ 4.5 parts by weight, CeO ₂ 11 parts by weight, The ratio of 26 parts by weight of ZrO ₂ and 9 parts by weight of Na ₂ CO ₃ is obtained from each raw material; the others are the same as any of Examples 13-22, and omitted.

Example 25:

A sodium zirconium phosphate-monazite glass ceramic solidified body, which is: (NH ₄ )H ₂ PO ₄ 30-62 parts by weight, Fe ₂ O ₃ 7-29 parts by weight, H ₃ BO ₃ 1.5-4.5 parts by weight, The proportions of CeO ₂ 3-11 parts by weight, ZrO ₂ 5-26 parts by weight, and Na ₂ CO ₃ 1.3-9 parts by weight are the raw materials; others are the same as any one of Examples 13-22, and omitted.

Embodiment 26～32:

A sodium zirconium phosphate-monazite glass ceramic solidified body, which is: (NH ₄ )H ₂ PO ₄ 30-62 parts by weight, Fe ₂ O ₃ 7-29 parts by weight, H ₃ BO ₃ 1.5-4.5 parts by weight, CeO ₂ 3～11 parts by weight, ZrO ₂ 5～26 parts by weight, Na ₂ CO ₃ 1.3～9 parts by weight proportioning to get each raw material; Others are the same as any one of Examples 13～21, omitted; In each embodiment, each The concrete weight portion consumption of raw material sees the following table:

Example 33:

A preparation method of sodium zirconium phosphate-monazite glass-ceramic solidified body, the steps are:

(1) Preparation of sodium zirconium phosphate-monazite glass-ceramic substrate raw material powder:

a _{. Ingredients} : with _P2O5 , _Fe2O3 , _B2O3 , _{CeO2 , ZrO2} , _{Na2CO3 as} raw materials, ₃₀ parts by weight of _P2O5 , ₁₀ parts by weight of _Fe2O3 , B ₂ O ₃ 1 weight part, CeO ₂ 3.5 weight parts, ZrO ₂ 6 weight parts, Na ₂ CO ₃ 1.5 weight parts take each raw material;

b. Mixing: Put the raw materials into the ball mill and mill them for 3 hours (fully mixed evenly);

c, pre-burning: the ball-milled material is pre-burned at a temperature of 550°C for 6 hours (hours);

d. Ball milling: mill the pre-fired material in a ball mill for 3 hours to obtain sodium zirconium phosphate-monazite glass ceramic substrate raw material powder;

(2) Preparation of sodium zirconium phosphate-monazite glass-ceramic solidified body:

a. Ingredients: Sodium zirconium phosphate-monazite glass ceramic substrate raw material powder is obtained according to the ratio of 45 parts by weight of sodium zirconium phosphate-monazite glass ceramic substrate raw material powder, and 55 parts by weight of high-level radioactive waste or simulated high-level radioactive waste. and high-level waste or simulated high-level waste;

b. Mixing materials: Put the sodium zirconium phosphate-monazite glass ceramic substrate raw material powder and high-level waste or simulated high-level waste into a ball mill for ball milling for 3 hours (mix well);

c. Molding: take the powder after ball milling (take a certain amount as required), and form it into a green body under a pressure of 40MPa;

d. Sintering: put the green body in a high-temperature furnace to raise the temperature to 850°C at a rate of 1°C/min and hold it for 16 hours, and then cool it in a natural furnace to obtain a solidified body of sodium zirconium phosphate-monazite glass ceramics.

