WO2023019563A1 - 废树脂湿法氧化的优化及利用氧化废液处理废物的方法 - Google Patents
废树脂湿法氧化的优化及利用氧化废液处理废物的方法 Download PDFInfo
- Publication number
- WO2023019563A1 WO2023019563A1 PCT/CN2021/113814 CN2021113814W WO2023019563A1 WO 2023019563 A1 WO2023019563 A1 WO 2023019563A1 CN 2021113814 W CN2021113814 W CN 2021113814W WO 2023019563 A1 WO2023019563 A1 WO 2023019563A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- waste
- degradation
- borate
- slurry
- waste liquid
- Prior art date
Links
- 239000002699 waste material Substances 0.000 title claims abstract description 315
- 239000007788 liquid Substances 0.000 title claims abstract description 120
- 238000000034 method Methods 0.000 title claims abstract description 88
- 239000011347 resin Substances 0.000 title claims description 77
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- 239000002002 slurry Substances 0.000 claims abstract description 78
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 66
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- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 30
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- 239000002910 solid waste Substances 0.000 claims abstract description 14
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims abstract description 11
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- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical group [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 85
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- 239000012535 impurity Substances 0.000 claims description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
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- 235000010339 sodium tetraborate Nutrition 0.000 claims description 15
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- 239000003054 catalyst Substances 0.000 claims description 12
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- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 10
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- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 4
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- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 3
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/06—Treatment of sludge; Devices therefor by oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/06—Treatment of sludge; Devices therefor by oxidation
- C02F11/08—Wet air oxidation
-
- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
- G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
- G21F9/28—Treating solids
-
- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
- G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
- G21F9/28—Treating solids
- G21F9/30—Processing
Definitions
- the invention relates to a treatment method of waste, in particular to a treatment method of 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.
- the most commonly used nuclear power units in the world are pressurized water units and boiling water units.
- the medium and low radioactive waste generated by the two can be roughly divided into two types: wet waste and dry waste.
- wet waste the generators of the pressurized water unit are mainly borate waste liquid, waste ion exchange resin (hereinafter referred to as waste resin) and waste activated carbon;
- waste resin waste ion exchange resin
- waste activated carbon the generators of the boiling water unit are mainly waste resin, waste activated carbon and filter waste.
- Filtration sludge because the regeneration of ion exchange resin is no longer carried out, so there is no sodium sulfate waste liquid generated by resin regeneration.
- dry waste its generation has little to do with the type of unit.
- the main difference lies in whether the combustible dry waste is incinerated. Significant volume reduction of dry waste. In addition, no matter what type of unit it is, it will also produce radioactive waste such as sludge, contaminated metals, and waste filter elements. All of the above are radioactive wastes that are suitable for processing by the technology of the present invention.
- cement solidification technology is the most commonly used traditionally, which is to prepare waste and cement into a slurry and put it in barrels. After the slurry hardens, it becomes a stable monolithic (monolithic) Solid waste form. Since different wastes have different characteristics, different curing conditions must be used for cement curing. Therefore, in addition to their own different technical difficulties, the final product is also difficult due to the low waste loading rate of the cement solidified body. The output of solidified waste remains high. The following is a description of some of the most challenging types of waste to deal with, as well as the technical situation.
- cement solidification is an early technology commonly used in the treatment of radioactive waste, and some nuclear power plants are still in use today.
- the borate generally sodium borate
- the cement curing of borate waste liquid can only be carried out at low boron concentration, or before adding cement curing agent, add slaked lime or other alkaline agents to reduce the curing retardation phenomenon, for example, U.S.
- these practices all lead to a substantial increase in the volume of the solidified body of borate waste liquid.
- the equipment of the cement solidification system is simple and can reduce the investment cost of equipment, the management cost of radioactive waste is increasing day by day, and it is hard to find a land for final disposal, so these methods are no longer economical.
- Japan's JGC Corporation JGC Corporation
- the so-called "advanced cementation technology (advanced cementation)" which is to heat the borate waste liquid to 40-60 ° C, and add lime for about 10 hours of reaction, so that Sodium borate is transformed into stable calcium borate precipitate, and after the precipitate is filtered and dehydrated, cement is added to solidify. It is said that the volume reduction effect has been significantly improved, but the operation is lengthy and will generate secondary waste containing sodium hydroxide, so complete treatment has not been achieved.
- the present inventor discloses a borate waste liquid solidification method in China Taiwan Patent Invention No. 68,875, U.S. Patent No. 5,457,262, U.S. Patent No. , After concentrating the borate waste liquid into a polymeric sodium borate solution with a boron content of 110,000ppm or more, it is then solidified with a specially formulated cement-based curing agent.
- the method can produce a solidified body with a very high borate loading rate, and the volume of the solidified body produced by treating the same amount of borate waste liquid is lower than 1/10 of that of the traditional cement solidification method, and the volume reduction effect is very excellent.
- due to the high borate content of the cured body its application will be limited when the water immersion resistance of the cured body is strictly required.
- borate waste liquid still has the so-called evaporation to dry method, which is to directly heat and evaporate the water after the waste liquid is packed in barrels, so as to form boric acid or borate solids containing crystal water.
- evaporation to dry method which is to directly heat and evaporate the water after the waste liquid is packed in barrels, so as to form boric acid or borate solids containing crystal water.
- this method will reduce the volume of the waste, the borate is still in a completely soluble state without stabilization or mineralization treatment, and there is no stability at all.
- waste resin has ion exchange capacity, it will conduct ion exchange with ions in the cement solidified body, which will affect the stability of the solidified body, and will also cause shrinkage-swelling and cracking of the solidified body due to absorption or release of water.
- the loading rate of the waste resin is greatly restricted, resulting in a substantial increase in the volume of the cement after curing.
- the waste resin cement has not been mineralized after solidification, and it still emits odor, pollutes the environment, and also undergoes biological degradation and decomposition, producing sulfides that destroy the barriers of the disposal project, making the safety of disposal unsafe.
- the treatment methods of waste resin include dry treatment and wet treatment.
- the dry treatment includes incineration, direct vitrification (direct vitrification) and high temperature pyrolysis (pyrolysis) method, Q-CEP Treatment method (Quantum-Catalytic Extraction Process), etc.; wet method includes acid digestion, wet oxidation and sub-or super-critical water oxidation, high temperature Steam reforming, etc.
- incineration direct vitrification
- pyrolysis high temperature pyrolysis
- Q-CEP Treatment method Quantum-Catalytic Extraction Process
- wet method includes acid digestion, wet oxidation and sub-or super-critical water oxidation, high temperature Steam reforming, etc.
- the waste resin When the incineration method is used, the waste resin is generally incinerated mixed with other combustible wastes to control the emission concentration of SOx, NOx or other harmful gases; the emission control of radioactive nuclei is a key issue in the incineration method, unless it can be effectively Avoid the discharge of volatile carbon-14, tritium, cesium-137 and other nuclear species, otherwise the waste resin must be removed in advance to reduce the radioactivity before incineration, which also causes difficulties in the incineration of waste resin.
- High-temperature treatment methods for waste resins all face problems such as material corrosion, treatment and discharge of nuclei and toxic gases, and residues and secondary wastes that have yet to be properly treated, resulting in difficulties in practical application; in addition, High-temperature processing also has disadvantages such as high equipment cost and low flexibility in system operation and manpower scheduling.
- the wet oxidation method using the Fenton reaction has the basic advantages of low reaction temperature (about 100°C), no toxic gas, and no nuclear species escape, which is beneficial to development of practical applications.
- the wet oxidation method developed by the British AEA company uses ferrous sulfate as the catalyst, hydrogen peroxide as the oxidant, hydrated lime and sulfuric acid to adjust the pH, and oxidizes and decomposes the granular waste ion exchange resin at a temperature of about 100°C and a pH of 3 to 4. Decompose organic components into CO 2 and H 2 O. According to literature reports, the waste liquid and residue obtained by treating the waste resin by the method are cemented. Although the volume of the solidified body produced at the end is not reduced compared with the volume of the waste resin before treatment, compared with the direct cement solidification of the waste resin, then It has a relatively good volume reduction effect.
- the treatment of radioactive waste in the prior art is basically as shown in Figure 1, which is divided into two stages: in the first stage, according to the characteristics of the waste, dehydration, drying, evaporation concentration, precipitation, precipitation, etc. Incineration or pyrolysis and other reduction and volume reduction treatment, and obtain high-concentration waste liquid, waste slurry or solid powder, particles or residues and other intermediate products; in the second stage, according to the characteristics of the intermediate products, use appropriate methods to solidify Or fixed, in order to obtain the waste form of qualified quality.
- solidification treatment refers to the preparation of waste liquid or waste slurry into a monolithic waste solidification body (referred to as solidification body); fixation treatment refers to the waste that was originally solid in barrels, and then uses hardenable slurry The waste is perfused and embedded, and a monolithic waste fixer (fixed body for short) is formed after the hardenable slurry is hardened; if the characteristics of the solid intermediate product meet the conditions of encapsulation, it is also possible not to carry out fixation treatment, but directly Use a qualified high integrity container (High Integrity Container, HIC) for packaging.
- HIC High Integrity Container
- waste ion exchange resin, sludge, residue and other small wet solid wastes are prepared by adding a curing agent in a slurry state to prepare a solid. Therefore, it is customarily called curing treatment, and the product is also called cured body. This customary title will also be used in the following descriptions.
- the second stage includes curing, fixing, and encapsulation, all of which will have a capacity-enhancing effect.
- the extent of capacity increase depends on the concentration of waste and the amount of additional curing agent; the fixation depends on the volume of the waste barrel and the amount of hardenable pulp used; Depends on the volume filling rate of the packaging barrel.
- the capacity increase range of the second-stage treatment is about 50% to 500% due to different methods.
- the invention provides a method for preparing hardenable pulp from waste liquid produced by wet degradation of waste resins (including anion and cation exchange resins), and treating other wastes with the hardenable pulp, and a method for degrading waste ion exchange resins Improved wet oxidation process with organic waste.
- waste resins including anion and cation exchange resins
- the method for treating other wastes with degradation products of waste resins comprises the following steps: performing wet degradation treatment of waste resins to generate sulfate-containing degradation waste liquid; concentrating the degradation waste liquid, and adding a transforming agent to Generate conversion waste slurry containing stable sulfate particles; add hardenable pulp raw materials to the conversion waste slurry, and mix uniformly to prepare hardenable slurry, and use it for solidification or immobilization of at least one other waste.
- the stable sulfate particles contained in the conversion waste pulp of the present invention are derived from the sulfonic acid groups contained in the cation exchange resin, so the waste ion exchange resin should contain a relatively high proportion of cation exchange resin to be sufficient for the preparation of the required amount hardenable pulp.
- spent ion exchange resins from nuclear power plants contain more cation exchange resins than anion exchange resins and are therefore well suited for the application of the method of the present invention.
