Synergistic volume reduction and solidification method and system for 68Ge production waste liquid

Abstract

The invention provides a synergistic volume reduction and solidification method and system for 68Ge production waste liquid. The method comprises the following steps: dividing waste liquid into different aqueous-phase waste liquid according to sources and key components of the waste liquid; a nuclear-grade cross-linked polyacrylate polymer with wide pH tolerance is adopted for water-phase waste liquid, a polyolefin polymer with a lipophilic long chain and a three-dimensional network structure is adopted for organic waste liquid, and a phosphate stabilizer is introduced into high-gallium waste liquid to form GaPO4 precipitate, so that directional curing is realized; then, multiple addition-curing cycles are carried out in the same container, and the filling density is improved; microwave sensitizers such as activated carbon are added, and dehydration, pyrolysis and mineralization / ceramization inerting treatment are completed in a microwave field under multi-stage closed-loop control. Compared with a traditional cement solidification technology and the like, integrated, high-volume-reduction and high-stabilization treatment on multiple types of 68Ge production waste liquid is achieved, the overall volume reduction ratio is high, the treatment cost is reduced, and the long-term safe fixing capacity of radionuclides is improved.

Description

Technical Field

[0001] This invention relates to the field of radioactive waste treatment technology, and more specifically, to a... 68 A method and system for synergistic volume reduction and solidification of waste liquid from Ge production. Background Technology

[0002] Gallium-68 ( 68 Ga (Ga) is an excellent positron emitter and is widely used in positron emission tomography (PET) imaging. Its parent nuclide, germanium-68 (Ga), is... 68 (Ge) is mainly prepared by bombarding gallium targets or gallium-nickel alloy targets with a cyclotron. During the subsequent chemical separation and purification process, various complex and diverse liquid radioactive wastes are continuously or intermittently generated. These waste liquids mainly include the following categories: First, strongly acidic aqueous waste liquid, originating from the raffinate or column eluent of the extraction process, typically containing high concentrations of nitric acid, hydrochloric acid, and incompletely separated metal ions; second, organic waste liquid, from the organic phase of the extraction process, which may contain toxic or volatile organic solvents such as kerosene and CCl4; and third, alkaline waste liquid, mainly from the fractionation process used to capture volatile organic compounds. 68 Ge's sodium hydroxide solution. This type of waste liquid has a complex composition, significantly different physical properties, and is radioactive; therefore, its safe and efficient treatment is crucial. 68 It is an indispensable key link in the Ge production and application industry chain.

[0003] Currently, in the field of radioactive waste treatment, there is a lack of unified, efficient, and economical treatment strategies for such mixed radioactive waste liquids. The industry commonly uses cement solidification for treatment, but this method has limitations in application... 68 The production of waste liquids using cement has revealed several significant drawbacks: Direct solidification of highly acidic aqueous waste liquids severely interferes with the cement hydration process and corrodes equipment, necessitating a cumbersome and difficult-to-control neutralization pretreatment. This pretreatment process is not only complex to operate but also prone to boiling or splashing due to exothermic neutralization, posing safety risks. Furthermore, cement solidification itself introduces a large amount of inert matrix, causing the final solidified body to expand dramatically compared to the original waste liquid volume, resulting in a severe "volume expansion" effect. This significantly increases the burden and cost of subsequent waste transportation, storage, and final disposal. Cement solidification has poor tolerance for organic waste liquids; organic matter hinders the normal hydration reaction of cement, leading to low mechanical strength and high leaching rates of radioactive nuclides in the resulting solidified body, raising concerns about its long-term stability and safety. Overall, traditional cement solidification is a crude, inefficient containment technology, ill-suited for addressing specific environmental risks. 68 Effective and long-term stabilization and fixation of specific harmful components (such as specific metal ions and organic solvents) in Ge production waste liquid.

[0004] Besides cement curing, other technical approaches exist in the industry, such as asphalt curing and glass curing. However, asphalt curing suffers from high process temperatures, potential fire risks, and limited waste packing capacity; glass curing requires extremely high processing temperatures, involves highly complex equipment, and incurs high investment and operating costs. These methods are unsuitable for practical applications due to stringent safety requirements or poor economics. 68 This is a routine, continuous production scenario for medical isotopes like Ge.

[0005] Therefore, facing 68 The production of Ge generates a variety of mixed waste liquids with diverse properties, necessitating the development of a novel treatment solution that overcomes the shortcomings of existing technologies. This solution should enable unified and efficient treatment of various waste liquids, including those containing strong acids, organic phases, and alkalinity, fundamentally addressing the waste volume increase problem caused by existing technologies and achieving significant volume reduction, while ensuring the solidified body possesses excellent long-term stability and intrinsic safety. Summary of the Invention

[0006] One of the technical problems to be solved by the present invention is to provide a 68 A synergistic volume reduction and solidification method for Ge production waste liquid is proposed to solve the problems of complex treatment process, serious waste volume increase, poor long-term stability and poor compatibility with organic waste liquid in existing technologies.

