Emulsion explosive production waste liquid degradation treatment process

Abstract

The invention discloses an emulsion explosive production waste liquid degradation treatment process, and relates to the technical field of emulsion explosive production. Through gradient treatment, full-process intelligent regulation and control and accurate matching of a corresponding treatment scheme based on the characteristics of the waste liquid and the intermediate product, thorough removal of pollutants is realized, the waste liquid treatment effect and the resource utilization efficiency are synchronously improved, and the problems of incomplete removal and easy residue of pollutants in the prior art are solved; accurate regulation and control and abnormal early warning of process parameters are realized, and waste liquid treatment requirements under different working conditions can be flexibly met; biodegradation and solid-liquid separation are synchronously integrated, so that the treatment process is simplified, circular reuse of magnetic nanoparticles, adsorbents and other consumables is realized, the operation cost is reduced, and the resource utilization rate is further improved through resource reuse of a pellicle complex, a regenerated liquid component and deeply purified effluent; and a more reliable solution is provided for efficient and green treatment of the emulsion explosive production waste liquid.

Description

Technical Field

[0001] This invention relates to the field of emulsion explosives production technology, and in particular to a process for the degradation and treatment of waste liquid from emulsion explosives production. Background Technology

[0002] As an energy material widely used in the field of industrial blasting, emulsion explosives involve multiple complex processes such as emulsification and sensitization in their production process, which will generate industrial waste liquid with extremely complex composition. If directly discharged, it will cause serious and lasting damage to the ecological environment such as water bodies and soil. Therefore, it must be strictly treated to meet the requirements for environmental protection discharge or reuse. For example, Chinese patent application CN109516611A discloses a method for treating emulsion explosive waste liquid, including the following steps: (1) collecting the emulsion explosive waste liquid into a waste collection tank; (2) pumping the emulsion explosive waste liquid into a decomposition reactor; (3) adding treatment agents into the decomposition reactor; (4) filling the decomposition reactor with compressed air from the bottom; (5) injecting water from the bottom of the decomposition reactor; (6) collecting waste oil from the top of the decomposition reactor into a treatment tank, and injecting the emulsion explosive waste liquid (with the waste oil removed) into the treatment tank from the bottom; (7) adding polyaluminum chloride and polyacrylamide into the treatment tank; and (8) pumping the emulsion explosive waste liquid treated in step (7) into a sand filter. This patent application achieves the treatment of emulsion explosive waste liquid by adding treatment agents to cause the emulsifier to react and automatically disintegrate, thereby achieving the effect of demulsification, oil-water separation, and decontamination.

[0003] Although the aforementioned patent achieves preliminary oil-water separation and suspended solids removal through chemical demulsification and flocculation filtration, the following problems still exist:

[0004] 1. The core highly toxic pollutants such as nitrates and TNT derivatives are not targeted for degradation, resulting in incomplete removal of pollutants and easy secondary pollution. Furthermore, the simple combination of demulsification with a single agent and sand filtration process has poor adaptability to complex water quality, and key indicators such as COD and TN are difficult to meet the high standards for discharge or reuse.

[0005] 2. The lack of recycling of consumables and resource utilization of by-products results in a large consumption of consumables such as reagents and filter media during the treatment process, leading to high operating costs. Furthermore, the inability to adjust process parameters according to fluctuations in wastewater quality results in insufficient stability of treatment effects and difficulty in adapting to the wastewater treatment needs under different production conditions. Summary of the Invention

[0006] The purpose of this invention is to provide a degradation treatment process for emulsion explosive production waste liquid. Through tiered treatment and intelligent control of the entire process, pollutants are completely removed, and the waste liquid treatment effect and resource utilization efficiency are improved simultaneously. It can flexibly adapt to the waste liquid treatment needs under different working conditions, and the recycling of consumables improves resource utilization. It provides a more reliable solution for the efficient and green treatment of emulsion explosive production waste liquid, thereby solving the problems mentioned in the background technology.

[0007] To achieve the above objectives, the present invention provides the following technical solution:

[0008] A process for degrading and treating waste liquid from the production of emulsion explosives includes the following steps:

[0009] S1: Pretreatment to obtain aqueous waste liquid: Obtain emulsion explosive production waste liquid. Based on the emulsion stability characteristics of emulsion explosive production waste liquid, the emulsion explosive production waste liquid is introduced into the reaction chamber. Based on the water quality parameters of the emulsion explosive production waste liquid, the working parameters of the reaction chamber are determined. The emulsion explosive production waste liquid is pretreated to obtain aqueous waste liquid.

[0010] S2: Targeted oxidation degradation to obtain primary degradation liquid: Degradation parameters are determined based on the type and content of target pollutants in the aqueous waste liquid. Based on the degradation parameters, the catalyst in the catalytic reactor is configured, and the aqueous waste liquid is passed into the catalytic reactor for targeted oxidation degradation treatment to obtain primary degradation liquid.