- the aforementioned wet degradation treatment is a wet oxidation method, and is preferably carried out under the condition of pH ⁇ 3.
- the pH of the water slurry of mixed waste resins of yin and yang will decrease with the increase of the proportion of cation resins, otherwise the pH will increase.
- the degradation of the cation resin produces sulfuric acid, when the proportion of the cation resin is high, the pH of the degradation waste liquid will decrease as the degradation progresses.
- the anion-yang mixed waste resin produced by nuclear power generally has a relatively high proportion of anion resin, so there are not many cases where the pH needs to be lowered, but if necessary, it can be adjusted with sulfuric acid. If the continuous production of sulfuric acid leads to too high acidity, it can be adjusted with barium hydroxide.
- the at least one other waste mentioned above is selected from: borate waste liquid, solid borate, waste activated carbon, sludge, incineration ash, waste filter core, metal waste and the waste compaction block, and the step of processing the at least one waste further includes forming a solidified or fixed body with the at least one waste and the hardenable slurry.
- the above-mentioned treatment method further includes the following steps: providing borate waste liquid; adjusting the composition of borate waste liquid and concentrating to prepare high-concentration borate containing polymeric borate Waste liquid; use a granulation device and at least one granulating agent to manufacture high-concentration borate waste liquid into borate granules; mix borate granules and hardenable pulp, and mix evenly to form a hardenable pulp granular slurry body, and then put it into a waste bucket, and form a solidified body package after the granular slurry hardens.
- the above-mentioned borate waste liquid is sodium borate solution.
- the present invention also provides an improved method for degrading waste ion exchange resins or organic matter, including using persulfate and hydrogen peroxide as degradation agents to degrade waste ion exchange resin or organic matter, thereby increasing the degradation efficiency and reducing the The residual TOC concentration in the degradation solution is greatly reduced, and the consumption of hydrogen peroxide is greatly reduced.
- the present invention uses a wet method to degrade waste ion exchange resins, and prepares hardenable slurry with the generated degradation waste liquid, which is used to process other wastes including borate waste liquid, solid borate, waste activated carbon, sewage, etc.
- Combined treatment of mud, polluted metals, waste filter elements, etc. thus greatly reducing the use of additional materials, and suppressing the expansion of the second stage of treatment, to minimize radioactive waste.
- Figure 1 shows the two-stage treatment diagram of radioactive waste
- FIG. 2 is a schematic flow diagram of the waste treatment method of the present invention.
- Figure 3 is a schematic diagram of a device used for degradation treatment of waste resins in an embodiment of the present invention.
- Fig. 4 is a schematic diagram of a device for treating ammonia-containing outgas in an embodiment of the present invention.
- the present invention completes the following novel method for treating radioactive waste.
- waste 001 for combined treatment refers to waste to be solidified or fixed with hardenable pulp, and these wastes need to be pretreated to be solidified or fixed state. Basically, all solid wastes can be solidified or immobilized, but those with good stability and mechanical strength are preferred. Wet solid wastes such as waste activated carbon or sludge need to remove too much water. Liquid waste, such as sodium borate waste liquid from nuclear power plants, needs to be pretreated into solid particles, or an alkaline agent such as calcium hydroxide is added to form calcium borate solid precipitation, and then dehydrated into fine-grained solids with moderate moisture content. The calcium borate solid can be muddy, powdery, granular or lumpy.
- Coarse dry waste must first be adjusted in shape and size to be suitable for barreling and fixing; if fine powder or granular waste is not selected for solidification or has reasons that are not suitable for solidification treatment, it can be barreled and compressed first After being compressed into a block, it is fixed. In summary, pretreatment renders other waste 001 with the proper moisture content, shape, size and compactness to be suitable for final solidification or immobilization.
- the preferred wet degradation method is wet oxidation, and the obtained waste resin degradation liquid is used to prepare hardenable pulp (S300).
- the characteristics of hardenable pulp have a key influence on the quality of the waste objects finally produced by the present invention, and it is better to have the following characteristics: good fluidity, so as to facilitate the mixing or pouring operation when it solidifies or fixes other wastes;
- the product has excellent stability and mechanical strength, which is conducive to the production of cured or fixed bodies with excellent performance.
- the waste for preparing hardenable pulp needs to have a relatively large amount to meet the demand, and the waste resin produced by nuclear power plants basically meets the above conditions.
- waste ion exchange resin is used to prepare hardenable pulp
- sodium borate waste liquid needs to be pretreated to become solid particles
- waste activated carbon needs to adjust its water content to make it have an appropriate low water content without dripping water.
- FIG. 2 the order of FIG. 2 is only an example, except that step S100 and steps S200-S300 must be completed before step S400, there is no order limitation for S100 and S200-S300, as long as it needs to cooperate with the hardening of the hardenable slurry program to work.
- Step S100 Pretreat borate waste liquid into borate particles. This step includes preparing borate waste liquid into high-concentration borate waste liquid containing polymeric borate (step S100a), and preparing high-concentration borate waste liquid into borate particles (step S100b), respectively described as follows.
- Step S100a adjust the composition of the borate waste liquid (001, other wastes) and concentrate the borate waste liquid to prepare a high-concentration borate waste liquid containing polymeric borate.
- Step S100b Using a granulation device and a granulation agent, the high-concentration borate waste liquid is made into borate granules (002, solid waste generated by pretreatment).
- Step S200 Perform degradation treatment of the waste resin 003, and generate degradation waste liquid 004.
- the degradation treatment of the waste resin 003 can be a step of a wet oxidation method, and in addition to generating the degradation waste liquid 004, the degradation treatment also oxidatively decomposes the hydrocarbon components of the waste resin 003 into gaseous CO 2 and H 2 O , wherein the gas is discharged after being filtered to remove mist droplets.
- Degradation waste liquid 004 contains ammonium hydroxide, sulfuric acid or ammonium sulfate, as well as residues and a small amount of organic carbides according to the ratio of anion and cation resins and impurity content of the waste resin feed.
- the impurities contained in the waste resin are mainly solid state mixed in the pores of the resin, as well as the cations adsorbed by the cation resin and the anions adsorbed by the anion resin, etc. Some of the impurities may hinder the degradation efficiency of wet oxidation, while some Adsorbed ions, such as H 14 CO 3 -ions containing carbon-14 ( 14 C) adsorbed by the anion resin, may release gas containing carbon-14 nuclei during the degradation process, causing radiation to personnel and the environment harm.
- the present invention removes the impurities contained in the waste resin before the wet oxidation, including adding water to the waste resin to form a water slurry, and using ultrasonic waves to generate vibrations to remove the solid impurities from the pores. removal, and washing with a desorbent solution to desorb the H 14 CO 3 - ions adsorbed by the waste resin into water;
- the desorbent used can be a solution of salts or compounds of alkali metals, alkaline earth metals or ammonium, etc.
- the waste slurry produced by the above removal of solid impurities can be allowed to stand in the tank to allow the solid impurities to settle, and the supernatant liquid is recovered as water for pulping resin, and the slurry containing solid impurities at the bottom of the tank is merged into step 300 Subsequent treatment is carried out in the prepared conversion waste slurry.
- the washing waste liquid produced by the desorption of H 14 CO 3 - ions can also be incorporated into the conversion waste slurry prepared in step 300 for subsequent treatment, or it can be treated separately if necessary; if it is combined into the conversion waste slurry,
- the desorbent can also be directly added to the slurry water, so that the removal of solid impurities and the desorption of carbon-14 can be combined.
- Step S300 Prepare hardenable pulp 006 with degradation waste liquid 004. This step includes step S300a of preparing converted waste pulp from degraded waste liquid 004 and step S300b of preparing hardenable pulp from converted waste pulp 006 , respectively described as follows.
- Step S300a Prepare conversion waste slurry from degradation waste liquid 004. Firstly, the degradation 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 the sulfuric acid and ammonium sulfate in the degradation waste liquid into insoluble barium sulfate, so as to obtain the converted waste slurry containing barium sulfate particles.
- the pH value of the waste slurry is increased, so that the ammonium root in it is converted into ammonia gas and released. Ammonia gas is oxidized and decomposed into nitrogen and water vapor and then discharged.
- Step S300b Prepare hardenable pulp 006 from converted waste pulp. Add hardenable slurry raw material 005 (ie curing agent powder) to the conversion waste slurry and mix evenly to prepare hardenable slurry 006.
- the hardenable slurry 006 can be used to treat at least one solid waste 002 from pre-treatment, here borate granules.
- Step S410 This belongs to the preparation of the package 013 of borate particle cured body. Mix the borate granules prepared in step S100 (002, solid waste generated by pretreatment) and the hardenable slurry 006 prepared in step S300 to obtain the hardenable granule slurry and then put it in the waste bucket. The body is hardened into a cured body, and then sealed to become a cured body package 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, and it is better to be more than 110,000ppm. If the boron concentration is lower than 100,000ppm, the degree of polymerization of sodium borate is insufficient, and the borate produced after step S100b granulation The mechanical strength of the granules is not good, but if the boron concentration is too high, it should prevent the blockage of the conveying pipeline due to too high viscosity, and the problem of poor material mixing during granulation.
- the production of borate particles in step S100b can be carried out by using a stirring tank equipped with planetary stirring blades.
- a stirring tank equipped with planetary stirring blades When granulating, put the granulating agent into the stirring tank first, make the height of the granulating agent powder higher than the stirring blade, then start stirring, and then slowly drop the high-concentration sodium borate waste liquid into the stirring granulating agent powder, The droplets and the powder form initial particles under rolling contact; the high-concentration sodium borate waste liquid and the granulating agent form borate particles through a solidification reaction.
- the liquid sodium borate with a high degree of polymerization is replaced by the granulating agent
- the reaction becomes solid borate particles with a high degree of polymerization.
- the borate composition and mechanical strength of the particles are mainly determined by the composition of the granulating agent.
- continuous granulation can be carried out by adding high-concentration sodium borate waste liquid and granulating agent in a cross cycle; the weight of the added waste liquid and granulating agent must maintain an appropriate ratio, and the adding rate must also It must be properly controlled to prevent the granules from sticking due to excessive viscous liquid; continuous granulation can be suspended when the granules reach the capacity limit of the granulation device, and granulation can be continued after taking out some granules until the granules reach the required number.
- the degradation treatment of the waste resin 003 in step S200 can be performed by other wet degradation methods besides the wet oxidation method, but the degradation treatment using the wet oxidation method using the Fenton reaction is preferred.
- the wet oxidation method using the Fenton reaction has the advantages of low reaction temperature and pure composition of the degradation waste liquid, which is beneficial to the subsequent treatment.
- the purpose of degrading waste resin 003 is to reduce volume, another important purpose is to make waste resin 003 inorganic (mineralized), so as to prevent waste resin 003 from emitting foul smell and biological degradation, so as to facilitate environmental protection and final disposal safety . Therefore, step S200 preferably achieves a certain degree of degradation, and a degradation rate of 99% should be a reasonable target.
