Environmental risk assessment method for oxidation products after incineration of molybdenum-containing organic waste liquid

Abstract

The present invention provides an environmental risk assessment method for oxidation products after incineration disposal of molybdenum-containing organic waste liquid, which belongs to the technical field of environmental risk assessment. The environmental risk assessment method for oxidation products after incineration disposal of molybdenum-containing organic waste liquid comprises the following steps: S1, pollutant identification; S2, initial screening analysis; S3, content detection analysis; S4, environmental risk assessment. The present invention solves the problem that due to the complex components in molybdenum-containing organic waste liquid, the prior art lacks a simple and efficient environmental risk assessment method for oxidation products after incineration disposal of molybdenum-containing organic waste liquid, and has the advantages of being simple and efficient.

Description

Technical Field

[0001] The invention relates to the technical field of environmental risk assessment, and in particular to an environmental risk assessment method for oxidation products after incineration and disposal of molybdenum-containing organic waste liquid. Background Art

[0002] Molybdenum (Molybdenum) has the chemical symbol Mo and the atomic number 42. It is a transition metal element and an essential trace element for humans, animals and plants. Molybdenum is a silvery-white metal that is hard and tough.

[0003] Molybdenum is a heavy metal element with potential pollution risks to the environment and human health. The following are possible sources and impacts of molybdenum pollution: 1. Industrial emissions: Molybdenum can enter the environment through wastewater, waste gas and solid waste emissions from industrial activities, such as mining, smelting, chemical and other processes; 2. Agricultural application: Molybdenum is widely used as an additive to agricultural fertilizers, but excessive application may lead to increased molybdenum concentrations in soil and water; 3. Natural occurrence: The soil and water in some areas have high molybdenum content, which may be caused by natural geology or mineral deposits.

[0004] The impacts of molybdenum on ecosystems and human health are as follows: 1. Water pollution: High concentrations of molybdenum can cause toxic effects on the aquatic environment, affecting the survival and reproduction of aquatic organisms. 2. Soil pollution: Excessive molybdenum can affect the ecological functions of soil microorganisms, reduce soil quality and the growth of crops. 3. Plant absorption: Some crops and plants are sensitive to molybdenum, and excessive molybdenum absorption may cause abnormal plant growth and quality degradation. 4. Animal health: Long-term intake of high concentrations of molybdenum by animals may cause vomiting, diarrhea, anemia and other health problems in livestock. 5. Human health: Long-term exposure to an environment with high molybdenum concentrations may cause some health effects on the human body, such as gastrointestinal discomfort, kidney damage, and effects on the reproductive system.

[0005] Molybdenum-containing catalysts are widely used in organic reactions, such as olefin cyclization and oxidation. A large amount of molybdenum-containing catalyst residues generated during the production process are currently incinerated as hazardous waste. The comprehensive utilization of molybdenum catalyst residues can not only effectively recover molybdenum metal, but also explore a method for nearby disposal of hazardous waste. However, during the comprehensive utilization and treatment of molybdenum-containing catalysts, due to the particularity of their raw materials and the complex composition, the products are polluting and harmful during the comprehensive utilization process, and the environmental risk assessment of the comprehensive utilization of hazardous wastes has become increasingly important. At present, China has not yet established a systematic and complete risk assessment system for the products generated during the incineration and utilization of molybdenum residues. Summary of the invention

[0006] The technical problem solved by the present invention is that due to the complex components of molybdenum-containing organic waste liquid, the prior art lacks a simple and efficient environmental risk assessment method for oxidation products after incineration disposal of molybdenum-containing organic waste liquid.

[0007] To solve the above problems, the technical solution of the present invention is as follows:

[0008] The environmental risk assessment method of oxidation products after incineration of molybdenum-containing organic waste liquid includes the following steps:

[0009] S1. Pollutant identification: Based on the production process, regeneration and disposal process and comparison of raw and auxiliary materials, determine the initial screening indicators of oxidation products after incineration and disposal of molybdenum-containing organic waste liquid;

[0010] S2. Preliminary screening analysis: Based on the preliminary screening indicators, the inorganic pollutants in the oxidation products after the incineration and disposal of molybdenum-containing organic waste liquid are detected to determine the detection indicators for content detection and analysis;

[0011] S3. Content detection and analysis: Based on the detection index, the oxidation products after the incineration of molybdenum-containing organic waste liquid are tested, and the detection index and the maximum detection value are obtained after the test;

[0012] S4. Environmental risk assessment:

[0013] Construct application scenarios and environmental exposure scenarios for molybdenum oxide, and determine the multiple subsequent uses and emission scenarios of molybdenum oxide;

[0014] The detection indicators are judged and evaluated, that is, when the detection indicators are judged to belong to the molybdenum oxide product quality standard, the molybdenum oxide subsequent product quality standard, dioxins or inorganic pollutants, the content of the detected pollutants is evaluated. When the content of the detected pollutants is higher than the standard limit, the environmental risk is assessed to be unacceptable; otherwise, the environmental risk is assessed to be acceptable.