[0011] S3: Biodegradation and solid-liquid separation coupled treatment: Based on the characteristics of residual pollutants in the primary degradation liquid, the biological treatment parameters are determined. The coupled reactor performs biodegradation and pollutant assimilation treatment on the primary degradation liquid based on the biological treatment parameters, while simultaneously performing solid-liquid separation to obtain membrane filtered effluent and a bacterial membrane complex.

[0012] S4: Specific adsorption and online regeneration of adsorbent: Adsorption parameters are determined based on the characteristics of residual pollutants in the membrane filtration effluent. Based on the adsorption parameters, the membrane filtration effluent is subjected to specific adsorption treatment to obtain deeply purified effluent. At the same time, the adsorbent is regenerated online based on the adsorption state of the adsorbent, and the regenerated liquid is collected.

[0013] S5: Resource recovery and compliant disposal: Obtain the biofilm complex, regenerated liquid and deep purified effluent, dehydrate and dry the biofilm complex, recover components from the regenerated liquid, test the water quality of the deep purified effluent, and reuse or discharge it after it meets the standards.

[0014] Furthermore, the reaction chamber in S1 is an ultrasonic pulse reaction chamber. The water quality parameters include oil phase content and suspended solids concentration. Based on the water quality parameters obtained from water quality detection, the operating parameters of the ultrasonic pulse reaction chamber are determined, including an ultrasonic frequency of 30-40kHz and a high-frequency pulse electric field voltage of 5-8kV. During the pretreatment process, while the emulsion explosive production waste liquid is introduced, magnetic nanoparticles are added to the ultrasonic pulse reaction chamber. The amount of magnetic nanoparticles added is 0.1-0.2% of the mass of the emulsion explosive production waste liquid. The mixture in the ultrasonic pulse reaction chamber is separated by a magnetic field device to obtain a complex of magnetic particles, pollutants and oil droplets. The liquid after separating the complex is clarified by sedimentation to obtain an aqueous waste liquid.

[0015] Furthermore, the magnetic nanoparticles are Fe3O4 nanoparticles with a particle size of 50-100 nm. Based on the recycling requirements of the magnetic particles, the magnetic field strength of the magnetic field device is set to 0.3-0.5T. After separation, the magnetic particles are magnetically separated and recycled after acid washing and activation.

[0016] Furthermore, the degradation parameters in S2 include catalyst type, catalyst dosage, reaction temperature, and reaction pressure. The catalyst is a single-atom iron-supported metal oxide catalyst, the catalyst dosage is 0.3-0.5% of the mass of the aqueous waste liquid, the reaction temperature for directional oxidation degradation is 40-60℃, the reaction pressure is 0.8-1.2MPa, and the residence time of the aqueous waste liquid in the catalytic reactor is 15-25min.

[0017] Furthermore, the preparation process of the single-atom iron-supported metal oxide catalyst is as follows:

[0018] Ferric nitrate was used as the iron source and metal oxide as the carrier. Based on the requirement of monodispersity of iron atoms, ferric nitrate was added to the metal oxide carrier at a preset mass ratio and mixed evenly by wet impregnation.

[0019] The mixed materials are placed in a rotary evaporator and evaporated under reduced pressure at 60-80℃ until dry.

[0020] The dried material is placed in a tube furnace, which is heated to 450-550℃ at a heating rate of 3-5℃ / min and held at that temperature for 2-3 hours. After cooling, a single-atom iron-supported metal oxide catalyst is obtained.

[0021] Furthermore, the specific steps of S3 are as follows:

[0022] Obtain the primary degradation solution, detect the types, concentrations and biodegradability of residual pollutants in the primary degradation solution, determine the characteristics of residual pollutants in the primary degradation solution, and determine the corresponding biological treatment parameters based on the characteristics of residual pollutants. The biological treatment parameters include bacterial species, bacterial dosage, dissolved oxygen content and reaction pH value.

[0023] Add a compound microbial community of the corresponding microbial community type and dosage into the coupled reactor, and adjust the dissolved oxygen concentration and pH value of the reaction system in the coupled reactor to the preset parameters;

[0024] The primary degradation liquid is fed into a well-regulated coupled reactor for biodegradation and pollutant assimilation. At the same time, the hollow fiber membrane module built into the coupled reactor is activated for cross-flow filtration. The flow rate on the membrane surface is controlled based on the biofilm stability requirements to achieve simultaneous solid-liquid separation.

[0025] The effluent obtained from the filtration of the hollow fiber membrane module is collected, and the bacterial membrane complex generated in the reactor is also collected. The hollow fiber membrane module has nitrate-reducing bacteria and nitrate-assimilating bacteria immobilized on its surface.

[0026] Furthermore, the inoculation mass ratio of nitrate-reducing bacteria to nitrate-assimilating bacteria is 1:1-2:1; based on the biofilm stability requirements, the pore size and membrane surface flow velocity of the hollow fiber membrane module are determined, and the sludge age in the coupled reactor is controlled within the range of 20-25 days.

