JP2022052694A - Method used for preparing curable slurry by wet decomposition waste liquid of waste ion exchange resin, and solidifying/fixing other waste, waste ion exchange resin and improved wet oxidation method of organic matter - Google Patents

Abstract

To provide a method used for preparing a curable slurry by a wet decomposition waste liquid of a waste ion exchange resin, and using for solidifying/fixing other waste, and a waste ion exchange resin, and an improved wet oxidation method of an organic matter.SOLUTION: There is provided a method for preparing a curable slurry by wet-decomposing a waste ion exchange resin containing a cation exchange resin, preparing a curable slurry from the generated decomposition waste liquid, and using the slurry for solidifying/fixing other waste, so as to obtain a solid waste object excellent in properties and achieve great volume reduction of a waste. There is also provided a method for decomposing a waste ion exchange resin or an organic matter (including organic waste) using hydrogen peroxide containing a persulfate as a decomposer. The method can increase efficiency of decomposition, remarkably reduces consumption of hydrogen peroxide, and can obtain a better effect of mineralization.SELECTED DRAWING: Figure 2

Description

The present invention relates to a waste treatment method, particularly a radioactive waste treatment method.

Currently, the most commonly used nuclear power plants in the world are pressurized water reactors and boiling water reactors. The medium- and low-level radioactive waste generated by both can be roughly divided into wet waste and dry waste. Regarding wet waste, the ones produced by the pressurized water reactor are mainly borate waste liquid, waste ion exchange resin (hereinafter referred to as waste resin), waste activated charcoal, etc., and the boiling water reactor The products produced are mainly waste resin, waste activated charcoal and sludge. At present, the regeneration of the ion exchange resin is no longer performed, so that the sodium sulfate waste liquid generated by the regeneration of the resin is eliminated. For dry waste, its production has little to do with the reactor type. The main difference is whether or not the flammable dry waste is incinerated. When incinerated, combustible waste is incinerated and converted into slag and ash, resulting in a significant reduction in the volume of dry waste. Also, regardless of the type of reactor, they still produce radioactive waste such as sludge, contaminated metal, and waste filter elements. The above are all radioactive wastes suitable for treatment by applying the technique according to the present invention.

Traditionally most commonly used in the treatment of radioactive liquid or wet waste, waste and cement are prepared into slurries and placed in barrels for stable monolithic solid disposal after the slurry has hardened. It is a cement solidification technology that becomes an object (Solid Waste Form). Since different wastes have different properties, it is necessary to carry out each treatment using different solidification conditions when cement solidification is performed. Therefore, in addition to the existence of different technical problems for each, the load factor of the waste of the cement solidified body is low, so that the amount of the finally produced waste solidified body remains high. The treatment problems and technical status of some of the wastes that are challenging for the treatment process will be described below.

As mentioned above, cement solidification is a common technique used early in the treatment of radioactive waste and is still used in some nuclear power plants. When treating borate effluent using cement solidification technology, the borate in the effluent (usually sodium borate) strongly impedes the hydration of the cement and prevents the cement slurry from hardening. , So-called Solidification Delayation phenomenon. In order to reduce this phenomenon, the borate effluent should be cemented only at a low boron concentration, or slaked lime or other alkaline agent should be added first before adding the cement solidifying agent to delay the solidification phenomenon. Reduce. For example, US Pat. Nos. 4293437, 4210619, 4620947, 4800042 and 4906408, Chinese Patent CN 102254579B, Japanese Patent Application Laid-Open No. CN 102800377A, and the like. However, all of these methods result in a significant increase in the volume of the borate effluent solidified product produced. The equipment of the cement solidification system is simple and it is possible to reduce the investment cost of the equipment, but the management cost of radioactive waste is increasing day by day and it is difficult to find the final disposal site. It is no longer economical.

JGC Corporation of Japan heats borate effluent to 40-60 ° C, adds lime, and reacts for about 10 hours to convert sodium borate into a stable calcium borate precipitate. , The so-called "advanced cementation", in which the precipitate is filtered and dehydrated and then cement is added to solidify it, has been developed. Although it was said to bring about a remarkable improvement in volume reduction, it has not been completely treated because the operation is long and produces a secondary waste liquid containing sodium hydroxide (Secondary Waste).

The present inventor has concentrated borate waste liquid to have a boron content of 110,000 ppm or more in Taiwan Patent No. 68875, US Patent US 5457262, US Patent US 5998690, European Patent EP 0644555, European Patent EP 0929079, and the like. Disclosed is a method for solidifying borate waste liquid, which is made into a polymerized sodium borate solution and then solidified with a specially prepared cement-based solidifying agent. The above method can prepare a solidified body having a very high borate load factor, and the volume of the solidified body produced by treating the same amount of borate waste liquid is one tenth of that of the conventional cement solidification method. The volume reduction effect is very excellent. However, due to the high borate content of the solidified body, its application is limited if the requirements for immersion resistance of the solidified body are strict.

The treatment of borate effluent also comprises a so-called evaporative drying method in which the effluent is placed in a barrel and then directly heated to evaporate the water in order to form boric acid or a borate solid containing water of crystallization. .. This method reduces the volume of waste, but the borate is still in a fully soluble state without stabilization or mineralization treatment and is not stable.

Similarly, there are problems in treating waste resin using cement solidification techniques. Since the waste resin has an ion exchange capacity, it exchanges ions with ions in the cement solidified body and affects the stability of the solidified body. Further, by absorbing or releasing water, the solidified body shrinks and expands, causing breakage and cracking. Therefore, the load factor of the waste resin of the solidified body is greatly limited, and the volume is significantly increased after the cement is solidified. In addition, waste resin cement is not mineralized even after solidification, it still emits odor, pollutes the environment, generates biodegradation, produces sulfide, destroys the disposal engineering barrier, and is safe for disposal. I'm worried.

The waste resin treatment method includes two methods, a dry treatment method and a wet treatment method, in addition to the cement solidification method. Among them, the dry method includes an incineration method, a direct vibration method, a high temperature thermal decomposition method, a Q-CEP treatment method (Quantum-Catalytic Extension Process), and the like, and the wet method includes an acid decomposition method (steam reforming method). Acid Definition), wet oxidation method, subcritical or supercritical water oxidation method, high temperature steam reforming method, etc. are included. Among them, the development of the incinerator method was the earliest and has been implemented in some countries. When treated using the incinerator method, waste resin and other combustible waste are usually mixed and incinerated to control the emission concentration of SO _x , NO _x or other harmful gases. Controlling the emission of radionuclides is an important issue in the incinerator method. Unless the emission of nuclides such as volatile carbon-14, tritium and cesium-137 can be effectively prevented, the waste resin needs to be incinerated after removing the nuclides in advance to reduce the radioactivity. This also makes it difficult to incinerate the waste resin.

The above-mentioned high-temperature treatment methods for waste resins all face problems such as corrosion of materials, treatment and discharge of nuclides and toxic gases, and proper treatment of residues and secondary waste, and are practically applied. Caused the above difficulties. In addition, high temperature treatment has drawbacks such as high equipment cost and low flexibility in system operation and staffing scheduling.

In contrast to the drawbacks of the high temperature treatment method, the wet oxidation method using the Fenton Reaction has a low reaction temperature (about 100 ° C), does not generate toxic gas, and does not escape nuclides. It has various advantages and is advantageous for the development of actual applications.