- the research of the present invention finds that the degradation efficiency of hydrogen peroxide will be greatly reduced when the concentration of organic carbides is low.
- the hydrogen peroxide consumed to degrade the last 5% of organic carbon may be more than the first 95%, and the amount of hydrogen peroxide consumed for the degradation rate of 98% and 99% is more than 30% different.
- the present invention found after a series of studies: the use of a two-component degradation agent containing peroxysulfate and hydrogen peroxide can effectively improve the degradation efficiency at low TOC concentrations and greatly reduce Degradant consumption.
- Applicable persulfates include ammonium persulfate, sodium persulfate, potassium persulfate, calcium persulfate, etc., and ammonium persulfate is preferred, because the composition of the final degradation waste liquid 004 is exactly the same as when hydrogen peroxide is used.
- the two-component degradation agent of the present invention is not only suitable for ion exchange resins, but also suitable for wet oxidation of other organic substances such as polymer resins, organic compounds, vegetable fibers, vegetable oils, animal oils and mineral oils.
- the degradation waste liquid 004 generated in step S200 may contain ammonium hydroxide, sulfuric acid, ammonium sulfate, residue and a small amount of organic carbon due to different conditions.
- Step S300a can carry out the conversion of sulfate in the degradation waste liquid 004 after adding the conversion agent, which is to convert the sulfate radical and ammonium sulfate in the degradation waste liquid 004 into insoluble stable precipitates, and make the ammonium ions (NH 4 + ) into ammonia gas (NH 3 ) and escape. The escaped ammonia gas is then harmlessly treated.
- this step also includes concentrating the converted waste slurry to adjust its water content.
- the conversion agent is preferably barium hydroxide, barium hydroxide solution can be used, barium hydroxide slurry or barium hydroxide powder can also be used. Since the solubility of barium hydroxide at room temperature is not high, in order to avoid adding too much water, barium hydroxide can be dissolved in hot water to increase the solubility.
- the ammonia-containing outgas generated by the transformation of sulfate radical and ammonium sulfate is firstly passed through the demister to remove mist droplets, then transported into the ammonia gas tank by the suction pump, and then quantitatively transported to the ammonia oxidation decomposer (Oxidation-decomposer).
- Oxidation-decomposer ammonia oxidation decomposer
- a certain proportion of air is injected at the same time, so that the ammonia is oxidized and decomposed into N 2 and H 2 O under the catalysis of the oxidation decomposition catalyst.
- N 2 and H 2 O are discharged through the exhaust gas system.
- water can also absorb ammonia-containing outgas to become ammonia water, and then oxidize and decompose ammonium hydroxide in water to convert it into nitrogen and water.
- Step S300b is to prepare hardenable pulp 006 by converting waste pulp.
- Hardenable paste 006 is preferably with excellent fluidity and can form a cured body with excellent performance.
- the characteristics of hardenable paste 006 and cured body are based on the selected hardenable paste raw material 005 (that is, curing agent powder).
- Hardenable pulp raw material 005 can be formulated with pozzolanic materials, or a special formula can be used.
- Step S410 is to use hardenable paste 006 to solidify borate particles.
- the borate particles are added into the hardenable slurry 006 according to a predetermined ratio, and the hardenable particle slurry is obtained after stirring and mixing.
- the granular slurry is put into a waste bin, and left to harden (solidify) to form a monolithic solidified body (granular solidified body).
- the sulfate contained in the conversion waste slurry is barium sulfate, which is a solid solid with a high specific gravity (4.5), and has the characteristics of fine aggregate, while borate The particles are also hard solids with high mechanical strength. Therefore, the solidified body of borate particles prepared by the present invention has the characteristics of compact structure and high mechanical strength, which can avoid the reduction of compressive strength after water immersion and solidify borate waste liquid. The water resistance of the product has been greatly improved.
- the hardenable slurry 006 can be used for solidification/immobilization of other solid wastes such as spent activated carbon, sludge, incineration ash, metal waste, spent filter cartridges, etc., in addition to solidifying borate particles. If the consolidated waste is in solid state, it does not need to be granulated, so the pretreatment is relatively simple.
- the radioactive waste activated carbon produced by nuclear power units has adsorbed various toxic substances and nuclei, and if it is incinerated, it may cause pollution. Therefore, directly using the hardenable slurry of the present invention for solidification is a feasible treatment method.
- the method of the present invention embodies the concept of "disposing waste with waste", fully realizes the minimization of radioactive waste, and produces high-quality solidified/immobilized waste objects.
- the processing methods and effects of the present invention will be exemplified below. These embodiments are only application examples of the present invention, and do not represent the entire implementation scope of the present invention, so they should not be regarded as limiting the application scope of the present invention.
- Comparative Example 1 Using hydrogen peroxide for wet oxidative degradation of simulated waste resin
- This comparative example demonstrates the degradation of simulated waste resin by wet oxidation using hydrogen peroxide, and the device 1 used is shown in FIG. 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 2.5-liter tank body 01, and the upper part is the tank cover 02.
- the tank cover 02 and the tank body 01 are clamped tightly with metal clips, and can be separated by loosening the metal clips.
- the tank cover 02 is equipped with four openings, of which the opening 07 can be used as a feed port for the degradant, and the graduated cylinder 06 is placed on it for inputting the degradant solution manually or with a peristaltic pump (Peristaltic pump); the opening 08 can be used as a feed port for the defoamer, It is used for adding defoamer when necessary; opening 04 can be used as the feed port for catalyst solution and ion exchange resin, as well as the measurement port for pH and temperature and the sampling port for degradation waste liquid, and is closed with a silica gel plug when not in use; Opening 09 can be used as a gas outlet, and is connected with a glass cooling pipe 10 for the condensation of the escaped steam; A return pipe 11 is provided to return the condensate to the glass reaction tank when necessary to keep the liquid level stable, and the non-condensable gas is discharged to the smoke cabinet through the outlet 14 of the Erlenmeyer glass bottle 12 .
- the opening 07 can be used as a feed port for
- the whole device 1 is erected on a support platform, and the electric heater 05 is placed under the glass reaction tank, and the electric heater 05 is placed on a height-adjustable support platform (not shown), and the height can be adjusted as required. and can be removed at any time.
- the defoamer used in this example is a commercially available product containing silicone resin and fatty acid ester, which is diluted 10 times with water before use.
- 1 milliliter of defoamer is added when the degradation agent is added to 275 milliliters, 350 milliliters, and 550 milliliters, totaling 3 milliliters; when the liquid level is excessively reduced due to evaporation, the condensate is refluxed to replenish to maintain The liquid level is within a certain range of variation.
- sampling is performed after the resin is completely dissolved, and the addition of the degradant is suspended after the predetermined amount is added, and sampling is started 10 minutes later.
- Pause heating and stirring when sampling and take 2 grams of degradation waste liquid sample from opening 04 for analysis, then remove heater 05, place an electronic scale under the glass tank, and place a spacer on the electronic scale platform.
- After heating the plate reset the weight reading of the electronic scale to zero, and then loosen the metal clip connecting the tank cover 02 and the tank body 01, so that the glass reaction tank sits on the heat shield on the electronic scale, weigh and record .
- sampling and weighing After sampling and weighing, immediately restore the device to its original state, then start stirring and heating if necessary, and resume the addition of degradation agent, until the next sampling and then carry out the same sampling and weighing steps.
- the time of each sampling was controlled to be 5 minutes.
- the results of the treatment are shown in Table 1, including the added weight of hydrogen peroxide (hydrogen peroxide addition), the weight of the degradation waste liquid, and the total organic carbon (Total Organic Carbon, TOC) content of the degradation waste liquid, etc. are shown in Table 1.
- the carbon content of the anion and cation exchange resins used in this experiment was 149.5 and 150.7 grams per liter respectively by elemental analysis, that is, the total organic carbon contained in the ion exchange resin before degradation was 19.12 grams in total .
- the calculated degradation rate change is also shown in Table 1, where the degradation rate is calculated as follows:
- Degradation rate (%) 100 - waste liquid weight (grams) x waste liquid TOC (ppm) x 10-4/19.12
- the degradation test results in Table 1 show that the degradation rate is 95.49% when the amount of hydrogen peroxide added reaches 550 ml, and the degradation rate is 98.91% when the amount of hydrogen peroxide added reaches 1,000 ml.
- the degradation rate of 95.49% was obtained by adding 550 milliliters in the front section. Although 450 milliliters were added in the latter section, the degradation rate was only increased by 3.42%, indicating that the level of TOC had a great influence on the degradation effect of hydrogen peroxide; The degradation effect becomes very weak.
- This example demonstrates the wet oxidative degradation of waste resin simulated in Comparative Example 1 and its effect by using a double-dose degradation agent (hydrogen peroxide + persulfate) according to the present invention.
- the device used is the same as that of Comparative Example 1.
- the conditions of this example except the degradation agent used In addition to the 550 ml of 35% hydrogen peroxide added in the stage, a double-dose degradation agent containing 5 points of ammonium persulfate and 95 points of 35% hydrogen peroxide is used instead of 550 ml, and the timing of adding the defoamer is to add 285 ml of the degradation agent solution , 380 milliliters, 440 milliliters, 470 milliliters, and 515 milliliters respectively add 1 milliliter except totally 5 milliliters, other conditions are all identical with comparative example one.
- This example demonstrates the preparation of hardenable pulp by simulating the degradation waste liquid of waste resin (ion exchange resin) to embed and solidify borate particles obtained by pretreatment of borate waste liquid, and demonstrates the preparation of borate waste liquid Pretreatment process of borate pellets.
- waste resin ion exchange resin
- Pretreatment of borate waste liquid granulation.
- the granulation in this example may also include the preparation of granulation agent, initial granulation and continuous granulation, etc., as described below.
- the granulation is temporarily stopped, and half of the weight of the granules is taken out, and then the cyclic cross-feeding granulation is continued until a total of simulated borate is added.
- the waste liquid and the granulating agent each reach 100 times, stop when the weight reaches 20,000 grams and 8,000 grams respectively, continue to stir for 5 minutes, and then mix all the granules (including the ones taken out first and those completed later) together for further processing. solidified.
- the material conditions used in the above two stages of granulation are shown in Table 3.
- the diameters of the obtained particles are mainly distributed between 2 and 5 mm, and the boron content is 9.09 wt%, which is equivalent to the boric acid content of 52.48 wt%.
- the device and simulated waste resin used are the same as in Comparative Example 1, and the step of removing impurities from simulated waste resin is also omitted. Due to the large amount of waste liquid required, it was divided into 4 batches. Described as follows.
- the resin When the resin is 270 grams and 35% hydrogen peroxide is 4,500 milliliters, it is degraded with a double-dosage degrader, and the addition rate of the degradant is reduced to 10 ml/min until the amount of the double-dosage degrader reaches 245 milliliters, and then continues to maintain After stirring for 30 minutes, the degradation operation was terminated.
