A method and system for determining the emission amount of antimony in copper / lead / zinc smelting, a terminal and a medium

Abstract

The application discloses a kind of copper / lead / zinc smelting antimony emission determination method, system, terminal and medium, wherein the method comprises: data acquisition: obtain the copper / lead / zinc smelting data of past years;Model construction: construct including concentrate input in copper / lead / zinc smelting process, roasting / melting, leaching / blast refining and the probability mass flow model of refining stage;Parameter estimation: based on the copper / lead / zinc smelting data of past years collected, the key parameter estimation distribution in probability mass flow model is obtained using bootstrap random sampling simulation;Emission determination: the key parameter estimation distribution is substituted into probability mass flow model, and the distribution of antimony emission in copper / lead / zinc smelting process is obtained.By using bootstrap method to obtain the key parameter estimation distribution in probability mass flow model, the prior assumption on the form of parameter probability distribution is removed, the uncertainty of calculation result is reduced, so that the calculation result is more accurate.

Description

Technical Field

[0001] The present invention relates to the field of heavy metal emissions in nonferrous smelting processes, and in particular to a method, system, terminal and medium for determining antimony emissions in copper / lead / zinc smelting. Background Art

[0002] The main evolution of the estimation methods for heavy metal emissions from nonferrous metal smelting processes is as follows: (1) The product / raw material-based emission factor method, in which the emissions calculated by this method are the product of the emission factor and the metal output / raw material input. (2) The shift from emission factor models to mass flow models, which allow emission estimates to cover the entire drying-smelting-converting-refining process of nonferrous metal smelting, thereby making the estimation results more accurate. (3) The introduction of Monte Carlo simulation in the method of converting deterministic models into probabilistic models, taking into account the probability distribution of key parameters and avoiding underestimation of the geometric mean.

[0003] However, the accuracy of the emission factor method depends on the assignment of emission factors, which are mainly obtained from the following sources: estimates of a few key emission sources, publication of public literature, and data provided by experts or relevant smelters in various countries. This leads to large differences in the emission factors of heavy metals in different documents or reports, and it is impossible to accurately quantify the emission of heavy metals in the smelting process on a large scale; the parameter values ​​and result values ​​of the deterministic mass flow model are definite and unique, and are not widely applicable; the most commonly used Monte Carlo simulation method in the more advanced probabilistic mass flow model is implemented by assuming the probability distribution form of key parameters in advance. Such assumptions may cause large errors in the results. Summary of the Invention

[0004] In view of the above-mentioned deficiencies in the prior art, the object of the present invention is to provide a method, system, terminal and medium for determining antimony emissions from copper / lead / zinc smelting, by using bootstrap random sampling simulation for key parameters in a probabilistic mass flow model, that is, no prior probability distribution assumption is made for the key parameters, thereby reducing the uncertainty of the calculation results.

[0005] In a first aspect, a method for determining antimony emissions from copper / lead / zinc smelting is provided, comprising the following steps:

[0006] Data collection: Obtain copper / lead / zinc smelting data over the years;

[0007] Model building: Constructing a probabilistic mass flow model for the concentrate input, roasting / smelting, leaching / converting, and refining stages of the copper / lead / zinc smelting process;

[0008] Parameter estimation: Based on the collected copper / lead / zinc smelting data over the years, bootstrap random sampling simulation is used to obtain the estimated distribution of key parameters in the probability mass flow model;

[0009] Emission determination: The estimated distributions of key parameters are substituted into the probabilistic mass flow model to obtain the distribution of antimony emissions from the copper / lead / zinc smelting process.

[0010] Furthermore, in the data collection step, the copper, lead and zinc smelting data obtained over the years specifically include:

[0011] Domestic copper / lead / zinc concentrate production and import and export volumes over the years;

[0012] Antimony concentration in copper / lead / zinc concentrates;

[0013] The distribution coefficient of antimony in flue gas and waste residue during the roasting / smelting, leaching / converting and refining stages of copper / lead / zinc smelting;

[0014] Types and percentages of air pollution control devices installed at each stage of copper / lead / zinc smelting over the years;

[0015] Antimony removal rate of air pollution control devices.

[0016] Furthermore, the concentrate input stage model is expressed as follows:

[0017] Q com =C com *M com (1)

[0018] Where Q com Indicates the antimony input of copper / lead / zinc concentrate smelting; C com Indicates the antimony concentration in copper / lead / zinc concentrate; M com Indicates the input of copper / lead / zinc concentrate over the years.