The wet oxidation method developed by the British AEA company uses ferrous sulfate as a catalyst, hydrogen peroxide as an oxidant, adjusts the pH with slaked lime and sulfuric acid, and is granular at a temperature of about 100 ° C and a pH of 3 to 4. Oxidative decomposition of the waste ion exchange resin is performed to decompose organic components into CO ₂ and H ₂ O. According to the reports in the literature, when the waste liquid and the residue obtained by treating the waste resin by the above method are cement-solidified, the volume of the finally produced solidified body is compared with the volume of the waste resin before the treatment. Although it does not decrease, a relatively good volume reduction effect can be obtained as compared with the direct cement solidification of waste resin.

The present inventor adjusts the pH by using barium hydroxide instead of slaked lime in Taiwan Patent No. 255277, US Patent US 7482387 B2, Japanese Patent No. 44142414, European Patent No. 1137014, etc. Disclosed is a technique for decomposing anions and cation waste resins by a wet oxidation method using a Fenton reaction, in which the decomposition waste liquid and the residue are solidified by the solidifying agent prepared in 1. When the above-mentioned technique processes an anion and cation mixed resin having an equal volume ratio, the volume of the solidified body produced is about 1/3 of the volume of the original waste resin, and the quality of the solidified body is different. No secondary waste remains that meets the requirements of major nuclear energy countries and needs to be treated.

From the above description, the treatment of radioactive waste of the prior art is basically divided into two stages as shown in FIG. In the first stage, weight reduction / volume reduction treatment such as dehydration, drying, evaporation / concentration, precipitation, incineration or decomposition is performed first based on the characteristics of the waste, and high-concentration waste liquid, waste slurry or solid. To obtain intermediate products such as powders, granules or residues of. In the second stage, in order to obtain a waste body of suitable quality (Waste Form), it is further solidified or fixed using an appropriate method based on the characteristics of the intermediate product. Among them, the solidification process refers to preparing a waste liquid or a waste slurry into a monolithic waste solidified body (abbreviated as a solidified body), and the fixing process puts a waste that is originally a solid into a barrel. After that, the curable slurry is poured into the waste and embedded, and after the curable slurry is cured, a monolithic waste fixed body (abbreviated as a fixed body) is formed. If the properties of the solid intermediate product satisfy the sealing conditions, no immobilization process may be required and the seal is made directly using a qualified High Integrity Container (HIC). Among them, the preparation of waste objects for fine wet solid waste such as waste ion exchange resin, sludge, and residue is habitually solidified because it is prepared as a solid by adding a solidifying agent in the form of a slurry. The product is also referred to as a solidified body. In the following description, these idioms will be used as they are.

Basically, all the treatments such as solidification, fixing, and sealing included in the second stage have a volume increasing effect. The degree of volume increase depends on the concentration of waste and the amount of additional solidifying agent for solidification of waste liquid and waste slurry, the volume capacity of the waste barrel and the amount of curable slurry used for fixing, and sealing for sealing. It depends on the volume capacity of the barrel. In the current situation, the degree of volume increase in the second stage treatment is between about 50% and 500% due to different methods.

The present invention comprises a method of preparing a curable slurry using a waste liquid generated by wet decomposition of a waste resin (including anion and cation exchange resin) and treating other waste with the curable slurry. Provided are an improved wet oxidation method for decomposing a waste ion exchange resin and organic waste.

The method provided by the present invention for treating other waste using the decomposition product of the waste resin includes a step of performing a wet decomposition treatment of the waste resin to generate a decomposition waste liquid containing a sulfate and a decomposition waste liquid. To produce a conversion waste slurry containing stable sulfate fine particles by concentrating and adding a conversion agent, and a curable slurry raw material is added to the conversion waste slurry and mixed uniformly to prepare a curable slurry. , Includes steps used to solidify or immobilize at least one other waste. Since the stable sulfate fine particles contained in the conversion waste slurry of the present invention are derived from the sulfonic acid group contained in the cation exchange resin, it is sufficient to prepare a required amount of curable slurry for the waste ion exchange resin. It is preferable to contain a relatively high proportion of cation exchange resins so that they can be provided. Basically, since the amount of cation exchange resin contained in the waste ion exchange resin produced by the nuclear power plant is larger than that of the anion exchange resin, it is very suitable for the application of the method according to the present invention.

In one embodiment of the present invention, the above-mentioned wet decomposition treatment is a wet oxidation method, and is preferably performed under the condition of pH <3. The pH of the water slurry of the waste resin mixed with anions and cations decreases with increasing proportion of the cation resin, and conversely, the pH increases. Since the decomposition of the cationic resin produces sulfuric acid, when the proportion of the cationic resin is higher, the pH of the decomposition waste liquid decreases as the decomposition progresses. The anion-cationic waste resin produced by nuclear power plants usually has a higher proportion of cation resin, so it is not often necessary to lower the pH, but if necessary, sulfuric acid is used. It is possible to lower it using. If the continuous production of sulfuric acid causes the acidity to be too high, it is possible to reduce it with barium hydroxide.

In one embodiment of the invention, at least one of the other wastes described above is borate waste liquid, solid borate, waste activated charcoal, sludge, incinerator ash, waste filter element, metal waste and waste compression. The step of treating at least one waste selected from black further comprises the step of forming at least one waste and curable slurry into a solidified or fixed body.

In one example of the present invention, the above-mentioned treatment method comprises a step of providing a borate waste liquid and a component of the borate waste liquid for preparing a high-concentration borate waste liquid containing a polymerized borate. And the process of producing borate granules from high-concentration borate effluent using a granulator and at least one granulator, and the borate granules and curable slurry. Is mixed and uniformly stirred to form a granulated slurry body of a curable slurry, which is then placed in a waste barrel, and after the granulated slurry body is cured, a step of forming a solidified body package is further included.

In one embodiment of the invention, the borate effluent described above is a sodium borate solution.

The present invention also provides an improved method for decomposing a waste ion exchange resin or an organic substance, which comprises using persulfate and hydrogen peroxide as a decomposing agent to decompose the waste ion exchange resin or the organic substance. .. The maintenance increases the decomposition efficiency, reduces the residual TOC concentration in the decomposition liquid, and significantly reduces the consumption of hydrogen peroxide.

In the present invention, waste ion exchange resin is decomposed using a wet type, and a curable slurry is prepared from the generated decomposition waste liquid, and borate waste liquid, solid borate, waste activated charcoal, sludge, and contaminated metal are prepared. Since it is used for the combined treatment of other wastes including waste filter elements, etc., the use of additional materials is greatly reduced, the volume increase of the second stage treatment is reduced, and the reduction of radioactive waste is realized. ..

In order to make the above and other purposes, features, and advantages of the present invention easier to understand, examples will be given below and described in detail together with the accompanying drawings as follows.

The two-step treatment diagram of radioactive waste is shown. The flow schematic diagram of the waste treatment method which concerns on this invention is shown. The schematic diagram of the apparatus used for the decomposition treatment of the waste resin of the Example of this invention is shown. The schematic diagram of the apparatus used for the ammonia-containing outgas treatment of the Example of this invention is shown.

The present invention has completed the following novel methods of treating radioactive waste through experiments and research.

