CN114255901A - Optimization of waste resin wet oxidation and method for treating waste by using oxidized waste liquid - Google Patents
Optimization of waste resin wet oxidation and method for treating waste by using oxidized waste liquid Download PDFInfo
- Publication number
- CN114255901A CN114255901A CN202110961176.3A CN202110961176A CN114255901A CN 114255901 A CN114255901 A CN 114255901A CN 202110961176 A CN202110961176 A CN 202110961176A CN 114255901 A CN114255901 A CN 114255901A
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- Prior art keywords
- waste
- borate
- degradation
- slurry
- treatment
- Prior art date
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- 238000009279 wet oxidation reaction Methods 0.000 title claims description 27
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Images
Classifications
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- G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
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- G—PHYSICS
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- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
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- G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
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- G21F9/36—Disposal of solid waste by packaging; by baling
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
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- Processing Of Solid Wastes (AREA)
- Treatment Of Water By Ion Exchange (AREA)
Abstract
本发明公开了一种将含阳离子交换树脂的废离子交换树脂进行湿法降解，并将产生的降解废液制备成可硬化浆，以供进行其他废弃物的固化/固定处理，以获得性能优良的固态废弃物体，并达成废弃物大幅减容的方法。本发明还公开了一种使用含过硫酸盐的双氧水为降解剂，以降解废离子交换树脂或有机物(包括有机废弃物)的方法，其可提高降解的效率，显著减少双氧水的消耗量并得到较好的矿化效果。
The invention discloses a method for degrading waste ion exchange resin containing cation exchange resin by wet method, and preparing the generated degraded waste liquid into hardenable pulp for curing/fixing treatment of other wastes, so as to obtain excellent performance solid waste, and achieve a method of greatly reducing the volume of waste. The invention also discloses a method for degrading waste ion exchange resin or organic matter (including organic waste) by using hydrogen peroxide containing persulfate as a degrading agent, which can improve the efficiency of degradation, significantly reduce the consumption of hydrogen peroxide and obtain Better mineralization effect.
Description
Technical Field
The invention relates to a method for treating waste, in particular to a method for treating radioactive waste ion exchange resin. The ion exchange resin refers to styrene-divinylbenzene polymers (styrene-divinylbenzene polymers) containing sulfonic acid groups or quaternary ammonium groups.
Background
The most commonly used nuclear power units in the world at present are a water-pressing type unit and a water-boiling type unit, and the low-and-medium-radioactivity wastes generated by the water-pressing type unit and the water-boiling type unit can be roughly divided into two types, namely wet wastes and dry wastes. In the wet waste aspect, the generators of the pressurized water type unit mainly include borate waste liquid, waste ion exchange resin (hereinafter referred to as waste resin), waste activated carbon and the like; the producer of the boiling water type unit mainly comprises waste resin, waste activated carbon and filtering residue (filtration slurry), and no sodium sulfate waste liquid generated by resin regeneration is generated because the regeneration of the ion exchange resin is not carried out at present. The main difference in dry waste is that the generation of combustible dry waste is not much related to the type of unit, and if the combustible dry waste is incinerated, the combustible waste is converted into slag and furnace ash after incineration, and the volume of the dry waste is greatly reduced. In addition, in any type of plant, radioactive wastes such as sludge, contaminated metals, and waste filter cartridges are generated. All of the above are radioactive wastes suitable for treatment using the techniques of the present invention.
The most common treatment of radioactive waste or wet waste is traditionally the cement solidification technique, in which the waste and cement are made into a slurry and barreled, and the slurry is hardened to form a stable monolithic solid waste (solid waste). Because different wastes have different characteristics, different curing conditions are required to be adopted for respectively treating when cement curing is carried out, so that the cement curing body has different technical problems, and the finally produced waste curing body has high yield due to low waste load rate of the cement curing body. The following describes the treatment problems and technical conditions of several kinds of wastes that are challenging to treat.
As mentioned above, cement solidification is a technique that was commonly adopted in the early days for the disposal of radioactive waste, and so far, some nuclear power plants are still in use. When the cement curing technology is used for treating the borate waste liquid, the borate (generally sodium borate) in the waste liquid can seriously hinder the hydration of cement, hinder the hardening of cement paste and generate a so-called solidification retardation (solidification retardation) phenomenon. In order to reduce this phenomenon, the cement curing of borate waste liquid can be performed only at a low boron concentration, or slaked lime or other alkaline agent is added to reduce the curing retardation before adding the cement curing agent, for example, US4,293,437, US4,210,619, US4,620,947, US4,800,042 and US4,906,408, and chinese patents CN102254579B, CN102800377A, etc. However, these methods all result in a large increase in the volume of the solidified borate waste liquid. Although cement solidification systems are simple in equipment and can reduce equipment investment costs, radioactive waste is increasingly expensive to manage, and the final disposal site is difficult to demand, and these methods are not economical.
In the development of advanced cement solidification technology (advanced solidification), Nikkiso Corporation (JGC Corporation) in Japan, sodium borate waste liquid is heated to 40 to 60 ℃ and lime is added to the waste liquid to react for about 10 hours, so that sodium borate is converted into stable calcium borate precipitate, and the precipitate is filtered and dehydrated, and then cement is added to the precipitate to solidify the precipitate. It is said that the volume reduction effect is remarkably improved, but the operation is lengthy and secondary waste liquid (secondary waste) containing sodium hydroxide is generated, and thus complete treatment is not achieved.
The present inventors have disclosed a method for solidifying a borate waste liquid in taiwan patent No. 68,875, U.S. patent No. 5,457,262, U.S. patent No. 5,998,690, european union patent EP0644,555, european union patent EP0929,079, and the like, in which the borate waste liquid is concentrated into a sodium polyborate solution having a boron content of 110,000ppm or more, and then solidified with a specially prepared cement-based solidifying agent. The method can produce the solidified body with extremely high borate load rate, the volume of the solidified body produced by treating the same amount of borate waste liquid is less than 1/10 of that of the solidified body produced by the traditional cement solidification method, and the volume reduction effect is very excellent. However, since the borate content of the cured product is high, the application of the cured product is limited in the case where the water-immersion resistance of the cured product is required to be strict.
The treatment of borate waste liquid is also called as steaming method, which is to heat the waste liquid directly after barreling to evaporate water to form boric acid or borate solid containing crystal water. Although this method reduces the volume of the waste, the borate is not stabilized or mineralized, and is still in a completely soluble state and is not stable.
The same problems exist with the use of cement curing techniques to treat waste resins. The waste resin has ion exchange capacity, and can perform ion exchange with ions in the cement solidified body to influence the stability of the solidified body, and can also absorb or release water to cause the solidified body to shrink-expand and break and crack, so that the waste resin load rate of the solidified body is greatly limited, and the volume of the cement after solidification is greatly increased. In addition, the waste resin cement is not mineralized after being cured, still emits odor, pollutes the environment, is also subjected to biological degradation and decomposition, generates sulfide to destroy the barrier of the disposal engineering, and leads to the worry of the disposal.
The method for treating waste resin includes two types of dry treatment and wet treatment besides cement curing, wherein the dry treatment includes incineration, direct vision and pyrolysis, Q-CEP treatment (Quantum-Catalytic Extraction Process), etc.; examples of the wet method include an acid hydrolysis method (acid digestion), a wet oxidation method (wet oxidation), a subcritical or supercritical water oxidation method (sub-or super-critical water oxidation), and a high-temperature steam reforming method (team reforming). Among them, incineration was first developed and was carried out by some countries. When the incineration method is used for treatment, the waste resin is generally mixed with other combustible waste to be incinerated so as to control the emission concentration of SOx, NOx or other harmful gases; the control of the emission of radioactive nuclides is a key problem in incineration, and unless the emission of volatile carbon-14, tritium, cesium-137 and other nuclides can be effectively avoided, the waste resin must be removed in advance, so that the radioactivity is reduced and then the waste resin is incinerated, which also causes difficulty in the incineration treatment of the waste resin.