[0019] Furthermore, the roasting / melting stage model is expressed as follows:

[0020] I ss =Q com *ξ ss (2)

[0021] GEs=Q com *γ s *Σθ m (1-η m ) (3)

[0022] I wa =Q com *γ s *Σθ m (1-η dc )*ηfgs+esd (4)

[0023] I sa =Q s *γ s *Σθ m (1-η dc )*(1-η fgs+esd )*η sa (5)

[0024] I Sfgd =Q s *γ s *Σθ m (1-η dc )*(1-η fgs+esd )*(1-η sa )*η fgd (6)

[0025] Where Q com Indicates the antimony input of copper / lead / zinc concentrate smelting; I ss Indicates the antimony content of copper smelting slag / high-lead slag / zinc roasted sand; ξ ss represents the antimony slag phase distribution ratio during the smelting stage; GEs represents the atmospheric antimony emission during the smelting stage; γ s represents the antimony gas phase distribution rate during the smelting stage; θ m Indicates the combined utilization rate of air pollution control devices during the smelting stage; η m Indicates the antimony removal rate of the combination of air pollution control devices during the smelting stage; I wa Indicates the antimony content of the waste acid in the smelting stage; η dc Indicates the antimony removal rate of electrostatic precipitator + waste heat boiler equipment in the smelting stage; I sa Indicates the antimony content of sulfuric acid; η fgs+esd Indicates the antimony removal rate of the flue gas scrubbing equipment during the smelting stage; η sa Indicates the antimony removal rate of the acid-making equipment; I Sfgd Indicates the antimony content of desulfurization by-products; η fgd Indicates the antimony removal rate of the desulfurization equipment.

[0026] Furthermore, the leaching / converting stage model is expressed as follows:

[0027] Q e =Q com (1-ξ ss -γ s ) (7)

[0028] Q e =Q com *ξ ss (8)

[0029] I es =Q e*ξ es (9)

[0030] GEe=Q e *ξ e (1-η e ) (10)

[0031] I ex =θ x *Q e (11)

[0032] Σθ x =1 (12)

[0033] In the formula, Q com represents the input amount of antimony in the smelting of copper / lead / zinc concentrates; Q e represents the input amount of antimony in the blowing stage of copper or lead, Q e in formula (7) represents the input amount of antimony in the blowing stage of copper, Q e in formula (8) represents the input amount of antimony in the blowing stage of lead; ξ ss represents the slag phase distribution rate of antimony in the smelting stage; γ s represents the gas phase distribution rate of antimony in the smelting stage; I es represents the amount of antimony in the blowing slag; ξ es represents the slag phase distribution rate of antimony in the blowing stage; GEe represents the atmospheric antimony emission in the blowing stage; ξ e represents the gas phase distribution rate of antimony in the blowing stage; η e represents the antimony removal rate of the type combination of air pollution control devices in the blowing stage; I ex represents the amount of antimony in the final product in the zinc smelting leaching + refining stage; θ x represents the distribution rate of different products in the zinc smelting.

[0034] Further, the model of the refining stage is represented as follows:

[0035] Q r = Q com (1-ξ ss -γ s )*(1-ξ es -ξ e ) (13)

[0036] Q r = Q com *(1-ξ ss -γ s )+Q com *ξ ss (1-ξ es -ξ e ) (14)

[0037] FI r = Q r*(1-γ r -ξ r ) (15)

[0038] GEr=Q r *γ r *(1-η r ) (16)

[0039] OD r =Q r *(ξ r +γ r *η r ) (17)

[0040] Where Q com Indicates the antimony input of copper / lead concentrate smelting; Q r represents the antimony input in the copper or lead refining stage, Q in formula (13) r represents the antimony input in the copper refining stage, Q in formula (14) r represents the antimony input in the lead refining stage; ξ ss represents the antimony slag phase distribution ratio during the smelting stage; γ s represents the antimony gas phase distribution rate during the smelting stage; ξ e Indicates the antimony gas phase distribution rate during the blowing stage; FI r Indicates the antimony content of refined products; γ r represents the antimony gas phase distribution rate in the refining stage; ξ r represents the antimony slag phase distribution ratio during the refining stage; GEr represents the atmospheric antimony emission during the refining stage; η r Indicates the antimony removal rate of the combination of air pollution control device types in the refining stage; OD r Indicates the antimony content of refining by-products.

[0041] Furthermore, the parameter estimation process specifically includes:

[0042] Based on the collected copper / lead / zinc smelting data over the years, a data set of key parameters in the probabilistic mass flow model was obtained;

[0043] For each key parameter, its probability is obtained as follows:

[0044] Randomly sample B times with replacement from a key parameter data set, and the number of samples in each sampling is n;

[0045] Calculate the average of each sampling result;

[0046] A sampling distribution of the key parameter is formed according to the B average values ​​of the key parameter.

[0047] In a second aspect, a system for determining antimony emissions from copper / lead / zinc smelting is provided, comprising:

[0048] Data acquisition module, used to obtain historical copper / lead / zinc smelting data;

[0049] Model building module for constructing probabilistic mass flow models for the concentrate input, roasting / smelting, leaching / converting, and refining stages of copper / lead / zinc smelting processes;

[0050] The parameter estimation module is used to obtain the estimated values ​​of key parameters in the probability mass flow model using bootstrap random sampling simulation based on the collected copper / lead / zinc smelting data over the years;

[0051] The emission determination module is used to substitute the estimated values ​​of key parameters into the probabilistic mass flow model to obtain the distribution of antimony emissions in the copper / lead / zinc smelting process.