- the temperature is kept between 95°C and the boiling point, and if necessary, it is heated to help maintain the temperature; when the liquid level decreases due to boiling, the liquid level is kept from changing too much by reflux of condensate; if there is accumulation of air bubbles That is to suppress with antifoaming agent in due course, add 12 milliliters of antifoaming agent in total in this experiment.
- a total of 4 batches of 2,160 g (2,700 ml) of cation resin and 1,080 g (1,464 ml) of anion resin were degraded under the same conditions.
- the obtained degradation waste liquids were mixed together, concentrated and adjusted to a total weight of 1,540 g, and the sulfate content was analyzed to be 4.02 mol/kg.
- the device for degrading waste liquid conversion is the same as device 1 in Fig. 3, except for the device for ammonia-containing outgas treatment part as shown in Figure 4, the other devices including conversion reaction and outgas cooling are the same as the device 1 in Figure 3, in which the glass reaction tank cover Among the four openings 04, 07, 08, and 09 on the 02, the opening 04 is used as the feed inlet of the conversion agent, and is also used as a measurement port for temperature and pH when necessary; The measuring cylinder funnel is used for manual addition of waste liquid; the opening 09 is used as the outlet of the transformation gas.
- the device 2 that is used to handle ammonia outgas is schematically shown in Figure 4, and the conical glass bottle 12a is used for collecting condensate and the temporary retention of non-condensable ammonia outgas, that is, as a buffer tank for ammonia; the opening of the conical glass bottle 12a 16a is used as air inlet; Flow meter 17 and control valve 18 are air conditioning devices, for the regulation of air flow; Outlet 14a is the transformation escape gas outlet, is connected with ammonia oxidation decomposition device 19 with silicone hose; The heater and high-temperature catalyst bed can provide a temperature below 600°C for preheating ammonia-containing outgas and using an ammonia oxidation decomposition catalyst to oxidize and decompose ammonia into N 2 and H 2 O; The air overcomes the flow resistance; the air regulating valve 20 is used to adjust the air flow, so as to adjust the negative pressure generated by the air extractor.
- the ammonia oxidation decomposition device 19 is preheated to 300° C. for subsequent use; then get barium hydroxide monohydrate powder and water to prepare 1466.5 grams of conversion agent water slurry in a weight ratio of 4:6 (containing barium hydroxide monohydrate 586.6 gram), and put it into the glass reaction tank from opening 04, start stirring, and then slowly input the prepared degradation waste liquid with a peristaltic pump, and stop when the total input is 770 grams, then heat to maintain a temperature of about 90°C and continue stirring for 2 hours to completely remove the ammonia gas. Then, the heating was stopped and the mixture was placed in a beaker to let it cool for use. The weight of the obtained concentrated conversion waste slurry was 1,305 grams.
- the ammonia-containing gas produced in the conversion process enters the Erlenmeyer flask 12a through the glass cooling pipe 10a, and the condensed liquid is left in the bottle. After the non-condensable ammonia-containing gas is mixed with the input air, it flows to the ammonia oxidation decomposition device 19 and is decomposed into water. After the gas and nitrogen are exhausted, they are exhausted by the exhaust machine to the fume cabinet.
- This embodiment demonstrates the combined treatment of waste resin and waste activated carbon.
- waste activated carbon solidified slurry is for The title of slurry formed by mixing waste activated carbon and hardenable pulp is the precursor of waste activated carbon solidified body); the specific gravity of the solidified waste body is determined to be 2.02, that is, the volume is 2,684 ml. Therefore, the waste solidified body
- the activated carbon volume loading rate is 41.3%.
- waste resin was degraded and 2,588 grams of converted waste pulp with a moisture content of 43% was prepared, and then 1,540 grams of the same hardenable pulp raw material was added to prepare 4,128 grams of hardenable pulp.
- This hardenable slurry was then mixed with 1,510 grams (1,425 ml) of spent activated carbon to prepare a slurry of 5,638 grams, the composition of which is also shown in Table 6.
- the specific gravity of the solidified body was determined to be 1.996, that is, the volume was 2,825 milliliters, so the volume loading rate of the waste activated carbon was 50.44%.