[0027] Furthermore, S4 also includes:

[0028] Real-time adsorption capacity data during the specific adsorption process is obtained, and based on the comparison between the real-time adsorption capacity data and the preset saturation adsorption capacity threshold, it is determined whether the adsorbent has reached adsorption saturation.

[0029] If it is determined that adsorption saturation has been reached, the online regeneration program is started immediately. The type of regenerant and regeneration conditions are determined based on the type of adsorbent. The regenerant is a hydrochloric acid solution with a mass fraction of 5-8%, and the regeneration conditions are a regeneration temperature of 25-35℃ and a contact time between the regenerant and the adsorbent of 20-30 minutes.

[0030] After regeneration, the adsorption capacity of the regenerated adsorbent is tested. Based on the test results, it is determined whether the requirements for recycling are met. If they are met, the regenerated adsorbent is recovered by distillation and returned to the adsorption system for recycling.

[0031] Furthermore, the bacterial film complex, regenerated liquid, and deeply purified effluent in S5 also include:

[0032] Based on the detection results of organic matter content in the microbial film complex, the direction of resource utilization was determined.

[0033] Based on the component detection results of the regenerated liquid, the components of the regenerated liquid are separated and recovered by vacuum distillation process, and the recovered target components are returned to the raw material system for emulsion explosive production for recycling.

[0034] When conducting water quality testing on the effluent from deep purification, the testing indicators and compliance thresholds are determined based on the different treatment requirements of reuse or discharge.

[0035] Furthermore, it also includes:

[0036] Online monitoring equipment is deployed at key target nodes to determine monitoring indicators, and water quality parameters and process operation parameters of each key target node are collected in real time based on the online monitoring equipment.

[0037] Analyze the collected water quality parameters and process operating parameters, and output the optimal process parameters;

[0038] The operating parameters of the acid and alkali dosing device, oxidant dosing device, aeration device, reflux pump and other process unit equipment are automatically adjusted according to the optimal process parameters to achieve adaptive process optimization.

[0039] The system presets normal operating thresholds for each monitoring indicator. When the monitoring data exceeds the preset normal operating threshold, a fault warning is automatically triggered, and staff are notified through audible and visual alarms. At the same time, based on the comparison results of historical operating data and real-time abnormal data, a fault cause analysis and corresponding handling suggestions are generated.

[0040] Compared with the prior art, the beneficial effects of the present invention are:

[0041] This invention employs a tiered treatment process with intelligent control throughout the entire process. Based on the characteristics of the waste liquid and intermediate products, it precisely matches corresponding treatment schemes to achieve complete removal of pollutants. The waste liquid treatment effect and resource utilization efficiency are simultaneously improved, solving the problems of incomplete pollutant removal and easy residue in existing technologies. It enables precise control of process parameters and abnormal early warning, flexibly adapting to waste liquid treatment needs under different operating conditions. By simultaneously integrating biodegradation and solid-liquid separation, the treatment process is simplified, enabling the recycling and reuse of consumables such as magnetic nanoparticles and adsorbents, reducing operating costs. Furthermore, through the resource reuse of the microbial membrane composite, regenerated liquid components, and deeply purified effluent, resource utilization is further improved, providing a more reliable solution for the efficient and green treatment of emulsion explosive production waste liquid. Attached Figure Description

[0042] Figure 1 This is a flow chart of the process for degrading and treating waste liquid from the production of emulsion explosives according to the present invention. Detailed Implementation

[0043] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0044] Please see Figure 1 A process for degrading and treating waste liquid from the production of emulsion explosives includes the following steps:

[0045] S1: Pretreatment to obtain aqueous waste liquid: Obtain emulsion explosive production waste liquid. Based on the emulsion stability characteristics of emulsion explosive production waste liquid, the emulsion explosive production waste liquid is introduced into the reaction chamber. Based on the water quality parameters of the emulsion explosive production waste liquid, the working parameters of the reaction chamber are determined. The emulsion explosive production waste liquid is pretreated to obtain aqueous waste liquid.

[0046] S2: Targeted oxidation degradation to obtain primary degradation liquid: Degradation parameters are determined based on the type and content of target pollutants in the aqueous waste liquid. Based on the degradation parameters, the catalyst in the catalytic reactor is configured, and the aqueous waste liquid is passed into the catalytic reactor for targeted oxidation degradation treatment to obtain primary degradation liquid.

[0047] S3: Biodegradation and solid-liquid separation coupled treatment: Based on the characteristics of residual pollutants in the primary degradation liquid, the biological treatment parameters are determined. The coupled reactor performs biodegradation and pollutant assimilation treatment on the primary degradation liquid based on the biological treatment parameters, while simultaneously performing solid-liquid separation to obtain membrane filtered effluent and a bacterial membrane complex.

[0048] S4: Specific adsorption and online regeneration of adsorbent: Adsorption parameters are determined based on the characteristics of residual pollutants in the membrane filtration effluent. Based on the adsorption parameters, the membrane filtration effluent is subjected to specific adsorption treatment to obtain deeply purified effluent. At the same time, the adsorbent is regenerated online based on the adsorption state of the adsorbent, and the regenerated liquid is collected.