[0007] To overcome the shortcomings of the prior art, the present invention provides a 68 A synergistic volume reduction and solidification method for Ge production waste liquid includes the following steps: S1: Waste liquid classification, based on the source and key components of the waste liquid, is divided into: Class A strongly acidic aqueous waste liquid, Class B organic waste liquid, Class C high gallium concentration acidic waste liquid, and Class D alkaline collection liquid; S2: Directional solidification, solidifying the waste liquid after classification in step S1: For Class A strongly acidic aqueous waste liquid, Class C high gallium concentration acidic waste liquid, and Class D alkaline collection liquid, nuclear-grade cross-linked polyacrylate polymers are used as the main curing agent. For Class B organic waste liquid, polyolefin polymers with oleophilic long chains and three-dimensional network structures are used as the main curing agent; For Class C high gallium concentration acidic waste liquid, a stabilizer is further added to form GaPO4 precipitate; S3: Multiple additions and curing cycle: After the curing treatment in step S2, after the solidified body forms a preliminary load-bearing structure, a new batch of waste liquid and curing agent is added to the same container, and the cycle continues until the container filling rate reaches more than 90%. S4: Microwave-induced pyrolysis inertization treatment, adding a microwave sensitizer to the cured body and applying microwave irradiation, causing the cured body to undergo dehydration, pyrolysis and mineralization / ceramization transformation, in order to further achieve deep volume reduction and long-term stabilization.

[0008] This invention is a 68 Compared with existing technologies, the synergistic volume reduction and solidification method for Ge production wastewater has the following advantages: This invention solves the technical problems of complex treatment processes, severe waste volume increase, poor long-term stability, and poor tolerance to organic wastewater in existing technologies through a refined treatment route of multi-technology synergy of directional solidification, multi-cycle, and microwave inerting. First, the precise classification of S1 wastewater lays the foundation for subsequent targeted treatment. Second, in S2 directional solidification, a nuclear-grade cross-linked polyacrylate polymer with wide pH tolerance is selected as a universal solidification matrix for A / C / D type aqueous phase wastewater, breaking through the limitations of traditional materials on the acidity and alkalinity of wastewater, eliminating the cumbersome neutralization pretreatment steps, and simultaneously introducing a phosphate stabilizer for C type wastewater to achieve Ga 3+ The method employs specific chemical fixation, while for Class B organic waste liquid, it utilizes similarly compatible polyolefin polymers to achieve efficient encapsulation of organic molecules. This combination of features constitutes the first layer of guarantee for achieving efficient waste stabilization. In step S3, multiple rounds of addition-solidification cycles utilize the early load-bearing characteristics of the polymer solidified body to achieve high-density filling within the same container, achieving significant primary physical volume reduction. Further, in S4, microwave-induced pyrolysis inertization treatment, under the action of a sensitizer, triggers deep thermal transformation of the solidified body, removing not only moisture and organic matter but also promoting mineralization / ceramization transformation, achieving secondary chemical volume reduction and intrinsically safe stabilization. Furthermore, in the method of this invention, the physical filling in S3 and the chemical transformation in S4 have a synergistic volume reduction effect, with the combined effect resulting in an overall volume reduction ratio as high as 5:1 to 15:1. The polymer encapsulation and chemical precipitation in S2 and the microwave bonding in S4 also complement each other, jointly ensuring that radionuclides are fixed stably and permanently in the final product. Through the close correlation and synergistic effect of the above steps, this invention achieves efficient stabilization of complex components. 68 The core objective is to achieve unified, efficient, and deep volume reduction and intrinsically safe stabilization of wastewater from Ge production.

[0009] In one possible implementation, in step S2, the stabilizer is a phosphate stabilizer.

[0010] Compared with existing technologies, the above technical solution utilizes phosphate ions (PO4) to... 3- ) and Ga in waste liquid 3+A specific precipitation reaction occurs, generating GaPO4 precipitate with extremely low solubility. This chemical precipitation enables highly selective fixation of the target nuclide, reducing the migration and leaching risks of gallium in the solidified body and ensuring the long-term safe disposal of gallium-containing waste.

[0011] In one possible implementation, the number of cycles in step S3 is 2–5.

[0012] Compared with existing technologies, the above-mentioned technical solution can make full use of the load-bearing structure formed in the early stage of polymer curing, achieve high-density encapsulation of waste liquid through multiple layered filling, improve the effective volume utilization rate of a single disposal container, further improve the primary volume reduction ratio, significantly reduce the number of disposal containers used, and at the same time provide a pre-treatment body with a uniform structure for subsequent microwave treatment.

[0013] In one possible implementation, in step S4, the microwave sensitizer is activated carbon, and the amount of activated carbon added is 1–3 wt.

[0014] Compared with existing technologies, the above technical solution utilizes the excellent microwave absorption characteristics of activated carbon to generate local high-temperature hot spots in a microwave field. By using activated carbon as a sensitizer, dielectric heating initiates a stepwise thermal conversion of the solidified body, ensuring that the solidified body quickly reaches the pyrolysis temperature, achieving deep decomposition of organic matter and sintering of inorganic matter. This not only ensures pyrolysis efficiency but also avoids the risk of increased energy consumption or secondary pollution caused by excessive addition, improves the total organic carbon removal rate, achieves a high secondary volume reduction ratio, and simultaneously fixes radioactive nuclides in a stable ceramic phase.