Example 34:

A preparation method of sodium zirconium phosphate-monazite glass-ceramic solidified body, the steps are:

(1) Preparation of sodium zirconium phosphate-monazite glass-ceramic substrate raw material powder:

a. Ingredients: using P ₂ O ₅ , Fe ₂ O ₃ , B ₂ O ₃ , CeO ₂ , ZrO ₂ , Na ₂ CO ₃ as raw materials, 60 parts by weight of P ₂ O ₅ , 35 parts by weight of Fe ₂ O ₃ , 4 parts by weight of B ₂ O ₃ , 14 parts by weight of CeO ₂ , 32 parts by weight of ZrO ₂ , and 8 parts by weight of Na ₂ CO ₃ take each raw material;

b. Mixing: Put the raw materials into the ball mill and mill them for 5 hours (fully mixed evenly);

c. Pre-burning: Pre-burning the ball milled material at a temperature of 700°C for 2 hours (hours);

d. Ball milling: mill the pre-fired material in a ball mill for 5 hours to obtain sodium zirconium phosphate-monazite glass ceramic substrate raw material powder;

(2) Preparation of sodium zirconium phosphate-monazite glass-ceramic solidified body:

a. Ingredients: Sodium zirconium phosphate-monazite glass-ceramic substrate raw material powder is obtained according to the ratio of 100 parts by weight of sodium zirconium phosphate-monazite glass-ceramic substrate raw material powder, and 0 weight part of high-level radioactive waste or simulated high-level radioactive waste. and high-level waste or simulated high-level waste;

b. Mixing materials: put sodium zirconium phosphate-monazite glass-ceramic substrate raw material powder and high-level waste or simulated high-level waste into a ball mill for ball milling for 5 hours (mix well);

c, forming: take the powder after ball milling (take a certain amount according to needs), and form it into a green body under a pressure of 60MPa;

d. Sintering: put the green body in a high-temperature furnace to raise the temperature to 1400°C at a rate of 4°C/min and keep it warm for 6 hours, and then cool it in a natural furnace to obtain a solidified body of sodium zirconium phosphate-monazite glass ceramics.

Example 35:

A preparation method of sodium zirconium phosphate-monazite glass-ceramic solidified body, the steps are:

(1) Preparation of sodium zirconium phosphate-monazite glass-ceramic substrate raw material powder:

a. Ingredients: with P ₂ O ₅ , Fe ₂ O ₃ , B ₂ O ₃ , CeO ₂ , ZrO ₂ , Na ₂ CO ₃ as raw materials, 45 parts by weight of P ₂ O ₅ , 22 parts by weight of Fe ₂ O ₃ , 2.5 parts by weight of B ₂ O ₃ , 8.8 parts by weight of CeO ₂ , 19 parts by weight of ZrO ₂ , and 4.8 parts by weight of Na ₂ CO ₃ take each raw material;

b. Mixing: Put the raw materials into the ball mill and mill them for 4 hours (fully mixed evenly);

c. Pre-burning: pre-burning the ball-milled material at a temperature of 630°C for 4 hours (hours);

d. Ball milling: mill the pre-fired material for 4 hours in a ball mill to obtain sodium zirconium phosphate-monazite glass ceramic substrate raw material powder;

(2) Preparation of sodium zirconium phosphate-monazite glass-ceramic solidified body:

a. Ingredients: Sodium zirconium phosphate-monazite glass-ceramic substrate raw material powder is obtained according to the ratio of 74 parts by weight of sodium zirconium phosphate-monazite glass-ceramic substrate raw material powder, and 26 parts by weight of high-level radioactive waste or simulated high-level radioactive waste. and high-level waste or simulated high-level waste;

b. Mixing materials: put the sodium zirconium phosphate-monazite glass ceramic substrate raw material powder and high-level waste or simulated high-level waste into a ball mill for ball milling for 4 hours (mix well);

c, forming: take the powder after ball milling (take a certain amount according to needs), and form it into a green body under a pressure of 50MPa;

d. Sintering: put the green body in a high-temperature furnace to raise the temperature to 1150°C at a rate of 2.5°C/min and hold it for 11 hours, and then cool it in a natural furnace to obtain a solidified body of sodium zirconium phosphate-monazite glass ceramics.