[0049] In this embodiment, the specific adsorption treatment is achieved through a molecularly imprinted adsorption column, and the adsorption parameters include the type of adsorbent, the amount of adsorbent filled, and the adsorption residence time.

[0050] S5: Resource recovery and compliant disposal: Obtain the biofilm complex, regenerated liquid and deep purified effluent, dehydrate and dry the biofilm complex, recover components from the regenerated liquid, test the water quality of the deep purified effluent, and reuse or discharge it after it meets the standards.

[0051] In this embodiment, by matching the corresponding treatment parameters with the characteristics of the waste liquid and intermediate products, the parameters can be dynamically adjusted according to the actual water quality and pollutant characteristics of the emulsion explosive production waste liquid. This allows for adaptation to the waste liquid treatment needs generated under different production conditions. The directional oxidation process enhances the degradation of target pollutants through precise catalyst configuration, and achieves precise capture of residual pollutants using molecularly imprinted adsorption columns. This ensures the stability and reliability of the treatment effect under different scenarios, realizing the synergistic coupling of biodegradation and solid-liquid separation. The adsorbent adopts an online regeneration mode, eliminating the need to interrupt the treatment process to replace the adsorbent material. This ensures the continuity of treatment, reduces the consumption of adsorbent consumables, and improves the economic efficiency of the process operation. The bacterial film complex and regenerated liquid generated during the treatment process are specifically recycled and treated to achieve the resource reuse of waste. At the same time, it avoids the environmental impact of direct discharge of waste liquid.

[0052] In this embodiment, the reaction chamber is an ultrasonic pulse reaction chamber. The water quality parameters include oil phase content and suspended solids concentration. Based on the water quality parameters obtained from water quality detection, the operating parameters of the ultrasonic pulse reaction chamber are determined, including an ultrasonic frequency of 30-40kHz and a high-frequency pulse electric field voltage of 5-8kV. During the pretreatment process, while the emulsion explosive production waste liquid is introduced, magnetic nanoparticles are added to the ultrasonic pulse reaction chamber. The amount of magnetic nanoparticles added is 0.1-0.2% of the mass of the emulsion explosive production waste liquid. The mixture in the ultrasonic pulse reaction chamber is separated by a magnetic field device to obtain a complex of magnetic particles, pollutants and oil droplets. The liquid after separating the complex is clarified by precipitation to obtain an aqueous waste liquid.

[0053] In this embodiment, the magnetic nanoparticles are Fe3O4 nanoparticles with a particle size of 50-100nm. Based on the need for recycling magnetic particles, the magnetic field strength of the magnetic field device is set to 0.3-0.5T. After separation, the magnetic particles are magnetically separated and recycled after acid washing and activation.

[0054] The initial water quality parameters of the emulsion explosive production wastewater treated in this embodiment are:

[0055] COD 8500 mg / L, TN 1200 mg / L, nitrate ester content 320 mg / L, TNT derivative content 85 mg / L, oil phase content 1500 mg / L, suspended solids concentration 800 mg / L, pH 6.2;

[0056] The above-mentioned emulsified explosive production waste liquid is pumped to the equalization tank by a booster pump for water quality and quantity homogenization, with a retention time of 2 hours.

[0057] Based on the emulsification stability characteristics of emulsified explosive production waste liquid, the homogenized emulsified explosive production waste liquid was passed into an ultrasonic pulse reaction chamber to obtain the water quality parameters of the emulsified explosive production waste liquid, with an oil phase content of 1500 mg / L and a suspended solids concentration of 800 mg / L.

[0058] The operating parameters of the ultrasonic pulse reaction chamber were determined as follows: ultrasonic frequency 35kHz and high-frequency pulse electric field voltage 6.5kV. Based on these operating parameters, ultrasonic pulses and magnetic adsorption were applied, followed by magnetic separation to obtain aqueous waste liquid.

[0059] Testing revealed that the oil content of the aqueous waste liquid was reduced to below 50 mg / L, the suspended solids concentration was reduced to below 50 mg / L, the COD removal rate reached 22%, and the emulsion system was completely demulsified.

[0060] In addition, the magnetic particles obtained by magnetic separation are recovered by magnetic separation, then activated by acid washing with 5% hydrochloric acid solution for 30 minutes. After washing until neutral, they are recycled for the magnetic adsorption and composite process in this step, with a particle recovery rate of over 95%, which reduces the processing cost.

[0061] In this embodiment, the reaction parameters are precisely matched according to the actual water quality parameters of the emulsion explosive production waste liquid, which can effectively achieve complete demulsification of the emulsion system and efficiently capture the composite of pollutants and oil droplets. The selected magnetic nanoparticles can be recycled and reused after magnetic separation and acid washing activation, without the need for additional large amounts of adsorption materials, reducing the consumption of consumables and lowering the processing cost caused by material consumption. It is suitable for emulsion explosive production waste liquid with different water quality conditions, and can stably achieve efficient separation of oil phase, suspended solids and water phase. While achieving demulsification, it simultaneously reduces the pollutant load in the aqueous waste liquid and improves the smoothness of the overall waste liquid treatment process.