[0015] In one possible implementation, in step S4, the microwave irradiation conditions are: irradiation for 10-30 minutes within a power range of 500-800W.

[0016] Compared with existing technologies, the above technical solution uses microwave irradiation with a power range of 500-800W for 10-30 minutes, which provides sufficient but not excessive energy input, ensuring that the solidified body undergoes a complete thermal conversion process. Furthermore, by optimizing the matching relationship between power and time, the pyrolysis efficiency and energy consumption control are balanced, achieving full evaporation of moisture, complete decomposition of organic matter, and sintering reaction of inorganic phase.

[0017] In one possible implementation, in step S2, the mass ratio of the nuclear-grade crosslinked polyacrylate polymer to the Class A, Class C, or Class D waste liquid is 1:(1.5-2.5).

[0018] Compared with existing technologies, the above-mentioned technical solution, by controlling the mass ratio of the nuclear-grade crosslinked polyacrylate polymer to the waste liquid, ensures that the polymer chain segments fully expand and form a dense crosslinked network. This allows the waste liquid with extreme pH to quickly transform into a stable gel, and the curing agent to maintain a stable three-dimensional crosslinked structure even under extreme pH conditions. This achieves efficient containment of strongly acidic aqueous phases, high-gallium acidic aqueous phases, and strongly alkaline waste liquids. The nuclear-grade crosslinked polyacrylate polymer has functional groups that can automatically switch the dominant adsorption mechanism over a wide pH range. Under strongly acidic conditions, the carboxyl groups in the polymer are protonated to carboxyl groups, achieving stable encapsulation of hydrated hydrogen ions and anions through hydrogen bonding, van der Waals forces, and steric hindrance. Under strongly alkaline conditions, the carboxyl groups are deprotonated and carry a negative charge, which can efficiently bind metal cations and hydroxide ions through electrostatic adsorption and ion exchange mechanisms, preventing the polymer network from collapsing or swelling and becoming unstable.

[0019] In one possible implementation, in step S2, the mass ratio of the polyolefin polymer to the Class B organic waste liquid is 1:(2.5-4).

[0020] Compared with existing technologies, the above-mentioned technical solution enables the polyolefin curing agent to fully swell and absorb organic waste liquids such as the TBP-kerosene system and CCl4 system from the extraction process, so that the organic solvent is permanently fixed in the three-dimensional cross-linked network. In this embodiment, the polyolefin curing agent has a long non-polar alkyl chain, which makes it highly compatible with organic solvents such as TBP, kerosene, and CCl4. A significant swelling effect can occur through the principle of like dissolves like. The three-dimensional cross-linked structure can form a stable gel block after absorbing the solvent, rather than surface encapsulation or simple adsorption. This can fundamentally prevent the risk of organic phase leakage, volatilization, and longitudinal migration. By further controlling the mass ratio of Class B waste liquid and polyolefin polymer, sufficient polymer chain segments and cross-linking points can be provided, allowing the system to quickly enter a stable colloidal structure, while ensuring that the cured body has sufficient mechanical strength and low volatility.

[0021] In one possible implementation, in step S2, the microwave irradiation in step S4 employs a multi-stage closed-loop control strategy, including: Initially, the microwave power is controlled to rapidly heat the cured body to the moisture evaporation threshold. In the middle stage, the power is adjusted to maintain the temperature within a constant range to ensure complete pyrolysis; In the final stage, when the monitored rate of change in weight loss approaches zero, microwave irradiation is terminated.

[0022] Compared with existing technologies, the above-mentioned technical solution, in the initial stage, generates a strong absorption peak in the microwave field by the activated carbon sensitizer. The local high temperature causes the system to quickly reach the water evaporation threshold, promoting rapid dehydration of the solidified body and activating the thermal decomposition reaction of the polymer. In the middle stage, the microwave power is adjusted according to the real-time temperature feedback to keep the solidified body in the optimal pyrolysis temperature range, promoting polymer chain scission and carbonization, and causing complete decomposition and oxidative removal of organic matter. In the final stage, the solidified body gradually transforms into carbonaceous or ceramic precursors, with its mass change rate approaching zero. This serves as a termination signal to avoid structural damage or unnecessary energy consumption caused by overheating, thereby ensuring the pyrolysis uniformity of the solidified body, realizing a continuous transition from complete removal of organic matter to sintering of the inorganic matrix, and improving the degree of formation of ceramic or glassy structures.

[0023] Another technical problem that this invention aims to solve is to provide a... 68 A system for the synergistic volume reduction and solidification of Ge production waste liquid is proposed to address the problems in existing technologies, such as the lack of unified treatment equipment for various types of complex radioactive waste liquids, the large footprint of traditional cement solidification facilities, fragmented process flow, low degree of automation, and the serious increase in the volume of the final waste package.