[0052] In a third aspect, an electronic terminal is provided, comprising:

[0053] a memory having a computer program stored thereon;

[0054] A processor is used to load and execute the computer program to implement the method for determining antimony emissions from copper / lead / zinc smelting as described above.

[0055] In a fourth aspect, a computer-readable storage medium is provided, on which a computer program is stored. When the computer program is executed by a processor, the method for determining antimony emissions from copper / lead / zinc smelting as described above is implemented.

[0056] The present invention proposes a method, system, terminal and medium for determining antimony emissions from copper / lead / zinc smelting, which has the following advantages:

[0057] (1) The estimated distribution of key parameters in the probability mass flow model is obtained by random sampling simulation using the bootstrap method, removing the prior assumptions about the probability distribution form of the parameters, reducing the uncertainty of the calculation results, and making the calculation results more accurate;

[0058] (2) Replace the deterministic mass flow model with a probabilistic mass flow model to enhance the model's applicability and enable quantitative analysis of the impact of key parameters on the results;

[0059] (3) The mass flow model replaces the traditional emission factor method, and the estimation of heavy metal emissions from non-ferrous metal smelting is expanded to all stages of the entire process, making the flow and enrichment routes of target heavy metals clearer and more accurate. BRIEF DESCRIPTION OF THE DRAWINGS

[0060] In order to more clearly illustrate the technical solutions in the embodiments of the present application or the prior art, the following will briefly introduce the drawings required by the embodiments or prior art description. Obviously, the drawings in the following description only constitute some embodiments of the present application, and for those skilled in the art, other drawings can also be obtained from these drawings without creative labor.

[0061] Figure 1 is a copper / lead / zinc smelting antimony emission determination method flowchart provided by the embodiment of the present application;

[0062] Figure 2 is a copper / lead / zinc smelting process simplified schematic diagram provided by the embodiment of the present application;

[0063] Figure 3 is a probability distribution diagram of the input antimony amount of the copper concentrate smelting in China from 2000 to 2020 provided by the embodiment of the present application;

[0064] Figure 4 is a probability distribution diagram of the input antimony amount of the lead smelting in China from 2000 to 2020 provided by the embodiment of the present application;

[0065] Figure 5 is a probability distribution diagram of the input antimony amount of the copper concentrate smelting in China from 2000 to 2020 provided by the embodiment of the present application;

[0066] Figure 6 is an estimated value of the input antimony amount of the copper / lead / zinc concentrate smelting in China from 2000 to 2020 provided by the embodiment of the present application;

[0067] Figure 7 is a distribution ratio of antimony in the smelting, blowing and refining stages of the copper smelting, lead smelting and zinc smelting process, wherein (a) is a distribution ratio of antimony in the smelting, blowing and refining stages of the copper smelting process, (b) is a distribution ratio of antimony in the smelting, blowing and refining stages of the lead smelting process, and (c) is a distribution ratio of antimony in the smelting, blowing and refining stages of the zinc smelting process;

[0068] Figure 8 is a final flow direction and proportion of antimony in the copper / lead / zinc smelting process provided by the embodiment of the present application, wherein (a) and (b) are the final flow direction and proportion of antimony in the copper smelting process, (c) and (d) are the final flow direction and proportion of antimony in the lead smelting process, and (e) and (f) are the final flow direction and proportion of antimony in the zinc smelting process;

[0069] Figure 9 is a circulation situation of antimony in the copper / lead / zinc smelting process from 2000 to 2020 provided by the embodiment of the present application;

[0070] Figure 10 This is the emission of antimony in the copper, lead and zinc smelting process from 2000 to 2020 provided by the embodiment of the present invention;

[0071] Figure 11 This is the production and discharge of antimony in APCD during the copper, lead and zinc smelting process from 2000 to 2020 provided by the embodiment of the present invention;

[0072] Figure 12 This is a sensitivity analysis of antimony emission factors in the copper, lead and zinc smelting process provided by an embodiment of the present invention; wherein (a) copper smelting (b) lead smelting (c) zinc smelting. DETAILED DESCRIPTION

[0073] To make the objectives, technical solutions, and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. Obviously, the embodiments described are only some of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other implementations obtained by those of ordinary skill in the art without inventive effort are within the scope of protection of the present invention.

[0074] After investigation, the full-process emission of antimony was estimated by taking the most widely used copper / lead / zinc smelting processes as an example. The copper smelting processes are flash copper smelting and oxygen-enriched bath copper smelting; the lead smelting processes are bath lead smelting and SKS lead smelting; and the zinc smelting process is roasting-leaching smelting. In summary, if Figure 2 As shown in the figure, the copper / lead / zinc smelting process generally includes four stages: drying, roasting / smelting, leaching / blowing and refining.