[0062] In this embodiment, the catalytic reactor is a plasma and single-atom catalytic reactor; the target pollutants include nitrate esters, TNT derivatives, and surfactants; the degradation parameters include catalyst type, catalyst dosage, reaction temperature, and reaction pressure; wherein the catalyst is a single-atom iron-supported metal oxide catalyst, the catalyst dosage is 0.3-0.5% of the mass of the aqueous waste liquid, the reaction temperature for the directional oxidation degradation treatment is 40-60℃, the reaction pressure is 0.8-1.2MPa, and the residence time of the aqueous waste liquid in the catalytic reactor is 15-25min.

[0063] In this embodiment, the preparation process of the single-atom iron-supported metal oxide catalyst is as follows:

[0064] Ferric nitrate was used as the iron source and metal oxide as the carrier. The metal oxide carrier was γ-Al2O3 or ZrO3. Based on the requirement of monodispersity of iron atoms, ferric nitrate was added to the metal oxide carrier at a preset mass ratio of 2-4%, and the mixture was uniformly mixed by wet impregnation.

[0065] The mixed materials are placed in a rotary evaporator and evaporated under reduced pressure at 60-80℃ until dry.

[0066] The dried material is placed in a tube furnace and heated to 450-550°C at a heating rate of 3-5°C / min in an air atmosphere. The temperature is held for 2-3 hours and then cooled to obtain a single-atom iron-supported metal oxide catalyst.

[0067] In this embodiment, a catalytic reactor combined with a single-atom iron-supported metal oxide catalyst is used to precisely target and degrade pollutants such as nitrate esters, TNT derivatives, and surfactants in aqueous wastewater. This method can efficiently decompose recalcitrant organic pollutants, achieve monodisperse loading of iron atoms, increase the number and utilization rate of active sites on the catalyst, and allow degradation parameters to be flexibly adjusted according to the characteristics of the aqueous wastewater, ensuring that the catalytic reaction proceeds efficiently under stable conditions and improving the consistency of degradation results.

[0068] In this embodiment, the specific steps of S3 are as follows:

[0069] Obtain the primary degradation solution, detect the types, concentrations, and biodegradability of residual pollutants in the primary degradation solution, determine the characteristics of residual pollutants in the primary degradation solution, and determine the corresponding biological treatment parameters based on the characteristics of residual pollutants. The biological treatment parameters include the types of bacteria, the amount of bacteria added, the dissolved oxygen content (0.5-1.0 mg / L), and the reaction pH value.

[0070] In this embodiment, the coupled reactor is a functional bacteria immobilization and MBR coupled reactor, with a hollow fiber membrane module built in. Nitro-reducing bacteria and nitrate-assimilating bacteria are immobilized on the surface of the hollow fiber membrane module by an embedding method.

[0071] Add a compound microbial community of the corresponding species and dosage to the coupled reactor, adjust the dissolved oxygen concentration and pH value of the reaction system in the coupled reactor to 7.2, and adjust the dissolved oxygen concentration to 0.8 mg / L through the aeration device;

[0072] The primary degradation liquid is passed into a well-regulated coupled reactor for biodegradation and pollutant assimilation. Nitro-reducing bacteria in the complex microbial community reduce residual nitro compounds to amino compounds, while nitrate-assimilating bacteria convert organic nitrogen compounds into their own bacterial proteins, thereby achieving the assimilation and removal of pollutants.

[0073] Simultaneously, the hollow fiber membrane module built into the coupling reactor is activated for cross-flow filtration. The flow rate on the membrane surface is controlled based on the biofilm stability requirements to achieve simultaneous solid-liquid separation.

[0074] The effluent from the hollow fiber membrane module was collected, along with the biofilm complex generated within the reactor. The hollow fiber membrane module contained immobilized nitrifying bacteria and nitrate-assimilating bacteria, with an inoculum mass ratio of 1:1 to 2:1. Based on biofilm stability requirements, the pore size of the hollow fiber membrane module was determined to be 0.1-0.2 μm, the membrane surface velocity to be 0.5-1.0 m / s, and the sludge age within the coupled reactor was controlled within the range of 20-25 days.

[0075] In this embodiment, biological treatment parameters are precisely matched based on the characteristics of residual pollutants in the primary degradation liquid. The composite microbial community fixed in the coupled reactor has a clear functional division of labor, which reduces and transforms residual nitro compounds and assimilates and integrates organic nitrogen compounds. Through the targeted transformation and assimilation removal of pollutants, the degradation of residual pollutants is improved, avoiding the risks caused by pollutant residues or secondary transformation. The process coupling efficiency is high, the process is simplified, the stability of the biofilm and the solid-liquid separation effect are guaranteed, the quality of membrane filtered water remains stable, the reliability of process operation is improved, and the biological treatment has wide adaptability.