The above methods for treating waste resin at high temperature all face the problems of material corrosion, treatment and discharge of nuclear species and toxic gas, and the problems that residues and secondary waste (secondary waste) are still to be treated properly, which causes difficulties in practical application; in addition, the high-temperature treatment also has the defects of high equipment cost, low flexibility of system operation and manpower scheduling and the like.
Compared with the disadvantages of the high-temperature treatment method, the wet oxidation method using Fenton reaction (Fenton reaction) has the basic advantages of low reaction temperature (about 100 ℃), no toxic gas generation, no nuclear species escape and the like, and is beneficial to the development of practical application.
A wet oxidation method developed by AEA of UK comprises adjusting pH with slaked lime and sulfuric acid at 100 deg.C and pH 3-4 to perform oxidative decomposition of granular waste ion exchange resin to decompose organic components into CO2And H2And O. According to the literature reports, the waste liquid and the residue obtained by treating the waste resin by the method are subjected to cement curing, and the volume of the finally generated cured body is not reduced compared with the volume of the waste resin before treatment, but has relatively good volume reduction effect compared with the direct cement curing of the waste resin.
The present inventors have disclosed a technique for degrading a waste resin by a wet oxidation method of Fenton reaction, in Taiwan patent No. I255,277, U.S. Pat. No. US7,482,387B2, Japanese patent No. JP4,414,214, European Union patent No. EP1,137,014, etc., and have used barium hydroxide instead of slaked lime to adjust pH, and have used a specially prepared curing agent to solidify the degraded waste liquid and residue. When the technology is used for treating the mixed resin of the cathode and the anode in equal volume ratio, the volume of the produced solidified body is about 1/3 of the volume of the original waste resin, the quality of the solidified body meets the requirement standard of each main nuclear energy country, and no secondary waste to be treated remains.
As is clear from the above description, the conventional radioactive waste treatment is basically as shown in fig. 1, and is carried out in two stages: in the first stage, according to the characteristics of the waste, the reduction and volume reduction treatment such as dehydration, drying, evaporative concentration, precipitation, incineration or cracking is carried out according to the needs, and high-concentration waste liquid, waste pulp or intermediate products such as solid powder, particles or residues are obtained; in the second stage, the intermediate product is solidified or fixed by a proper method according to the characteristics of the intermediate product, so as to obtain waste object (waste form) with qualified quality. Wherein the solidification treatment refers to preparing the waste liquid or the waste slurry into a monoblock (monolithic) waste solidified body (solidified body for short); the fixing treatment is that the solid waste is barreled and then is filled with the hardenable slurry to embed the waste, and a massive waste fixing body (a fixing body for short) is formed after the hardenable slurry is hardened; if the properties of the solid intermediate product meet the packaging conditions, the solid intermediate product can be packaged directly by using a qualified High Integrity Container (HIC) without performing a fixing process. Among them, the preparation of waste materials of fine wet solid waste such as waste ion exchange resin, sludge, and residue is a process of adding a curing agent in the form of slurry to prepare a solid, and therefore, conventionally, the process is also called a curing treatment, and the product is also called a cured product. This convention will also be used throughout the following description.
Basically, the second stage includes curing, fixing, and encapsulating processes, all of which produce a compatibilizing effect. The extent of the capacity increase depends on the concentration of the waste and the dosage of the added curing agent in terms of the solidification of the waste liquid and the waste slurry; the fixation depends on the capacity holding rate of the waste barrel and the use amount of the hardenable pulp; the packaging is determined by the volume holding rate of the packaging barrel. The magnitude of the compatibilization in the second stage treatment, as in the current case, is between about 50% and 500% depending on the process.
Disclosure of Invention
The invention provides a method for preparing hardenable pulp by using waste liquid generated by wet degradation of waste resin (including anion and cation exchange resin) and treating other wastes with the hardenable pulp, and an improved wet oxidation method for degrading waste ion exchange resin and organic wastes.
The method for treating other wastes by using the degradation products of the waste resin comprises the following steps: performing wet degradation treatment on the waste resin to generate degradation waste liquid containing sulfate; concentrating the degradation waste liquid, and adding a conversion agent to generate conversion waste pulp containing stable sulfate particles; adding the raw material of the hardenable slurry into the converted waste slurry, uniformly mixing to prepare the hardenable slurry, and curing or fixing at least one other waste. The stabilized sulfate particles contained in the converted waste pulp of the present invention are derived from the sulfonic acid groups contained in the cation exchange resin, and therefore the waste ion exchange resin preferably contains a relatively high proportion of cation exchange resin sufficient to prepare a desired amount of hardenable pulp. Basically, the spent ion exchange resin from the nuclear power plant contains more cation exchange resin than anion exchange resin and is therefore well suited for use in the process of the present invention.
In an embodiment of the present invention, the wet degradation process is a wet oxidation (wet oxidation) process, and is preferably performed at a pH of less than 3. The pH of the aqueous slurry of the cation-anion mixed waste resin is reduced along with the increase of the proportion of the cation resin, and the pH is increased on the contrary. Since the degradation of the cation resin can generate sulfuric acid, when the cation resin accounts for a high proportion, the pH of the degradation waste liquid can be reduced along with the progress of the degradation. The proportion of cation-anion mixed waste resin generated by nuclear power is generally higher, so that the pH needs to be adjusted slightly, but if necessary, the pH can be adjusted by sulfuric acid. If the continued production of sulfuric acid results in too high acidity, it can be adjusted with barium hydroxide.
In an embodiment of the invention, the at least one other waste is selected from: borate waste liquid, solid borate, waste activated carbon, sludge, incineration ash, waste filter cartridges, metal waste, and waste compressed blocks, and the step of treating at least one of the wastes further comprises forming the at least one of the wastes into a solidified body or a fixed body with the hardenable slurry.
In an embodiment of the invention, the processing method further includes the following steps: providing borate waste liquid; adjusting the components of the borate waste liquid and concentrating to prepare high-concentration borate waste liquid containing polymerized borate; preparing high-concentration borate waste liquid into borate particles by using a granulating device and at least one granulating agent; mixing borate particles with the hardenable slurry, uniformly mixing to form particle slurry of the hardenable slurry, then filling the particle slurry into a waste barrel, and forming a solidified body package after the particle slurry is hardened.
In an embodiment of the invention, the borate waste liquid is a sodium borate solution.
The invention also provides an improved degradation method of the waste ion exchange resin or the organic matter, which comprises the step of carrying out degradation treatment on the waste ion exchange resin or the organic matter by using persulfate and hydrogen peroxide as degradation agents, thereby improving the degradation efficiency, reducing the concentration of TOC (total organic carbon) remained in degradation liquid and greatly reducing the consumption of the hydrogen peroxide.
The invention adopts wet method to degrade waste ion exchange resin, and prepares the generated degradation waste liquid into hardenable slurry for merging other wastes including borate waste liquid, solid borate, waste activated carbon, sludge, polluted metal, waste filter core and the like, thereby greatly reducing the use of additional materials, inhibiting the capacity increase of second stage treatment and realizing the minimization of radioactive wastes.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical means of the present invention more clearly understood, the present invention may be implemented in accordance with the content of the description, and in order to make the above and other objects, features, and advantages of the present invention more clearly understood, the following preferred embodiments are described in detail with reference to the accompanying drawings.
Drawings
FIG. 1 is a diagram showing two-stage treatment of radioactive waste;
FIG. 2 is a schematic flow diagram of the waste treatment method of the present invention;
FIG. 3 is a schematic view showing an apparatus for degradation treatment of a waste resin according to an embodiment of the present invention;
FIG. 4 is a schematic diagram of an apparatus for ammonia-containing off-gas treatment according to an embodiment of the present invention.