(1) Pretreatment of other waste 001 to be merged (S100): The other waste 001 to be merged refers to the waste solidified or fixed by the curable slurry. These wastes need to be pretreated to a state suitable for solidification or fixation. Basically, all solid wastes can be solidified or fixed, but those having good stability and mechanical strength are preferable. Wet solid waste, such as waste activated carbon or sludge, needs to be stripped of excess water. Liquid waste, such as sodium borate effluent from nuclear power plants, is either pretreated into solid granules first, or an alkaline agent, such as calcium hydroxide, is added to form a calcium borate solid precipitate and then dehydrated. It is necessary to make a fine granular solid containing an appropriate amount of water. The calcium borate solid can be muddy, powdery, granular, or lumpy. Oversized dry waste needs to be suitable for barreling and fixing, so the shape and size should be adjusted first. Fine powder or granule waste can be placed in barrels first, compressed into compressed black, and then fixed if there is a cause that is not selected for solidification or is not suitable for solidification treatment. In short, the pretreatment ensures that the other waste 001 has the appropriate moisture content, shape, size and density and is compatible with the final solidification or fixation treatment.

(2) Wet decomposition of waste resin (S200): The most preferable wet decomposition method is a wet oxidation method, and a curable slurry is prepared from the obtained waste resin decomposition waste liquid (S300). Good fluidity and excellent stability and mechanical strength of the cured product, as the properties of the curable slurry have a decisive effect on the quality of the final product of the invention. It is preferable to have the characteristic of being provided with. Good fluidity is advantageous for mixing or injecting operations when it solidifies or immobilizes other waste. The property that the cured product has excellent stability and mechanical strength is advantageous in producing a solidified or fixed body having excellent properties. Also, the amount of waste used to prepare the curable slurry needs to be relatively large in order to meet the needs. The waste resin produced by the nuclear power plant basically satisfies the above-mentioned conditions.

(3) Preparation of final waste object (S400, FIG. 2): When preparing a solidified body (S410, FIG. 2), the pretreated waste granules or powder are uniformly mixed with the prepared curable slurry. The granule slurry is stirred to form a curable granule slurry, the granule slurry is placed in a waste barrel, and after it is cured, a solidified body is formed. When preparing a fixed body (S420, FIG. 2), the other pretreated waste 001 is first placed in the waste barrel and then poured into and around the gaps in the barrel using a curable slurry. After filling and curing the curable slurry, a fixed body is formed.

In order to describe a more specific method, the combined treatment of three major wastes of a pressurized water reactor containing waste ion exchange resin and sodium borate waste liquid or waste activated carbon will be described as an example. Since these three are the most challenging in the treatment of pressurized water reactor waste, the present invention has practical value in the treatment of pressurized water reactor waste. Among them, the waste ion exchange resin is used for preparing a curable slurry, the sodium borate waste liquid needs to be pretreated into solid granules, and the waste activated carbon has an appropriately low water content by adjusting its water content. , It is necessary to have a water content that does not allow water to drip. The main implementation steps S100, S200, S300, S400 and the like are as shown in FIG. Among them, the preparation of the waste object package of S400 is divided into S410 which is the preparation of the solidified body package 013 and S420 which is the preparation of the fixed body package 014. It should be understood that the order in FIG. 2 is only exemplary. Among them, the order of S100 and S200 to S300 is not limited except that the steps S100 and S200 to S300 need to be completed prior to the step S400, but the order is not limited, but the curable slurry is cured according to the timing of curing. I need to work.

In step S100, the borate waste liquid is pretreated into borate granules. In this step, a step of preparing a borate waste liquid into a high-concentration borate waste liquid containing a polymerized borate (step S100a) and a step of preparing a high-concentration borate waste liquid into borate granules (step). S100b) and the like. Each will be described as follows.

In step S100a, in order to prepare a high-concentration borate waste liquid containing a polymerized borate, the components of the borate waste liquid (001, other waste) are adjusted, and the borate waste liquid is concentrated.

In step S100b, a granulator and a granulator are used to produce high-concentration borate waste liquid into borate granules (002, solid waste produced by pretreatment).

In step S200, the waste resin 003 is decomposed to generate the decomposed waste liquid 004. The decomposition treatment of the waste resin 003 can be a single wet oxidation method step. In addition to the generation of decomposition waste liquid 004, the decomposition treatment oxidatively decomposes the hydrocarbon component of the waste resin 003 into gaseous CO ₂ and H ₂ O, in which the gas is discharged after removing mist droplets by filtration. Will be done. The decomposition waste liquid 004 contains ammonium hydroxide, sulfuric acid or ammonium sulfate, and a residue and a small amount of organic carbide depending on the anion, the ratio of the cationic resin and the content of impurities in the waste resin feed.

The impurities contained in the waste resin are mainly solids sandwiched between the gaps of the resin, cations adsorbed by the cation resin, anions adsorbed by the anion resin, and the like. Among them, some impurities may interfere with the decomposition potency of wet oxidation and contain carbon-14 ( ¹⁴ C) adsorbed by certain adsorbed ions, such as an anionic resin ^, H ¹⁴ CO _3- . Ions release gases containing carbon-14 nuclei during the decomposition process, which can cause radiation damage to personnel and the environment. In the present invention, in order to prevent the above-mentioned problems, depending on the situation, water is added to the waste resin to form a water slurry, and then a step of removing solid impurities from the gap using vibration by ultrasonic waves and a desorbing agent solution are used. Impurities contained in the waste resin are removed before wet oxidation, which includes a step of desorbing H ¹⁴ CO ₃ ^- ions adsorbed by the waste resin to water after washing. The desorbing agent used is, for example, alkali metals such as perchlorate, sulfate, nitrate, phosphate, monohydrogen phosphate, dihydrogen phosphate, oxalate, iodide, bromide, and alkaline earth. It is possible to select a solution of a salt or compound such as metal or ammonium, and it is preferable that the solution is advantageous for desorbing the waste liquid and performing the subsequent stabilization treatment, and particularly the desorbed H ¹⁴ CO ₃ ^- ion. Those formed into a solid precipitate are more preferable. The waste slurry generated by the removal of the solid impurities can be left to stand in a barrel to precipitate the solid impurities, and then the supernatant liquid can be recycled into water for resin slurry. The slurry containing solid impurities at the bottom of the barrel is incorporated into the conversion waste slurry prepared in step S300 for further processing. The cleaning waste liquid generated by the desorption of H ¹⁴ CO ₃ ^- ion can be incorporated into the conversion waste slurry similarly prepared in step S300 for subsequent treatment, or can be treated separately according to demand. be. When the treatment is carried out by using the method of incorporating into the conversion waste slurry, it is also possible to directly add a desorbing agent to the slurrying water to remove solid impurities and desorb carbon-14 in combination. The pH of the waste resin washed with the alkaline desorbent needs to be adjusted to <3 after being mixed with the wet oxidation catalyst solution and before being decomposed.

In step S300, the curable slurry 006 is prepared by the decomposition waste liquid 004. This step includes a step S300a for preparing a conversion waste slurry with the decomposition waste liquid 004 and a step S300b for preparing a curable slurry 006 with the conversion waste slurry. Each will be described as follows.

In step S300a, a conversion waste slurry is prepared by the decomposition waste liquid 004. First, the decomposition waste liquid 004 is concentrated to an appropriate concentration, and then a conversion agent is added to form a conversion waste slurry. The conversion agent in this step is preferably barium hydroxide, which converts sulfuric acid and ammonium sulfate in the decomposition waste liquid into insoluble barium sulfate to obtain a conversion waste slurry containing barium sulfate fine particles. At the same time, the pH value of the waste slurry is raised, and the ammonium ions in the waste slurry are converted into ammonia gas and escaped. Ammonia gas is discharged after being converted into nitrogen gas and water vapor by oxidative decomposition.