[0076] In this embodiment, step S4 further includes:

[0077] Real-time adsorption capacity data during the specific adsorption process is obtained, and based on the comparison between the real-time adsorption capacity data and the preset saturation adsorption capacity threshold, it is determined whether the adsorbent has reached adsorption saturation.

[0078] If it is determined that adsorption saturation has been reached, the online regeneration program is started immediately. The type of regenerant and regeneration conditions are determined based on the type of adsorbent. The regenerant is a hydrochloric acid solution with a mass fraction of 5-8%, and the regeneration conditions are a regeneration temperature of 25-35℃ and a contact time between the regenerant and the adsorbent of 20-30 minutes.

[0079] After regeneration, the adsorption capacity of the regenerated adsorbent is tested. Based on the test results, it is determined whether the requirements for recycling are met. If they are met, the regenerated adsorbent is recovered by distillation and returned to the adsorption system for recycling.

[0080] In this embodiment, the specific adsorption treatment is achieved through a molecularly imprinted adsorption column. During the adsorption process, the molecularly imprinted adsorbent accurately adsorbs residual small molecule organic pollutants and trace heavy metal ions through specific recognition sites. When the COD at the adsorption column outlet is ≥100mg / L, it is determined that the adsorbent has reached adsorption saturation, and the online regeneration program is immediately started.

[0081] In this embodiment, the bacterial film complex, regenerated liquid, and deeply purified effluent in step S5 further include:

[0082] Based on the organic matter content test results of the microbial film complex, the direction of resource utilization is determined; if the organic matter content is not less than 40%, the dehydrated and dried microbial film complex is mixed with decomposed straw at a mass ratio of 3:1, and then bio-organic fertilizer is prepared after composting and fermentation.

[0083] Based on the component detection results of the regenerated liquid, the components of the regenerated liquid are separated and recovered by vacuum distillation process, and the recovered target components are returned to the raw material system for emulsion explosive production for recycling.

[0084] When testing the water quality of the deep-purified effluent, the testing indicators and compliance thresholds are determined based on the different treatment requirements of reuse or discharge. If it is used for production process makeup water, it must meet the following requirements: COD≤50mg / L, ammonia nitrogen≤5mg / L, and conductivity≤100μS / cm. If it is used for discharge, it must meet the Class I standard of the integrated wastewater discharge standard.

[0085] In this embodiment, a molecularly imprinted adsorption column is used to achieve specific adsorption, accurately capturing residual small-molecule organic pollutants and trace heavy metal ions, and specifically removing residual pollutants at the end. After regeneration, the quality of recycling is controlled by adsorption capacity detection, achieving efficient recycling of the adsorbent, reducing adsorption material loss, lowering operating costs, and ensuring the continuity of the adsorption process. The target components are separated and recovered using a vacuum distillation process, and the recovered components can be returned to the production raw material system for reuse, realizing the tiered resource utilization of waste and improving resource utilization rate. Differentiated detection indicators and compliance thresholds are set for different treatment needs of the deep-purified effluent, realizing water resource recycling, reducing the total amount of pollutant emissions, and reducing the impact on the environment.

[0086] In this embodiment, to visually demonstrate the differences between this solution and conventional technologies, as well as the role of the single-atom iron-supported metal oxide catalyst, the process and effect parameters are shown in the table below:

[0087] Comparison indicators conventional technology Example Comparative Example Core process combination <![CDATA[Flocculation and demulsification, ordinary Fe2O3 catalysis, activated sludge, disposable activated carbon]]> <![CDATA[Ultrasonic pulse, Fe3O4 magnetic adsorption, single-atom iron catalysis, coupled biological treatment, online regeneration adsorption]]> <![CDATA[Ultrasonic pulse, Fe3O4 magnetic adsorption, ordinary Fe2O3 catalysis, coupled biological treatment, online regeneration adsorption]]> TNT derivative removal rate 70% 96.5% 65% Nitrate removal rate 72% 100% (Not detected) 68% Total COD removal rate 90% 99.4% 92% Cost of consumables per ton of water (yuan) 8.5 3.2 5.8 COD removal rate fluctuates ±12% ±2.5% ±3.0%

[0088] As shown in the table, compared with conventional technologies, this embodiment can efficiently decompose highly toxic and recalcitrant pollutants such as TNT derivatives and nitrate esters in waste liquid. The removal rates of highly toxic and recalcitrant pollutants such as TNT derivatives and nitrate esters have been significantly improved, achieving the removal of highly toxic pollutants or even zero residue. In contrast, the removal rate of key pollutants in the comparative embodiment has been significantly reduced, demonstrating the strong targeting and stable activity of the single-atom iron-supported metal oxide catalyst in this embodiment, which enhances the synergistic conversion effect of pollutants. The cost of consumables per ton of water in this embodiment has also been significantly reduced, which meets the development needs of green environmental protection and resource recycling, and further improves the economic feasibility of the process.