Detailed Description
Through experimental research, the invention completes the following novel method for treating radioactive wastes.
(first) pretreatment of the other waste 001 to be combined (S100): the other waste 001 to be combined is a waste to be solidified or fixed in a hardenable slurry, and is pretreated in a state suitable for solidification or fixation. Basically, all solid wastes can be solidified or fixed, but preferably with good stability and mechanical strength, wet solid wastes such as waste activated carbon or sludge require removal of excess water. Liquid waste such as sodium borate waste from nuclear power plants is pre-treated to solid particles or added with an alkaline agent such as calcium hydroxide to form a calcium borate solid precipitate which is then dehydrated to a fine particulate solid containing moderate moisture. The calcium borate solid can be in the form of mud, powder, granule or block. The shape and size of the thick dry waste must be adjusted to fit for fixing in barrel; if the solidification is not selected or the reason for unsuitable solidification treatment exists, the fine powder or particle waste can be barreled and compressed into a compressed block and then subjected to fixing treatment. In general, the pretreatment provides other waste 001 with the proper moisture content, shape, size and consistency to be suitable for the final curing or fixing treatment.
(II) performing wet degradation of the waste resin (S200): the preferred wet degradation method is a wet oxidation method, and the preparation of the hardenable paste is performed with the resulting waste resin degradation waste liquid (S300). The properties of the hardenable pulp are critical to the quality of the final waste product of the invention, and preferably have the following properties: good fluidity, so as to facilitate the mixing or pouring operation when the material is solidified or other wastes are fixed; the hardened product has excellent stability and mechanical strength, and is favorable for producing a cured body or a fixed body with excellent performance. Furthermore, the waste from the production of hardenable pulp needs to be in relatively large quantities to meet the requirements, and the waste resins from nuclear power plants essentially meet the above conditions.
(iii) preparation of final waste object (S400, fig. 2): when preparing a solidified body (S410, fig. 2), uniformly mixing the pretreated waste particles or powder with the prepared hardenable slurry to form a hardenable particle slurry, filling the particle slurry into a waste barrel, and hardening to form a solidified body; when preparing the fixing body (S420, fig. 2), the other pretreated waste 001 is first put into a waste barrel, and then the hardenable slurry is poured to fill the gap and the periphery in the barrel, and the fixing body is formed after the hardenable slurry is hardened.
For a more specific description of the method, the combined treatment of three main wastes of a pressurized-water nuclear power plant, including waste ion exchange resin and sodium borate waste liquid or waste activated carbon, will be described as an example. The three are most challenging to treat in the waste of the pressurized water unit, so the three represent practical values of the invention in the waste treatment of the pressurized water unit. The waste ion exchange resin is used for preparing hardenable slurry, sodium borate waste liquid needs to be pretreated into solid particles, and the water content of the waste activated carbon needs to be adjusted to have a proper low degree without dripping water. The main implementation steps S100, S200, S300, S400 and the like are shown in fig. 2, wherein the preparation of the waste material pack at S400 can be divided into the preparation of the cured body pack 013 at S410 and the preparation of the fixed body pack 014 at S420. It is understood that the sequence of FIG. 2 is only exemplary, and the steps S100 and S200-S300 are not limited to the sequence except that the steps S100 and S200-S300 are completed before the step S400, but only need to be performed in accordance with the hardening time course of the hardenable paste.
Step S100: pretreating the borate waste liquid into borate particles. This step comprises preparing the borate waste liquid into a high-concentration borate waste liquid containing polymerized borate (step S100a), and preparing the high-concentration borate waste liquid into borate particles (step S100b), which are described below, respectively.
Step S100 a: the composition of the borate waste liquor (001, other waste) is adjusted and the borate waste liquor is concentrated to produce a high concentration borate waste liquor containing polymeric borate.
Step S100 b: the high-concentration borate waste liquid was made into borate particles (002, solid waste generated by pretreatment) using a granulating apparatus and a granulating agent.
Step S200: the degradation treatment of the waste resin 003 is carried out, and a degradation waste liquid 004 is produced. The degradation treatment of the waste resin 003 may be a step of a wet oxidation method, and in addition to the generation of the degradation waste liquid 004, the degradation treatment oxidatively decomposes the hydrocarbon component of the waste resin 003 into gaseous CO2And H2And O, wherein the gas is filtered to remove the fog drops and then is discharged. The degradation waste liquid 004 contains ammonium hydroxide, sulfuric acid or ammonium sulfate, and residues and a small amount of organic carbides according to the ratio of the negative resin to the positive resin and the content of impurities in the waste resin.
The impurities contained in the waste resin are mainly solid state which is included in the pores of the resin, cation adsorbed by the cation resin and anion adsorbed by the anion resin, etc., wherein a part of the impurities can hinder the degradation effect of the wet oxidation, and some adsorbed ions, such as carbon-14 (C-14) adsorbed by the anion resin14C) H of (A) to (B)14CO3 -Ions are then likely to be inDuring the degradation process, gas containing carbon-14 nuclear species is released, and radiation damage to personnel and the environment is caused. The present invention is to eliminate the above problems, and optionally, the process for removing impurities contained in the waste resin before wet oxidation comprises adding water to the waste resin to form a slurry, removing solid impurities from the pores by ultrasonic vibration, washing with a desorbent solution, and adsorbing H adsorbed by the waste resin14CO3 -Desorbing ions into water; the desorbent used may be a solution of salts or compounds of alkali metals, alkaline earth metals, or ammonium, for example: perchlorate, sulfate, nitrate, phosphate, monohydrogen phosphate, dihydrogen phosphate, oxalate, iodide, bromide, etc., and is preferably used for subsequent stabilization treatment of desorption waste liquid, especially for desorption of H14CO3 -More preferably, the ions form a solid precipitate. The waste slurry generated by removing the solid impurities can be kept still in a bucket tank to allow the solid impurities to settle, the supernatant liquid is recycled as water for slurrying resin, and the slurry containing the solid impurities at the bottom of the bucket is merged into the converted waste slurry prepared in the step 300 for subsequent treatment. Desorption of H14CO3 -The waste washing liquid generated by the ions can be also merged into the waste conversion pulp prepared in the step 300 for subsequent treatment or separately treated as required; if the method is treated by combining the conversion waste slurry, the desorption agent can also be directly added into the slurried water, so that the removal of the solid impurities and the desorption of the carbon-14 are combined. After the waste resin washed by the alkaline desorption agent is mixed with the wet oxidation catalyst solution, the pH of the waste resin is required to be adjusted before the waste resin is degraded<3。
Step S300: the hardenable pulp 006 is prepared from the degraded waste liquid 004. This step includes the preparation of the converted waste pulp from the degraded waste liquid 004 of step S300a and the preparation of the hardenable pulp 006 from the converted waste pulp of step S300b, respectively, as described below.
Step S300 a: the conversion waste slurry is prepared from the degradation waste liquid 004. The degradation waste liquid 004 is first concentrated to an appropriate concentration, and then a conversion agent is added to form a conversion waste slurry. The converting agent in this step is preferably barium hydroxide, which converts the sulfuric acid and ammonium sulfate in the degradation waste liquid into insoluble barium sulfate, and thus obtains a conversion waste slurry containing barium sulfate particles. And simultaneously, the pH value of the waste slurry is increased, so that ammonium radicals in the waste slurry are converted into ammonia gas to escape. The ammonia gas is oxidized and decomposed into nitrogen and water gas, and then the nitrogen and the water gas are discharged.
Step S300 b: hardenable pulp 006 is prepared from the converted waste pulp. Hardenable slurry material 005 (i.e., curing agent powder) is added to the converted waste slurry and mixed uniformly to prepare hardenable slurry 006. The hardenable slurry 006 can be used to treat at least one solid waste 002, here, borate pellets, resulting from the pretreatment.