[0075] Air pollution control devices (APCDs) are primarily used to control gaseous pollutant emissions during the smelting process. The drying process primarily produces particulate matter, and dust collectors are typically installed for dust removal. Since only a small amount of antimony volatilizes during this stage, and the dust from the dust removal process is used as raw material for the smelting stage, it is believed that the drying process does not cause antimony loss. During the roasting / smelting stage, most smelters use a dust removal, purification, and acid production system to control particulate matter in the dust. Dust removal (DC) equipment typically includes a waste heat boiler (WHB) and an electrostatic precipitator (ESP), while purification equipment typically includes flue gas scrubbers (FGS) and electrostatic mist eliminators (ESD). During the copper converting stage, the APCD equipment is the same as that used in the smelting stage. During the refining stage, the APCD combination consists of bag filters and flue gas scrubbers (FF+FGS). During the lead converting stage, bag filters (FF) are used, and during the refining stage, a combination of flue gas scrubbers and bag filters (FGS+FF) is used for pollution control. Zinc smelting is a roasting-leaching hydrometallurgical process. Zinc concentrate is roasted to produce zinc calcine, which is then leached. The resulting leachate is purified and then electrolytically deposited to produce cathode zinc. Because all subsequent stages are hydrometallurgical, no APCD equipment is required. The technical solution of the present invention is described in detail below with reference to specific embodiments.

[0076] like Figure 1 As shown, an embodiment of the present invention provides a method for determining antimony emissions from copper / lead / zinc smelting, comprising the following steps:

[0077] S1. Data collection: Obtain copper / lead / zinc smelting data over the years.

[0078] In this embodiment, the copper, lead and zinc smelting data obtained over the years specifically include:

[0079] (1) Domestic copper / lead / zinc concentrate production and import and export volumes from 2000 to 2020;

[0080] (2) Antimony concentration in copper / lead / zinc concentrates;

[0081] (3) The distribution coefficient (percentage) of antimony in flue gas and waste residue during the roasting / smelting, leaching / blowing, and refining stages of copper / lead / zinc smelting;

[0082] (4) Types and percentages of air pollution control devices installed at each stage of copper / lead / zinc smelting over the years;

[0083] (5) Antimony removal rate of air pollution control devices.

[0084] S2. Model construction: Construct a probabilistic mass flow model for the concentrate input, roasting / smelting, leaching / converting, and refining stages of the copper / lead / zinc smelting process.

[0085] The following formula is used to describe the estimated input and distribution of antimony at each stage of copper / lead / zinc concentrate smelting:

[0086] The concentrate input stage model is expressed as follows:

[0087] Q com =C com *M com (1)

[0088] Where Q com Indicates the antimony input of copper / lead / zinc concentrate smelting; C com Indicates the antimony concentration in copper / lead / zinc concentrate; M com represents the input of copper / lead / zinc concentrates over the years. The antimony content input from copper, lead and zinc concentrate smelting in China from 2000 to 2020 is obtained by formula (1).

[0089] The roasting / melting stage model is expressed as follows:

[0090] I ss =Q com *ξ ss (2)

[0091] GEs=Q com *γ s *Σθ m (1-η m ) (3)

[0092] I wa =Q com *γ s *Σθ m (1-η dc )*η fgs+esd (4)

[0093] I sa =Q s *γ s *Σθ m (1-η dc )*(1-η fgs+esd )*η sa (5)

[0094] I Sfgd =Q s *γ s *Σθ m (1-η dc )*(1-η fgs+esd )*(1-η sa )*η fgd (6)

[0095] Where Q com Indicates the antimony input of copper / lead / zinc concentrate smelting; I ss Indicates the antimony content of copper smelting slag / high-lead slag / zinc roasted sand; ξ ssrepresents the antimony slag phase distribution ratio during the smelting stage; GEs represents the atmospheric antimony emission during the smelting stage; γ s represents the antimony gas phase distribution rate during the smelting stage; θ m represents the combined utilization rate of air pollution control devices during the smelting stage, η m represents the antimony removal rate of the combination of air pollution control devices during the smelting stage, and the subscript m represents different air pollution control device combination types; I wa Indicates the antimony content of the waste acid in the smelting stage; η dc Indicates the antimony removal rate of electrostatic precipitator + waste heat boiler equipment in the smelting stage; I sa Indicates the antimony content of sulfuric acid; η fgs+esd Indicates the antimony removal rate of the flue gas scrubbing equipment during the smelting stage; η sa Indicates the antimony removal rate of the acid-making equipment; I Sfgd Indicates the antimony content of desulfurization by-products; η fgd Indicates the antimony removal rate of the desulfurization equipment.

[0096] The leaching / converting stage model is represented as follows:

[0097] Q e =Q com (1-ξ ss -γ s ) (7)

[0098] Q e =Q com *ξ ss (8)

[0099] I es =Q e *ξ es (9)

[0100] GEe=Q e *ξ e (1-η e ) (10)

[0101] I ex =θ x *Q e (11)

[0102] Σθ x =1 (12)

[0103] Where Q com Indicates the antimony input of copper / lead / zinc concentrate smelting; Q e represents the antimony input in the copper or lead smelting stage, Q in formula (7) e represents the antimony input in the copper blowing stage, Q in formula (8) e represents the antimony input in the lead converting stage; ξ ss represents the antimony slag phase distribution ratio during the smelting stage; γs Indicates the antimony gas phase distribution rate during the smelting stage; I es Indicates the antimony content in blowing slag; ξ es represents the antimony slag phase distribution ratio during the blowing stage; GEe represents the atmospheric antimony emission during the blowing stage; ξ e represents the antimony gas phase distribution rate during the blowing stage; η e Indicates the antimony removal rate of the combination of air pollution control devices in the blowing stage; I ex Indicates the antimony content of the final products in the zinc smelting leaching + refining stage; θ x Indicates the distribution rate of different products in zinc smelting.