[0089] In this embodiment, the process also includes a process-wide intelligent monitoring and adaptive control stage, specifically including:

[0090] Online monitoring equipment was deployed at key nodes in each process stage, including the equalization tank, catalytic reactor, coupling reactor, molecularly imprinted adsorption column, and effluent tank, to determine the monitoring indicators, including COD, TN, and NH4. + -N, NO3 - -N, DO, pH, flow rate, temperature, membrane flux of hollow fiber membrane modules, etc., are all monitored and transmitted to the intelligent control system in real time to provide data support for algorithm optimization and parameter control.

[0091] Based on the real-time collection of water quality parameters and process operation parameters of each target key node by online monitoring equipment, the data is transmitted to the control center via 5G or Ethernet. The control center has built-in random forest regression model, BP neural network model and LSTM time series prediction model.

[0092] The control center analyzes the collected water quality parameters and process operation parameters, and outputs the optimal process parameters adapted to each process step, such as ultrasonic pulse reaction chamber operating parameters, catalytic reaction parameters, biological treatment parameters, acid and alkali dosage, aeration intensity, reflux ratio, etc.

[0093] The intelligent control system automatically adjusts the operating parameters of the acid and alkali dosing device, oxidant dosing device, aeration device, reflux pump, and other process unit equipment according to the optimal process parameters, thereby achieving adaptive process optimization.

[0094] The system presets normal operating thresholds for each monitoring indicator. When the monitoring data exceeds the preset normal operating thresholds, such as COD removal rate below 80% or membrane flux decrease by 30%, a fault warning is automatically triggered, and staff are notified through audible and visual alarms. At the same time, based on the comparison results of historical operating data and real-time abnormal data, a fault cause analysis and corresponding handling suggestions are generated.

[0095] In this embodiment, the operating status of each link is monitored in real time, and the real-time monitoring data is deeply analyzed by relying on multiple data analysis models. The process parameters are automatically optimized to ensure that the parameter control is highly matched with the waste liquid characteristics and process operating status under different operating conditions. This improves the rationality and pertinence of the entire process operation. The operating status of various equipment is automatically adjusted according to the optimal parameters to reduce the error caused by manual intervention, realize the adaptive optimization of process operation, provide timely early warning of faults and provide handling suggestions, reduce the intensity of manual operation, and ensure the long-term stable operation of the process.

[0096] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope of the technology disclosed in the present invention, based on the technical solution and inventive concept of the present invention, should be covered within the scope of protection of the present invention.

Claims

1. A process for degrading and treating waste liquid from the production of emulsion explosives, characterized in that, Includes the following steps: S1: Obtain emulsion explosive production waste liquid. Based on the emulsion stability characteristics of the emulsion explosive production waste liquid, the emulsion explosive production waste liquid is introduced into the reaction chamber. Based on the water quality parameters of the emulsion explosive production waste liquid, the working parameters of the reaction chamber are determined. The emulsion explosive production waste liquid is pretreated to obtain aqueous phase waste liquid. S2: Determine the degradation parameters based on the type and content of the target pollutants in the aqueous waste liquid, configure the catalyst in the catalytic reactor based on the degradation parameters, and pass the aqueous waste liquid into the catalytic reactor for directional oxidation degradation treatment to obtain the primary degradation liquid; S3: Based on the characteristics of residual pollutants in the primary degradation liquid, biological treatment parameters are determined. The coupled reactor performs biodegradation and pollutant assimilation treatment on the primary degradation liquid based on the biological treatment parameters, while simultaneously performing solid-liquid separation to obtain membrane filtered effluent and a bacterial membrane composite. S4: Determine adsorption parameters based on the characteristics of residual pollutants in the membrane filtration effluent, perform specific adsorption treatment on the membrane filtration effluent based on the adsorption parameters to obtain deeply purified effluent, and simultaneously regenerate the adsorbent online based on the adsorption state of the adsorbent and collect the regenerated liquid. S5: Obtain the biofilm complex, regenerated liquid, and deeply purified effluent; dehydrate and dry the biofilm complex; recover components from the regenerated liquid; test the water quality of the deeply purified effluent; and reuse or discharge it after it meets the standards.

2. The process for degrading and treating emulsion explosive production waste liquid as described in claim 1, characterized in that, The reaction chamber in S1 is an ultrasonic pulse reaction chamber. The water quality parameters include oil phase content and suspended solids concentration. Based on the water quality parameters obtained by water quality detection, the working parameters of the ultrasonic pulse reaction chamber are determined. In the pretreatment process, magnetic nanoparticles are added into the ultrasonic pulse reaction chamber. The mixture in the ultrasonic pulse reaction chamber is separated by a magnetic field device to obtain a complex of magnetic particles, pollutants and oil droplets. The liquid after separation of the complex is clarified by precipitation to obtain aqueous waste liquid.

3. The process for degrading and treating emulsion explosive production waste liquid as described in claim 2, characterized in that, The magnetic nanoparticles are Fe3O4 nanoparticles with a particle size of 50-100 nm. Based on the need for magnetic particle recycling, the magnetic field strength of the magnetic field device is set to 0.3-0.5T. After separation, the magnetic particles are magnetically separated and recycled after acid washing and activation.