Step S410: this is the preparation of a solidified body pack 013 of borate particles. The borate particles prepared in step S100 (002, solid waste generated by pretreatment) and the hardenable slurry 006 prepared in step S300 are uniformly mixed to obtain a hardenable particle slurry, and then the hardenable particle slurry is contained in a waste barrel, and after the particle slurry is hardened into a solidified body, the solidified body is covered to form a solidified body packaging member 013.
The high-concentration borate waste liquid prepared in the above step S100a mainly contains sodium borate. The boron concentration of the high-concentration sodium borate waste liquid needs to be more than 100,000ppm, preferably more than 110,000ppm, if the boron concentration is less than 100,000ppm, the polymerization degree of the sodium borate is insufficient, the mechanical strength of borate particles produced after granulation in the step S100b is poor, but if the boron concentration is too high, the problems that conveying pipelines are blocked due to too high viscosity and materials are not well mixed during granulation are prevented.
The borate particles of step S100b can be produced by using a stirring tank equipped with planetary stirring blades. During granulation, firstly, placing the granulating agent into a stirring tank, enabling the powder of the granulating agent to be higher than the stirring blades, then starting stirring, slowly dripping the high-concentration sodium borate waste liquid into the powder of the granulating agent in stirring, and enabling the liquid drops to form initial particles under rolling contact with the powder; the high-concentration sodium borate waste liquid and the granulating agent form borate particles through a solidification reaction, in the reaction, liquid high-polymerization degree sodium borate and the granulating agent generate a displacement reaction to become solid high-polymerization degree borate particles, and the borate composition and the mechanical strength of the particles are mainly determined according to the components of the granulating agent.
After the initial particles are formed, continuous granulation can be carried out by adopting a mode of adding high-concentration sodium borate waste liquid and granulating agent in a crossed loop; the weight of the added waste liquid and the granulating agent must be kept in a proper proportion, and the adding speed must be controlled properly so as to prevent the particles from being bonded due to excessive viscous liquid; continuous granulation can be suspended when the granules reach the capacity limit of the granulation device, and granulation is continued after a part of granules are taken out until the granules reach the required quantity.
The degradation treatment of the waste resin 003 in the step S200 may be a wet degradation treatment other than the wet oxidation method, but is preferably a degradation treatment by a wet oxidation method using a Fenton reaction. The wet oxidation method utilizing Fenton reaction has the advantages of low reaction temperature, simple components of the generated degradation waste liquid and contribution to subsequent treatment. The purpose of performing the degradation of the waste resin 003 is to make the waste resin 003 inorganic (mineralize) in addition to the volume reduction, so as to prevent the waste resin 003 from emitting a bad odor and causing biological deterioration, thereby contributing to the environmental protection and the safety of the final disposal. Therefore, step S200 is preferably performed to achieve a certain degree of degradation, and a degradation rate of 99% should be a reasonable target.
The wet oxidation method utilizing the Fenton reaction traditionally uses hydrogen peroxide as a degradation agent, but the research of the invention finds that the degradation efficiency of the hydrogen peroxide is greatly reduced when the concentration of organic carbides is lower. Taking wet oxidation of waste resin 003 as an example, more hydrogen peroxide may be consumed to degrade the last 5% of organic carbon than 95% before degradation, and the difference between the amounts of hydrogen peroxide consumed to degrade 98% and 99% is more than 30%.
In order to achieve high degradation rate and reduce the consumption of hydrogen peroxide, the invention discovers through a series of researches: the degradation efficiency at low TOC concentration can be effectively improved and the consumption of the degradation agent is greatly reduced by using the double-component degradation agent containing persulfate (peroxisulfonate) and hydrogen peroxide. Suitable persulfate includes ammonium persulfate, sodium persulfate, potassium persulfate, calcium persulfate, etc., and preferably ammonium persulfate, because the components of the finally produced degradation waste liquor 004 are completely the same as those of the hydrogen peroxide. The two-component degradation agent is not only suitable for ion exchange resin, but also suitable for wet oxidation of other organic matters such as high molecular resin, organic compounds, plant fiber matters, plant oil, animal oil and mineral oil.
Because the sulfate concentration in the degradation waste liquid can be increased when the persulfate is used, namely, the quantity of the produced degradation waste liquid or solidified bodies can be increased, the occasion of adding the persulfate is preferably selected under the conditions of low TOC concentration and low degradation efficiency of the hydrogen peroxide. For solid organic materials (e.g., ion exchange resins), it is preferable that the organic materials are completely dissolved; while the overall treatment efficiency can be significantly affected by, for example, the yield of degraded waste liquid or solidified bodies, it is also contemplated to add the solid organic compounds at a lower TOC concentration after they have been completely dissolved. For liquid organic substances, the influence of the timing of addition on the overall treatment efficiency also needs to be considered, for example, in the case of low polymer organic substance ratio and high single molecule organic substance ratio, which is not limited by the technology but is considered in the benefit.
The degradation waste liquid 004 generated in step S200 may contain ammonium hydroxide, sulfuric acid, ammonium sulfate, residues, and a small amount of organic carbon depending on conditions. Step S300a, after adding transforming agent, can transform sulfate in the degraded waste liquid 004, i.e. transform sulfate and ammonium sulfate in the degraded waste liquid 004 into insoluble stable precipitate, and make ammonium ion (NH) in the precipitate4 +) Conversion to ammonia (NH)3) And (4) escaping. And carrying out innocent treatment on the escaped ammonia gas. In addition, this step also includes concentration of the conversion waste slurry to adjust the water content thereof, in order to make the solid content (equivalent to the aforementioned insoluble precipitate) of the conversion waste slurry suitable for the subsequent treatment.
The conversion agent is preferably barium hydroxide, and a barium hydroxide solution, a barium hydroxide aqueous slurry or barium hydroxide powder may be used. Since the solubility of barium hydroxide at normal temperature is not high, barium hydroxide can be dissolved with hot water to improve the solubility in order to avoid adding too much water.
The ammonia-containing gas generated by the conversion of sulfate radical and ammonium sulfate is firstly delivered into an ammonia tank by an air pump after fog drops are removed by a demister, and then is quantitatively delivered to an ammonia oxidation decomposer (Oxid)a corporation-decomposition). When the ammonia is sent to the ammonia oxidation decomposer, air with a certain proportion is injected at the same time, so that the ammonia is oxidized and decomposed into N under the catalysis of an oxidative decomposition catalyst2And H2And O. Finally, N is carried out by an exhaust system2And H2And (4) discharging O. In addition, ammonia water can be obtained by absorbing ammonia-containing outgas with water, and then the ammonia water is converted into nitrogen and water by oxidative decomposition of ammonium hydroxide in the water.
The ammonia gas tank may be a space tank for buffering ammonia gas flow, a storage tank, a cooling and heating device, and calcium chloride (CaCl) placed in the space tank2) As an ammonia adsorbent. The calcium chloride can adsorb ammonia gas at low temperature to form CaCl2·nNH3(n-2 to 8), when ammonia is adsorbed to a certain degree, ammonia desorption can be carried out by heating, and the ammonia desorption can be repeatedly used, so that storage and buffer space for ammonia is provided, and the operation flexibility is improved.
Step S300b is to prepare the hardenable paste 006 by converting the waste paste. The curable syrup 006 is preferable to have excellent fluidity and to form a cured body having excellent properties. The advantages and disadvantages of the hardenable paste 006 and the cured body characteristics are exhibited based on the selected hardenable paste raw material 005 (i.e., the curing agent powder). The hardenable paste material 005 may be prepared using a boswellia material (pozzolanic materials), or may be prepared using a special formulation.
Step S410 is to perform solidification of the borate particles using the hardenable paste 006. The borate particles are added into the hardenable slurry 006 according to a predetermined ratio, and a slurry of the hardenable particles is obtained after stirring and mixing are completed. The granular slurry is then put into a waste container and left to stand to harden (solidify) to form a solid mass (solidified granular material).