[0015] As one aspect of the present invention, the contents of comparison in step S1 include: analysis of inorganic elements in oxidation products after incineration of molybdenum-containing organic waste liquid and comparative analysis of production processes.

[0016] Note: The above operation can more effectively and comprehensively identify harmful substances that may be contained in comprehensive utilization products.

[0017] As one aspect of the present invention, the detection in step S2 includes on-site XRF inspection and laboratory detection.

[0018] Description: Through existing environmental testing methods, harmful substances that may be contained in comprehensive utilization products can be quickly and effectively identified.

[0019] As one aspect of the present invention, the method for detecting the oxidation products after incineration disposal of molybdenum-containing organic waste liquid based on the detection index in step S3 is a molybdenum chemical analysis method.

[0020] Note: Since the molybdenum content of comprehensive utilization products is relatively high, general detection methods will be affected by molybdenum. The molybdenum chemical analysis method is more accurate in detecting the content of harmful substances.

[0021] As one aspect of the present invention, the detection indicators are divided into metals, dioxins and inorganic substances.

[0022] Note: The above operation classifies possible pollutants into three categories to facilitate indicator identification and subsequent benchmarking analysis.

[0023] As one aspect of the present invention, metals include aluminum, iron, magnesium, cadmium, manganese, chromium, nickel, copper, tin, antimony, bismuth, tungsten, arsenic, and mercury; inorganic substances include calcium, fluoride, and cyanide.

[0024] Note: Clarifying the indicators and how to test will enable faster screening of pollutants.

[0025] As one aspect of the present invention, in step S4, the method for judging and evaluating the detection index is:

[0026] Determine the type of detected indicators:

[0027] When the detection index belongs to the quality standard of molybdenum oxide products, and when the maximum detection value of the detection index is higher than the standard limit of the corresponding product quality standard, it is assessed that the oxidation products after the incineration of molybdenum-containing organic waste liquid have environmental risks, otherwise it is assessed that the detected pollutants do not have environmental risks;

[0028] When the detected index belongs to the quality standard of subsequent products of molybdenum oxide, and when the maximum value of the detected index is higher than the standard limit of the corresponding subsequent product quality standard, it is assessed that the oxidation product after the incineration of molybdenum-containing organic waste liquid has environmental risks, otherwise it is assessed that the detected pollutants have no environmental risks;

[0029] When the detected index belongs to dioxins, and when the maximum value of the detected index is higher than the standard limit of dioxins, it is assessed that the oxidation products after the incineration of molybdenum-containing organic waste liquid have environmental risks, otherwise it is assessed that the detected pollutants have no environmental risks;

[0030] When the detected indicators belong to inorganic pollutants, health exposure assessment is carried out on the detected indicators. The assessment result is that the oxidation products after the incineration and disposal of molybdenum-containing organic waste liquid have health exposure risks or the detected pollutants are assessed to have no health exposure risks;

[0031] When the assessment result of the detection indicators is that the detected pollutants do not pose an environmental risk, the environmental risk of the oxidation products after incineration disposal of molybdenum-containing organic waste liquid is assessed to be acceptable, and only a health exposure assessment is given; otherwise, an environmental risk and health exposure assessment of the oxidation products after incineration disposal of molybdenum-containing organic waste liquid is given.

[0032] Note: Clarify the benchmarking analysis methods for each standard and whether to conduct an assessment, so as to conduct a full process assessment.

[0033] As one aspect of the present invention, the standard limit value of dioxin is 40 ng TEQ / kg.

[0034] Description: Clarify dioxin limits to more effectively assess environmental risks.

[0035] As one aspect of the present invention, the method for conducting health exposure assessment on the detection indicators is: conducting health risk assessment on the detection indicators, and calculating the exposure amount ADD of the detection target for each detection target according to the environmental exposure pathway and the maximum monitoring result, and then determining the health toxicity parameter RfD of the detection target, and calculating the health risk characterization When the ecological risk assessment result shows that there is no exposure pathway and the health risk characterization is less than 1, it is assessed that there is no health exposure risk to the oxidation products after incineration disposal of molybdenum-containing organic waste liquid; otherwise, it is assessed that there is a health exposure risk to the oxidation products after incineration disposal of molybdenum-containing organic waste liquid.

[0036] Note: It is necessary to clarify the evaluation methods of health risk assessment indicators and the basis for judging whether risks exist.

[0037] The beneficial effect of the present invention is that the present invention provides an environmental risk assessment scheme for the products of incineration disposal of molybdenum-containing waste organic solvents, clarifies the corresponding environmental protection measures and specific management requirements for comprehensive utilization, thereby avoiding the problem of difficult disposal, and also promotes the recovery of molybdenum. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] Figure 1 This is a flow chart of the environmental risk assessment method of the oxidation products after incineration and disposal of molybdenum-containing organic waste liquid according to the present invention;

[0039] Figure 2 It is a schematic diagram of the environmental risk assessment method of the oxidation products after the incineration disposal of molybdenum-containing organic waste liquid according to the present invention. DETAILED DESCRIPTION

[0040] In order to make the purpose, technical scheme and advantages of the present invention clearer, the present invention will be further described in detail below with reference to the accompanying drawings. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0041] The terms used in the embodiments of the present invention are only for the purpose of describing specific embodiments, and are not intended to limit the present invention. The singular forms "a", "said" and "the" used in the embodiments of the present invention and the appended claims are also intended to include plural forms, unless the context clearly indicates other meanings, and "multiple" generally includes at least two.