[0104] The copper matte produced by copper smelting and the high-lead slag produced by lead smelting enter the blowing stage, while the roasted sand produced by zinc smelting enters the leaching stage. Here, the final flow of antimony is estimated by the distribution rate of antimony in the final products produced by leaching and electrolytic refining (Equations (11)-(12)), and the sum of the distribution coefficients of each product is 1.

[0105] The refinement stage model is represented as follows:

[0106] Q r =Q com (1-ξ ss -γ s )*(1-ξ es -ξ e ) (13)

[0107] Q r =Q com *(1-ξ ss -γ s )+Q com *ξ ss (1-ξ es -ξ e ) (14)

[0108] FI r =Q r *(1-γ r -ξ r ) (15)

[0109] GEr=Q r *γ r *(1-η r ) (16)

[0110] OD r =Q r *(ξ r +γ r *η r ) (17)

[0111] Where Q rrepresents the antimony input in the copper or lead refining stage, Q in formula (13) r represents the antimony input in the copper refining stage, Q in formula (14) r represents the antimony input in the lead refining stage; ξ ss represents the antimony slag phase distribution ratio during the smelting stage; γ s represents the antimony gas phase distribution rate during the smelting stage; ξ e Indicates the antimony gas phase distribution rate during the blowing stage; FI r Indicates the antimony content of refined products; γ r represents the antimony gas phase distribution rate in the refining stage; ξ r represents the antimony slag phase distribution ratio during the refining stage; GEr represents the atmospheric antimony emission during the refining stage; η r Indicates the antimony removal rate of the combination of air pollution control device types in the refining stage; OD r Indicates the antimony content of refining by-products.

[0112] The above formulas together constitute the probability mass flow model of antimony in copper, lead and zinc smelting process; the parameters for bootstrap simulation are copper smelting: C com \ξ ss \γ s \η dc \η wfgd \ξ es \ξ e \η e , Lead smelting: C com \η dc \η wfgd \η e , Zinc smelting: C com \η dc \η wfgd .

[0113] S3. Parameter estimation: Based on the collected copper / lead / zinc smelting data over the years, the estimated distribution of key parameters in the probability mass flow model is obtained using bootstrap random sampling simulation.

[0114] Furthermore, the parameter estimation process specifically includes:

[0115] Based on the collected copper / lead / zinc smelting data over the years, a data set of key parameters in the probabilistic mass flow model was obtained;

[0116] For each key parameter, its probability is obtained as follows:

[0117] Randomly sample B times with replacement from a key parameter data set, and the number of samples in each sampling is n;

[0118] Calculate the average of each sampling result;

[0119] A sampling distribution of the key parameter is formed according to the B average values ​​of the key parameter.

[0120] S4. Emission determination: Substitute the estimated distribution of key parameters into the probabilistic mass flow model to obtain the distribution of antimony emissions during the copper / lead / zinc smelting process.

[0121] The present invention proposes a method for determining antimony emissions from copper / lead / zinc smelting, which has the following advantages:

[0122] (1) The estimated distribution of key parameters in the probability mass flow model is obtained by random sampling simulation using the bootstrap method, removing the prior assumptions about the probability distribution form of the parameters, reducing the uncertainty of the calculation results, and making the calculation results more accurate;

[0123] (2) Replace the deterministic mass flow model with a probabilistic mass flow model to enhance the model's applicability and enable quantitative analysis of the impact of key parameters on the results;

[0124] (3) The mass flow model replaces the traditional emission factor method, and the estimation of heavy metal emissions from non-ferrous metal smelting is expanded to all stages of the entire process, making the flow and enrichment routes of target heavy metals clearer and more accurate.

[0125] The embodiment of the present invention further provides a system for determining antimony emissions from copper / lead / zinc smelting, comprising:

[0126] Data acquisition module, used to obtain historical copper / lead / zinc smelting data;

[0127] Model building module for constructing probabilistic mass flow models for the concentrate input, roasting / smelting, leaching / converting, and refining stages of copper / lead / zinc smelting processes;

[0128] The parameter estimation module is used to obtain the estimated values ​​of key parameters in the probability mass flow model using bootstrap random sampling simulation based on the collected copper / lead / zinc smelting data over the years;

[0129] The emission determination module is used to substitute the estimated values ​​of key parameters into the probabilistic mass flow model to obtain the distribution of antimony emissions in the copper / lead / zinc smelting process.