In step S300b, a curable slurry 006 is prepared by the conversion waste slurry. The curable slurry raw material 005 (that is, the solidifying agent powder) is added to the conversion waste slurry and mixed uniformly to prepare the curable slurry 006. The curable slurry 006 can be used to treat at least one type of solid waste 002 produced by pretreatment, in this case borate granules.

Step S410 belongs to the preparation of the borate granulated solidified package 013. After uniformly mixing the borate granules (002, solid waste generated by the pretreatment) prepared in step S100 and the curable slurry 006 prepared in step S300 to obtain a curable granule slurry body, It is housed in a waste barrel, and after the granule slurry is hardened into a solidified body, it is capped into a solidified body package 013.

The high-concentration borate waste liquid prepared in the above-mentioned step S100a mainly contains sodium borate. The boron concentration of the high-concentration sodium borate waste liquid needs to be 100,000 ppm or more, and is preferably 110,000 ppm or more. When the boron concentration is less than 100,000 ppm, the degree of polymerization of sodium borate is insufficient, and the mechanical strength of the borate granules produced after granulation in step S100b is not good. However, if the boron concentration is too high, it should be prevented that the viscosity is too high and the transport line is blocked, and that the material is not well mixed during granulation.

The borate granules in step S100b can be produced using a stirring tank provided with a planetary stirring blade. When granulating, first put the granulator in the stirring tank, make the height of the granulator powder higher than the stirring blade, start stirring continuously, and then raise the height to the stirred granulator powder. Concentration Sodium borate Waste liquid is slowly dropped, and initial granules are formed by rolling and contacting the droplets and powder. High-concentration sodium borate waste liquid and granulator form borate granules by solidification reaction. During the reaction, the liquid sodium borate with a high degree of polymerization causes a substitution reaction with the granulator, so that it becomes solid borate granules with a high degree of polymerization. The borate composition and mechanical strength of the granules are mainly determined by the components of the granulator.

After the initial granules are formed, continuous granulation can be performed using a method of adding a high concentration sodium borate waste liquid and a granulator by a cross loop. The weights of the added effluent and granulators need to be maintained in appropriate proportions and the speed of addition also needs to be appropriately controlled to prevent the granules from sticking due to too much mucus. Continuous granulation is to pause when the granules reach the capacity limit of the granulator, take out some granules, continue to granulate, and stop granulation after the granules reach the required amount. Is possible.

The decomposition treatment of the waste resin 003 in step S200 may be another wet decomposition method in addition to the wet oxidation method, but is preferably a decomposition treatment of a wet oxidation method using a Fenton reaction. The wet oxidation method using the Fenton reaction has the advantages that the reaction temperature is relatively low, the components of the generated decomposition waste liquid are simple, and it is advantageous for the subsequent treatment. The purpose of decomposing the waste resin 003 is to mineralize (mineralize) the waste resin 003 in addition to reducing the volume. This is an important purpose because it is advantageous for preventing the emission of malodor and the occurrence of biodegradation of the waste resin 003, protecting the environment, and maintaining the safety of final disposal. Therefore, it is preferable that the step S200 can achieve a certain degree of decomposition, and the decomposition rate of 99% should belong to a reasonable target.

The wet oxidation method using the Fenton reaction traditionally uses hydrogen peroxide as a decomposing agent, but in the study according to the present invention, the decomposing effect of hydrogen peroxide is effective when the concentration of organic carbide is relatively low. Has been found to decrease significantly. Taking the wet oxidation of waste resin 003 as an example, the hydrogen peroxide consumed by decomposing the last 5% of organic carbon may be more than the previous 95% decomposition, with 98% and 99% decomposition rates. The amount of hydrogen peroxide consumed in is different by more than 30%.

In order to reach a high decomposition rate and reduce the consumption of hydrogen peroxide, the present invention may use a two-component decomposition agent containing peroxysulfate and hydrogen peroxide after a series of studies. It has been discovered that the decomposition efficiency at low TOC concentrations can be effectively improved and the consumption of the decomposition agent can be significantly reduced. Suitable persulfates include ammonium persulfate, sodium persulfate, potassium persulfate, calcium persulfate and the like. Ammonium persulfate is preferred because the components of the finally produced decomposition effluent 004 are exactly the same as when hydrogen peroxide is used. In addition to being suitable for ion exchange resins, the two-component decomposition agent of the present invention is suitable for wet oxidation of other organic substances such as polymer resins, organic compounds, vegetable fibers, vegetable fats and oils, animal fats and oils and mineral fats and oils. Also suitable.

When persulfate is used, the concentration of sulfate in the decomposition effluent increases, that is, the amount of decomposition effluent or solidified body produced increases. Therefore, it is preferable to select the timing of adding the persulfate when the TOC concentration is relatively low and the decomposing effect of hydrogen peroxide is low. For solid organic substances (for example, ion exchange resins), it is preferable that they are completely dissolved. If the amount of decomposition waste liquid or solidified body produced has a significant effect on the overall treatment efficiency, it may be considered to be added at a lower TOC concentration after the solid organic matter is completely dissolved. good. For liquid organic matter, it is also necessary to consider the effect of the timing of addition on the overall treatment efficiency. For example, the proportion of high molecular weight organic matter is relatively low, and the proportion of monomolecular organic matter is relatively high. Time is possible. This is not due to technical limitations, but due to efficiency considerations.

The decomposition waste liquid 004 produced in step S200 can contain ammonium hydroxide, sulfuric acid, ammonium sulfate, a residue, and a small amount of organic carbon depending on the conditions. After adding the conversion agent in step S300a, the conversion of sulfate in the decomposition waste liquid 004, that is, the sulfate ion and ammonium sulfate in the decomposition waste liquid 004 are converted into an insoluble stable precipitate, and the ammonium ion (NH ₄₊ ) in the decomposition waste liquid 004 is converted into an insoluble stable precipitate ^. ) Can be converted to ammonia gas (NH ₃ ) and escaped. The escaped ammonia gas is further detoxified. Further, in order to make the solid content (corresponding to the insoluble precipitate described above) of the conversion waste slurry suitable for the subsequent treatment, this step further comprises concentrating the conversion waste slurry to adjust its water content. ..

As the conversion agent, barium hydroxide is preferably used, and a barium hydroxide solution may be used, or barium hydroxide water slurry or barium hydroxide powder may be used. The solubility of barium hydroxide at room temperature is not high, and in order to prevent the addition of too much water, barium hydroxide can be dissolved using boiling water to increase the solubility.

The ammonia-containing outgas produced by the conversion of sulfate ion and ammonium sulfate is first removed through a demister to remove mist droplets, then transported by a suction pump and placed in an ammonia gas tank, and then quantitatively oxidized-decomposer. ). At the same time, a certain proportion of air is poured into the ammonia oxidative decomposition device to oxidatively decompose ammonia into N ₂ and H ₂ O by the catalytic action of the oxidative decomposition catalyst. Finally, the exhaust system exhausts N ₂ and H ₂ O. Further, the ammonia-containing outgas may be absorbed by water to be converted into ammonia water, and then ammonium hydroxide may be oxidatively decomposed in water to be converted into nitrogen gas and water.