When barium hydroxide is used as a conversion agent, sulfate contained in the waste conversion slurry is barium sulfate, is solid with high specific weight (4.5) and excellent fine aggregate (fine aggregate) characteristics, and borate particles are hard solids with high mechanical strength, so that the borate particle solidified body prepared by the invention has the characteristics of compact structure and high mechanical strength, the reduction of the compressive strength after water immersion can be avoided, and the water resistance of the solidified product of the borate waste liquid is greatly improved.
The hardenable slurry 006 may be used for solidification/fixation of other solid wastes such as waste activated carbon, sludge, incineration ash, metal wastes, waste filter cartridges, etc., in addition to the solidification of the solidified borate particles. The combined waste is solid, so that the pretreatment is relatively simple because granulation is not needed. The radioactive waste activated carbon produced by the nuclear power unit adsorbs various toxic substances and nuclear species, and the pollution can be caused by incineration treatment, so that the direct curing by using the hardenable pulp of the invention is a feasible treatment method.
The method of the present invention specifically practices the concept of "waste disposal with waste", also fully achieves minimization of radioactive waste, and yields high quality solidified/fixed waste. The following examples are provided to demonstrate the processing method and effects of the present invention, and these examples are only application examples of the present invention, and do not represent the whole implementation scope of the present invention, and therefore should not be construed as limiting the scope of the present invention.
Comparative example one: hydrogen peroxide is used for simulating wet oxidative degradation of waste resin
This comparative example demonstrates the use of hydrogen peroxide to simulate the degradation of waste resins by wet oxidation, using an apparatus 1 as shown in figure 3.
The device 1 for degradation treatment of waste resin comprises a closed glass reaction tank and an attached feeding and discharging device. The lower part of the glass reaction tank is a tank body 01 with 2.5 liters, the upper part is a tank cover 02, the tank cover 02 and the tank body 01 are tightly connected by metal clamping buckles, and the tank body 01 and the tank cover can be separated by loosening the metal clamping buckles. The tank cover 02 is provided with four openings, wherein the opening 07 can be used as a feed port for the degradation agent, and a measuring cylinder 06 is arranged on the tank cover for feeding the degradation agent solution manually or by a Peristaltic pump (peristatic pump); the opening 08 can be used as a defoaming agent charging port for adding a defoaming agent when necessary; the opening 04 can be used as a feed inlet for catalyst solution and ion exchange resin, and also can be used as a measuring port for pH and temperature and a sampling port for degrading waste liquid, and is sealed by a silica gel plug when not in use; the opening 09 can be used as a gas outlet and is connected with a glass cooling pipe 10 for condensing escaping steam; the outlet of the glass cooling pipe 10 is connected with a conical glass bottle 12 for receiving condensate, the glass cooling pipe 10 is also provided with a return pipe 11 for returning the condensate to the glass reaction tank when necessary so as to keep the liquid level stable, and the uncondensed gas is discharged to the smoke cabinet through the outlet 14 of the conical glass bottle 12.
The whole device 1 is erected on a supporting rack, an electric heater 05 is arranged under a glass reaction tank, and the electric heater 05 is arranged on a supporting table (not shown) with adjustable height, can be adjusted in height according to needs and can be moved away at any time.
At the beginning of the degradation treatment, 600 ml of catalyst solution (0.06M ferrous sulfate), 66 g (82.5 ml) of strong acid type cation exchange resin and 33 g (44.72 ml) of strong base type anion exchange resin used in a nuclear power plant are taken as simulated waste resins. Because the simulated waste resin does not contain solid impurities and does not adsorb carbon-14 nuclear species, the steps of removing the solid impurities and the carbon-14 nuclear species are eliminated, the simulated waste resin is sequentially added into a glass reaction tank through an opening 04, then the opening 04 is sealed by a silica gel plug, and the pH value of the solution is measured and determined to be lower than 2.5. Then the stirring motor is started to stir and start heating. When the temperature in the tank reaches 95 ℃, the heating is stopped, and a peristaltic pump is started to feed 35 percent hydrogen peroxide into the glass reaction tank at the flow rate of 5 milliliters per minute. Because of the exothermicity of the reaction, the temperature is raised to the boiling point and the reaction is maintained at the boiling point of ; when the gas generated by the reaction passes through the glass cooling pipe 10, the water vapor is condensed and collected in the conical glass bottle 12, and the non-condensed carbon dioxide is connected to the smoke cabinet for discharging; during the reaction, if foam accumulation is found to increase, then the injection of antifoam inhibits. The defoaming agent used in this example was a commercially available product containing a silicone resin and a fatty acid ester component, and was used after diluted 10 times with water. In the example, 1 ml of defoaming agent is added when the degradation agent is added to 275 ml, 350 ml and 550 ml, and the total volume is 3 ml; if the liquid level is excessively reduced due to evaporation, the condensate reflux is supplemented to keep the liquid level within a certain variation range.
In order to understand the degradation efficiency of the resin, the sampling is performed after the resin is completely dissolved, the addition is suspended after the predetermined addition amount of the degradation agent is reached, and the sampling is started after 10 minutes. Heating and stirring are suspended during sampling, 2 g of degraded waste liquid sample is taken from the opening 04 for analysis, then the heater 05 is removed, an electronic scale is placed below the glass tank, a heat insulation plate is placed on the platform surface of the electronic scale, the weight reading of the electronic scale is reset to zero, then the metal clamp connecting the tank cover 02 and the tank body 01 is loosened, the glass reaction tank is seated on the heat insulation plate on the electronic scale, and the weight is weighed and recorded.
After sampling and weighing, the device is immediately returned to the original state, stirring and heating are started as required, and the addition of the degradation agent is returned until the next sampling and weighing steps are carried out. The time for each sampling was controlled to 5 minutes.
The treatment results are shown in table 1, and include the hydrogen peroxide addition weight (hydrogen peroxide addition), the weight of the degraded waste liquid, the Total Organic Carbon (TOC) content of the degraded waste liquid, and the like, which are shown in table 1. According to analysis, the carbon content (carbon content) of the anion and cation exchange resins used in this experiment was found to be 149.5 and 150.7 g/L, respectively, by elemental analysis, i.e., the total organic carbon content of the ion exchange resin before degradation was 19.12 g. The calculated degradation rate change is also shown in table 1, ignoring the small amount of TOC carried away by the boil-off gas, where the degradation rate is calculated as follows:
degradation rate (%) -100-weight of waste liquor (g) x waste liquor toc (ppm) x 10-4/19.12
The degradation experiment results in table 1 show that the degradation rate was 95.49% when the amount of hydrogen peroxide added reached 550 ml, and 98.91% when the amount of hydrogen peroxide added reached 1,000 ml. The degradation rate of 95.49% is obtained by adding 550 ml in the front section, and the degradation rate is only improved by 3.42% by adding 450 ml in the rear section, which shows that the degradation effect of the hydrogen peroxide is greatly influenced by the TOC level; it was also shown that the degradation efficiency of hydrogen peroxide became very weak when the TOC was below 500 ppm.
Table 1: results of simulating waste resin wet oxidation degradation by using hydrogen peroxide
The first embodiment is as follows:
this example demonstrates the effect of the present invention on the same simulated wet oxidative degradation of waste resin as the comparative example one using two-agent degradation agents (hydrogen peroxide + persulfate). The apparatus used was the same as in comparative example one.
Since the degradation efficiency is affected by factors including the addition rate of the degradation agent, the organic form, the TOC concentration, and the like, and the processing results can be compared on the basis of the same conditions, the conditions of this example are the same as those of the comparative example except that 550 ml of the degradation agent used in the previous stage is 35% hydrogen peroxide, a two-agent type degradation agent containing 5 parts of ammonium persulfate and 95 parts of 35% hydrogen peroxide is used instead from 550 ml, and the defoaming agent is added at 5 ml times of 285 ml, 380 ml, 440 ml, 470 ml, and 515 ml in the degradation agent solution, respectively.