[0024] To address the above problems, the present invention provides a... 68 A system for the synergistic volume reduction and solidification of Ge production waste liquid includes: Waste liquid sorting unit, used for receiving 68 Ge production waste liquid is classified into Class A strongly acidic aqueous waste liquid, Class B organic waste liquid, Class C high gallium concentration acidic waste liquid, or Class D alkaline collection liquid according to the composition of the waste liquid. The directional curing batching unit is communicatively connected to the waste liquid sorting unit and is used to match the curing agent according to the waste liquid sorting results; this unit is equipped with a nuclear-grade crosslinked polyacrylate polymer source, a polyolefin polymer source, and a stabilizer source; The circulating filling curing unit is connected to the waste liquid classification unit and the directional curing batching unit, respectively, and is used to receive waste liquid and curing agent for mixing and injecting the mixture into the curing container; the unit is equipped with a circulation control module for controlling multiple rounds of waste liquid addition; The microwave pyrolysis unit is used to receive the solidified container after it has been circulated and filled, and to apply microwave irradiation to the solidified body inside the container for dehydration and pyrolysis treatment. The main control unit is electrically connected to the above-mentioned units and is used to regulate the operation of the system.

[0025] In one possible implementation, the waste liquid classification unit includes an online detection module, which includes a pH sensor for identifying the acidity and alkalinity of aqueous waste liquid and a near-infrared spectral probe for identifying organic waste liquid components. The detection signal output by the online detection module is used to drive the main control unit to automatically determine the waste liquid category.

[0026] This invention is a 68 Compared with existing technologies, the system for synergistic volume reduction and solidification of Ge production waste liquid has the following advantages: The system of the present invention replaces the independent and decentralized treatment facilities required for different types of waste liquid (including strong acid, organic and alkaline) in the prior art with an integrated system in which a waste liquid classification unit and a directional solidification batching unit work together. Through the coordination of the main control unit, the same system can automatically switch the addition strategy of nuclear-grade polymer or stabilizer according to the type of waste liquid. The addition of reagents is precisely controlled by the directional solidification batching unit, and stabilizers are automatically introduced for high gallium waste liquid, avoiding the risk of exposure to radioactive materials during manual operation. Attached Figure Description

[0027] Figure 1 For the present invention 68 A flowchart of a synergistic volume reduction and solidification method for Ge production waste liquid. Detailed Implementation

[0028] First, those skilled in the art should understand that these embodiments are merely illustrative of the technical principles of the present invention and are not intended to limit the scope of protection of the present invention. Those skilled in the art can make adjustments as needed to adapt to specific application scenarios.

[0029] This invention provides 68 A synergistic volume reduction and solidification method for Ge production waste liquid includes the following steps: S1: Waste liquid classification, based on the source and key components of the waste liquid, is divided into: Class A strongly acidic aqueous waste liquid, Class B organic waste liquid, Class C high gallium concentration acidic waste liquid, and Class D alkaline collection liquid; S2: Directional solidification, solidifying the waste liquid after classification in step S1: For Class A strongly acidic aqueous waste liquid, Class C high gallium concentration acidic waste liquid, and Class D alkaline collection liquid, nuclear-grade cross-linked polyacrylate polymers are used as the main curing agent. For Class B organic waste liquid, polyolefin polymers with oleophilic long chains and three-dimensional network structures are used as the main curing agent; For Class C high gallium concentration acidic waste liquid, a stabilizer is further added to form GaPO4 precipitate; S3: Multiple additions and curing cycle: After the curing treatment in step S2, after the solidified body forms a preliminary load-bearing structure, a new batch of waste liquid and curing agent is added to the same container, and the cycle continues until the container filling rate reaches more than 90%. S4: Microwave-induced pyrolysis inertization treatment, adding a microwave sensitizer to the cured body and applying microwave irradiation, causing the cured body to undergo dehydration, pyrolysis and mineralization / ceramization transformation, in order to further achieve deep volume reduction and long-term stabilization.

[0030] In step S2, the method of the present invention selects high-performance polymers with specific functional groups and spatial structures as the main curing agent according to the chemical characteristics of different waste liquids. This selection is the key to overcoming the bias of existing technologies. For aqueous waste liquids of types A, C, and D, core-grade cross-linked polyacrylate polymers with wide pH tolerance (including Nochar® N960) are selected. The key to this polymer lies in its stable cross-linking network and pH-responsive functional groups; under strongly acidic conditions, its carboxylate groups (-COO) - The protonation of the polymer chain forms a carboxyl group (-COOH), which mainly captures hydrated hydrogen ions and anions through hydrogen bonding, van der Waals forces, and steric hindrance. Under strongly alkaline conditions, the carboxyl group deprotonates, and the negatively charged polymer chain stabilizes and fixes metal cations and hydroxide ions through electrostatic attraction and ion exchange. This characteristic of automatically switching the dominant adsorption mechanism under different pH conditions effectively overcomes the technical bottleneck of ordinary polymers where the network structure easily collapses and the adsorption capacity drops sharply under extreme pH conditions, breaking the cognitive limitation that this type of material is only applicable to a narrow pH range. For Class C waste liquid, phosphate stabilizers (including Na2HPO4) are added simultaneously, which react with Ga... 3+ The formation of GaPO4 with extremely low solubility achieves effective stabilization of Ga.