The above-mentioned ammonia gas tank may be a space tank or a storage tank that buffers one ammonia gas stream, or may be provided with a cooling and heating device to place calcium chloride (CaCl ₂ ) as an ammonia gas adsorbent. Calcium chloride can adsorb ammonia gas at low temperature to form CaCl ₂ · nNH ₃ (n = 2-8), and when it adsorbs ammonia and reaches a certain level, it heats to release ammonia gas. It can be attached and detached. Repeated use in this way provides a storage and buffer space for ammonia gas and increases operational flexibility.

In step S300b, a curable slurry 006 is prepared by the conversion waste slurry. It is preferable that the curable slurry 006 has excellent fluidity and can form a solidified body having excellent properties. The quality of the properties of the curable slurry 006 and the solidified body is expressed based on the selected curable slurry raw material 005 (that is, the solidifying agent powder). The curable slurry raw material 005 may be prepared using Pozzolan material (Pozzolanic Materials) or may use a special compounding composition.

In step S410, the curable slurry 006 is used to solidify the borate granules. Borate granules are added to the curable slurry 006 according to a predetermined ratio, and after stirring and mixing are completed, a curable granule slurry is obtained. Next, the granule slurry body is placed in a waste barrel, and after standing and hardening (solidification), a monolithic solidified body (granule solidified body) is formed.

When barium hydroxide is used as a conversion agent, the sulfate contained in the conversion waste slurry is barium sulfate, a solid with a high specific gravity (4.5), a hard texture, and an excellent fine aggregate. The borate granules are also solid solids with high mechanical strength. Therefore, the borate granulated solidified product prepared in the present invention has the characteristics of a dense structure and high mechanical strength, can prevent a decrease in resistance strength after immersion, and is water resistant to the borate waste liquid solidification product. Is greatly improved.

In addition to being used for solidifying borate granules, the curable slurry 006 can also be used for solidifying / fixing other solid wastes such as waste activated carbon, sludge, incinerator ash, metal waste, waste filter elements and the like. It is possible. If the waste of the merged treatment is solid, the pretreatment is relatively simple because it does not need to be granulated. Radioactive waste activated carbon produced by nuclear power generation facilities adsorbs various toxic substances and nuclides, so if incineration is used, it may cause pollution. Therefore, direct solidification using the curable slurry of the present invention is a feasible treatment method.

The method according to the present invention concretely puts into practice the idea of "treating waste with waste", fully practices the minimization of radioactive waste, and produces high-quality solidified / fixed waste objects. In the following, examples will be given to demonstrate the processing method and effect of the present invention. These examples are only application examples of the present invention and do not represent the entire scope of the invention and should not be restricted to the scope of use of the invention.

In Comparative Example 1, hydrogen peroxide was used to perform wet oxidative decomposition of the simulated waste resin.

This comparative example demonstrates that the simulated waste resin was decomposed by wet oxidation using hydrogen peroxide, and the apparatus 1 used is as shown in FIG.

The device 1 used for the decomposition treatment of the waste resin included one closed glass reaction tank and an attached supply / discharge device. The lower part of the glass reaction tank was one 2.5 liter tank body 01, and the upper part was a tank cover 02. The tank cover 02 and the tank body 01 were sandwiched between metal clips and brought into close contact with each other, and the metal clips could be loosened and separated. The tank cover 02 has four openings. Among them, the opening 07 can be used as a defoaming agent supply port, on which a female cylinder 06 is placed and used to carry in the defoaming agent solution manually or by a peristaltic pump. The opening 08 can be used as a defoaming agent supply port and is used to add a defoaming agent when necessary, and the opening 04 is used as a supply port for a catalyst solution and an ion exchange resin, and at the same time, the pH and temperature are adjusted. It can be used as a measuring port and a sampling port for decomposition waste liquid, closed with a silicon plug when not in use, and the opening 09 can be used as a gas outlet, connected to the glass cooling tube 10 and escaped. It was used to condense the steam. The outlet of the glass cooling tube 10 was connected to the conical glass bottle 12 and was used to receive the condensate. The glass cooling tube 10 is also provided with a separate reflux tube 11, which is used to recirculate the condensed liquid to the glass reaction tank to maintain the stability of the liquid level when necessary, and the uncondensed gas is collected in the conical glass bottle 12. It was discharged to the fume hood via the exit 14 of the.

The entire apparatus 1 is provided on one support stand, an electric heater 05 is placed under the glass reaction tank, and the electric heater 05 is placed on a support base (not shown) whose height can be adjusted. It was possible to adjust the height according to the demand, and it was possible to remove it at any time.

At the start of the decomposition process, 600 ml of the catalyst solution (0.06 M ferrous sulfate) and 66 grams (82.5 ml) of the strong acid cation exchange resin used in the nuclear power plant and 33 grams (44.72 ml) of strong base type anion exchange resin was taken as a simulated waste resin. Since the simulated waste resin did not contain solid impurities and did not adsorb carbon-14 nuclei, the step of removing solid impurities and carbon-14 nuclei was omitted, and the glass reaction tank was sequentially added from opening 04, and then opened with a silicon plug 04. Was closed and measured to confirm that the pH of the solution was below 2.5. Subsequently, the stirring motor was started to stir and start heating. When the temperature in the tank reached 95 ° C., heating was stopped and the peristaltic pump was started to carry 35% hydrogen peroxide into the glass reaction tank at a flow rate of 5 ml / min. Due to the heat generated by the reaction, the temperature rose to the boiling point, and the reaction was maintained in a boiling state. When the gas produced by the reaction was passed through the glass cooling tube 10, the water vapor was condensed and collected in the conical glass bottle 12, and the uncondensed carbon dioxide was discharged to the fume hood by the tube. When foam accumulation / increase was found during the reaction, an antifoaming agent was poured to suppress it. The defoaming agent used in this example was a product containing a commercially available silicone resin and fatty acid ester component, and was used after being diluted 10-fold with water. In this example, when the decomposition agent was added and the total reached 275 ml, 350 ml, and 550 ml, 1 ml each was added, for a total of 3 ml of defoaming agent. When the liquid level was excessively lowered due to evaporation, the condensed liquid was refluxed and replenished in order to keep the liquid level within a certain fluctuation range.

In this embodiment, sampling is performed after the resin is completely dissolved so that the decomposition efficiency of the resin can be understood. After the decomposition agent reaches a predetermined addition amount, the addition is temporarily stopped, and sampling is started 10 minutes later. Was selected. At the time of sampling, heating and stirring are temporarily stopped, 2 grams of decomposition waste liquid sample is taken from the opening 04 for analysis, then the heater 05 is removed, one electronic scale is placed under the glass tank, and the electronic scale. After placing one insulation board on the surface of the platform, zero reset the weight measurement of the electronic scale, then loosen the metal clip connecting the tank cover 02 and the tank body 01, and put the glass reaction tank on the electronic scale. They were seated on an insulating board, weighed and recorded.

Immediately after sampling and weighing are complete, the device is returned to its original state, then stirring is started, heated on demand, decomposing agent addition is resumed, and the same sampling is performed again at the next sampling. And a weight measurement step was performed. The time for each sampling was controlled to 5 minutes.