Example 36:

A preparation method of sodium zirconium phosphate-monazite glass-ceramic solidified body, the steps are:

(1) Preparation of sodium zirconium phosphate-monazite glass-ceramic substrate raw material powder:

a _. Ingredients: Using _P2O5 , _Fe2O3 , _B2O3 , _{CeO2 , ZrO2} , _{Na2CO3 as} raw _materials , according to _{P2O5 30} ~60 parts by weight, _{Fe2O3 10} ~ 35 parts by weight, 1-4 parts by weight of B ₂ O ₃ , 3.5-14 parts by weight of CeO ₂ , 6-32 parts by weight of ZrO ₂ , 1.5-8 parts by weight of Na _{2 CO 3} ; It can be the same as any one of Embodiments 13 to 22, and omitted;

b. Mixing: Put the raw materials into the ball mill and mill for 3-5 hours (mix well);

c. Pre-burning: Pre-burning the ball-milled material at a temperature of 550-700°C for 2-6 hours (hours);

d. Ball milling: mill the pre-fired material in a ball mill for 3 to 5 hours to obtain sodium zirconium phosphate-monazite glass ceramic substrate raw material powder;

(2) Preparation of sodium zirconium phosphate-monazite glass-ceramic solidified body:

a. Ingredients: Sodium zirconium phosphate-monazite glass-ceramic substrate is obtained according to the ratio of 45-100 parts by weight of raw material powder of sodium zirconium phosphate-monazite glass ceramics, and 0-55 parts by weight of high-level radioactive waste or simulated high-level radioactive waste. Raw material powder and high-level radioactive waste or simulated high-level radioactive waste;

b. Mixing materials: Put the sodium zirconium phosphate-monazite glass ceramic base material powder and high-level radioactive waste or simulated high-level radioactive waste into a ball mill for ball milling for 3 to 5 hours (fully mixed evenly);

c. Forming: Take the powder after ball milling (take a certain amount according to the need), and form it into a green body under a pressure of 40-60 MPa;

d. Sintering: put the green body in a high-temperature furnace to raise the temperature to 850-1400°C at a rate of 1-4°C/min and keep it warm for 6-16 hours, and then cool in the natural furnace to obtain sodium zirconium phosphate-monazite glass ceramics and solidify body.

Example 37:

A preparation method of sodium zirconium phosphate-monazite glass ceramic solidified body, according to (NH ₄ )H ₂ PO ₄ 30 weight parts, Fe ₂ O ₃ 7 weight parts, H ₃ BO ₃ 1.5 weight parts, CeO ₂ 3 weight parts , ZrO ₂ 5 parts by weight, and Na ₂ CO ₃ 1.3 parts by weight are selected from each raw material, and others are the same as any one of Examples 33 to 36, and are omitted.

Example 38:

A preparation method of sodium zirconium phosphate-monazite glass ceramic solidified body, according to (NH ₄ )H ₂ PO ₄ 62 weight parts, Fe ₂ O ₃ 29 weight parts, H ₃ BO ₃ 4.5 weight parts, CeO ₂ 11 weight parts , ZrO ₂ 26 parts by weight, and Na ₂ CO ₃ 9 parts by weight are selected from each raw material, and others are the same as any one of Examples 33 to 36, and are omitted.

Example 39:

A preparation method of sodium zirconium phosphate-monazite glass ceramic solidified body, according to (NH ₄ )H ₂ PO ₄ 46 weight parts, Fe ₂ O ₃ 18 weight parts, H ₃ BO ₃ 3 weight parts, CeO ₂ 7 weight parts , ZrO ₂ 15 parts by weight, and Na ₂ CO ₃ 5.1 parts by weight are the raw materials, and the others are the same as those in any of Examples 33 to 36, and are omitted.