[0031] For Class B organic waste liquid, polyolefin polymers with oleophilic long chains and three-dimensional network structures (including Nochar® N910) are selected. This polymer follows the principle of like dissolves like, and its molecular chains are highly compatible with organic solvents. Through a strong swelling effect, organic molecules are absorbed and permanently fixed in its cross-linked network, rather than simply being coated on the surface, thus fundamentally eliminating the risk of organic phase leakage and volatilization.

[0032] In the microwave field of step S4, the microwave sensitizer (such as activated carbon) generates local high temperature, triggering a stepwise thermal conversion process: the polymer matrix and the encapsulated organic matter first undergo chain scission and volatilization, followed by deep carbonization to form a stable carbon skeleton. Finally, the inorganic components (such as phosphates and metal oxides) undergo sintering reaction under hot spot catalysis to form a stable ceramic phase that chemically bonds radionuclides. This process thoroughly removes moisture and organic matter, achieving the essential mineralization / ceramization transformation of waste. In addition to thoroughly removing moisture and organic matter, it may also induce local melting to form a microscopic glass body, chemically bonding radionuclides and heavy metal ions into a stable network structure, achieving the mineralization / ceramization transformation of waste. This step can achieve a secondary volume reduction ratio of 3:1 to 5:1.

[0033] As a preferred embodiment, in step S2, the stabilizer is a phosphate stabilizer.

[0034] As a preferred embodiment, in step S3, the number of cycles is 2–5.

[0035] As a preferred embodiment, in step S4, the microwave sensitizer is activated carbon, and the amount of activated carbon added is 1–3 wt%.

[0036] As a preferred embodiment, in step S4, the microwave irradiation conditions are: irradiation for 10-30 minutes within a power range of 500-800W.

[0037] As a preferred embodiment, in step S2, the mixing mass ratio of the nuclear-grade cross-linked polyacrylate polymer to the Class A, Class C, or Class D waste liquid is 1:(1.5-2.5).

[0038] As a preferred embodiment, in step S2, the mixing mass ratio of the polyolefin polymer to the Class B organic waste liquid is 1:(2.5-4).

[0039] As a preferred embodiment, in step S2, the microwave irradiation in step S4 employs a multi-stage closed-loop control strategy, including: Initially, the microwave power is controlled to rapidly heat the cured body to the moisture evaporation threshold. In the middle stage, the power is adjusted to maintain the temperature within a constant range to ensure complete pyrolysis; In the final stage, when the monitored rate of change in weight loss approaches zero, microwave irradiation is terminated.

[0040] As a preferred embodiment, the waste liquid classification unit includes an online detection module, which includes a pH sensor for identifying the acidity and alkalinity of aqueous waste liquid and a near-infrared spectral probe for identifying organic waste liquid components. The detection signal output by the online detection module is used to drive the main control unit to automatically determine the waste liquid category.

[0041] The classification-solidification method provided by this invention uses nuclear-grade cross-linked polyacrylate polymers as a universal solidification matrix, breaking through the limitations of traditional materials on the pH range of waste liquids. It achieves efficient stabilization treatment of various types of aqueous waste liquids ranging from strong acid to strong alkalinity, overcoming the drawbacks of configuring independent treatment lines for waste liquids with different properties, significantly simplifying the process and reducing costs. Furthermore, it employs a two-stage volume reduction strategy combining multi-cycle filling solidification and microwave-induced pyrolysis inertization. First, high-density encapsulation is achieved through multiple cycles to achieve primary volume reduction, followed by microwave treatment to achieve dehydration, pyrolysis, and mineralization transformation of the solidified body to complete secondary volume reduction. The overall system can achieve a volume reduction ratio as high as 5:1 to 15:1, fundamentally solving the waste volume expansion problem. In a further preferred embodiment, by introducing a phosphate-based special stabilizer and combining it with the ceramic / vitrified products formed under the action of a microwave field, the leaching risk of radionuclides and heavy metal ions is significantly reduced, ensuring long-term disposal safety.

[0042] The present invention also provides a system using the aforementioned synergistic volume reduction curing method, comprising: Waste liquid sorting unit, used for receiving 68 Ge production waste liquid is classified into Class A strongly acidic aqueous waste liquid, Class B organic waste liquid, Class C high gallium concentration acidic waste liquid, or Class D alkaline collection liquid according to the composition of the waste liquid. The directional curing batching unit is communicatively connected to the waste liquid sorting unit and is used to match the curing agent according to the waste liquid sorting results; this unit is equipped with a nuclear-grade crosslinked polyacrylate polymer source, a polyolefin polymer source, and a stabilizer source; The circulating filling curing unit is connected to the waste liquid classification unit and the directional curing batching unit, respectively, and is used to receive waste liquid and curing agent for mixing and injecting the mixture into the curing container; the unit is equipped with a circulation control module for controlling multiple rounds of waste liquid addition; The microwave pyrolysis unit is used to receive the solidified container after it has been circulated and filled, and to apply microwave irradiation to the solidified body inside the container for dehydration and pyrolysis treatment. The main control unit is electrically connected to the above-mentioned units and is used to regulate the operation of the system.