As shown in Table 1, the treatment results include the hydrogen peroxide addition weight (hydrogen peroxide addition amount), the decomposition waste liquid weight, the total organic carbon (TOC) content of the decomposition waste liquid, and the like. It is as shown in 1. Further, according to the analysis, it was found that the carbon contents of the anion and cation exchange resins used in this experiment were 149.5 and 150.7 g / liter, respectively, by elemental analysis. That is, the total amount of organic carbon contained in the ion exchange resin before decomposition was 19.12 grams in total. Table 1 also shows the change in decomposition rate obtained by calculation, ignoring the small amount of TOC brought out by the evaporation of the gas. Among them, the calculation of the decomposition rate is as follows.
Decomposition rate (%) = 100-waste liquid weight (gram) x waste liquid TOC (ppm) x 10 ^-4 / 19.12

The decomposition experiment results in Table 1 show that the decomposition rate is 95.49% when the hydrogen peroxide addition reaches 550 ml, and the decomposition rate is 98.91% when the hydrogen peroxide addition reaches 1000 ml. It shows that it was. The TOC level was excessive because the decomposition rate was increased by 3.42% even though the decomposition rate was 95.49% by adding 550 ml in the previous stage and 450 ml was added in the later stage. It is shown that it has a very large effect on the decomposition effect of hydrogen peroxide. It is also shown that when the TOC is 500 ppm or less, the decomposing effect of hydrogen peroxide becomes very weak.

This example demonstrates the wet oxidative decomposition of the same simulated waste resin as in Comparative Example 1 with the two-component decomposition agent (hydrogen peroxide + persulfate) of the present invention, and its effect. The device used was the same as in Comparative Example 1.

Since the decomposition efficiency is affected by various factors including the addition speed of the decomposition agent, the morphology of the organic substance, the TOC concentration, etc., it is possible to compare the treatment results under the same conditions. The conditions of this example were 550 ml to 5 parts ammonium persulfate and 95 parts 35%, except that the decomposition agent used was 550 ml added in the previous step was 35% hydrogen peroxide. It is used instead of the hydrogen peroxide two-component decomposition agent, and the timing of adding the defoaming agent is 1 ml when the decomposition agent solution is added 285 ml, 380 ml, 440 ml, 470 ml, and 515 ml, respectively. All other conditions were the same as in Comparative Example 1, except that a total of 5 ml was added.

As a result of the treatment, as shown in Table 2, after the reaction was carried out by adding 550 ml of 35% hydrogen peroxide, the decomposition rate measured was 95.31%, which was almost the same as that of Comparative Example 1. there were. It was subsequently used in place of the above-mentioned two-component decomposition agent, and the total amount of the decomposition agent added was 700 ml (including 550 ml of 35% hydrogen peroxide and 150 ml of the two-component decomposition agent). The decomposition rate reached 99.01%, and when added to 1000 ml, the TOC of the waste liquid was less than 50 ppm, and the decomposition rate reached 99.88%. It is shown that the TOC still has a good decomposition effect when it decreases to 500 ppm or less. If the goal is to achieve a decomposition rate of 99%, the use of a two-component decomposition agent can save 30% or more of usage.

This example demonstrates that a curable slurry was prepared by the decomposition waste liquid of a simulated waste resin (ion exchange resin) in order to embed and solidify the borate granules obtained by the pretreatment of the borate waste liquid. Demonstrate the process of pretreatment to prepare borate granules with borate effluent.

In the preparation of simulated borate effluent, 640 grams of deionized water is taken and placed in one 6 liter glass beaker for stirring, then 900 grams of 99% sodium hydroxide and 4800 grams of 99% borate. Take the acid and divide it into 4 portions each, add sodium hydroxide first, then add boric acid in 4 batches each by a cross method, slowly add to the beaker, and after the boric acid is completely dissolved, by evaporation The lost water was replenished with deionized water, then the temperature was adjusted to 85 ° C. and then kept warm for later use. After analyzing the resulting solution, its boron concentration is 131,080 ppm, i.e. 13.108% by weight, which corresponds to a conversion of 75.71% by weight of boric acid and a sodium / boron molar ratio. Was 0.29.

The pretreatment of the borate effluent was granulation. The granulation in this example can further include steps such as preparation of a granulating agent, initial granulation, continuous granulation, and the like, and is described as follows.

In the preparation of granulators, 40 parts of commercially available sludge solidifying agent STA-110 (a product of Eign Green International Inc.), 30 parts of Type II Portland cement were taken and 30 parts of barium hydroxide were taken. It was mixed with hydrate, pulverized with a pulverizer, passed through a 150 mesh screen, and then sealed to obtain a granulator.

In the start granulation, 2000 grams of the above-mentioned granulator powder is taken and placed in one 20 liter revolving / rotating planetary stirrer, after setting an appropriate rotation speed, the stirring blade is started, and then 2640. Grams of simulated borate effluent were taken and slowly added dropwise to the granulated powder that had been stirred in several batches. The amount of each addition was adjusted so that the powder was not overly moistened and sticky to form large agglomerates, and after each addition the solution was evenly dispersed and reacted with the granulator to make it moist. I waited until it became dull. It was necessary to re-add, and after the addition of the simulated borate effluent was completed, stirring was continued for another 5 minutes, and the initial granulation step was completed for the first time.

In continuous granulation, the granules prepared in the initial granulation stage are kept in the granule machine, kept stirring, then 200 grams of simulated borate waste liquid is taken and slowly dropped onto the granules on the granules. 80 grams of granulation agent was subsequently taken and added onto the agitated granules, waited until the granules no longer exhibited a moist luster, and the simulated borate effluent was added again. In this way, the simulated borate waste liquid and the granulation agent were added with a circulating cloth to reach 50 times each, and when the reaction was completed, the granulation was suspended and half the weight of the granules was taken out. After that, the material was added again with a circulating cloth to continue granulation, and the addition of the total simulated borate waste liquid and the granulating agent reached 100 times, respectively, and the addition was stopped when the weight reached 20000 g and 8000 g, respectively. And after continuing to stir for 5 minutes, all granules (including those removed earlier and those completed later) were mixed in preparation for solidification.

As shown in Table 3, the conditions of the materials used in the above two-step granulation are as follows: a total of 10,000 grams of granulator and 22640 grams of simulated borate waste liquid are added, and the granulator / simulated borate is added. The weight ratio of the waste liquid was 0.442. The diameters of the granules produced were predominantly distributed between 2 and 5 mm, with a boron content of 9.09% by weight, corresponding to a boric acid content of 52.48% by weight.

In the decomposition of the simulated waste resin, the equipment used and the simulated waste resin were the same as in Comparative Example 1, and the step of removing impurities from the simulated waste resin was also omitted. Since the amount of waste liquid required was relatively large, it was divided into 4 batches. It states as follows.

When processing each batch, first, 1200 grams of 0.06 M ferrous sulfate solution and 180 grams of cationic resin and 90 grams of anionic resin used in Comparative Example 1 were added to the reaction tank. Then stirring and heating were started. When the temperature of the solution reached 95 ° C., heating was stopped and 35% hydrogen peroxide was added at a rate of 12 ml / min and the heat of reaction kept the reaction boiling. When the amount of hydrogen peroxide added reached 1500 ml, 90 grams of cation resin and 45 grams of anion resin were added, and 750 ml of hydrogen peroxide was continuously added at the same speed. When it was reached that a total of 540 grams of cation resin, 270 grams of anion resin, and 4500 ml of 35% hydrogen peroxide were added, the two-component decomposition agent was further added. After decomposing to 10 ml / min, stopping when the addition amount of the two-component decomposing agent reached 245 ml, and continuing to maintain stirring for 30 minutes. The disassembly operation has been completed. In the above decomposition process, the temperature was kept between 95 ° C. and boiling point, and the temperature was maintained by heating when necessary. When the liquid level was lowered by boiling, the liquid level was maintained by a condensed liquid reflux method so that the fluctuation did not become large. When there was a bubble accumulation phenomenon, it was suppressed with a defoaming agent in a timely manner. In this experiment, a total of 12 ml of defoaming agent was added.