- the cured body prepared above was prepared according to the method of Example 2 and then tested for quality. The results are shown in Table 7, which shows that its quality is very good.
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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。
Description
本发明涉及一种废弃物的处理方法，尤其涉及一种放射性废离子交换树脂的处理方法。所述离子交换树脂系指含有磺酸基或季铵基的苯乙烯-二乙烯基苯聚合物(styrene–divinylbenzene polymers)。
目前世界上最普遍采用的核电机组是压水式机组与沸水式机组，两者所产生的中低放射性废弃物，大致可分为湿性废弃物与干性废弃物两类。湿性废弃物方面，压水式机组产生者主要为硼酸盐废液、废离子交换树脂(以下称废树脂)与废活性碳等；沸水式机组产生者主要为废树脂、废活性碳与过滤残渣(filtration sludge)，如今因已不再进行离子交换树脂的再生(regeneration)，因此已无树脂再生产生的硫酸钠废液。干性废弃物方面，其产生与机组型式的关系不大，主要的差别在于可燃性干性废弃物是否采用焚化处理，如是，则可燃性废弃物焚化后将转变为炉渣和炉灰，并使干性废弃物大幅减容。此外，不论是哪一型的机组，都还会产生污泥、污染金属、废过滤器芯等放射性废弃物。以上所述都是适合应用本发明技术进行处理的放射性废弃物。
对放射性废液或湿性废弃物的处理，传统上最常用的是水泥固化技术，是将废弃物与水泥制备成浆体并装桶，待浆体硬化后即成为安定的整块的(monolithic)固态废弃物体(solid waste form)。由于不同的废弃物拥有不同的特性，进行水泥固化时，必须采用不同的固化条件分别进行处理，因此除了各自存在不同的技术难题外，也因水泥固化体的废弃物荷载率低，使最终产出的废弃物固化体产量居高不下。以下就几种处理上具挑战性的废弃物，说明其处理问题以及技术情况。
如上所述，水泥固化是早期被普遍采用于处理放射性废弃物的技术，至今仍有部分核电站在使用中。采用水泥固化技术处理硼酸盐废液时，废液中的硼酸盐(一般为硼酸钠)会严重阻碍水泥的水合作用，阻碍水泥浆的硬化，产生所谓固化阻滞(solidification retardation)现象。为了降低这种现象，硼酸盐废液的水泥固化只能在低硼浓度下进行，或在添加水泥固化剂之前，先添加熟石灰或其它碱性剂以降低固化阻滞现象，例如，美国专利US4,293,437、US4,210,619、US4,620,947、US4,800,042及US4,906,408，以及中国专利CN102254579B、CN102800377A等。但这些做法皆导致产生的硼酸盐废液固化体体积大幅增加。虽然水泥固化系统的设备简单，可以降低设备投资成本，但放射性废弃物的管理成本日益高昂，而最终处置的用地一处难求，这些方法已不具经济性。
日本的日挥公司(JGC Corporation)，曾开发所谓“进步水泥固化技术(advanced cementation)”，是将硼酸盐废液加温至40～60℃，并添加石灰进行约10小时的反应，使硼酸钠转化为安定的硼酸钙沉淀，将沉淀过滤脱水后，再添加水泥进行固化。据称对减容效果有显著的改善，惟其操作冗长，并会产生含氢氧化钠的二次废液(secondary waste)，因此并未达成完整的处理。
本发明人在中国台湾专利发明第68,875号、美国专利US5,457,262号、美国专利US5,998,690、 欧盟专利EP0644,555、欧盟专利EP0929,079等中，公开了一种硼酸盐废液固化方法，是将硼酸盐废液浓缩成为硼含量110,000ppm以上的聚合硼酸钠溶液后，再以特别配制的水泥基固化剂进行固化。所述方法能产制硼酸盐荷载率极高的固化体，处理同量的硼酸盐废液产出的固化体体积低于传统水泥固化法的10分之1，减容效果十分优异。但因固化体的硼酸盐含量很高，在固化体抗水浸性要求严格的情况下，其应用会受到限制。
硼酸盐废液的处理尚有所谓蒸干法，是将废液装桶后直接加热蒸出水分，以形成含结晶水的硼酸或硼酸盐固体。此法虽然会使废弃物的体积减少，但硼酸盐没有经过安定化或矿化处理，仍处于完全可溶的状态，并无安定性可言。
采用水泥固化技术处理废树脂也同样存在问题。因废树脂具有离子交换能力，会与水泥固化体内的离子进行离子交换，而影响固化体的安定性，也会因吸收或释放水分导致固化体发生收缩-膨胀而破损龟裂，因此固化体的废树脂荷载率受到很大限制，导致水泥固化后体积大幅增加。此外，废树脂水泥固化后并未被矿化，仍会发散臭味，对环境产生污染，也会发生生物劣化分解，产生硫化物破坏处置工程障壁，使处置的安全性堪虞。
废树脂的处理方法除了水泥固化法以外，尚包括干法处理与湿法处理两类，其中干法包括焚化法、直接玻璃固化(direct vitrification)法及高温热裂解(pyrolysis)法、Q-CEP处理法(Quantum-Catalytic Extraction Process)等；湿法则有酸解法(acid digestion)、湿法氧化法(wet oxidation)及次临界或超临界水氧化法(sub-or super-critical water oxidation)、高温蒸汽重组法(steam reforming)等。其中焚化法的开发最早，曾有部分国家付之实施。使用焚化法处理时，一般是将废树脂与其它可燃性废弃物进行混合焚化，以控制SOx、NOx或其它有害气体的排放浓度；放射性核种的排放控制是焚化法的关键问题，除非能有效避免挥发性的碳-14、氚以及铯-137等核种的排放，否则废树脂必须事先进行核种的脱除，使放射性降低后再行焚化，而这也形成废树脂焚化处理的困难。
以上的废树脂高温处理方法皆面临了材料腐蚀、核种与毒性气体的处理与排放，以及残渣与二次废弃物(secondary waste)尚待妥善处理等问题，造成实际应用上的困难；另外，高温处理也有设备成本高，系统运转与人力调度弹性低等缺点。
相对于高温处理法的缺点，利用芬顿反应(Fenton reaction)的湿法氧化法，则具有反应温度低(约100℃左右)、不产生毒性气体、无核种逸出等基本优点，有利于实际应用的发展。
英国AEA公司发展的湿式氧化法，以硫酸亚铁为触媒，以双氧水为氧化剂，以消石灰和硫酸调节pH，在约100℃温度及pH 3～4下，进行粒状废离子交换树脂的氧化分解，使有机成分分解成CO
2及H
2O。根据文献报导，以所述法处理废树脂得到的废液与残渣进行水泥固化，虽然最后产生的固化体体积与处理前的废树脂体积比较并未减少，但与废树脂直接水泥固化比较，则具有相对良好的减容效果。
本发明人在中国台湾发明专利第I255,277号、美国专利US7,482,387 B2号、日本专利特许JP4,414,214号，以及欧盟专利EP1,137,014号等中，曾揭示了利用芬顿反应的湿法氧化法进行阴、阳 废树脂降解的技术，使用氢氧化钡取代消石灰调节pH，并以特别配制的固化剂进行降解废液与残渣的固化。该技术处理等体积比的阴、阳混合树脂时，产出的固化体体积是原废树脂体积的约1/3，固化体品质符合各主要核能国家的要求标准，而且未余留任何尚待处理的二次废弃物。
由以上的说明可知，先前技术对放射性废弃物的处理基本上如图1所示，是分两阶段进行处理：第一阶段先依照废弃物特性，视需要进行脱水、干燥、蒸发浓缩、沉淀、焚化或裂解等减量、减容处理，并得到高浓度的废液、废浆或固态的粉末、颗粒或残渣等中间产物；第二阶段则再依照中间产物的特性，采用适当的方法进行固化或固定，以得到品质合格的废弃物体(waste form)。其中固化处理是指将废液或废浆制备成整块性的(monolithic)废弃物固化体(简称固化体)；固定处理是指将原为固体的废弃物装桶后，再用可硬化浆灌注包埋该废弃物，并在可硬化浆硬化后形成整块性的废弃物固定体(简称固定体)；如果固态中间产物的特性符合封装的条件时，也可不需进行固定处理，而直接使用合格的高完整性桶(High Integrity Container，HIC)进行封装。其中对废离子交换树脂、污泥、残渣等细小湿固体废弃物的废弃物体制备，是在浆体型态下添加固化剂制备成固体，因此，习惯上也称为固化处理，产物也称为固化体。以下的说明中也将沿用此习惯称呼。
基本上，第二阶段包括固化、固定，以及封装等处理，都会产生增容效果。增容的幅度以废液、废浆的固化而言，取决于废弃物的浓度以及外加的固化剂用量；固定则取决于废弃物桶的容积盛装率，以及可硬化浆的使用量；封装则取决于封装桶的体积盛装率。以现行的情况而言，第二阶段处理的增容幅度，因方法的不同约在50％至500％之间。
发明内容
本发明提供一种利用废树脂(包括阴、阳离子交换树脂)的湿法降解所产生的废液制备可硬化浆，并以可硬化浆处理其他废弃物的方法，以及一种降解废离子交换树脂与有机废弃物的改良湿法氧化方法。
本发明所提供的利用废树脂的降解产物处理其他废弃物的方法包括以下步骤：进行废树脂的湿法降解处理，以产生含硫酸盐的降解废液；浓缩降解废液，并添加转化剂以产生含安定性硫酸盐微粒的转化废浆；添加可硬化浆原料至转化废浆中，并混合均匀制备成可硬化浆，并用以进行至少一种其他废弃物的固化或固定处理。本发明的转化废浆所含的安定性硫酸盐微粒，源自于阳离子交换树脂所含的磺酸基，因此废离子交换树脂宜含较高比例的阳离子交换树脂，以足供制备所需数量的可硬化浆。基本上，核电厂产生的废离子交换树脂所含的阳离子交换树脂多于阴离子交换树脂，因此十分适合于本发明方法的应用。
在本发明的一实施例中，上述的湿法降解处理为湿法氧化(wet oxidation)法，并宜在pH<3的条件下进行。阴阳混合废树脂的水浆的pH，会随阳树脂占比的增加而降低，反之pH就提高。因阳树脂的降解会产生硫酸，因此阳树脂占比较高时，降解废液的pH会随降解的进行而降低。核电所产生的阴阳混合废树脂一般是阳树脂的占比较高，因此需要调低pH的情况不多，但如有需要，则可以用硫酸调节。如硫酸的持续产生导致酸性太高，则可以氢氧化钡调节。
在本发明的一实施例中，上述的至少一种其他废弃物选自：硼酸盐废液、固态硼酸盐、废活性碳、污泥、焚化灰渣、废过滤器芯、金属废弃物以及废弃物压缩块，且处理至少一种废弃物的步骤还包括将至少一种废弃物与可硬化浆形成固化体或固定体。
在本发明的一实施例中，上述的处理方法还包括以下步骤：提供硼酸盐废液；调节硼酸盐废液的成分并进行浓缩，以制备含聚合硼酸盐的高浓度硼酸盐废液；使用造粒装置与至少一种造粒剂，将高浓度硼酸盐废液制造成硼酸盐颗粒；混合硼酸盐颗粒与可硬化浆，拌合均匀形成可硬化浆的颗粒浆体，然后装入废弃物桶，并于颗粒浆体硬化后形成固化体包件。
在本发明的一实施例中，上述的硼酸盐废液为硼酸钠溶液。
本发明另也提供一种改良的废离子交换树脂或有机物的降解方法，包括使用过硫酸盐与双氧水做为降解剂进行废离子交换树脂或有机物的降解处理，并因此提高降解的效率，抑低降解液中残留的TOC浓度，并大幅减少双氧水的消耗量。