Example 40:

A preparation method of sodium zirconium phosphate-monazite glass ceramic solidified body, according to (NH ₄ )H ₂ PO ₄ 30-62 weight parts, Fe ₂ O ₃ 7-29 weight parts, H ₃ BO ₃ 1.5-4.5 weight parts , CeO ₂ 3～11 parts by weight, ZrO ₂ 5～26 parts by weight, Na ₂ CO ₃ 1.3～9 parts by weight proportioning to get each raw material, the specific weight part consumption of each raw material is any one of the same as embodiment 26～32; Others are the same as any one of Embodiments 33 to 36, and are omitted.

In the above-mentioned embodiments 13-40: the high-level radioactive waste is high-level radioactive waste containing plutonium and/or transuranic elements.

In the above embodiment: the simulated high-level radioactive waste is radioactive waste or non-radioactive waste similar in chemical properties to high-level radioactive waste containing plutonium and/or transuranic elements.

In the above-mentioned embodiments 13-40: the ball mill is a planetary ball mill, or other existing ball mill equipment.

Among the above-mentioned Examples 13-40: _the raw material described in the step (1)a can _also be decomposed into _P2O5 , _Fe2O3 , _B2O3 , _CeO2 , _{ZrO2 and} /or other raw materials of Na ₂ O.

In above-mentioned embodiment: each raw material that adopts is commercially available product.

In the above-mentioned embodiment: described weight (mass) part can all be gram or kilogram.

Among the above-mentioned embodiments: the process parameters (temperature, time, pressure, etc.) in each step and the numerical value of the amount of each component are within the range, and any point is applicable.

The content of the present invention and the technical content not specifically described in the above embodiments are the same as the prior art.

The present invention is not limited to the above-mentioned embodiments, and all of the contents of the present invention can be implemented and have the above-mentioned good effects.

Claims (7)

1. a kind of sodium zirconium phosphate-monazite glass ceramics firming body, it is characterized in that：By P₂O₅ 30~60 parts by weight, Fe₂O₃ 10~ 35 parts by weight, B₂O₃ 1~4 parts by weight, CeO₂ 3.5~14 parts by weight, ZrO₂ 6~32 parts by weight, Na₂CO₃ 1.5~8 parts by weight Proportioning take each raw material, through mixing, the substrate material powder obtained after 2~6h of pre-burning and ball milling at a temperature of 550~700 DEG C Material；45~100 parts by weight of substrate material powder, high-level waste or the proportioning mixing for simulating 0~55 parts by weight of high-level waste are pressed again Afterwards, through ball milling, forming under the pressure and after being warming up to 850~1400 DEG C with the rate of 1~4 DEG C/min and keeping the temperature 6~16h sintering The firming body arrived.

2. a kind of sodium zirconium phosphate-monazite glass ceramics firming body, it is characterized in that：By (NH₄)H₂PO₄ 30~62 parts by weight, Fe₂O₃ 7~29 parts by weight, H₃BO₃ 1.5~4.5 parts by weight, CeO₂ 3~11 parts by weight, ZrO₂ 5~26 parts by weight, Na₂CO₃ The proportioning of 1.3~9 parts by weight takes each raw material, through mixing, is obtained after 2~6h of pre-burning and ball milling at a temperature of 550~700 DEG C Substrate material powder；45~100 parts by weight of substrate material powder, high-level waste or simulation 0~55 parts by weight of high-level waste are pressed again Proportioning mixing after, through ball milling, forming under the pressure and with the rate of 1~4 DEG C/min be warming up to 850~1400 DEG C and keep the temperature 6~ The firming body obtained after 16h sintering.

3. sodium zirconium phosphate as described in claim 1 or 2-monazite glass ceramics firming body, it is characterized in that：The high-level waste It is the high-level waste containing plutonium or/and transuranic element.