[0042] It should be understood that although the terms first, second, third, etc. may be used to describe ... in the embodiments of the present invention, these ... should not be limited to these terms. These terms are only used to distinguish .... For example, without departing from the scope of the embodiments of the present invention, the first ... may also be referred to as the second ..., and similarly, the second ... may also be referred to as the first ....

[0043] In the process of comprehensive utilization and treatment of molybdenum-containing catalysts, due to the particularity of its raw materials and the complex composition, the products in the process of comprehensive utilization are polluting and harmful, and the environmental risk assessment of the comprehensive utilization of hazardous wastes is becoming increasingly important. At present, there is no systematic and complete risk assessment system for the products generated during the incineration and utilization of molybdenum residual liquid in China.

[0044] In order to solve the above problems, this embodiment provides an environmental risk assessment method for oxidation products after incineration of molybdenum-containing organic waste liquid, such as Figure 1 and Figure 2 As shown, the following steps are included:

[0045] S1. Pollutant identification: Based on the production process, regeneration and disposal process and comparison of raw and auxiliary materials, determine the initial screening indicators of oxidation products after incineration and disposal of molybdenum-containing organic waste liquid;

[0046] It can be understood that in this embodiment, the contents of the comparison in step S1 include: analysis of inorganic elements in the oxidation product after incineration and disposal of molybdenum-containing organic waste liquid and comparative analysis of production processes;

[0047] Specifically, this embodiment uses molybdenum-containing organic waste liquid of a certain enterprise. The raw material used in the production of ammonium molybdate of the company is relatively high-purity industrial molybdenum oxide. The industrial molybdenum oxide is washed with water to remove some impurities, and then leached with ammonia and purified to obtain a high-purity purified ammonium molybdate liquid; the purified ammonium molybdate liquid is subjected to forced circulation and continuous evaporation and crystallization to obtain ammonium dimolybdate crystals; the wet ammonium dimolybdate crystals are dried, sieved, batched, and inspected to be qualified, and then the final product of non-agglomerated ammonium monomolybdate is obtained;

[0048] The above-mentioned process flow of ammonium molybdate production includes water washing, ammonia leaching, adjustment and ion exchange, evaporation crystallization and centrifugal separation system, drying and product transportation, storage and inspection, etc., which are specifically described as follows:

[0049] 1. Washing

[0050] The raw material highly soluble molybdenum oxide is added to a hot water washing tank with a heating coil of pure water or wastewater through an air delivery system, and is kept warm at a certain temperature to react to remove water-soluble impurities such as potassium and sodium ions in the raw material highly soluble molybdenum oxide; after the reaction, the filtered filter cake enters the ammonia leaching process, and the wastewater is reused and then transported to the newly built ammonia nitrogen wastewater treatment system in the factory area for treatment and then discharged after meeting the standards;

[0051] 2. Ammonia leaching

[0052] The washed filter cake is transported to an ammonia dissolving tank with a stirrer through a belt filter. The filter cake is dissolved in the ammonia solution. Two ammonia dissolving tanks are set up and used alternately every 8 hours. One dissolving tank is used to dissolve the material, and ammonium sulfide is added to remove copper in the solution. After the reaction is completed, a plate and frame filter press is used for solid-liquid separation, and the liquid enters the regulating kettle. The slag is dried in a mesh belt furnace and then packaged; the other dissolving tank is used for feeding;

[0053] 3. Regulation and ion exchange

[0054] After entering the regulating kettle, the ammonia leaching liquid is self-circulated through the cardboard filter and the precision filter to further remove the impurity ions in the solution; the self-circulated regulating liquid is then removed by the ion exchange resin to remove the calcium and copper impurity ions and then enters the buffer tank; the backwash wastewater is transported to the newly built ammonia nitrogen wastewater treatment system in the plant area for treatment and then discharged after meeting the standards;

[0055] 4. Evaporation crystallization and centrifugal separation system

[0056] After the ammonium molybdate in the buffer tank is self-circulated, it is sent to the continuous evaporation crystallization device through a delivery pump, and the ADM product is produced through continuous forced circulation evaporation crystallization; the outlet steam of the crystallizer enters the air cooling system to liquefy the ammonia gas into a dilute ammonia condensate of about 4%, which is used for the ammonia dissolving tank, ion exchange column regeneration and pipeline flushing; the crystal slurry at the bottom of the crystallizer is sent to one of the two centrifuges through a slurry pump; the solid-liquid separation is carried out by drying, and the solid enters the drying process. The mother liquor is collected in the mother liquor tank and returned to the continuous crystallizer through a delivery pump, or sent to the ammonia dissolving tank;