[0043] The following specific embodiments, combined with concrete data, are provided to further elaborate on the technical solution of the present invention: Example 1: Treatment of Class A Strongly Acidic Waste Liquid This embodiment provides a68 A synergistic volume reduction and solidification method and system for Ge production waste liquid, specifically for treating Class A strongly acidic aqueous waste liquid, the method comprising the following steps: S1: Waste liquid classification: Strongly acidic waste liquid produced by the fractionation process enters the system. The online pH meter detects that it is strongly acidic, and the central control unit determines that it is a Class A waste liquid.

[0044] S2: Directional Curing: The central control unit instructs the polymer dispensing unit to accurately measure the core-grade cross-linked polyacrylate polymer (Nochar® No. 960) and mix it with the waste liquid at a mass ratio of approximately 1:0.5 (i.e., polymer: waste liquid = 1:2) in a mixer. After stirring, a uniform, non-flowing gel-like solid is formed.

[0045] S3: Multiple Addition-Cure Cycle: Transfer the above mixture to a 200-liter final disposal container and allow it to solidify. After approximately 24 hours, when the system detects that the container still has about 50% of its effective volume, receive the second batch of Class A waste liquid. Repeat the mixing and solidification operation of step S2, and fill the same disposal container with the newly generated mixture. Repeat this cycle 2 to 3 times until the container reaches more than 90% capacity.

[0046] S4: Microwave-induced pyrolysis inertization treatment: In the solidified body after the final batch filling is completed, activated carbon powder equivalent to 2% of the total mass of the solidified body is dispersed as a microwave sensitizer; then the treatment container is moved into the microwave final treatment unit and irradiated for 20 minutes in the power range of 500-800W under ventilated conditions. During the treatment, the polymer matrix undergoes pyrolysis and carbonization, and finally transforms into a black, loose and dry inorganic residue.

[0047] Effect evaluation: After step S3, a total of 150 liters of simulated waste liquid from 3 batches was integrated into a 200-liter treatment container, with an initial volume reduction ratio of 3:1; after further treatment in step S4, the final solid product volume was approximately 35 liters; the ratio of the initial total waste liquid volume to the final product volume was 4.3:1, achieving deep volume reduction.

[0048] This embodiment also provides a system using the aforementioned synergistic volume reduction curing method to implement the above method, including: Waste liquid sorting unit, used for receiving 68 Ge production waste liquid is classified into Class A strongly acidic aqueous waste liquid, Class B organic waste liquid, Class C high gallium concentration acidic waste liquid, or Class D alkaline collection liquid according to the composition of the waste liquid. The directional curing batching unit is communicatively connected to the waste liquid sorting unit and is used to match the curing agent according to the waste liquid sorting results; this unit is equipped with a nuclear-grade crosslinked polyacrylate polymer source, a polyolefin polymer source, and a stabilizer source; The circulating filling curing unit is connected to the waste liquid classification unit and the directional curing batching unit, respectively, and is used to receive waste liquid and curing agent for mixing and injecting the mixture into the curing container; the unit is equipped with a circulation control module for controlling multiple rounds of waste liquid addition; The microwave pyrolysis unit is used to receive the solidified container after it has been circulated and filled, and to apply microwave irradiation to the solidified body inside the container for dehydration and pyrolysis treatment. The main control unit is electrically connected to the above-mentioned units and is used to regulate the operation of the system.

[0049] Example 2: Treatment of Class C High Gallium Concentration Acidic Wastewater This embodiment provides a 68 A synergistic volume reduction and solidification method and system for Ge production waste liquid, wherein the method specifically involves treating Class C high-gallium-concentration acidic waste liquid, and the system is the same as in Example 1, the method including the following steps: The processing flow in this embodiment is basically similar to that in embodiment 1, with the core difference being step S2: S2: Directional Curing: During the mixing process, in addition to adding a nuclear-grade crosslinked polyacrylate polymer (No. 960), disodium hydrogen phosphate (Na2HPO4) at 1% of the waste liquid mass was simultaneously incorporated as a phosphate stabilizer, which reacts with Ga... 3+ The reaction produces a GaPO4 precipitate with extremely low solubility, achieving effective stabilization of gallium.

[0050] Example 3: Treatment of Class D alkaline trapping solution This embodiment provides a 68 A synergistic volume reduction and solidification method and system for Ge production wastewater, wherein the method specifically involves treating a type D alkaline collection solution, and the system is the same as in Example 1, and the method includes the following steps: The processing flow in this embodiment is similar to that in embodiment 1, and is intended to verify the versatility of the method in treating waste liquid with extreme pH.

[0051] S2: Directional solidification: Using the same nuclear-grade cross-linked polyacrylate polymer (Nochar® No. 960) used to treat Class A waste liquid, it is mixed and solidified with Class D alkaline waste liquid at a mass ratio of approximately 1:0.6 (i.e., polymer: waste liquid = 1:1.67); Example 3 further demonstrates the core technological advantage of using a single polymer variety to efficiently treat strongly acidic to strongly alkaline aqueous waste liquids.