The results of the treatment are shown in Table 2, and the degradation rate was 95.31% after the reaction with 550 ml of 35% hydrogen peroxide, which was approximately the same as that of comparative example one. When the total addition of the degradation agent is 700 ml (comprising 550 ml of 35% hydrogen peroxide and 150 ml of the two-agent degradation agent), the degradation rate reaches 99.01%; when the waste liquid is added into 1000 ml, the TOC of the waste liquid is lower than 50ppm, and the degradation rate reaches 99.88%. It was shown that good degradation was still obtained when TOC was reduced to 500ppm or even below 100 ppm. If the goal is to achieve 99% degradation rate, more than 30% of the amount of the degradation agent can be saved by using two types of degradation agents.
Table 2: processing results of embodiment one
Example two:
this example demonstrates the preparation of a hardenable slurry with a waste liquid simulating the degradation of waste resin (ion exchange resin) to embed and solidify borate particles obtained from the pretreatment of the borate waste liquid, and demonstrates the pretreatment process for preparing borate particles from the borate waste liquid.
Preparation of simulated borate waste liquid:
putting 640 g of deionized water into a 6L glass beaker, stirring, then dividing 900 g of 99% sodium hydroxide and 4,800 g of 99% boric acid into 4 parts respectively, and slowly adding the sodium hydroxide and the boric acid into the beaker in a cross mode of adding sodium hydroxide and then boric acid for 4 times respectively; after the boric acid is completely dissolved, the deionized water is used for supplementing the water lost by evaporation, and then the temperature of the deionized water is adjusted to 85 ℃ and the deionized water is kept for standby. The resulting solution was analyzed to have a boron concentration of 131,080ppm, i.e., 13.108 wt%, converted to an equivalent boric acid concentration of 75.71 wt%, and a sodium/boron molar ratio of 0.29.
Pretreatment of borate waste liquid: and (6) granulating. The granulation in this example may further include the steps of preparation of a granulating agent, initial granulation and continuous granulation, and the like, as described below.
Preparation of granulating agent:
a sludge curing agent STA-110 (a product of International company of the ancient cooking vessel) of market vendor is taken for 40 minutes, Portland II type cement is taken for 30 minutes and barium hydroxide monohydrate is taken for 30 minutes to be mixed, and the mixture is crushed by a crusher and is sealed and packaged to be used as a granulating agent after passing through a 150-mesh screen.
And (3) initial granulation:
putting 2,000 g of the granulating agent powder into a 20L revolution-rotation planetary stirrer, setting a proper rotating speed, starting stirring blades, then taking 2,640 g of the simulated borate waste liquid, slowly dripping the simulated borate waste liquid into the stirred granulating agent powder in several times, wherein the adding amount of the powder in each time is determined to be that the powder is not excessively moist and is bonded into a large block, and the powder is added again after the adding of each time needs to wait for the solution to be evenly dispersed and does not react with the granulating agent to show moist luster any more; after the simulated borate waste liquid is added, stirring is continued for about 5 minutes, and the initial granulation stage is finished.
And (3) continuous granulation:
and (3) continuously keeping the granules prepared in the initial granulation stage in a granulator, continuously stirring, slowly dripping 200 g of the simulated borate waste liquid into the granulator to uniformly distribute the simulated borate waste liquid on the granules, then adding 80 g of the granulating agent on the stirred granules, and adding the simulated borate waste liquid again when the granules do not show damp luster. When the reaction is completed after the simulated borate waste liquid and the granulating agent are added in a circulating and cross mode for 50 times respectively, the granulation is temporarily stopped, half weight of particles are taken out, the circulating and cross feeding granulation is continued until the simulated borate waste liquid and the granulating agent are added for 100 times respectively and the weights of the particles reach 20,000 g and 8,000 g respectively, the granulation is stopped, and after the stirring is continued for 5 minutes, all the particles (including the former and the latter) are mixed together for solidification.
The material conditions for the two-stage granulation are shown in table 3, and 10,000 g of a granulating agent and 22,640 g of a simulated borate waste liquid were added in total, and the weight ratio of the granulating agent/the simulated borate waste liquid was 0.442. The diameter of the prepared particles is mainly distributed between 2 mm and 5mm, and the boron content is 9.09wt percent, which is equivalent to 52.48wt percent of boric acid.
Table 3: material for simulating granulation of borate waste liquid
Simulating the degradation of the waste resin:
the apparatus and the simulated waste resin used were the same as in the first comparative example, and the step of removing impurities from the simulated waste resin was also eliminated. The required amount of waste liquid was large, and therefore, the treatment was carried out in 4 batches. As described below.
For each batch, 1,200 g of 0.06M ferrous sulfate solution, and 180 g of the same cation resin and 90 g of the same anion resin used in comparative example one were added to the reaction vessel, and then stirring and heating were started. When the solution temperature reached 95 ℃, heating was stopped and 35% hydrogen peroxide was added at a rate of 12 ml/min, the heat of reaction maintaining the reaction at boiling. When the addition amount of the hydrogen peroxide reaches 1,500 ml, adding 90 g of the cation resin and 45 g of the anion resin, maintaining the same rate, and continuously adding 750 ml of hydrogen peroxide, repeating the adding for 4 times in the way until 540 g of the cation resin and 270 g of the anion resin are added in total, and 4,500 ml of 35% hydrogen peroxide, degrading by using the two-agent type degradation agent, reducing the addition rate of the degradation agent to 10 ml/min, stopping until the addition amount of the two-agent type degradation agent reaches 245 ml, and then continuously stirring for 30 min, and finishing the degradation operation. The temperature during the above degradation process is kept between 95 ℃ and the boiling point, and heating is carried out if necessary to help maintain the temperature; when the liquid level is reduced due to boiling, the liquid level is kept not to change too much in a condensate reflux mode; if the bubble accumulation phenomenon occurs, the defoaming agent is used for inhibiting timely, and 12 ml of the defoaming agent is added in total in the experiment.
Degradation of a total of 4 batches of 2,160 g (2,700 ml) of the plus resin and 1,080 g (1,464 ml) of the minus resin was performed under the same conditions. The obtained degradation waste liquids were mixed together, and concentrated to adjust the total weight to 1,540 g, and then analyzed to obtain a sulfate group content of 4.02 mol/kg.
And (3) conversion of the degradation waste liquid:
the device for converting the degraded waste liquid is the same as the device 1 in FIG. 3 except for the device comprising an ammonia gas emission treatment part as shown in FIG. 4, wherein, of the four openings 04, 07, 08 and 09 on the cover 02 of the glass reaction tank, the opening 04 is used as a converting agent feeding port and is also used as a temperature and pH measuring port if necessary; the opening 07 is used as a feed inlet for degrading waste liquid, and a measuring cylinder type funnel is arranged on the opening for manually adding the waste liquid; opening 09 serves as a conversion escape outlet.
The apparatus 2 for ammonia-containing off-gas treatment is schematically shown in FIG. 4, a conical glass flask 12a for collecting the condensate and for retaining the ammonia-containing off-gas without condensation, i.e. as a buffer tank for ammonia gas; the opening 16a of the glass cone 12a serves as an air inlet; the flowmeter 17 and the regulating valve 18 are air regulating devices for regulating the air flow; the outlet 14a is a conversion gas escape outlet and is connected with an ammonia oxidation decomposition device 19 by a silica gel hose; the ammoxidation decomposition apparatus 19 comprises a preheater and a high-temperature catalyst bed, and is capable of providing a constant temperature of 600 ℃ or lower, preheating the ammonia-containing off-gas, and ammoxidation-decomposing the ammonia into N by using an ammoxidation decomposition catalyst2And H2O; drawerThe air engine 21 is used for assisting in converting escaped air and overcoming flow resistance; the air regulating valve 20 is used for regulating the air flow so as to regulate the negative pressure generated by the air pumped by the air pump.