本发明因采用湿法进行废离子交换树脂的降解，并以产生的降解废液制备成可硬化浆，用以进行其他废弃物包括硼酸盐废液、固态硼酸盐、废活性碳、污泥、污染金属、废过滤器芯等的合并处理，因此大幅降低外加物料的使用，并抑低第二阶段处理的增容，实现放射性废弃物的最小化。
上述说明仅是本发明技术方案的概述，为了能够更清楚了解本发明的技术手段，而可依照说明书的内容予以实施，并且为了让本发明的上述和其他目的、特征和优点能够更明显易懂，以下特举较佳实施例，并配合附图，详细说明如下。
图1所示为放射性废弃物的二阶段处理图；
图2所示为本发明废弃物处理方法的流程示意图；
图3所示为用于本发明实施例废树脂降解处理的装置示意图；
图4所示为用于本发明实施例含氨逸气处理的装置示意图。
经过实验研究，本发明完成以下处理放射性废弃物的新颖方法。
(一)合并处理的其他废弃物001的预处理(S100)：合并处理的其他废弃物001是指要以可硬化浆固化或固定的废弃物，这些废弃物需预处理为适合固化或固定的状态。基本上，所有固态废弃物皆可进行固化或固定，但以具备良好安定性与机械强度者为佳，潮湿固体废弃物例如废活性碳或污泥，需去除过多的水分。液态废弃物如核电厂的硼酸钠废液，需先预处理为固体颗粒，或添加碱性剂例如氢氧化钙，以形成硼酸钙固体沉淀后，再脱水成为含适度水分的细粒状固体。所述硼酸钙固体可为泥状、粉状、粒状或块状。粗大的干性废弃物须先进行外形与大小的调整，以适合进行装桶固定；细小的粉末或颗粒废弃物如不选择固化或有不适合固化处理的原因者，则可先装桶并压缩成压缩块后再进行固定处理。总而言之，预处理使其他废弃物001具适当的含水量、外型、尺寸与密实度，俾适合进 行最后的固化或固定处理。
(二)进行废树脂的湿法降解(S200)：首选的湿法降解法是湿法氧化法，并以所得到的废树脂降解废液进行可硬化浆的制备(S300)。可硬化浆的特性对本发明最终产出的废弃物体品质具有关键性的影响，以具备以下的特性为佳：良好的流动性，以利于其固化或固定其他废弃物时的混合或灌注操作；硬化产物具备优良的安定性与机械强度，以利于产制性能优良的固化体或固定体。此外，制备可硬化浆的废弃物需有相对较多的数量以满足需求，核电厂产生的废树脂基本上满足以上的条件。
(三)最终废弃物体的制备(S400，图2)：制备固化体(S410，图2)时，将完成预处理的废弃物颗粒或粉末与制备好的可硬化浆拌合均匀并形成可硬化的颗粒浆体，将颗粒浆体装入废弃物桶，待其硬化后形成固化体；制备固定体(S420，图2)时，则将预处理后的其他废弃物001先行装入废弃物桶，再用可硬化浆灌注填满桶内空隙与四周，待可硬化浆硬化后形成固定体。
为进行更具体的方法描述，将以压水式核电机组三种主要废弃物包括废离子交换树脂与硼酸钠废液或废活性碳的合并处理为例加以说明。由于这三种是压水式机组废弃物中处理上最具挑战性者，因此代表了本发明在压水式机组废弃物处理上的实用价值。其中废离子交换树脂是用以制备可硬化浆，硼酸钠废液需预处理成为固体颗粒，废活性碳则需调节其含水量，使其具适当低度而不滴水的含水率。主要的实施步骤S100、S200、S300、S400等如图2所示，其中S400的废弃物体包件制备可分为S410的固化体包件013制备以及S420的固定体包件014制备。可理解的是，图2的顺序仅为例示，其中除步骤S100与步骤S200～S300需先于步骤S400完成外，S100与S200～S300无顺序上的限制，惟须配合可硬化浆的硬化时程进行作业。
步骤S100：将硼酸盐废液预处理为硼酸盐颗粒。此步骤包含将硼酸盐废液制备成含聚合硼酸盐的高浓度硼酸盐废液(步骤S100a)，以及将高浓度硼酸盐废液制备为硼酸盐颗粒(步骤S100b)，分别说明如下。
步骤S100a：调节硼酸盐废液(001，其他废弃物)的成分并浓缩硼酸盐废液，以制备含聚合硼酸盐的高浓度硼酸盐废液。
步骤S100b：使用造粒装置与造粒剂，将高浓度硼酸盐废液制成硼酸盐颗粒(002，预处理产生的固态废弃物)。
步骤S200：进行废树脂003的降解处理，并产生降解废液004。所述废树脂003的降解处理可为一种湿法氧化法的步骤，而除产生降解废液004外，降解处理还使废树脂003的碳氢成分氧化分解为气态的CO
2和H
2O，其中气体经过滤脱除雾滴后排放。降解废液004依废树脂进料的阴、阳树脂比例与杂质含量的情况而含有氢氧化铵、硫酸或硫酸铵，以及残渣与少量有机碳化物。
废树脂所含的杂质主要为夹杂在树脂孔隙中的固态，以及阳树脂所吸附的阳离子与阴树脂所吸附的阴离子等，其中一部分的杂质可能对湿法氧化的降解效力产生阻碍，而某些被吸附的离子，例如阴树脂所吸附的含碳-14(
14C)的H
14CO
3
-离子，则可能在降解过程中释放出含碳-14核种的气体，造成人员与环境的辐射伤害。本发明为免除上述问题，视情况的需要，在湿法氧化之前进行废树脂所含杂 质的脱除处理，包括将废树脂加水成为水浆后，利用超音波产生震荡将固体杂质自孔隙中脱除，以及以脱附剂溶液洗涤，将废树脂所吸附的H
14CO
3
-离子脱附进入水中；所用的脱附剂可以选用碱金属、碱土金属或铵等的盐类或化合物的溶液，例如：过氯酸盐、硫酸盐、硝酸盐、磷酸盐、磷酸一氢盐、磷酸二氢盐、草酸盐、碘化物、溴化物等，并以利于脱附废液进行后续安定化处理者为佳，尤其能使脱附后的H
14CO
3
-离子形成固体沉淀者为更佳。以上脱除固体杂质所产生的废浆，可使其在桶槽中静置让固体杂质沉降后，将上澄液回收作为浆化树脂的用水，桶底含固体杂质的泥浆则并入步骤300所制备的转化废浆中进行后续处理。脱附H
14CO
3
-离子所产生的洗涤废液，同样可并入步骤300所制备的转化废浆中进行后续处理，或视需要另行单独处理；如采取并入转化废浆的方式处理，也可将脱附剂直接添加在浆化水中，使固体杂质的脱除与碳-14的脱附合并进行。经过碱性脱附剂洗涤的废树脂在与湿法氧化触媒溶液混合后，须于进行降解前调节其pH<3。
步骤S300：以降解废液004制备可硬化浆006。此步骤包含步骤S300a的由降解废液004制备转化废浆，以及步骤S300b的由转化废浆制备可硬化浆006，分别说明如下。
步骤S300a：由降解废液004制备转化废浆。首先将降解废液004浓缩至适当浓度，然后添加转化剂而形成转化废浆。此步骤的转化剂较佳为氢氧化钡，其使降解废液中的硫酸与硫酸铵转化为不溶性的硫酸钡，而得到含硫酸钡微粒的转化废浆。同时使废浆的pH值提升，从而使其中的铵根转化为氨气逸出。氨气经氧化分解变成氮气和水气后排放。
步骤S300b：由转化废浆制备可硬化浆006。添加可硬化浆原料005(亦即固化剂粉末)至转化废浆中并混合均匀，制备成可硬化浆006。可硬化浆006能用以处理至少一种预处理产生的固态废弃物002，此处即为硼酸盐颗粒。
步骤S410：此处属于硼酸盐颗粒固化体包件013的制备。将步骤S100备妥的硼酸盐颗粒(002，预处理产生的固态废弃物)以及步骤S300备妥的可硬化浆006混合均匀得到可硬化颗粒浆体后再盛装于废弃物桶，待颗粒浆体硬化成固化体，然后封盖成为固化体包件013。
以上步骤S100a所制备的高浓度硼酸盐废液主要包含硼酸钠。高浓度硼酸钠废液的硼浓度需在100,000ppm以上，而以110,000ppm以上较宜，硼浓度如低于100,000ppm，硼酸钠的聚合度不足，在步骤S100b造粒后产出的硼酸盐颗粒机械强度欠佳，但如硼浓度太高，则应预防因黏度太高而发生输送管路堵塞，以及造粒时物料混合不佳的问题。
步骤S100b硼酸盐颗粒的制造可采用装设行星式搅拌叶的搅拌槽进行。造粒时，先将造粒剂置入搅拌槽，使造粒剂粉末高度高于搅拌叶，然后启动搅拌，再将高浓度硼酸钠废液缓慢地滴进搅动中的造粒剂粉末中，使液滴与粉末在滚动接触下形成初始颗粒；高浓度硼酸钠废液与造粒剂是通过固化反应形成硼酸盐颗粒，反应中，液态的高聚合度硼酸钠因与造粒剂产生置换反应而变成固态的高聚合度硼酸盐颗粒，颗粒的硼酸盐组成与机械强度主要随造粒剂的成分而定。
初始颗粒形成后，即可采用交叉回圈添加高浓度硼酸钠废液与造粒剂的方式进行连续性造粒；添加的废液与造粒剂的重量必须保持适当的比例，添加的速率也必须控制适当，以免颗粒因黏稠液过多 发生黏结；连续性造粒可于颗粒达到造粒装置容量限制时暂停，取出部分颗粒后再继续造粒，直至颗粒达到需要数量后停止造粒。
步骤S200废树脂003的降解处理除湿法氧化法外，亦可为其他湿法的降解方法，惟较佳为利用芬顿反应的湿法氧化法的降解处理。利用芬顿反应的湿法氧化法有反应温度较低，产生的降解废液成分单纯，有利于后续的处理的优点。进行废树脂003降解的目的除了减容之外，另外的重要目的是使废树脂003无机化(矿化)，以免除废树脂003发散恶臭气味与发生生物劣化，以利环境保护及最终处置安全。因此步骤S200较佳能达成一定程度的降解，而99％的降解率应属可合理的目标。
利用芬顿反应的湿法氧化法传统上是使用双氧水为降解剂，但本发明的研究发现，双氧水的降解效力在有机碳化物浓度较低时会大幅降低。以废树脂003的湿法氧化为例，降解最后5％有机碳所消耗的双氧水可能比降解前面95％还多，而降解率98％和99％所消耗的双氧水数量则相差30％以上。
为了达成高降解率并减少双氧水的消耗，本发明经过一系列的研究后发现：使用含过硫酸盐(peroxysulfate)与双氧水的双成分降解剂，能有效改善低TOC浓度时的降解效率，大幅降低降解剂的消耗量。适用的过硫酸盐包括过硫酸铵、过硫酸钠、过硫酸钾、过硫酸钙等，而以过硫酸铵为佳，因为最后产生的降解废液004成分与使用双氧水时完全相同。本发明双成分降解剂除了适用于离子交换树脂外，也适用于其他有机物如高分子树脂、有机化合物、植物性纤维物、植物性油脂、动物性油脂及矿物性油脂的湿法氧化。
由于使用过硫酸盐时会提高降解废液中的硫酸盐浓度，亦即会增加产出的降解废液或固化体的数量，因此添加过硫酸盐的时机宜选择在TOC浓度较低，双氧水的降解效力低下的情况。对固态有机物(例如离子交换树脂)而言，以在完全溶解的情况为佳；而如降解废液或固化体的产量对整体的处理效益会产生显著影响时，也可考虑在固态有机物已完全溶解后的更低TOC浓度时添加。对液态有机物而言，同样需考虑添加时机对对整体处理效益的影响，例如在高分子有机物占比较低、单分子有机物占比较高的情况，而这并非由于技术的限制，而是效益的考量。
步骤S200所产生的降解废液004中可因条件的不同而含有氢氧化铵、硫酸、硫酸铵、残渣以及少量有机碳。步骤S300a加入转化剂后可进行降解废液004中硫酸盐的转化，就是使降解废液004中的硫酸根及硫酸铵等转化成不溶性的安定性沉淀，并使其中的铵离子(NH
4
+)转变为氨气(NH
3)逸出。对逸出的氨气再进行无害化处理。另外，为了使转化废浆的固体(相当于前述不溶性的沉淀)含量适合后续的处理，此步骤还包括转化废浆的浓缩以调节其含水量。
转化剂较佳为使用氢氧化钡，可以使用氢氧化钡溶液，也可使用氢氧化钡水浆或氢氧化钡粉末。由于氢氧化钡常温的溶解度不高，为免加入太多的水，氢氧化钡可使用热水溶解，以提高溶解度。