[0052] Example 4: Treatment of Class B Organic Waste Liquid This embodiment provides a 68 A synergistic volume reduction and solidification method and system for Ge production waste liquid, specifically for treating Class B organic waste liquid, wherein the system is the same as in Example 1, and the method includes the following steps: S1: Waste liquid classification: TBP-kerosene organic phase from the extraction process enters the system. Near-infrared spectroscopy probes identify its organic component characteristics, and the central control unit determines it to be Class B waste liquid based on this.

[0053] S2: Directional Curing: The controller commands the dispensing unit to precisely measure the polyolefin polymer (Nochar® No. 910). The waste liquid is mixed with this polymer at a mass ratio of approximately 1:0.3 (i.e., polymer:waste liquid = 1:3.33), and the system rapidly transforms into a structurally stable gel block.

[0054] S3: Multiple Addition-Cure Cycle: Transfer the gel block to the final disposal container. After it forms a load-bearing structure, continue adding a new batch of Class B waste liquid and polyolefin polymer to the same container, repeating the mixing and curing process of step S2. This cycle is performed twice until the container is filled to more than 90%.

[0055] S4: Microwave-induced pyrolysis inertization treatment: Add activated carbon powder equivalent to 3% of its total mass as a microwave sensitizer to the solidified body after filling. Then, move the treatment container into the microwave final treatment unit and irradiate for 30 minutes in the power range of 500-800W.

[0056] After microwave treatment, the total organic carbon removal rate in Example 4 was greater than 99.5%, and the final product was a non-flammable inorganic residue, achieving intrinsic safety.

[0057] Comparative Example 1 This comparative example provides a 68 A volume reduction and solidification method for Ge production waste liquid, but the difference lies in using a traditional cement solidification process to treat Class A waste liquid from the same source as in Example 1, including: During treatment, the waste liquid must first be neutralized to a pH of about 7 using NaOH solution, and then mixed with cement at a water-cement ratio of 0.5 for solidification.

[0058] Comparison of results: After neutralization and solidification, the volume of the final solidified body obtained from treating 100 liters of raw waste liquid is about 140 liters, with a volume increase ratio as high as 1:1.4, highlighting the significant volume increase defects of traditional methods.

[0059] Comparative Example 2 This comparative example provides a 68 The volume reduction and solidification method for Ge production waste liquid is the same as that for treating Class A waste liquid from the same source as in Example 2, but without adding phosphate stabilizer. Other conditions and methods are the same as in Example 2. A leaching experiment was conducted to compare Example 2 and Comparative Example 2. The leaching results showed that the leaching rate of Ga in the experimental group (with 1% Na2HPO4 added) was less than 1.0 × 10⁻⁶. -6 g / cm2 •d; while in Comparative Example 2 (without stabilizer), the leaching rate of Ga was 5.5 × 10⁻⁶. -4 g / cm 2 The addition of the stabilizer reduced the leaching rate of Ga by more than 500 times, demonstrating the effectiveness and necessity of this stabilization strategy for treating waste liquid containing special nuclides.

[0060] Through thorough comparison and verification of the above embodiments and comparative examples, the classification and solidification method provided by this invention is further demonstrated. It achieves high-density physical volume reduction through precise classification in S1, directional solidification based on polymer properties in S2 (including the introduction of special stabilizers for Class C waste liquid), combined with multi-round cyclic filling in S3, and finally, chemical bonding and mineralization transformation through microwave-induced pyrolysis in S4. This constitutes a complete, efficient, and universally applicable method. 68 The core principle of this invention, a wastewater treatment system for Ge production, lies in utilizing the molecular structure design of high-performance polymers to achieve universal inclusion and stabilization of wastewater with different properties. Through a two-stage volume reduction strategy involving physical filling and chemical transformation, it solves the volume expansion defects and long-term stability problems of traditional cement solidification methods. Examples 1-4 collectively demonstrate that this invention not only achieves a significant volume reduction ratio of over 4:1 for various wastewaters, including strong acids (Type A), organic phases (Type B), those containing specific nuclides (Type C), and strong alkalis (Type D), but also further reduces the leaching rate of nuclides by introducing stabilizers and microwave inertization processes, ensuring the intrinsic safety and long-term disposal stability of the solidified body. Comparative Example 1, through a comparison with traditional cement solidification, proves that this invention, through polymer solidification and multi-cycle technology, fundamentally reverses the volume expansion effect of traditional processes. Comparative Example 2, compared with Example 2, demonstrates that by controlling a single variable (adding a phosphate stabilizer), a leaching rate reduction of over 500 times is achieved, proving that for specific nuclides, the further introduction of a special stabilizer is a key step in achieving long-term safe disposal, rather than an obvious conventional choice. In summary, this invention successfully achieves the processing of complex components. 68 The unified, efficient, deep volume reduction, and inherently safe stabilization of Ge production waste liquid demonstrate significant process innovation and outstanding technical effects.