[0130] An embodiment of the present invention further provides an electronic terminal, including:

[0131] a memory having a computer program stored thereon;

[0132] A processor is used to load and execute the computer program to implement the method for determining antimony emissions from copper / lead / zinc smelting as described above.

[0133] An embodiment of the present invention further provides a computer-readable storage medium having a computer program stored thereon. When the computer program is executed by a processor, the method for determining antimony emissions from copper / lead / zinc smelting as described above is implemented.

[0134] The technical solution of the present invention is described in detail below with reference to a specific example.

[0135] Figure 3 The figure shows the probability distribution of antimony input into copper concentrate smelting in my country from 2000 to 2020; Figure 4 The probability distribution diagram of antimony input into lead smelting in my country from 2000 to 2020 is shown; Figure 5 Shown is the probability distribution map of the amount of antimony input into copper concentrate smelting in my country from 2000 to 2020. Figure 6 Shown are the estimated values ​​of antimony input into copper, lead and zinc concentrate smelting in my country from 2000 to 2020.

[0136] Figure 3-Figure 5 The simulated distribution result obtained according to formula (1) shows the amount of antimony input into copper, lead and zinc concentrate smelting in my country from 2000 to 2020. For the probability distribution results obtained by simulation, P50 is taken as the best estimate value for result analysis, as shown in the following example: Figure 6 As shown, from 2000 to 2020, the overall trend of antimony input for copper, lead and zinc smelting in my country was first increasing and then leveling off. This is because my country's economic construction developed rapidly from 2000 to 2015, and the amount of copper, lead and zinc smelting ore increased rapidly, resulting in a simultaneous increase in the amount of antimony input year after year, reaching a peak in 2015. Later, due to the increased attention to environmental protection, the amount of primary smelting ore decreased, and the amount of antimony input for smelting showed a gentle downward trend.

[0137] Figure 7 (a) shows that in the smelting stage of copper smelting, antimony mainly flows to copper matte (78.4%), followed by smelting slag (12.3%), and finally to smoke (4.3%); copper matte is the main raw material in the blowing stage, at this time antimony mainly flows to crude copper (49.2%) and blowing slag (39.4%); crude copper is the main raw material in the refining stage, at this time refined slag is the main enrichment product of antimony (74.1%). The above data show that antimony is enriched in the slag produced in each stage of the copper smelting process on the one hand, and is enriched in the intermediate product on the other hand, and then enters the next stage. The relevant smelting parameters show that the antimony content in the raw materials has a great influence on the production of refined copper in the copper smelting process. Therefore, controlling the antimony content of the intermediate product is crucial to improving production efficiency. At the same time Figure 8 (a) and (b) show the final destination of antimony in copper smelting. The data show that antimony production and emissions showed a clear upward trend from 2000 to 2020. Its final flow products include atmospheric emissions, sulfuric acid, dirty acid, desulfurization by-products, waste slag, and dust removal dust as recycled materials to continue to participate in the entire smelting process. Figure 8(b) shows that the antimony content in the waste slag produced by copper smelting accounts for 93.7% of the total output and 4.6% of the recycled materials.

[0138] Figure 7 Middle (b) shows that in the lead smelting stage, antimony is mainly concentrated in high-lead slag (76.3%) and primary crude lead (5.5%). Unlike copper smelting, high-lead slag is used as raw material for the blowing stage, and primary crude lead is used as part of the raw material for the refining stage; in the blowing stage, antimony is mainly concentrated in the secondary crude lead (87.3%), which enters the next stage as part of the refining raw material, followed by flowing into the blowing slag, accounting for 5.9%; the raw materials for the refining stage are primary crude lead and secondary crude lead, and almost all of the antimony flows into the refining slag. Combined Figure 8 Figures (c) and (d) show that the antimony content in the waste slag produced by lead smelting accounts for 84.7% of the total output, and the second largest amount is 10.9% which flows into the recycling material to participate in the smelting process.

[0139] Combine Figure 7 (c) and Figure 8 As shown in Figures (e) and (f), during the zinc smelting process, 35% of the antimony is leached with the roasted sand, while 65% is volatilized with the flue dust and discharged after APCD treatment. The antimony in the final waste slag accounts for 34.6% of the total antimony produced and discharged, while 44.4% of the antimony is recycled and continues to participate in the zinc smelting process. The reason why the antimony content in the recycled materials of zinc smelting is significantly higher than that of copper and lead smelting is that the antimony concentration in zinc smelting concentrate is much higher than that in copper and lead concentrates. Therefore, the antimony content in the flue dust captured by the dust removal equipment is higher, and this dust is recycled and re-enters the smelting process.