[0057] 5. Drying and product transportation and storage

[0058] The solid wet ADM material from the centrifugal separator enters the microwave dryer through the chute for drying. The dried ADM crystals are sent to the bucket through the conveyor belt, and then sent to the vibrating screen for screening. The qualified ADM crystals are introduced into the ADM storage tank and bagged, and the ADM crystals with unqualified particle size are sent to the ammonia leaching process;

[0059] For the above content, this example refers to the "Industrial Molybdenum Oxide Production Process and Pollution Control Analysis" and the high-purity molybdenum trioxide production process published by An Jing et al., and it can be seen that the commonly used molybdenum oxide production process is the roasting process; the production process evaluated in this example contains a lot of organic matter in the previous source, but after incineration, the subsequent organic matter residue can be ignored; the harmful substances in the molybdenum incineration product focus on the residual substances in the incineration process: salt, heavy metals, dioxins, etc.;

[0060] According to the preliminary analysis of the pollutants that may be contained in the molybdenum residual liquid incineration product and the subsequent application scenarios of using it as ammonium molybdate, the initial screening detection indicators of the molybdenum residual liquid incineration product are determined to be common heavy metals, impurities and dioxins involved in "Ammonium Molybdate" (GB / T 3460-2017); the detection method of this embodiment is in accordance with the chemical analysis method of the molybdenum industry, as shown in Table 1;

[0061] Table 1 Sample testing indicators and methods

[0062]

[0063]

[0064] S2. Preliminary screening analysis: Based on the preliminary screening indicators, the inorganic pollutants in the oxidation products after the incineration and disposal of molybdenum-containing organic waste liquid are detected to determine the detection indicators for content detection and analysis;

[0065] It can be understood that the testing in step S2 includes on-site XRF inspection and laboratory testing;

[0066] Specifically, the method and results of content detection in this embodiment are:

[0067] 1. On-site rapid test: On-site XRF (X-ray fluorescence spectrometry, achieved through an XRF handheld spectrometer) rapid test results show that the sample may contain arsenic, chromium, copper, lead, nickel, iron, manganese, titanium, tungsten and other elements, all of which are within the scope of subsequent initial screening tests;

[0068] 2. Laboratory testing: The results of the quantitative full scan preliminary screening test of organic matter in comprehensive utilization products showed that no organic matter was detected, which was consistent with the previous speculation results; the results of inorganic element detection showed that potassium, sodium, iron, aluminum, lead, magnesium, calcium, copper, chromium, arsenic, silicon, phosphorus, tungsten, fluoride, and mercury were detected to varying degrees; the dioxin test showed that dioxin-like substances were detected in both preliminary screening samples; the results of the quantitative full scan preliminary screening test of organic matter in comprehensive utilization products showed that no organic matter was detected, referring to the "Determination of Semi-volatile Organic Matter in Solid Waste by Gas Chromatography-Mass Spectrometry" (HJ 951-2018) and the "Determination of Volatile Organic Matter in Solid Waste by Headspace / Gas Chromatography-Mass Spectrometry" (HJ 643-2013);

[0069] S3. Content detection and analysis: Based on the detection index, the oxidation products after the incineration of molybdenum-containing organic waste liquid are tested, and the detection index and the maximum detection value are obtained after the test;

[0070] It can be understood that in this embodiment, the method for detecting the oxidation product after the incineration treatment of the molybdenum-containing organic waste liquid based on the detection index in step S3 is a molybdenum chemical analysis method;

[0071] It can be understood that in this embodiment, the detection indicators are divided into metals, dioxins and inorganic substances; metals include aluminum, iron, magnesium, cadmium, manganese, chromium, nickel, copper, tin, antimony, bismuth, tungsten, arsenic, and mercury; inorganic substances include calcium, fluoride, and cyanide;

[0072] Specifically, the number of samples for analysis of harmful substances in the comprehensive utilization products of this embodiment refers to the requirements of Section 8.1 of the Technical Guidelines for Pollution Prevention and Control of Solid Waste Recycling (HJ 1091-2020) for solid waste recycling enterprises to regularly sample and monitor solid waste recycling products: When a certain hazardous waste is recycled for the first time, the monitoring frequency of characteristic pollutants in the recycled products shall not be less than once a day; when the monitoring results for one week do not exceed the environmental risk assessment results, the frequency can be reduced to once a week on the premise that the source and dosage of the hazardous waste are stable; when the monitoring results for two consecutive months do not exceed the environmental risk assessment results, the frequency can be reduced to once a month; if the monitoring results are abnormal during this period, or the source of the hazardous waste changes, or the recycling is interrupted for more than half a year, the monitoring frequency will be readjusted to once a day, and repeated in sequence; since molybdenum oxide can meet the requirements of continuous production for one week; therefore, the number of samples for this sampling is determined to be 7 (once a day for one week) in combination with the production plan of the plant area;