A total of 2160 grams (2700 ml) of cationic resin and 1080 grams (1464 ml) of anionic resin were decomposed in a total of 4 batches according to the same conditions. The obtained decomposition waste liquid was mixed, the weight was concentrated and adjusted to 1540 g, and then analyzed. As a result, the sulfate ion content was 4.02 mol / kilogram.

In the conversion of decomposition waste liquid, the equipment for decomposition waste liquid conversion includes the other two parts of conversion reaction and outgas cooling, except that the equipment for the ammonia-containing outgas treatment part is as shown in FIG. , All were the same as the device 1 in FIG. Among them, in the four openings 04, 07, 08, 09 on the tank cover 02 of the glass reaction tank, 04 is used as a conversion agent supply port and is also used as a temperature / pH measurement port when necessary, and 07 is decomposed. A measuring cylinder type funnel was placed on the waste liquid supply port to manually add the waste liquid, and 09 was used as a conversion out gas outlet.

The device 2 used for the ammonia-containing outgas treatment is as shown in FIG. The conical glass bottle 12a is used for collecting the condensate and temporarily retaining the uncondensed ammonia-containing outgas, that is, as a buffer tank for the ammonia gas. The opening 16a of the conical glass bottle 12a was used as an air inlet. The flow meter 17 and the adjusting valve 18 are air adjusting devices and were used for adjusting the air flow rate. The outlet 14a is a conversion out gas outlet and is connected to the ammonia oxidative decomposition device 19 by a silicon hose. The ammonia oxidative decomposition apparatus 19 includes a preheater and a high temperature catalyst bed, provides a holding temperature of 600 ° C. or lower for preheating the ammonia-containing outgas, and uses an ammonia oxidative decomposition catalyst to generate ammonia in N ₂ and H ₂ . It was possible to oxidatively decompose to O. The air extractor 21 helped the converted outgas overcome the flow resistance. The air adjusting valve 20 adjusted the air flow rate in order to adjust the negative pressure generated by the air extraction by the air extractor.

Before the treatment begins, the ammonia oxidative decomposition apparatus 19 is first preheated to 300 ° C. for later use, then the barium hydroxide monohydrate powder and water are taken and 1466 in a weight ratio of 4: 6. A 5.5 g converter water slurry (containing 586.6 g barium hydroxide monohydrate) was prepared, placed in a glass reaction tank through opening 04, stirring was started, and then the prepared decomposition effluent was poured. It was slowly carried in by a peristaltic pump, stopped when a total of 770 grams was carried in, continued to be heated and maintained at a temperature of about 90 ° C., and stirred for 2 hours to completely remove ammonia gas. Subsequently, the heating was stopped, moved to a beaker to cool, and waited for use. The weight of the obtained concentrated conversion waste slurry was 1305 grams.

The ammonia-containing gas generated during the conversion process enters the cone-shaped bottle 12a through the glass cooling tube 10a, the condensed liquid remains in the bottle, and the uncondensed ammonia-containing gas mixes with the carried air and then ammonia. After flowing into the oxidative decomposition apparatus 19 and decomposing into steam and nitrogen gas, the liquid was extracted into a fume hood with an air extractor and discharged.

The same process was repeated once again to complete the conversion of a total of 1540 grams of decomposition effluent. The resulting conversion waste slurries were mixed to give a total of 2655 grams (dry weight was 1487 grams) of conversion waste slurry containing 44% water.

The convertible waste slurry was transferred to one 10 liter stirring mixer and mixed with 1565 grams of curable slurry by weight ratio of 1565 grams of borate sludge solidifying agent SPF-210 and type II Portland cement. The raw material and 1976 g of borate granules were added and mixed uniformly to obtain a slurry of borate granules. The composition was as shown in Table 4.

Subsequently, the granule slurry body is placed in a barrel, and in this embodiment, it is placed in a polyethylene plastic mold having an inner diameter of 5 cm and a height of 6 cm. It was placed in a constant temperature and humidity chamber of 95% or more and cured for 28 days. After the curing was completed, the compressive strength, weather resistance (freeze-thaw resistance), immersion resistance, etc. were tested in accordance with the Taiwan Low Radioactive Waste Material Quality Regulations. We also conducted an impact resistance test for a 9-meter drop. The results are as shown in Table 5, indicating that the quality of the solidified material meets the quality requirements stipulated by each nuclear energy country.

This example demonstrates the combined treatment of waste resin and waste activated carbon.

First, wet oxidative decomposition of the waste resin containing 540 grams (about 675 ml) of cation resin and 270 g (about 366 ml) of anion resin was performed by the same method as in Example 1, and the decomposition waste liquid was discharged into 2682. Prepare to a gram of conversion waste slurry containing 45% water, then add 1565 grams of the same curable slurry material as in Example 2 to prepare 4247 grams of curable slurry and store until use. did. The simulated waste activated carbon used in the experiment is the waste activated carbon used for water treatment by the nuclear power plant, which is moist granules with a size in the range of 6 to 40 mesh, and the water content is 10.79% by measurement. The specific gravity was 1.06. 1175 grams (1108 ml) of waste activated carbon and the prepared curable slurry were stirred and uniformly mixed to prepare 5422 grams of waste activated carbon solidified slurry, the composition of which was as shown in Table 6 (Table 6). Note: The discarded activated carbon solidified slurry is a name for a slurry formed by stirring the discarded activated carbon and the curable slurry, and was a precursor of the discarded activated carbon solidified body). By measurement, the specific gravity of the waste object after solidification was 2.02, that is, the volume was 2864 ml, and therefore the volume loading factor of the solidified waste activated carbon was 41.3%.

We also conducted an experiment to increase the load factor of waste activated carbon. The waste resin was decomposed in the same manner and a converted waste slurry having a water content of 43% of 2588 grams was prepared, and then 1540 grams of the same curable slurry raw material was added to prepare a curable slurry of 4128 grams. .. Further, this curable slurry was mixed with 1510 grams (1425 ml) of waste activated carbon to prepare a slurry of 5638 grams. Its composition is also shown in Table 6. By measurement, the solidified body had a specific gravity of 1.996, i.e., a volume of 2825 ml, and therefore its waste activated carbon volume loading factor was 50.44%.

The solidified body prepared above was prepared as a sample according to the method of Example 2, and then a quality test was performed. The results are as shown in Table 7, indicating that the quality was very excellent.

The present invention has been disclosed in the examples as described above, but it is not a limitation of the present invention. A person having ordinary knowledge in the field of technology to which the invention belongs may make some changes and modifications without departing from the spirit and scope of the invention. Therefore, the scope of protection of the present invention is defined by the appended claims.