[0140] As a toxic metal and an important resource, antimony deserves attention for its pollution control and green recycling. According to the above analysis, during the copper, lead and zinc smelting process, a considerable amount of antimony flows into the waste slag produced during the smelting process. These waste slags are usually sent to other smelting and processing plants for secondary resource recovery, but relevant information usually does not emphasize the recovery of antimony resources. On the other hand, Figure 9 It shows the circulating amount of antimony in the copper, lead and zinc smelting process from 2000 to 2020. The antimony content in the circulating materials is also considerable. The circulation of antimony-containing materials will increase the antimony content in the raw materials, thereby affecting the overall metallurgical efficiency, which needs to be controlled. Figure 10 Shows the environmental emissions of antimony, combined with Figure 11 With the continuous iteration of APCD types, the antimony removal efficiency has increased significantly, and the antimony in atmospheric emissions has dropped significantly. It is more concentrated in the by-product dirty acid produced by flue gas scrubbing and demisters, and a small amount exists in the desulfurization by-products.

[0141] Figure 12The sensitivity analysis of the model's simulation parameters to antimony emissions shows that during the copper, lead, and zinc smelting stage, the antimony concentration in the concentrate has the greatest positive impact on the antimony content of various products, making controlling the inflow of raw antimony crucial to the entire smelting process. Furthermore, electrostatic precipitators (ESPs) have a major negative impact on antimony emissions in waste acid. This suggests that improving the efficiency of front-end dedusting equipment in the APCD system can significantly reduce waste acid production and emissions, lowering treatment costs and facilitating resource recovery.

[0142] It can be understood that the same or similar parts of the above embodiments can be referenced to each other, and the contents not described in detail in some embodiments can refer to the same or similar contents in other embodiments.

[0143] It should be understood that the functional unit modules in various embodiments of the present invention can be concentrated in one processing unit, or each unit module can exist physically separately, or two or more unit modules can be integrated into one unit module, and can be implemented in the form of hardware or software.

[0144] Those skilled in the art will appreciate that the embodiments of the present application can be provided as methods, systems, or computer program products. Therefore, the present application can adopt the form of a complete hardware embodiment, a complete software embodiment, or an embodiment in combination with software and hardware. Moreover, the present application can adopt the form of a computer program product implemented on one or more computer-usable storage media (including but not limited to magnetic disk storage, CD-ROM, optical storage, etc.) that contain computer-usable program code.

[0145] The present application is described with reference to the flowcharts and / or block diagrams of the methods, devices (systems), and computer program products according to the embodiments of the present application. It should be understood that each process and / or box in the flowchart and / or block diagram, as well as the combination of the processes and / or boxes in the flowchart and / or block diagram, can be implemented by computer program instructions. These computer program instructions can be provided to a processor of a general-purpose computer, a special-purpose computer, an embedded processor, or other programmable data processing device to produce a machine, so that the instructions executed by the processor of the computer or other programmable data processing device generate instructions for implementing the steps in the process. Figure 1 a process or multiple processes and / or boxes Figure 1 A device that provides the functions specified in a block or multiple blocks.

[0146] These computer program instructions may also be stored in a computer readable memory that can direct a computer or other programmable data processing device to work in a specific manner, so that the instructions stored in the computer readable memory produce an article of manufacture comprising an instruction device, which implements the process Figure 1 a process or multiple processes and / or boxes Figure 1The function specified in one or more boxes.

[0147] These computer program instructions can also be loaded onto a computer or other programmable data processing device so that a series of operational steps are executed on the computer or other programmable device to produce a computer-implemented process, thereby providing the instructions executed on the computer or other programmable device for implementing the process. Figure 1 a process or multiple processes and / or boxes Figure 1 A step that specifies a function in one or more boxes.

[0148] Although the embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and are not to be construed as limitations on the present invention. A person skilled in the art may change, modify, replace and modify the above embodiments within the scope of the present invention.

Claims

1. A method for determining antimony emissions from copper, lead or zinc smelting, characterized in that: The steps include: Data collection: Obtain historical copper, lead or zinc smelting data; Model building: Constructing a probabilistic mass flow model covering the concentrate input, roasting or smelting, leaching or converting, and refining stages of a copper, lead, or zinc smelting process; Parameter estimation: Based on the collected copper, lead or zinc smelting data over the years, bootstrap random sampling simulation is used to obtain the estimated distribution of key parameters in the probability mass flow model; Emission determination: Substituting the estimated distribution of key parameters into the probabilistic mass flow model, the distribution of antimony emissions from the copper, lead or zinc smelting process is obtained; In the data collection step, the historical copper, lead or zinc smelting data obtained specifically include: Domestic production, import and export volumes of copper, lead or zinc concentrates over the years; Antimony concentration in copper, lead or zinc concentrates; The distribution coefficient of antimony in flue gases and waste residues during the roasting or smelting, leaching or blowing and refining stages of copper, lead or zinc smelting; Types and percentages of air pollution control devices installed at various stages of copper, lead, or zinc smelting over the years; Antimony removal rate of air pollution control devices.

2. The method for determining antimony emissions from copper, lead or zinc smelting according to claim 1, characterized in that: The concentrate input stage model is expressed as follows: （1） Where, Q com Indicates the input of antimony from copper, lead or zinc concentrate smelting; C com Indicates the antimony concentration in copper, lead or zinc concentrates; M com Indicates the input of copper, lead or zinc concentrate over the years.