[0073] S4. Environmental risk assessment:

[0074] Construct application scenarios and environmental exposure scenarios for molybdenum oxide, and determine the multiple subsequent uses and emission scenarios of molybdenum oxide;

[0075] Judge and evaluate the detection indicators, that is, when it is judged that the detection indicators belong to the quality standards of molybdenum oxide products, the quality standards of molybdenum oxide subsequent products, dioxins or inorganic pollutants, evaluate the content of the detected pollutants. When the content of the detected pollutants is higher than the standard limit, the environmental risk is evaluated as unacceptable; otherwise, the environmental risk is evaluated as acceptable;

[0076] Specifically, the environmental exposure assessment of the embodiment is usually based on a "reasonable worst-case scenario assumption", constructs emission scenarios for the actual use of comprehensive utilization products, identifies all emission sources in the production and processing use stages, and clarifies the generation of three wastes in the production process, pollution control measures, emission time, emission pathways and media, emission frequency patterns and surrounding environment. According to the information provided by Jinling Huntsman, the corresponding use pathways of molybdenum residual liquid incineration products are shown in Table 2;

[0077] Table 2 Analysis of emission scenarios of harmful substances from comprehensive utilization products

[0078]

[0079] Specifically, the process of constructing the environment exposure scene in this embodiment is:

[0080] Environmental exposure scenarios must further clarify environmental exposure pathways and health exposure pathways;

[0081] Environmental exposure pathways: Chemical substances enter the atmosphere or surface water through direct discharge, or enter the environment after being treated by centralized STPs; Chemical substances from consumer use sources enter surface water through direct discharge or indirect discharge from centralized STPs; Chemical substances enter sediments through the sedimentation of suspended matter in water; Chemical substances enter the soil through dry and wet deposition in the atmosphere and agricultural use of sludge, and enter groundwater through leaching of soil pore water; The exposure pathway for predators is to prey on earthworms in the soil or fish in surface water;

[0082] Health exposure scenario: Based on the environmental exposure scenario, consider indirect exposure to the human body through the environment, such as inhalation of air, drinking surface water or groundwater, and ingestion (consider children's exposure to soil ingestion if necessary) to construct a health exposure scenario; the ingestion route focuses on the ingestion of fish, and more ingestion routes can be considered when applicable;

[0083] According to the construction of environmental exposure scenarios, there are health exposure scenarios in the subsequent use of molybdenum residual liquid incineration products. The subsequent production process as alternative raw materials does not consider the health effects of harmful substances on workers, but there is no application scenario that directly enters the ecological environment;

[0084] The final exposure scenario is shown in Table 3;

[0085] Table 3 Construction of exposure scenarios for hazardous substances in products from comprehensive utilization of solid waste

[0086]

[0087] The sampling of this embodiment is for the detection of the preliminary screening test substances. The exposure of harmful substances in the comprehensive utilization products evaluated in this embodiment is calculated according to the maximum detection value. The maximum concentration of harmful substances is shown in Table 4. The pollutant phosphorus in Table 4 belongs to the impurity item in "Molybdenum Oxide" (YB / T 5129-2012). Compared with the standard, the detection values ​​are all lower than the corresponding limit values. The calculation formula of the maximum detection value is:

[0088] C=max(C1,C2,C3,C4,C5,C6,C7);

[0089] In the above formula, C is the calculated concentration of a certain harmful substance; C1~C7 is the detected concentration of a certain harmful substance for 7 consecutive days;

[0090] Table 4 Maximum detection data of harmful substances in comprehensive utilization products

[0091] Detected substances Maximum Reference standard value standard silicon 0.005 0.0010 ％ iron 0.0005 0.0010 ％ calcium 0.0078 0.0015 ％ magnesium 0.0015 0.0010 ％ Potassium 0.012 0.0018 ％ sodium 0.0037 0.0015 ％ copper 0.0003 0.0005 ％ aluminum 0.58 0.0008 ％ phosphorus 0.0044 0.05 ％ arsenic 0.0053 0.0005 ％ fluorine 0.052 / ％ mercury 0.023 / mg / kg Dioxins 5.7E-07 4E-05 mg / kg

[0092] The pollutants identified in Table 4 are potassium, sodium, iron, aluminum, lead, magnesium, calcium, chromium, arsenic, silicon, and tungsten. They are impurities in the product standard of "Ammonium Molybdate" (GB / T3460-2017); compared with the standard, the maximum detection values ​​of silicon, calcium, magnesium, potassium, sodium, aluminum, and arsenic are higher than the corresponding limits; among them, silicon and magnesium are common elements in the natural environment and will not be considered in the future; aluminum and arsenic are included in the subsequent qualitative environmental risk assessment;