1, 2: Device 01: Tank body 02: Tank cover 03: Stirring blade 04, 07, 08, 09: Opening 05: Electric heater 06: Female cylinder 10, 10a: Glass cooling tube 11: Reflux tube 12, 12a: Conical Shaped glass bottle 13, 13a: Pressure gauge 14, 14a: Outlet 15, 15a: Drain plug 16, 16a: Opening 17: Flow meter 18: Adjustment valve 19: Ammonia heating / oxidation decomposition device 20: Air adjustment valve 21: Air extraction Vessel 001: Other waste 002: Solid waste generated by pretreatment 003: Waste resin supply 004: Waste resin decomposition waste liquid 005: Curable slurry raw material 006: Curable slurry 015: Solidified package 014: Fixed body Package S100: Pretreatment of other waste S200: Wet decomposition of waste resin S300: Preparation of curable slurry S400: Preparation of waste object package S410: Preparation of solidified body package S420: Preparation of fixed body package

Claims (26)

Waste that contains a cation exchange resin The process of removing impurities from the ion exchange resin and then performing a wet decomposition treatment to generate a decomposition waste liquid containing sulfate.
A step of concentrating the decomposition waste liquid and adding a conversion agent to generate a conversion waste slurry containing sulfate fine particles.
A step of adding a curable slurry raw material to the conversion waste slurry and mixing it uniformly to prepare a curable slurry, and solidifying or fixing at least one other waste using the curable slurry. A treatment method in which a curable slurry is prepared by a wet decomposition waste liquid of a waste ion exchange resin containing a waste ion exchange resin, and solidification / fixing treatment of other waste is performed. The first aspect of claim 1, wherein the at least one other waste is selected from borate waste liquid, solid borate, waste activated carbon, sludge, incinerator ash, waste filter element, metal waste and waste compressed black. Processing method. The at least one other waste includes liquid waste and
The treatment according to claim 1, further comprising a step of pretreating the liquid waste into solid granules or precipitates so as to be compatible with the solidification or fixation treatment using the curable slurry. Method. The at least one other waste includes solid waste and
The treatment method further comprises a step of pretreating the solid waste to have an appropriate moisture content, shape, size and density to suit the solidification or immobilization treatment with the curable slurry. The processing method according to claim 1. The step of removing the impurities of the waste ion exchange resin is a step of removing the solid impurities carried over by the water slurry after forming the water slurry of the waste ion exchange resin by an ultrasonic vibration method, and the step of adsorbing the water slurry. Further includes a step of removing the carbon 14 nuclei formed with an alkaline desorbing agent.
The treatment method according to claim 1, wherein the waste liquid generated by removing impurities is incorporated into a conversion waste slurry and treated together. The alkali desorbing agent includes perchlorate, sulfate, nitrate, phosphate, monohydrogen phosphate, dihydrogen phosphate, oxalate, iodide, alkali metal of bromide, alkaline earth metal or ammonium. The treatment method according to claim 5, which is at least one selected from a solution of a salt or a compound such as. The pretreatment step for further forming the borate waste liquid into borate granules is included, and the pretreatment step includes a pretreatment step.
The process of providing borate effluent and
In order to prepare a high-concentration borate waste liquid containing a polymerized borate, a step of adjusting the components of the borate waste liquid and concentrating the borate waste liquid, and
A step of producing the high-concentration borate waste liquid into borate granules using a granulator and at least one kind of granulating agent.
The process comprises uniformly mixing the borate granules and the curable slurry to form a granule slurry, then placing the granules in a waste barrel, curing the granule slurry, and then forming a solidified body.
The processing method according to claim 2. The processing method according to claim 7, wherein the step of forming the solidified body further includes a step of capping the waste barrel to form a solidified body package. The treatment method according to claim 7, wherein the borate waste liquid is a sodium borate solution. The treatment method according to claim 1, wherein the acid and alkali used for adjusting the pH of the decomposition reaction solution in the wet decomposition treatment are sulfuric acid and barium hydroxide, respectively. The treatment method according to claim 1, wherein the wet decomposition treatment is at least one selected from a wet oxidation method, a supercritical water oxidation method, and an acid decomposition method. The wet decomposition treatment is a wet oxidation method.
The step of generating the decomposition waste liquid is
The process of preparing the decomposition agent and the catalyst solution, and
The waste ion exchange resin after removing impurities is put into the catalyst solution, the pH of the solution is adjusted to <3, the solution is maintained at a temperature of 95 ° C to the boiling point, the decomposition agent is further added, and the disposal is performed. The step of producing the decomposition waste liquid containing CO ₂ and H ₂ O obtained by oxidatively decomposing the hydrocarbon component of the ion exchange resin and ammonium ion, sulfate ion, sulfate, residue and a small amount of organic carbon is included. The processing method according to claim 11. The treatment method according to claim 12, wherein the decomposing agent contains hydrogen peroxide and at least one persulfate selected from ammonium persulfate, sodium persulfate, potassium persulfate and calcium persulfate. The treatment method according to claim 12, wherein the catalyst solution is a ferrous sulfate solution having a concentration of 0.1 M or less. The step of adding the conversion agent to generate the conversion waste slurry further includes a step of using barium hydroxide as the conversion agent and a step of producing the conversion waste slurry containing barium sulfate fine particles. The processing method described in. In the step of adding the conversion agent to generate the conversion waste slurry, an ammonia-containing gas is further generated.
The treatment method according to claim 1, further comprising a step of treating the ammonia-containing gas into nitrogen gas and steam. The treatment of the ammonia-containing gas is
In order to directly convert ammonia into nitrogen gas and water vapor, a method of passing the ammonia-containing gas through an oxidative decomposition catalyst bed of ammonia, and absorbing the ammonia-containing gas with water to make ammonia water, and then ammonium hydroxide in water. The treatment method according to claim 16, which is at least one selected from the methods of performing oxidative decomposition of the above to convert into nitrogen gas and water. The treatment method according to claim 17, wherein the ammonia-containing gas first enters the ammonia gas storage tank before passing through the ammonia oxidative decomposition catalyst bed. The treatment method according to claim 2, wherein the solid borate is at least one kind of calcium borate in the form of mud, powder, granules, and lumps. The step of fixing the at least one type of solid waste is
The process of putting at least one kind of solid waste into a waste barrel and
A step of pouring the curable slurry into the waste barrel to fill the gaps in the waste barrel and sealing the at least one type of solid waste.
The treatment method according to claim 4, further comprising a step of waiting for the curing of the curable slurry to form a fixed body. The processing method according to claim 20, wherein the step of forming the fixed body further includes a step of capping the waste barrel to form a fixed body package. The step of solidifying the waste activated carbon is
A step of pretreating the granules of the discarded activated carbon to a low water content so that water does not drip, and
The treatment method according to claim 2, further comprising a step of uniformly mixing the granules of the discarded activated carbon and the curable slurry to form a granule slurry body and performing the solidification treatment. A method for wet oxidation of an organic substance, which comprises using hydrogen peroxide containing at least one persulfate selected from ammonium persulfate, sodium persulfate, potassium persulfate and calcium persulfate as a decomposing agent. The wet oxidation method for an organic substance according to claim 23, wherein the organic substance is at least one of an ion exchange resin, a polymer resin, an organic compound, a vegetable fiber, a vegetable fat and oil, an animal fat and oil, and a mineral fat and oil. The wet oxidation method for an organic substance according to claim 23, wherein the organic substance is a liquid and the proportion of a single molecule thereof is larger than the proportion of a polymer. The method for wet oxidation of an organic substance according to claim 25, wherein the organic substance which is a liquid is an ion exchange resin wet oxidation decomposition solution having a total organic carbon (TOC) concentration of 1000 ppm or less.

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