Before the treatment, the ammoxidation decomposition device 19 is preheated to 300 ℃ for standby; then, mixing the barium hydroxide monohydrate powder with water in a ratio of 4: 1466.5 g of transforming agent water slurry (containing 586.6 g of barium hydroxide monohydrate) is prepared according to the weight ratio of 6, the transforming agent water slurry is placed into a glass reaction tank from an opening 04, after stirring is started, the prepared degradation waste liquid is slowly input by a peristaltic pump until 770 g of the transforming agent water slurry is input totally, and then heating is carried out to keep the temperature at about 90 ℃ and stirring is continuously carried out for 2 hours so as to completely remove ammonia gas. Then, the heating was stopped and the slurry was transferred to a beaker and allowed to cool until it became a concentrated conversion waste slurry having a weight of 1,305 g.
The ammonia-containing gas generated in the conversion process enters a conical bottle 12a through a glass cooling pipe 10a, the condensed liquid is retained in the bottle, the uncondensed ammonia-containing gas is mixed with the input air, then the mixture flows to an ammonia oxidation decomposition device 19 to be decomposed into water vapor and nitrogen, and then the water vapor and the nitrogen are pumped to a smoke cabinet by an air pump to be discharged.
The same procedure was repeated one more time to convert a total of 1,540 g of the degradation waste liquid to completion, and the obtained conversion waste pulps were mixed to total 2,655 g (1,487 g in dry weight) of conversion waste pulp containing 44% of water.
The conversion waste slurry was transferred to a 10 liter agitation mixer, and 1,565 g of hardenable slurry raw material mixed with the ring-shaped sludge curing agent SPF-210 and portland type II cement in equal weight ratio and 1,976 g of borate particles were added under agitation, and after uniform mixing, a slurry of borate particles was obtained, the composition of which is shown in table 4.
Table 4: slurry composition of borate particles
Then, the granular slurry is barreled, in this example, poured into a polyethylene plastic mold with an inner diameter of 5 cm and a height of 6 cm, and after bubbles are removed and the surface is smoothed in a vibration mode, the barreled granular slurry is placed in a constant temperature and humidity box with the temperature of 25 ℃ and the relative humidity of more than 95 percent for curing for 28 days. After the curing, tests of compressive strength, weather resistance (freeze-thaw resistance), water immersion resistance and the like were carried out in accordance with the quality specifications of the low-level radioactive waste in taiwan, and further, an impact resistance test of 9 m drop was carried out, and the results are shown in table 5, which shows that the quality of the cured product meets the quality requirements stipulated in each nuclear energy country.
Table 5: quality test results of cured product of borate particles
| Test items | Compressive strength | Weather resistance | Water resistance | Impact resistance |
| Results | 9.57MPa | 11.18MPa | 13.69MPa | Qualified (no obvious fragmentation) |
Example three:
this example demonstrates the combined treatment of waste resin and waste activated carbon.
The wet oxidative degradation of the waste resin comprising 540 g (about 675 ml) of the male resin and 270 g (about 366 ml) of the female resin was first carried out in the same manner as in example one, and the degraded waste liquid was prepared into 2,682 g of the converted waste pulp containing 45% of water, and 1,565 g of the same raw material hardenable pulp as in example one was added to prepare 4,247 g of hardenable pulp for use. The simulated waste activated carbon used in the experiment is waste activated carbon used for nuclear power station water treatment, is wet particles with the size of 6-40 meshes, and has the water content of 10.79% and the specific gravity of 1.06. 1,175 g (1,108 ml) of waste activated carbon and prepared hardenable slurry are uniformly stirred and mixed to prepare 5,422 g of waste activated carbon solidified slurry, the composition of which is shown in table 6 (note: the waste activated carbon solidified slurry is the name of the slurry formed by mixing the waste activated carbon and the hardenable slurry and is the precursor of the waste activated carbon solidified slurry); the specific gravity of the solidified waste body was measured to be 2.02, that is, 2,684 ml in volume, and therefore, the volume loading rate of the waste activated carbon of the solidified body was 41.3%.
An experiment for increasing the loading rate of the waste activated carbon was also performed. Degradation of waste resin was carried out in the same manner, 2,588 g of converted waste pulp having a water content of 43% was prepared, and 4,128 g of the same raw material for hardenable pulp was added thereto. This hardenable paste was then mixed with 1,510 g (1,425 ml) of waste activated carbon to prepare 5,638 g of a paste, the composition of which is also shown in Table 6. The specific gravity of the cured body was determined to be 1.996, that is, 2,825 ml in volume, and therefore the volume loading rate of the waste activated carbon was 50.44%.
Table 6: waste activated carbon slurry composition
The cured product thus prepared was sampled in the same manner as in example two and subjected to quality testing, and the results are shown in table 7, which indicated that the cured product was excellent in quality.
Table 7: quality test results of waste activated carbon cured body
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (26)
1. A method for preparing hardenable pulp from waste liquid generated by wet degradation of waste ion exchange resin and solidifying/fixing other wastes, comprising the steps of:
removing impurities of waste ion exchange resin, performing wet degradation treatment, and generating degradation waste liquid containing sulfate, wherein the waste ion exchange resin contains cation exchange resin;
concentrating the degradation waste liquid, and adding a conversion agent to generate a conversion waste slurry containing sulfate particles; and
adding a hardenable slurry raw material into the converted waste slurry and uniformly mixing to prepare a hardenable slurry for curing or fixing at least one other waste.
2. The method of claim 1, wherein the at least one other waste is selected from borate waste liquor, solid borate, waste activated carbon, sludge, incineration ash, waste filter cartridges, metal waste, and waste compression blocks.
3. The method of claim 1, wherein the at least one other waste comprises a liquid waste; the treatment process further comprises pre-treating the liquid waste into solid particles or precipitates suitable for curing or fixing treatment using the hardenable slurry.
4. The method of claim 1, wherein the at least one other waste comprises a solid waste; the treatment method also comprises the step of pretreating the solid waste to have proper water content, shape, size and compactness, so that the treatment method is suitable for curing or fixing treatment by using the hardenable slurry.
5. The method of claim 1, wherein the step of removing impurities from the spent ion exchange resin further comprises slurrying the spent ion exchange resin with water and removing solid impurities entrained therein by ultrasonic vibration, and removing the adsorbed carbon-14 nuclei with an alkaline desorbent; the waste liquid generated by removing impurities is merged into the converted waste pulp for treatment.
6. The method of claim 5, wherein the basic desorbent is selected from at least one of the following solutions of alkali metal, alkaline earth metal or ammonium salts or compounds: perchlorates, sulfates, nitrates, phosphates, monohydrogen phosphates, dihydrogen phosphates, oxalates, iodides, bromides.
7. The method of claim 2, further comprising the step of pre-treating the borate waste stream into borate particles:
providing a borate waste liquid;
adjusting the content of the borate waste liquid and concentrating the borate waste liquid to prepare a high-concentration borate waste liquid containing polymerized borate;
preparing the high-concentration borate waste liquid into borate particles by using a granulating device and at least one granulating agent; and
and uniformly mixing the borate particles with the hardenable slurry to form a particle slurry, then filling the particle slurry into a waste barrel, and hardening the particle slurry to form a solidified body.
8. The method of claim 7, wherein the step of forming the solidified body further comprises capping the trashcan to form a solidified body enclosure.
9. The method of claim 7, wherein the borate waste solution is a sodium borate solution.
10. The method according to claim 1, wherein in the wet degradation treatment, the acid and the base used for adjusting the pH of the degradation reaction solution are sulfuric acid and barium hydroxide, respectively.
11. The method of claim 1, wherein the wet degradation treatment is selected from at least one of the following methods: wet oxidation, supercritical water oxidation, and acidolysis.