[0093] The pollutants fluorine, mercury, and dioxins identified in Table 4 need to be qualitatively evaluated for environmental risk, and the dioxin limit is determined to be 40n TEQ / kg based on the screening value of Class I land in the Soil Environmental Quality Construction Land Soil Pollution Risk Control Standard (Trial) (36600-2018). The detected contents are all lower than the corresponding limit and will not be considered in the future. The evaluation product of this example needs to pay attention to fluorine and mercury in the subsequent utilization process;

[0094] It can be understood that in this embodiment, the method for judging and evaluating the detection index is:

[0095] Determine the type of detected indicators:

[0096] When the detection index belongs to the quality standard of molybdenum oxide products, and when the maximum detection value of the detection index is higher than the standard limit of the corresponding product quality standard, it is assessed that the oxidation products after the incineration of molybdenum-containing organic waste liquid have environmental risks, otherwise it is assessed that the detected pollutants do not have environmental risks;

[0097] When the detected index belongs to the quality standard of subsequent products of molybdenum oxide, and when the maximum value of the detected index is higher than the standard limit of the corresponding subsequent product quality standard, it is assessed that the oxidation product after the incineration of molybdenum-containing organic waste liquid has environmental risks, otherwise it is assessed that the detected pollutants have no environmental risks;

[0098] When the detected index belongs to dioxins, and when the maximum value of the detected index is higher than the standard limit of dioxins, it is assessed that the oxidation products after the incineration of molybdenum-containing organic waste liquid have environmental risks, otherwise it is assessed that the detected pollutants have no environmental risks;

[0099] It can be understood that in this embodiment, the standard limit of dioxin is 40ng TEQ / kg;

[0100] When the detected indicators belong to inorganic pollutants, health exposure assessment is carried out on the detected indicators. The assessment result is that the oxidation products after the incineration and disposal of molybdenum-containing organic waste liquid have health exposure risks or the detected pollutants are assessed to have no health exposure risks;

[0101] It can be understood that in this embodiment, the method for conducting health exposure assessment on the detection indicators is: conducting health risk assessment on the detection indicators, and calculating the exposure amount ADD of the detection target for each detection target based on the environmental exposure pathway and the maximum monitoring result, and then determining the health toxicity parameter RfD of the detection target, and calculating the health risk representation When the ecological risk assessment result shows that there is no exposure pathway and the health risk characterization is less than 1, it is assessed that the detected pollutants do not pose an environmental risk. Otherwise, it is assessed that the oxidation products after the incineration of molybdenum-containing organic waste liquid pose an environmental risk.

[0102] It can be understood that in this embodiment, the inorganic pollutants include aluminum, arsenic, fluoride and mercury.

[0103] Specifically, human health focuses on the impact on workers' health, with a focus on substances that workers are exposed to in the form of raw materials, finished products, semi-finished products, intermediates, reaction by-products and impurities during production, and that can enter the human body through the respiratory tract, skin or mouth during operation and cause harm to health;

[0104] According to the Technical Guidelines for Environmental and Health Exposure Assessment of Chemical Substances (Trial) and the General Guidelines for Environmental Risk Assessment of Solid Waste Resource Products, health exposure assessment includes three direct exposure pathways: oral ingestion, inhalation, and skin contact; according to the evaluation receptors determined by the exposure scenario in Table 2, and in view that the pollutants of concern are all inorganic substances, and the molybdenum incineration products and ammonium molybdate are both in solid form, the evaluation of this example does not consider the exposure pathway through inhalation for the time being;

[0105] The calculation model for various exposure pathways is as follows:

[0106] a) Referring to the General Guidelines for Environmental Risk Assessment of Solid Waste Resource Products (T / CAEPI 69-2023), the formula for calculating exposure via oral ingestion is:

[0107]

[0108] Where:

[0109] ADD——average daily exposure, in milligrams per kilogram day, mg / (kg·d);

[0110] C——concentration of harmful substances in the medium;

[0111] CF——conversion factor, in kilograms per milligram, kg / mg;

[0112] IR – intake rate, in milligrams per day, mg / d;

[0113] EF – exposure frequency, in days per year, d / a;

[0114] ED——Exposure period, in years, a;

[0115] BW——body weight, in kilograms, kg;

[0116] AT——average time, in days, d;

[0117] b) Referring to the General Guidelines for Environmental Risk Assessment of Solid Waste Resource Products (T / CAEPI 69-2023), the formula for calculating the exposure amount for skin contact is as follows:

[0118]

[0119] Where:

[0120] AF - Skin Adhesion Factor, in milligrams per square centimeter, mg / cm 2 ;

[0121] SA——Skin contact area, in square centimeters per time, cm 2 / event;

[0122] ABS – skin absorption coefficient;

[0123] Specifically, the exposure parameters of this embodiment should be selected in the following order: a) exposure parameters in the "Handbook of Exposure Parameters for Chinese Populations";

[0124] b) Exposure parameters recommended by relevant domestic standards, scientific and technological literature, etc.;

[0125] c) Recommended values ​​of exposure parameters published by foreign authoritative organizations or scientific literature;

[0126] d) Exposure parameters obtained through on-site investigations based on standards such as HJ875, HJ876, and HJ877;