硫酸根及硫酸铵转化产生的含氨逸气，先使经过除雾器脱除雾滴后，由抽气泵输送进入氨气槽，然后再定量输送至氨氧化分解器(Oxidation-decomposer)。送至氨氧化分解器时同时注入一定比例的空气，使氨在氧化分解触媒的催化下，氧化分解为N
2和H
2O。最后由疏排气系统进行N
2与H
2O的排放。此外，亦可以水吸收含氨逸气成为氨水，再进行水中氢氧化铵的氧化分解以转化为氮气与水。
上述的氨气槽可以是一个缓冲氨气气流的空间槽、贮存槽，也可以配备冷却与加热装置，并置放氯化钙(CaCl
2)作为氨气吸附剂。氯化钙可在低温时吸附氨气形成CaCl
2·nNH
3(n＝2至8)，当吸附氨达到一定程度时，可加热进行氨气脱附，如此重复使用，提供氨气的贮存与缓冲空间，提高操作的弹性。
步骤S300b是以转化废浆制备可硬化浆006。可硬化浆006以具备优良流动性，并能形成性能优良的固化体为较佳。可硬化浆006与固化体特性的优劣是基于选用的可硬化浆原料005(亦即固化剂粉末)而表现。可硬化浆原料005可使用波索兰材料(pozzolanic materials)配制，也可以采用特殊配方。
步骤S410是使用可硬化浆006进行硼酸盐颗粒的固化。将硼酸盐颗粒按预定的比例加入可硬化浆006中，搅拌混合完成后得到可硬化的颗粒浆体。接着将该颗粒浆体装入废弃物桶，静置硬化(固化)后即形成整块性的固化体(颗粒固化体)。
当使用氢氧化钡为转化剂时，转化废浆所含的硫酸盐是硫酸钡，是高比重(4.5)、质地坚实的固体，具备优良细骨材(fine aggregate)的特性，而硼酸盐颗粒也是高机械强度的坚硬固体，因此，本发明所制备的硼酸盐颗粒固化体具有结构致密与高机械强度的特性，能免除水浸后抗压强度的降低，使硼酸盐废液固化产物的耐水性获得大幅度改善。
可硬化浆006除了供固化硼酸盐颗粒固化外，也可用于其他固态废弃物例如废活性碳、污泥、焚化灰渣、金属废弃物、废过滤器芯等的固化/固定。合并处理的废弃物如为固态，因不需进行造粒，因此预处理相对简单。核电机组产生的放射性废活性碳，因吸附了各种毒性物质与核种，如采用焚化处理可能导致污染，因此直接使用本发明的可硬化浆进行固化是可行的处理方法。
本发明的方法具体实践了“以废弃物处理废弃物”的理念，也充分实现了放射性废弃物的最小化，并产出高品质的固化/固定废弃物体。以下将以举例示范本发明的处理方法与效果，这些实施例仅是本发明的应用例，并不代表本发明的全部实施范围，因此不应被当作对本发明使用范围的限制。
比较例一：使用双氧水进行模拟废树脂的湿法氧化降解
本比较例示范使用双氧水进行模拟废树脂的湿法氧化的降解，所用的装置1如图3所示。
用于废树脂降解处理的装置1包括一个密闭式玻璃反应槽及附属的进出料装置。玻璃反应槽的下部为一个2.5公升的槽体01，上部为槽盖02，槽盖02与槽体01用金属夹扣夹紧密接，松开金属夹扣即可分开。槽盖02备有四个开口，其中开口07可作为降解剂加料口，其上置量筒06可供手动或以蠕动泵(Peristaltic pump)输入降解剂溶液；开口08可作为消泡剂加料口，供必要时添加消泡剂用；开口04可作为触媒溶液与离子交换树脂的进料口，也同时做为pH与温度的量测口以及降解废液的取样口，不用时以硅胶塞封闭；开口09可作为气体出口，与一玻璃冷却管10连接，以供逸出蒸汽的冷凝；玻璃冷却管10的出口与锥型玻璃瓶12连接，以供承接冷凝液，玻璃冷却管10也另装设回流管11，供必要时将冷凝液回流到玻璃反应槽，以保持液位的稳定，不凝结的气体则经由锥型玻璃瓶12的出口14排放至烟柜。
整个装置1是架设在一个支撑台架上，玻璃反应槽下放置电加热器05，而电加热器05是置放在 可调节高度的支撑台(图未示)上，可视需要调整高度，并可随时移走。
降解处理开始时，先取触媒溶液(0.06M硫酸亚铁)600毫升，以及核电站使用的强酸型阳离子交换树脂66克(82.5毫升)与强碱型阴离子交换树脂33克(44.72毫升)为模拟废树脂。由于模拟废树脂未夹杂固体杂质也未吸附碳-14核种，因此免除脱除固体杂质与碳-14核种的步骤，并依序由开口04加入玻璃反应槽，然后以硅胶塞封闭开口04，并量测确定溶液pH低于2.5。随之启动搅拌马达进行搅拌并开始加热。当槽内温度达到95℃时停止加热，并启动蠕动泵以每分钟5毫升的流速将35％双氧水输入玻璃反应槽。因为反应的放热，温度会升高至沸点，并维持在沸驣状态下反应；反应产生的气体经过玻璃冷却管10时，水蒸气会被冷凝并收集于锥形玻璃瓶12，不凝结的二氧化碳则管接至烟柜排放；在反应进行中，如发现泡沫累积增高时，即注入消泡剂抑制。本实施例使用的消泡剂为市售含硅树脂与脂肪酸酯成分的产品，经加水稀释10倍后使用。本实施例计在添加降解剂达到275毫升、350毫升、550毫升时各添加消泡剂1毫升，总共3毫升；液位如因蒸发而过度降低时，则将冷凝液回流加以补充，以保持液位在一定的变动范围之内。
为了解树脂的降解效率，本例选择在树脂完全溶解后进行取样，并于降解剂达到预定添加量后暂停添加，并于10分钟后开始取样。取样时暂停加热搅拌，并由开口04取降解废液样品2克供分析用，接着将加热器05移走，并将一电子秤置放在玻璃槽下方，在电子秤台面上置放一块隔热板后，再将电子秤重量读数归零，然后松开连接槽盖02与槽体01的金属夹扣，使玻璃反应槽落坐在电子秤上的隔热板上，秤取重量并记录。
取样及秤重完毕后，立即将装置回复为原来的状态，然后启动搅拌及视需要进行加热，并回复降解剂的添加，直至下次取样时再进行相同的取样与秤重步骤。每次取样的时间皆控制为5分钟。
处理的结果如表1所示，包括双氧水添加重量(双氧水加量)、降解废液重量，以及降解废液的总有机碳(Total Organic Carbon,TOC)含量等如表1所示。另依据分析，本实验所用阴、阳离子交换树脂的碳含量(carbon content)经元素分析得知分别为149.5与150.7克/升，亦即降解前离子交换树脂所含的总有机碳共为19.12克。忽略蒸发气体所带走的少量TOC不计，计算得到的降解率变化也显示于表1中，其中降解率计算如下式：
降解率(％)＝100–废液重量(克)x废液TOC(ppm)x 10-4/19.12
表1中的降解实验结果显示，双氧水添加量达到550毫升时的降解率为95.49％，当双氧水添加达到1,000毫升时，降解率为98.91％。前段添加550毫升得到95.49％降解率，后段虽添加450毫升，但降解率只提高3.42％，表明TOC的高低对双氧水的降解效果影响非常重大；此外也显示，当TOC在500ppm以下时，双氧水的降解效力变得十分微弱。
表1：使用双氧水进行模拟废树脂湿法氧化降解的结果
实施例一：
本实施例示范本发明以双剂型降解剂(双氧水+过硫酸盐)进行与比较例一相同的模拟废树脂的湿法氧化降解及其效果。所用的装置与比较例一相同。
由于降解的效率受到包括降解剂添加速率、有机物型态、TOC浓度等诸多因数的影响，为使处理结果可在相同的条件基础上进行比较，因此本例的条件除了所使用的降解剂在前阶段添加的550毫升为35％双氧水外，自550毫升起改用含5分过硫酸铵与95分35％双氧水的双剂型降解剂，以及添加消泡剂的时机是在降解剂溶液添加285毫升、380毫升、440毫升、470毫升、515毫升时各添加1毫升共5毫升外，其他条件皆与比较例一相同。
处理的结果如表2所示，在添加550毫升35％双氧水反应后，测得降解率为95.31％，与比较例一约略相同。后续改用上述的双剂型降解剂，当降解剂总添加量为700毫升(包括550毫升35％双氧水及150毫升的双剂型降解剂)时，降解率达到99.01％；添加到1000毫升时，废液的TOC低于50ppm，降解率达到99.88％。显示在TOC降低至500ppm甚至100ppm以下时，仍然有良好的降解效果。如以达成99％降解率为目标，则采用双剂型降解剂将可节省30％以上的用量。
表2：实施例一的处理结果
实施例二：
本实施例示范以模拟废树脂(离子交换树脂)的降解废液制备可硬化浆，以包埋固化由硼酸盐废液预处理得到的硼酸盐颗粒，并示范由硼酸盐废液制备硼酸盐颗粒的预处理过程。
模拟硼酸盐废液的制备：
取640克去离子水置入一6升的玻璃烧杯中，并加以搅拌，然后再取99％氢氧化钠900克与99％硼酸4,800克，各分成4等分，以先加氢氧化钠后加硼酸的交叉方式，各分4次缓缓加进烧杯中；待硼酸完全溶解后，再以去离子水补充蒸发损失的水分，然后调整其温度为85℃后保温备用。所得的溶液经分析，其硼浓度为131,080ppm，亦即13.108wt％，换算为相当硼酸的浓度是75.71wt％，钠/硼摩尔比为0.29。
硼酸盐废液的预处理：造粒。本例中的造粒可还包括造粒剂的制备、以及起始造粒与连续造粒等步骤，描述如下。
造粒剂的制备：
取市贩的污泥固化剂STA-110(环鼎国际公司产品)40分、波特兰II型水泥30分与单水氢氧化钡30分混合，并以粉碎机粉碎及过150目筛网后，密封包装做为造粒剂。
起始造粒：
取上述造粒剂粉末2,000克置入一个20升的公自转行星式搅拌器中，设定适当转速后启动搅拌叶，然后再取模拟硼酸盐废液2,640克，分次缓慢滴进搅动的造粒剂粉末中，每次添加的数量以不造成粉末过度潮湿而黏结成大块体为度，且每次添加后需等待溶液平均分散，并与造粒剂反应不再呈现潮湿的光泽时才再次添加；模拟硼酸盐废液添加完毕后，再继续搅拌约5分钟，起始造粒阶段即完成。
连续造粒：
将起始造粒阶段制备的颗粒继续留在造粒机中，并继续搅拌，然后取模拟硼酸盐废液200克缓慢滴入造粒机，使其均匀分布在颗粒上，然后再取造粒剂80克添加在搅动的颗粒上，等待颗粒不再呈现潮湿光泽时，又再次添加模拟硼酸盐废液。如此循环交叉添加模拟硼酸盐废液与造粒剂各达50次并反应完成时，暂时停止造粒，取出一半重量的颗粒后，再继续循环交叉加料造粒，迄共计添加模拟硼酸盐废液与造粒剂各达100次，重量分别达20,000克与8,000克后停止，继续搅拌5分钟后，再将所有的颗粒(包括先取出者以及后来完成者)混合在一起，以备进行固化。
以上两阶段造粒所用的物料条件如表3所示，总计共添加造粒剂10,000克、模拟硼酸盐废液22,640克，造粒剂/模拟硼酸盐废液的重量比为0.442。制得的颗粒直径主要分布在2～5mm之间，硼含量为9.09wt％，相当于硼酸含量52.48wt％。
表3：模拟硼酸盐废液造粒使用物料
模拟废树脂的降解：
使用的装置及模拟废树脂与比较例一相同，同样免除模拟废树脂脱除杂质的步骤。由于所需的废液数量较多，因此分成4批次进行。描述如下。
每一批次处理时，首先将0.06M硫酸亚铁溶液1,200克，以及比较例一所用的相同阳树脂180克与阴树脂90克加入反应槽中，然后启动搅拌及加热。当溶液温度达到95℃时停止加热，并以12毫升/分钟的速率添加35％双氧水，反应热会将反应维持在沸腾状态。当双氧水的添加量达到1,500毫升时，再另加入阳树脂90克及阴树脂45克，并维持同样的速率继续添加双氧水750毫升，如此重复添加总共4次，达总共添加阳树脂540克、阴树脂270克，以及35％双氧水4,500毫升时，再改以双剂型降解剂进行降解，并降低降解剂添加速率为10毫升/分钟，直至双剂型降解剂添加量达到245毫升时停止，随后继续维持搅拌30分钟后结束降解操作。以上降解过程中温度皆保持在95℃至沸点之间，必要时加热以帮助维持温度；液位因沸腾而降低时则以冷凝液回流方式保持液位不致变动太大；如有气泡累积现象时即适时以消泡剂抑制，本实验共计添加消泡剂12毫升。