12. The method of claim 11, wherein the step of performing a wet oxidation treatment of the spent ion exchange resin and producing the degradation waste stream comprises:
preparing a degradation agent and a catalyst solution; and
putting the waste ion exchange resin after removing impurities into the catalyst solution, and adjusting the pH value of the solution<3, maintaining the solution at a temperature of 95 ℃ to the boiling point, and adding the degradation agent to oxidatively decompose the hydrocarbon component of the waste ion exchange resin into CO2And H2O and produces said degradation effluent containing ammonium, sulfate, residues and small amounts of organic carbon.
13. The method of claim 12, wherein the degradation agent comprises hydrogen peroxide and a persulfate salt of at least one selected from the group consisting of: ammonium persulfate, sodium persulfate, potassium persulfate, and calcium persulfate.
14. The method according to claim 12, wherein the catalyst solution is a ferrous sulfate solution having a concentration of 0.1M or less.
15. The method of claim 1, wherein the step of adding said conversion agent to produce a conversion waste slurry further comprises using barium hydroxide as a conversion agent and producing a conversion waste slurry comprising barium sulfate particles.
16. The method of claim 1, wherein the step of adding said conversion agent to produce a conversion waste slurry further produces an ammonia-containing gas; the treatment method also comprises the step of treating the ammonia-containing gas into nitrogen and water vapor.
17. The method of claim 16, wherein the treatment of the ammonia-containing gas is selected from at least one of the following methods:
passing the ammonia-containing gas through an ammonia oxidative decomposition catalyst bed for directly converting ammonia into nitrogen and water vapor; and
absorbing the ammonia-containing gas with water to obtain ammonia water, and performing oxidative decomposition of ammonium hydroxide in the water to convert the ammonia water into nitrogen and water.
18. The method of claim 17, wherein the ammonia-containing gas is introduced into an ammonia gas storage tank before passing through the catalyst bed for oxidative decomposition of ammonia.
19. The method of claim 2, wherein the solid borate is at least one of the following forms of calcium borate: mud, powder, granule, and block.
20. The method of claim 4, wherein the step of immobilizing the at least one solid waste further comprises:
charging the at least one solid waste into a waste bin;
injecting the hardenable slurry into the waste bin to fill voids within the waste bin and encapsulate the at least one solid waste;
waiting for the hardenable slurry to harden and form a fixed body.
21. The method of claim 20, wherein the step of forming the retainer further comprises capping the waste bin to form a retainer pack.
22. The method of claim 2, wherein the step of subjecting the waste activated carbon to a curing process further comprises:
performing a pretreatment of the spent activated carbon particles to a water content of a suitable low degree without dripping water; and
and uniformly mixing the waste activated carbon particles with the hardenable slurry to form a particle slurry, and carrying out the solidification treatment.
23. The wet oxidation method of the organic matter is characterized by comprising the following steps of using hydrogen peroxide containing at least one persulfate selected from the following steps as a degradation agent: ammonium persulfate, sodium persulfate, potassium persulfate, and calcium persulfate.
24. The method of claim 23, wherein the organic material is at least one of: ion exchange resin, high molecular resin, organic compound, plant fiber, plant oil, animal oil and mineral oil.
25. The method of claim 23, wherein the organic material is in a liquid state and has a higher proportion of single molecules than high molecules.
26. The method of claim 25, wherein the liquid organic material is an ion exchange resin wet oxidation degradation liquid having a total organic carbon concentration of 1000ppm or less.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4710318A (en) * | 1982-06-04 | 1987-12-01 | Hitachi, Ltd. | Method of processing radioactive waste |
| US5457262A (en) * | 1993-09-16 | 1995-10-10 | Institute Of Nuclear Energy | Preparation of inorganic hardenable slurry and method for solidifying wastes with the same |
| JP2001208896A (en) * | 2000-01-28 | 2001-08-03 | Inst Nuclear Energy Research Rocaec | Co-solidification method of low-level radioactive wet waste generated from boiling water nuclear power plant |
| JP2005181256A (en) * | 2003-12-24 | 2005-07-07 | Inst Nuclear Energy Research Rocaec | Treatment method of waste ion exchange resin |
| EP1564188A1 (en) * | 2004-02-13 | 2005-08-17 | Institute of Nuclear Energy Research, Atomic Energy Council | A method for processing spent ion-exchange resins |
| TW200941502A (en) * | 2008-01-17 | 2009-10-01 | Areva Np Gmbh | Procedures for the conditioning of radioactive ion exchange resins |
| CN111196668A (en) * | 2020-02-17 | 2020-05-26 | 南京大学盐城环保技术与工程研究院 | Emergency treatment method for benzene-containing strong-acid chemical wastewater |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3866402B2 (en) * | 1998-02-17 | 2007-01-10 | 株式会社東芝 | Chemical decontamination method |
| TW459249B (en) * | 2000-12-22 | 2001-10-11 | Wang Hung Bo | Super critical wet processing method for low radiation waste |
| TWI255277B (en) * | 2003-10-17 | 2006-05-21 | Inst Nuclear Energy Res Aec | Processing method for spent ion-exchange resins |
| US8354567B2 (en) * | 2008-01-30 | 2013-01-15 | David Donald Leavitt | Destruction of mixed radioactive waste by catalyzed chemical oxidation |
| JP2011214971A (en) * | 2010-03-31 | 2011-10-27 | Toshiba Corp | Method and device for processing spent ion exchange resin |
| JP2013156227A (en) * | 2012-01-31 | 2013-08-15 | Nippon Steel & Sumikin Engineering Co Ltd | Method for removing radioactive material |
| CN103529162A (en) * | 2013-10-29 | 2014-01-22 | 四川农业大学 | Determination method for total organic carbon (TOC) of solid combustible matters |
| CN210180789U (en) * | 2019-04-26 | 2020-03-24 | 中国辐射防护研究院 | Pretreatment device for C-14 in environmental water sample |
| CN111048223B (en) * | 2019-11-22 | 2023-11-24 | 中广核工程有限公司 | Supercritical water oxidation reactor for treating radioactive organic waste |
-
2020
- 2020-09-23 TW TW109132805A patent/TWI755071B/en active
-
2021
- 2021-02-04 JP JP2021016462A patent/JP7095130B2/en active Active
- 2021-08-20 CN CN202110961176.3A patent/CN114255901A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4710318A (en) * | 1982-06-04 | 1987-12-01 | Hitachi, Ltd. | Method of processing radioactive waste |
| US5457262A (en) * | 1993-09-16 | 1995-10-10 | Institute Of Nuclear Energy | Preparation of inorganic hardenable slurry and method for solidifying wastes with the same |
| JP2001208896A (en) * | 2000-01-28 | 2001-08-03 | Inst Nuclear Energy Research Rocaec | Co-solidification method of low-level radioactive wet waste generated from boiling water nuclear power plant |
| JP2005181256A (en) * | 2003-12-24 | 2005-07-07 | Inst Nuclear Energy Research Rocaec | Treatment method of waste ion exchange resin |
| EP1564188A1 (en) * | 2004-02-13 | 2005-08-17 | Institute of Nuclear Energy Research, Atomic Energy Council | A method for processing spent ion-exchange resins |
| TW200941502A (en) * | 2008-01-17 | 2009-10-01 | Areva Np Gmbh | Procedures for the conditioning of radioactive ion exchange resins |
| CN111196668A (en) * | 2020-02-17 | 2020-05-26 | 南京大学盐城环保技术与工程研究院 | Emergency treatment method for benzene-containing strong-acid chemical wastewater |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115739929A (en) * | 2022-11-16 | 2023-03-07 | 华北电力大学 | Method for recycling glass fiber through pyrolysis of retired fan blade and regenerated glass fiber obtained through method |
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| TWI755071B (en) | 2022-02-11 |
| JP2022052694A (en) | 2022-04-04 |
| JP7095130B2 (en) | 2022-07-04 |
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