3. The method for determining antimony emissions from copper, lead or zinc smelting according to claim 1, characterized in that: The roasting or smelting stage model is expressed as follows: （2） （3） （4） （5） （6） Where, Q com Indicates the antimony input of copper, lead or zinc concentrate smelting; I ss Indicates the antimony content in copper smelting slag, high-lead slag, or zinc roasted sand; ξ ss represents the antimony slag phase distribution ratio during the smelting stage; GEs represents the atmospheric antimony emission during the smelting stage; γ s represents the antimony gas phase distribution rate during the smelting stage; θ m Indicates the combined utilization rate of air pollution control devices during the smelting stage; η m Indicates the antimony removal rate of the combination of air pollution control devices during the smelting stage; I wa Indicates the antimony content of the waste acid in the smelting stage; η dc Indicates the antimony removal rate of electrostatic precipitator + waste heat boiler equipment in the smelting stage; I sa Indicates the antimony content of sulfuric acid; η fgs+esd Indicates the antimony removal rate of the flue gas scrubbing equipment during the smelting stage; η sa Indicates the antimony removal rate of the acid-making equipment; I Sfgd Indicates the antimony content of desulfurization by-products; η fgd Indicates the antimony removal rate of the desulfurization equipment.

4. The method for determining antimony emissions from copper, lead or zinc smelting according to claim 1, characterized in that: The leaching or blowing stage model is expressed as follows: （7） （8） （9） （10） （11） （12） Where, Q com Indicates the input amount of antimony in copper, lead or zinc concentrate smelting; Q e represents the antimony input in the copper or lead smelting stage, Q in formula (7) e represents the antimony input in the copper blowing stage, Q in formula (8) e represents the antimony input in the lead converting stage; ξ ss represents the antimony slag phase distribution ratio during the smelting stage; γ s Indicates the antimony gas phase distribution rate during the smelting stage; I es Indicates the antimony content in blowing slag; ξ es represents the antimony slag phase distribution ratio during the blowing stage; GEe represents the atmospheric antimony emission during the blowing stage; ξ e represents the antimony gas phase distribution rate during the blowing stage; η e Indicates the antimony removal rate of the combination of air pollution control devices in the blowing stage; I ex Indicates the antimony content of the final products in the zinc smelting leaching + refining stage; θ x Indicates the distribution rate of different products in zinc smelting.

5. The method for determining antimony emissions from copper, lead or zinc smelting according to claim 1, characterized in that: The refinement stage model is represented as follows: （13） （14） （15） （16） （17） Where, Q com Indicates the input amount of antimony in copper or lead concentrate smelting; Q r represents the antimony input in the copper or lead refining stage, Q in formula (13) r represents the antimony input in the copper refining stage, Q in formula (14) r represents the antimony input in the lead refining stage; ξ ss represents the antimony slag phase distribution ratio in the smelting stage; ξ es represents the antimony slag phase distribution ratio during the blowing stage; γ s represents the antimony gas phase distribution rate during the smelting stage; ξ e Indicates the antimony gas phase distribution rate during the blowing stage; FI r Indicates the antimony content of refined products; γ r represents the antimony gas phase distribution rate during the refining stage; ξ r represents the antimony slag phase distribution ratio during the refining stage; GEr represents the atmospheric antimony emission during the refining stage; η r Indicates the antimony removal rate of the combination of air pollution control device types in the refining stage; OD r Indicates the antimony content of refining by-products.

6. The method for determining antimony emissions from copper, lead or zinc smelting according to claim 1, characterized in that: The parameter estimation process specifically includes: Based on the collected copper, lead or zinc smelting data over the years, a data set of key parameters in the probability mass flow model is obtained; For each key parameter, its probability is obtained as follows: Random sampling is performed with replacement B times from a key parameter data set, with the number of samples in each sampling being n; Calculate the average of each sampling result; An estimated distribution of the key parameter is formed based on the B average values ​​of the key parameter.

7. A system for determining antimony emissions from copper, lead or zinc smelting, characterized in that: The method for determining antimony emissions from copper, lead or zinc smelting as claimed in claim 1 comprises: Data acquisition module, used to obtain historical copper, lead or zinc smelting data; A model building module for building probabilistic mass flow models covering the concentrate input, roasting or smelting, leaching or converting, and refining stages of a copper, lead, or zinc smelting process; The parameter estimation module is used to obtain the estimated values ​​of key parameters in the probability mass flow model using bootstrap random sampling simulation based on the collected historical copper, lead or zinc smelting data; The emission determination module is used to substitute the estimated values ​​of key parameters into the probability mass flow model to obtain the distribution of antimony emissions in the copper, lead or zinc smelting process.

8. An electronic terminal, characterized in that: include: a memory having a computer program stored thereon; A processor, configured to load and execute the computer program to implement the method for determining antimony emissions from copper, lead or zinc smelting as claimed in any one of claims 1 to 6.

9. A computer-readable storage medium having a computer program stored thereon, characterized in that: When the computer program is executed by a processor, the method for determining antimony emissions from copper, lead or zinc smelting according to any one of claims 1 to 6 is implemented.

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