依相同条件进行总共4批次合计阳树脂2,160克(2,700毫升)与阴树脂1,080克(1,464毫升)的降解。将获得的降解废液混合在一起，并浓缩调整其总重量为1,540克后，分析得其硫酸根含量为4.02摩尔/公斤。
降解废液的转化：
降解废液转化的装置除了含氨逸气处理部分的装置如第4图所示外，其他包括转化反应与逸气冷却两部分的装置皆与图3的装置1相同，其中玻璃反应槽槽盖02上的四个开口04、07、08、09中，开口04作为转化剂进料口，并兼于必要时作为温度与pH的量测口；开口07作为降解废液的加料口，上置量筒型漏斗供手工加入废液；开口09作为转化逸气出口。
用于含氨逸气处理的装置2示意如图4，锥形玻璃瓶12a供收集冷凝液及不凝结含氨逸气的暂留，即作为氨气的缓冲槽；锥形玻璃瓶12a的开口16a作为空气入口；流量计17与调节阀18为空气调节装置，供空气流量的调节；出口14a为转化逸气出口，用硅胶软管与氨氧化分解装置19连接；氨氧化分解装置19含预热器及高温触媒床，可提供600℃以下的持温，供含氨逸气的预热及使用氨氧化分解触媒将氨氧化分解为N
2与H
2O；抽气机21供协助转化逸气克服流动阻力；空气调节阀20供调 节空气流量，以调节抽气机抽气产生的负压。
处理开始前，先将氨氧化分解装置19预热至300℃备用；然后取单水氢氧化钡粉末与水以4：6的重量比例调制1466.5克转化剂水浆(含单水氢氧化钡586.6克)，并从开口04置入玻璃反应槽，启动搅拌后，再将备妥的降解废液以蠕动泵缓慢输入，至共输入770克时停止，随后加热保持90℃左右温度并持续搅拌2小时，以完全去除氨气。然后，停止加热并移至于烧杯放冷待用，得到的浓缩转化废浆重为1,305克。
转化过程产生的含氨气体经玻璃冷却管10a进入锥型瓶12a，凝结的液体留置在瓶中，不凝结的含氨气体与输入的空气混合后，再流至氨氧化分解装置19分解为水气和氮气后，由抽气机抽放至烟柜排放。
再重复进行相同步骤一次，将总共1,540克的降解废液完成转化，并将得到的转化废浆混合，合计共得到含水44％的转化废浆2,655克(干重为1,487克)。
将转化废浆移置于一个10升的搅拌混合器，在搅拌下添加由环鼎污泥固化剂SPF-210与波特兰II型水泥等重量比例混合的可硬化浆原料1,565克及硼酸盐颗粒1,976克，混合均匀后即成为硼酸盐颗粒的浆体，其组成如表4所示。
表4：硼酸盐颗粒浆体组成
接着，将颗粒浆体装桶，在本例中即倒入内径5公分、高6公分的聚乙烯塑胶模型中，以震荡方式去除气泡及表面抹平后，置于温度25℃、相对湿度95％以上的恒温恒湿箱中进行28天的养护。养护完成后，依中国台湾低放射性废料体品质规范进行抗压强度、耐候性(抗冻融性)、抗水浸性等测试，此外，也另进行9公尺坠落的抗冲击性测试，结果如表5所示，显示固化体品质符合各核能国家规定的品质要求。
表5：硼酸盐颗粒固化体品质测试结果
| 测试项目 | 抗压强度 | 耐候性 | 耐水性 | 抗冲击性 |
| 结果 | 9.57MPa | 11.18MPa | 13.69MPa | 合格(无明显碎裂) |
实施例三：
本实施例示范废树脂与废活性碳的合并处理。
首先以与实施例一相同的方式进行包括阳树脂540克(约675毫升)与阴树脂270克(约366毫升)的废树脂湿法氧化降解，并将降解废液制备成含水45％的转化废浆2,682克，再添加和实施例二相同的可硬化浆原料1,565克制备成4,247克的可硬化浆备用。实验所用的模拟废活性碳为核电站水处理用的废活性碳，为大小6～40筛目范围的湿颗粒，经测得含水率为10.79％，比重为1.06。将废活性碳1,175克(1,108毫升)与备妥的可硬化浆搅拌混合均匀，制备成废活性碳固化浆体5,422克，其组成如表6所示(注：废活性碳固化浆体是对废活性碳与可硬化浆拌合形成的浆体的称呼，为废活性碳固化体的前驱物)；固化后的废弃物体比重经测定为2.02，即体积为2,684毫升，因此，固化体的废活性碳体积荷载率为41.3％。
另进行增加废活性碳荷载率的实验。以同样方式进行废树脂的降解及制备含水率43％的转化废浆2,588克，然后再添加相同的可硬化浆原料1,540克，制备成可硬化浆4,128克。再利用此可硬化浆与1,510克(1,425毫升)废活性碳混合，制备成浆体5,638克，其组成同样显示于表6。固化体比重经测定为1.996，即体积为2,825毫升，因此其废活性碳体积荷载率为50.44％。
表6：废活性碳浆体组成
将以上制备的固化体依照实施例二的方式制作样品后进行品质测试，其结果如表7所示，显示其品质十分优异。
表7：废活性碳固化体品质测试结果
以上所述，仅是本发明的较佳实施例而已，并非对本发明作任何形式上的限制，虽然本发明已以较佳实施例公开如上，然而并非用以限定本发明，任何熟悉本专业的技术人员,在不脱离本发明技术方案范围内，当可利用上述公开的方法及技术内容作出些许的更动或修饰为等同变化的等效实施例， 但凡是未脱离本发明技术方案的内容，依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与修饰，均仍属于本发明技术方案的范围内。
Claims (26)
- 一种以废离子交换树脂的湿法降解废液制备可硬化浆并用以固化/固定其他废弃物的方法，其特征在于，包括步骤：进行一废离子交换树脂的杂质脱除，然后进行湿法降解处理，并产生一含硫酸盐的降解废液，其中所述废离子交换树脂含有阳离子交换树脂；浓缩所述降解废液，并添加一转化剂使产生一含硫酸盐微粒的转化废浆；以及添加一可硬化浆原料至所述转化废浆中并混合均匀，以制备成一可硬化浆，用以对至少一种其他废弃物进行固化或固定处理。
- 如权利要求1所述的方法，其特征在于，所述至少一种其他废弃物选自硼酸盐废液、固态硼酸盐、废活性碳、污泥、焚化灰渣、废过滤器芯、金属废弃物以及废弃物压缩块。
- 如权利要求1所述的方法，其特征在于，所述至少一种其他废弃物包括一液态废弃物；处理方法还包括将所述液态废弃物预处理成为固体颗粒或沉淀物，使适合使用所述可硬化浆进行固化或固定处理。
- 如权利要求1所述的方法，其特征在于，所述至少一种其他废弃物包括一固态废弃物；处理方法还包括将所述固态废弃物预处理为具适当的含水率、外型、尺寸与密实度，使适合于使用所述可硬化浆进行固化或固定处理。
- 如权利要求1所述的方法，其特征在于，所述废离子交换树脂中的杂质脱除的步骤还包括使所述废离子交换树脂形成水浆后以超音波震荡方式脱除其所夹带的固体杂质，以及以一碱性脱附剂脱除其所吸附的碳-14核种；脱除杂质所产生的废液则并入转化废浆中一起进行处理。
- 如权利要求5所述的方法，其特征在于，所述碱性脱附剂选自以下的碱金属、碱土金属或铵的盐类或化合物的溶液的至少一种：过氯酸盐、硫酸盐、硝酸盐、磷酸盐、磷酸一氢盐、磷酸二氢盐、草酸盐、碘化物、溴化物。
- 如权利要求2所述的方法，其特征在于，所述方法还包括将所述硼酸盐废液预处理为硼酸盐颗粒的步骤：提供一硼酸盐废液；调节所述硼酸盐废液的成分并浓缩所述硼酸盐废液，以制备含聚合硼酸盐的一高浓度硼酸盐废液；使用一造粒装置与至少一种造粒剂，将所述高浓度硼酸盐废液制造成硼酸盐颗粒；以及将所述硼酸盐颗粒与所述可硬化浆混合均匀形成一颗粒浆体，然后装入一废弃物桶，并于所述颗粒浆体硬化后形成一固化体。
- 如权利要求7所述的方法，其特征在于，形成所述固化体的步骤还包括将所述废弃物桶封盖形成一固化体包件。
- 如权利要求7所述的方法，其特征在于，所述硼酸盐废液为硼酸钠溶液。
- 如权利要求1所述的方法，其特征在于，所述湿法降解处理中，调节降解反应液的pH所使用的酸、碱分别为硫酸与氢氧化钡。
- 如权利要求1所述的方法，其特征在于，所述湿法降解处理选自以下方法的至少一种：湿法氧化法、超临界水氧化法、酸解法。
- 如权利要求11所述的方法，其特征在于，进行所述废离子交换树脂的湿法氧化法处理，并产生所述降解废液的步骤包括：调制一降解剂与一触媒溶液；以及将脱除杂质后的所述废离子交换树脂置于所述触媒溶液中，调节溶液的pH<3，并使溶液维持在95℃至沸点的温度下，再添加所述降解剂而使废离子交换树脂的碳氢成分氧化分解成为CO 2与H 2O，且产生含铵根、硫酸根、硫酸盐、残渣以及少量有机碳的所述降解废液。
- 如权利要求12所述的方法，其特征在于，所述降解剂包含双氧水及选自以下的至少一种的过硫酸盐：过硫酸铵、过硫酸钠、过硫酸钾以及过硫酸钙。
- 如权利要求12所述的方法，其特征在于，所述触媒溶液为浓度0.1 M以下的硫酸亚铁溶液。
- 如权利要求1所述的方法，其特征在于，添加所述转化剂使产生转化废浆的步骤还包括以氢氧化钡作为转化剂，以及产生含硫酸钡微粒的转化废浆。
- 如权利要求1所述的方法，其特征在于，添加所述转化剂使产生转化废浆的步骤进一步产生一含氨气体；处理方法还包括将含氨气体处理为氮气及水气的步骤。
- 如权利要求16所述的方法，其特征在于，含氨气体的处理选自以下方法的至少一种：使所述含氨气体通过一氨的氧化分解触媒床，用以将氨直接转化为氮气与水气；以及以水吸收所述含氨气体成为氨水，再进行水中氢氧化铵的氧化分解以转化为氮气与水。
- 如权利要求17所述的方法，其特征在于，所述含氨气体在通过氨的氧化分解触媒床之前先进入一氨气贮存槽。
- 如权利要求2所述的方法，其特征在于，所述固态硼酸盐为以下型态硼酸钙的至少一种：泥状、粉状、粒状、块状。
- 如权利要求4所述的方法，其特征在于，对所述至少一种固态废弃物进行固定处理的步骤还包括：将所述至少一种固态废弃物装入一废弃物桶；在所述废弃物桶中注入所述可硬化浆，以充满所述废弃物桶内的空隙并包封所述至少一种固态废弃物；等待所述可硬化浆硬化并形成一固定体。
- 如权利要求20所述的方法，其特征在于，形成所述固定体的步骤还包括将废弃物桶封盖形成一固定体包件。
- 如权利要求2所述的方法，其特征在于，对所述废活性碳进行固化处理的步骤还包括：进行所述废活性碳颗粒的预处理，使含适当低度而不滴水的含水率；以及将所述废活性碳颗粒与所述可硬化浆混合均匀形成一颗粒浆体，并进行所述固化处理。
- 一种有机物的湿法氧化方法，其特征在于，包括使用含有选自以下的至少一种过硫酸盐的双氧水为降解剂：过硫酸铵、过硫酸钠、过硫酸钾以及过硫酸钙。
- 如权利要求23所述的方法，其特征在于，所述有机物为以下的至少一种：离子交换树脂、高分子树脂、有机化合物、植物性纤维物、植物性油脂、动物性油脂以及矿物性油脂。
- 如权利要求23所述的方法，其特征在于，所述有机物为液态且其单分子占比多于高分子占比。
- 如权利要求25所述的方法，其特征在于，所述液态有机物为总有机碳浓度1000ppm以下的离子交换树脂湿法氧化降解液。
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