[0061] In the description of this invention, the references to "one embodiment," "some embodiments," "in this embodiment," "specific example," or "some examples," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples. Moreover, without contradiction, those skilled in the art can combine and integrate the different embodiments or examples described in this specification, as well as the features of different embodiments or examples.

[0062] The above description is merely a specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention should be included within the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be determined by the scope of the claims.

Claims

1. A kind 68 A synergistic volume reduction and solidification method for Ge production waste liquid, characterized in that... Includes the following steps: S1: Waste liquid classification, based on the source and key components of the waste liquid, is divided into: Class A strongly acidic aqueous waste liquid, Class B organic waste liquid, Class C high gallium concentration acidic waste liquid, and Class D alkaline collection liquid; S2: Directional solidification, solidifying the waste liquid after classification in step S1: For Class A strongly acidic aqueous waste liquid, Class C high gallium concentration acidic waste liquid, and Class D alkaline collection liquid, nuclear-grade cross-linked polyacrylate polymers are used as the main curing agent. For Class B organic waste liquid, polyolefin polymers with oleophilic long chains and three-dimensional network structures are used as the main curing agent; For Class C high gallium concentration acidic waste liquid, a stabilizer is further added to form GaPO4 precipitate; S3: Multiple additions and curing cycle: After the curing treatment in step S2, after the solidified body forms a preliminary load-bearing structure, a new batch of waste liquid and curing agent is added to the same container, and the cycle continues until the container filling rate reaches more than 90%. S4: Microwave-induced pyrolysis inertization treatment, adding a microwave sensitizer to the cured body and applying microwave irradiation, causing the cured body to undergo dehydration, pyrolysis and mineralization / ceramization transformation, in order to further achieve deep volume reduction and long-term stabilization.

2. As described in claim 1 68 A synergistic volume reduction and solidification method for Ge production waste liquid, characterized in that... In step S2, the stabilizer is a phosphate stabilizer.

3. As described in claim 1 68 A synergistic volume reduction and solidification method for Ge production waste liquid, characterized in that... In step S3, the number of cycles is 2–5.

4. As described in claim 1 68 A synergistic volume reduction and solidification method for Ge production waste liquid, characterized in that... In step S4, the microwave sensitizer is activated carbon, and the amount of activated carbon added is 1–3 wt%.

5. The method according to claim 1 68 A synergistic volume reduction and solidification method for Ge production waste liquid, characterized in that... In step S4, the microwave irradiation conditions are: irradiation for 10-30 minutes within a power range of 500-800W.

6. The method according to claim 1 68 A synergistic volume reduction and solidification method for Ge production waste liquid, characterized in that... In step S2, the mixing mass ratio of the nuclear-grade crosslinked polyacrylate polymer to the Class A, Class C, or Class D aqueous waste liquid is controlled within the range of 1:(1.5 – 2.5).

7. The method according to claim 1 68 A synergistic volume reduction and solidification method for Ge production waste liquid, characterized in that... In step S2, the mass ratio of the polyolefin polymer to the Class B organic waste liquid is 1:(2.5-4).

8. The method according to claim 1 68 A synergistic volume reduction and solidification method for Ge production waste liquid, characterized in that... The microwave irradiation in step S4 employs a multi-stage closed-loop control strategy, including: Initially, the microwave power is controlled to rapidly heat the cured body to the moisture evaporation threshold. In the middle stage, the power is adjusted to maintain the temperature within a constant range to ensure complete pyrolysis; In the final stage, when the monitored rate of change in weight loss approaches zero, microwave irradiation is terminated.

9. A system for implementing the synergistic volume reduction curing method according to any one of claims 1-8, characterized in that, The system includes: Waste liquid sorting unit, used for receiving 68 Ge production waste liquid is classified into Class A strongly acidic aqueous waste liquid, Class B organic waste liquid, Class C high gallium concentration acidic waste liquid, or Class D alkaline collection liquid according to the composition of the waste liquid. The directional curing batching unit is communicatively connected to the waste liquid sorting unit and is used to match the curing agent according to the waste liquid sorting results; this unit is equipped with a nuclear-grade crosslinked polyacrylate polymer source, a polyolefin polymer source, and a stabilizer source; The circulating filling curing unit is connected to the waste liquid classification unit and the directional curing batching unit, respectively, and is used to receive waste liquid and curing agent for mixing and injecting the mixture into the curing container; the unit is equipped with a circulation control module for controlling multiple rounds of waste liquid addition; The microwave pyrolysis unit is used to receive the solidified container after it has been circulated and filled, and to apply microwave irradiation to the solidified body inside the container for dehydration and pyrolysis treatment. The main control unit is electrically connected to the above-mentioned units and is used to regulate the operation of the system.

10. The system according to claim 9, characterized in that, The waste liquid classification unit includes an online detection module, which includes a pH sensor for identifying the acidity and alkalinity of aqueous waste liquid and a near-infrared spectral probe for identifying organic waste liquid components. The detection signal output by the online detection module is used to drive the main control unit to automatically determine the waste liquid category.

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