[0127] Refer to the exposure parameters in the "Handbook of Chinese Population Exposure Parameters", Appendix B.3 of the "Technical Guidelines for Environmental and Health Exposure Assessment of Chemical Substances (Trial)" (December 23, 2020), and the "Technical Guidelines for Population Exposure Assessment of Environmental Pollutants" (HJ875); assuming the most unfavorable conditions, the emission coefficients for different comprehensive utilization products and different use pathways are selected as shown in Table 5.5-4; the concentration of harmful substances in the air is estimated with reference to the "Technical Guidelines for Soil Pollution Risk Assessment of Construction Land" (HJ 25.3-2019);

[0128] The skin adhesion factor refers to the maximum skin adhesion coefficient of "soil-related activities" in Table 5-2 of the "Handbook of Exposure Parameters for Chinese Populations"; the daily intake for adults refers to the intake for "general population" in Table 5-1 of the "Handbook of Exposure Parameters for Chinese Populations"; the skin contact area refers to the "skin surface area of ​​men aged 18 to 59" in Table 11-1 of the "Handbook of Exposure Parameters for Chinese Populations"; the daily exposure duration is determined according to the maximum daily working hours in the "Labor Law of the People's Republic of China" (revised on December 29, 2018);

[0129] According to calculations, the exposure amounts of harmful substances in the molybdenum incineration products finally obtained in this embodiment are shown in Table 5;

[0130] Table 5 List of exposure levels of harmful substances in comprehensive utilization products (adults)

[0131]

[0132] When the evaluation result of the detection index is that the detected pollutants do not pose an environmental risk, it is assessed that the oxidation products after the incineration of molybdenum-containing organic waste liquid do not pose a health exposure risk; otherwise, it is assessed that the oxidation products after the incineration of molybdenum-containing organic waste liquid do pose a health exposure risk;

[0133] RfD is a parameter that characterizes the dose-response relationship for non-carcinogenic effects and is estimated as follows:

[0134] The reference dose or concentration with threshold effects (chronic toxicity, subchronic toxicity, reproductive and developmental toxicity) can be estimated based on the quotient of the no-observed-adverse-effect level (NOAEL) or the low-observed-adverse-effect level (LOAEL) and the uncertainty factor (UF);

[0135] The value of UF includes: inter-species differences extrapolated from animals to humans, intra-species differences caused by individual sensitivity differences, and differences extrapolated from subchronic studies to chronic studies (UF = 10); differences caused by using LOAEL instead of NOAEL to extrapolate to RfD (UF = 10); other uncertainties caused by incomplete databases (UF is 1 to 10); the uncertainty coefficient of inter-species differences and intra-species differences can be 10; the relevant parameters and calculation results are shown in Table 6;

[0136] Table 6 Parameter list (unit: mg / kg-d)

[0137]

[0138] Specifically, the actual judgment and evaluation process of the above process in this embodiment is as follows:

[0139] Environmental risk assessment includes three judgment bases: the first judgment, the second judgment and the third judgment of the detected indicators. If any judgment result is that there is an environmental risk, it is considered that there is an environmental risk. If the judgment results of the three bases are all that the environmental risk is acceptable, then the environmental risk is considered acceptable.

[0140] First judgment: When the detection index is included in the quality standard of molybdenum oxide products / the quality standard of subsequent molybdenum oxide reprocessed products, and when the maximum detection value of the detection index is greater than or equal to the standard limit of molybdenum oxide product quality standard / subsequent molybdenum oxide, it is judged that there is an environmental risk;

[0141] Second judgment: When the detection index is included in the dioxin product quality standard, and when the maximum detection value of the detection index is greater than or equal to the standard limit of the dioxin product quality standard, it is judged that there is an environmental risk;

[0142] Third judgment: When the detection indicators are included in inorganic pollutants, a health exposure assessment is conducted, and based on the environmental exposure pathway and the maximum monitoring results, the exposure amount ADD is calculated for each detection target, and then the health toxicity parameter RfD is determined, and the health risk characterization is calculated. When the RCR value is less than 1, it is considered that there is no health risk, and when it is greater than or equal to 1, there is a health risk;

[0143] Specifically, the health risk characterization values ​​calculated in this embodiment are shown in Table 7. According to the calculation, the health risk characterizations of the five hazardous substances are all less than 1, and it is determined that there is no health risk;

[0144] Table 7 List of RCR1 values ​​for overall health risk characterization of hazardous substances in comprehensive utilization products

[0145] Hazardous substances Oral health risk characterization RCR value Skin health risk characterization RCR value aluminum 4.79E-03 3.21E-02 arsenic 1.46E-01 9.77E-01 Fluoride 1.07E-02 7.19E-02 mercury 6.33E-05 4.24E-04