4. The process for degrading and treating emulsion explosive production waste liquid as described in claim 1, characterized in that, The degradation parameters in S2 include catalyst type, catalyst dosage, reaction temperature and reaction pressure. The catalyst is a single-atom iron-supported metal oxide catalyst. The reaction temperature for the directional oxidation degradation treatment is 40-60℃, the reaction pressure is 0.8-1.2MPa, and the residence time of the aqueous waste liquid in the catalytic reactor is 15-25min.

5. The process for degrading and treating emulsion explosive production wastewater as described in claim 4, characterized in that, The preparation process of the single-atom iron-supported metal oxide catalyst is as follows: Ferric nitrate was used as the iron source and metal oxide as the carrier. Based on the requirement of monodispersity of iron atoms, ferric nitrate was added to the metal oxide carrier at a preset mass ratio and mixed evenly by wet impregnation. The mixed materials are placed in a rotary evaporator and evaporated under reduced pressure at 60-80℃ until dry. The dried material is placed in a tube furnace, which is heated to 450-550℃ at a heating rate of 3-5℃ / min and held at that temperature for 2-3 hours. After cooling, a single-atom iron-supported metal oxide catalyst is obtained.

6. The process for degrading and treating emulsion explosive production waste liquid as described in claim 1, characterized in that, The specific steps of S3 are as follows: Obtain the primary degradation solution, detect the types, concentrations and biodegradability of residual pollutants in the primary degradation solution, determine the characteristics of residual pollutants in the primary degradation solution, and determine the corresponding biological treatment parameters based on the characteristics of residual pollutants. The biological treatment parameters include bacterial species, bacterial dosage, dissolved oxygen content and reaction pH value. Add a compound microbial community of the corresponding microbial community type and dosage into the coupled reactor, and adjust the dissolved oxygen concentration and pH value of the reaction system in the coupled reactor to the preset parameters; The primary degradation liquid is fed into a well-regulated coupled reactor for biodegradation and pollutant assimilation. At the same time, the hollow fiber membrane module built into the coupled reactor is activated for cross-flow filtration. The flow rate on the membrane surface is controlled based on the biofilm stability requirements to achieve simultaneous solid-liquid separation. The effluent obtained from the filtration of the hollow fiber membrane module is collected, and the bacterial membrane complex generated in the reactor is also collected. The hollow fiber membrane module has nitrate-reducing bacteria and nitrate-assimilating bacteria immobilized on its surface.

7. The process for degrading and treating emulsion explosive production waste liquid as described in claim 6, characterized in that, The inoculation mass ratio of nitrate-reducing bacteria to nitrate-assimilating bacteria is 1:1-2:1; based on the biofilm stability requirements, the pore size and membrane surface flow velocity of the hollow fiber membrane module are determined, and the sludge age in the coupled reactor is controlled within the range of 20-25 days.

8. The process for degrading and treating emulsion explosive production waste liquid as described in claim 1, characterized in that, S4 also includes: Real-time adsorption capacity data during the specific adsorption process is obtained, and based on the comparison between the real-time adsorption capacity data and the preset saturation adsorption capacity threshold, it is determined whether the adsorbent has reached adsorption saturation. If it is determined that adsorption saturation has been reached, the online regeneration program should be started immediately, and the type of regenerant and regeneration conditions should be determined based on the type of adsorbent. After regeneration, the adsorption capacity of the regenerated adsorbent is tested. Based on the test results, it is determined whether the requirements for recycling are met. If they are met, the regenerated adsorbent is recovered by distillation and returned to the adsorption system for recycling.

9. The process for degrading and treating emulsion explosive production waste liquid as described in claim 1, characterized in that, The S5 microbial membrane complex, regenerated liquid, and deeply purified effluent also include: Based on the detection results of organic matter content in the microbial film complex, the direction of resource utilization was determined. Based on the component detection results of the regenerated liquid, the components of the regenerated liquid are separated and recovered by vacuum distillation process, and the recovered target components are returned to the raw material system for emulsion explosive production for recycling. When conducting water quality testing on the effluent from deep purification, the testing indicators and compliance thresholds are determined based on the different treatment requirements of reuse or discharge.

10. The process for degrading and treating emulsion explosive production wastewater as described in claim 1, characterized in that, Also includes: Online monitoring equipment is deployed at key target nodes to determine monitoring indicators, and water quality parameters and process operation parameters of each key target node are collected in real time based on the online monitoring equipment. Analyze the collected water quality parameters and process operating parameters, and output the optimal process parameters; The operating parameters of the acid and alkali dosing device, oxidant dosing device, aeration device, reflux pump and other process unit equipment are automatically adjusted according to the optimal process parameters to achieve adaptive process optimization. The system presets normal operating thresholds for each monitoring indicator. When the monitoring data exceeds the preset normal operating threshold, a fault warning is automatically triggered, and staff are notified through audible and visual alarms. At the same time, based on the comparison results of historical operating data and real-time abnormal data, a fault cause analysis and corresponding handling suggestions are generated.

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