4. the preparation method of a kind of sodium zirconium phosphate-monazite glass ceramics firming body, it is characterized in that step is：

（1）Prepare sodium zirconium phosphate-monazite glass-ceramic substrates raw material powder：

A, dispensing：With P₂O₅、Fe₂O₃、B₂O₃、CeO₂、ZrO₂、Na₂CO₃For raw material, by P₂O₅30~60 parts by weight, Fe₂O₃10~35 Parts by weight, B₂O₃1~4 parts by weight, CeO₂3.5~14 parts by weight, ZrO₂6~32 parts by weight, Na₂CO₃1.5~8 parts by weight take respectively Raw material；

B, it mixes：Raw material is put into 3~5h of ball milling in ball mill；

C, pre-burning：By the material after ball milling at a temperature of 550~700 DEG C 2~6h of pre-burning；

D, ball milling：By the material after pre-burning in ball mill 3~5h of ball milling, obtain sodium zirconium phosphate-monazite glass ceramics base Material raw material powder；

（2）Prepare sodium zirconium phosphate-monazite glass ceramics firming body：

A, dispensing：By sodium zirconium phosphate -45~100 parts by weight of monazite glass-ceramic substrates raw material powder, high-level waste or simulation The proportioning of 0~55 parts by weight of high-level waste takes sodium zirconium phosphate-monazite glass-ceramic substrates raw material powder and high-level waste or mould Quasi- high-level waste；

B, batch mixing：By sodium zirconium phosphate-monazite glass-ceramic substrates raw material powder and high-level waste or simulation high-level waste input 3~5h of ball milling in ball mill；

C, it is molded：The powder after ball milling is taken, is green body in 40~60MPa forming under the pressure；

D, it is sintered：Green body is placed in high temperature furnace and is warming up to 850~1400 DEG C and 6~16h of heat preservation with the rate of 1~4 DEG C/min, Then natural furnace cooling, obtains sodium zirconium phosphate-monazite glass ceramics firming body.

5. the preparation method of a kind of sodium zirconium phosphate-monazite glass ceramics firming body, it is characterized in that step is：

（1）Prepare sodium zirconium phosphate-monazite glass-ceramic substrates raw material powder：

A, dispensing：By (NH₄)H₂PO₄ 30~62 parts by weight, Fe₂O₃ 7~29 parts by weight, H₃BO₃ 1.5~4.5 parts by weight, CeO₂ 3~11 parts by weight, ZrO₂ 5~26 parts by weight, Na₂CO₃ The proportioning of 1.3~9 parts by weight takes each raw material；

B, it mixes：Raw material is put into 3~5h of ball milling in ball mill；

C, pre-burning：By the material after ball milling at a temperature of 550~700 DEG C 2~6h of pre-burning；

D, ball milling：By the material after pre-burning in ball mill 3~5h of ball milling, obtain sodium zirconium phosphate-monazite glass ceramics base Material raw material powder；

（2）Prepare sodium zirconium phosphate-monazite glass ceramics firming body：

A, dispensing：By sodium zirconium phosphate -45~100 parts by weight of monazite glass-ceramic substrates raw material powder, high-level waste or simulation The proportioning of 0~55 parts by weight of high-level waste takes sodium zirconium phosphate-monazite glass-ceramic substrates raw material powder and high-level waste or mould Quasi- high-level waste；

B, batch mixing：By sodium zirconium phosphate-monazite glass-ceramic substrates raw material powder and high-level waste or simulation high-level waste input 3~5h of ball milling in ball mill；

C, it is molded：The powder after ball milling is taken, is green body in 40~60MPa forming under the pressure；

D, it is sintered：Green body is placed in high temperature furnace and is warming up to 850~1400 DEG C and 6~16h of heat preservation with the rate of 1~4 DEG C/min, Then natural furnace cooling, obtains sodium zirconium phosphate-monazite glass ceramics firming body.

6. by the preparation method of the sodium zirconium phosphate of claim 4 or 5-monazite glass ceramics firming body, it is characterized in that：It is described High-level waste is the high-level waste containing plutonium or/and transuranic element.

7. by the preparation method of the sodium zirconium phosphate of claim 4 or 5-monazite glass ceramics firming body, it is characterized in that：It is described Ball mill is planetary ball mill.