Claims

1. A method for environmental risk assessment of oxidation products after incineration of molybdenum-containing organic waste liquid, characterized in that: The following steps are involved: S1. Pollutant identification: Based on the production process, regeneration and disposal process and comparison of raw and auxiliary materials, determine the initial screening indicators of oxidation products after incineration and disposal of molybdenum-containing organic waste liquid; S2. Preliminary screening analysis: Based on the preliminary screening indicators, the inorganic pollutants in the oxidation products after the incineration and disposal of molybdenum-containing organic waste liquid are detected to determine the detection indicators for content detection and analysis; S3. Content detection and analysis: Based on the detection index, the oxidation products after the incineration of molybdenum-containing organic waste liquid are tested, and the detection index and the maximum detection value are obtained after the test; S4. Environmental risk assessment: Construct application scenarios and environmental exposure scenarios for molybdenum oxide, and determine the multiple subsequent uses and emission scenarios of molybdenum oxide; Judge and evaluate the detection indicators, that is, when it is judged that the detection indicators belong to the quality standards of molybdenum oxide products, the quality standards of molybdenum oxide subsequent products, dioxins or inorganic pollutants, evaluate the content of the detected pollutants. When the content of the detected pollutants is higher than the standard limit, the environmental risk is evaluated as unacceptable; otherwise, the environmental risk is evaluated as acceptable; The method for judging and evaluating the detection indicators is: Determine the type of detected indicators: When the detection index belongs to the quality standard of molybdenum oxide products, and when the maximum detection value of the detection index is higher than the standard limit of the corresponding product quality standard, it is assessed that the oxidation products after the incineration of molybdenum-containing organic waste liquid have environmental risks, otherwise it is assessed that the detected pollutants do not have environmental risks; When the detected index belongs to the quality standard of subsequent products of molybdenum oxide, and when the maximum value of the detected index is higher than the standard limit of the corresponding subsequent product quality standard, it is assessed that the oxidation product after the incineration of molybdenum-containing organic waste liquid has environmental risks, otherwise it is assessed that the detected pollutants have no environmental risks; When the detected index belongs to dioxins, and when the maximum value of the detected index is higher than the standard limit of dioxins, it is assessed that the oxidation products after the incineration of molybdenum-containing organic waste liquid have environmental risks, otherwise it is assessed that the detected pollutants have no environmental risks; When the detected indicators belong to inorganic pollutants, health exposure assessment is carried out on the detected indicators. The assessment result is that the oxidation products after the incineration and disposal of molybdenum-containing organic waste liquid have health exposure risks or the detected pollutants are assessed to have no health exposure risks; When the assessment result of the detection indicators is that the detected pollutants do not pose an environmental risk, the environmental risk of the oxidation products after incineration disposal of molybdenum-containing organic waste liquid is assessed to be acceptable, and only a health exposure assessment is given; otherwise, an environmental risk and health exposure assessment of the oxidation products after incineration disposal of molybdenum-containing organic waste liquid is given.

2. The environmental risk assessment method for oxidation products after incineration of molybdenum-containing organic waste liquid according to claim 1, characterized in that: The contents of the comparison in step S1 include: analysis of inorganic elements in the oxidation products after incineration of molybdenum-containing organic waste liquid and comparative analysis of production processes.

3. The environmental risk assessment method for oxidation products after incineration of molybdenum-containing organic waste liquid according to claim 1, characterized in that: The detection in step S2 includes on-site XRF inspection and laboratory testing.

4. The environmental risk assessment method for oxidation products after incineration of molybdenum-containing organic waste liquid according to claim 1, characterized in that: The method for detecting the oxidation products after incineration of molybdenum-containing organic waste liquid based on the detection index in step S3 is a molybdenum chemical analysis method.

5. The environmental risk assessment method for oxidation products after incineration of molybdenum-containing organic waste liquid according to claim 1, characterized in that: The detection indicators are divided into metals, dioxins and inorganic substances.

6. The environmental risk assessment method for oxidation products after incineration of molybdenum-containing organic waste liquid according to claim 5, characterized in that: The metals include aluminum, iron, magnesium, cadmium, manganese, chromium, nickel, copper, tin, antimony, bismuth, tungsten, arsenic, and mercury; the inorganic substances include calcium, fluoride, and cyanide.

7. The environmental risk assessment method for oxidation products after incineration of molybdenum-containing organic waste liquid according to claim 1, characterized in that: The standard limit value of dioxins is 40 ng TEQ / kg.

8. The environmental risk assessment method for oxidation products after incineration of molybdenum-containing organic waste liquid according to claim 1, characterized in that: The method for conducting health exposure assessment on the detection indicators is: conduct health risk assessment on the detection indicators, and calculate the exposure amount ADD of the detection target for each detection target based on the environmental exposure pathway and the maximum monitoring result, and then determine the health toxicity parameter RfD of the detection target, and calculate the health risk characterization When the ecological risk assessment result shows that there is no exposure pathway and the health risk characterization is less than 1, it is assessed that there is no health exposure risk to the oxidation products after incineration disposal of molybdenum-containing organic waste liquid; otherwise, it is assessed that there is a health exposure risk to the oxidation products after incineration disposal of molybdenum-containing organic waste liquid.

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