阅读说明：本技术 用于处理砷渣的稳定化药剂的设计方法及处理砷渣的方法 (Design method of stabilizing agent for treating arsenic slag and method for treating arsenic slag ) 是由 余志元 李二平 杨厅 李瑾 戴欣 于 2021-08-23 设计创作，主要内容包括：本发明实施例公开了用于处理砷渣的稳定化药剂的设计方法及处理砷渣的方法,用于处理砷渣的稳定化药剂的设计方法包括：获取砷渣的基本参数；根据所述砷渣的基本参数,确定稳定化药剂的混料组分；利用不同配比的混料组分配制的稳定化药剂,对所述砷渣进行多次稳定化实验,得到所述砷渣中砷的浸出浓度；根据所述砷的浸出浓度、各所述混料组分的成本及各所述混料组分的配比,建立数学模型；对所述数学模型进行最优求解,得到最优的稳定化药剂。该方法利用混料设计成功开发出应用于高浓度砷渣稳定化的既高效又经济的稳定化药剂,克服了现有技术人员单纯依靠简单主观配比设计来确定配方的经验性缺陷,使稳定化药剂的配方设计更具科学性、合理性。(The embodiment of the invention discloses a design method of a stabilizing agent for treating arsenic slag and a method for treating the arsenic slag, wherein the design method of the stabilizing agent for treating the arsenic slag comprises the following steps: acquiring basic parameters of arsenic slag; determining the mixing components of the stabilizing agent according to the basic parameters of the arsenic slag; carrying out multiple stabilization experiments on the arsenic slag by using stabilizing agents prepared from mixing components with different proportions to obtain the leaching concentration of arsenic in the arsenic slag; establishing a mathematical model according to the leaching concentration of the arsenic, the cost of each mixed material component and the proportion of each mixed material component; and optimally solving the mathematical model to obtain the optimal stabilizing medicament. The method successfully develops the efficient and economic stabilizing agent applied to stabilizing the high-concentration arsenic slag by using the mixed material design, overcomes the empirical defect that the prior art personnel determine the formula by simply depending on simple subjective proportioning design, and ensures that the formula design of the stabilizing agent is more scientific and reasonable.)

1. A method for designing a stabilizing agent for treating arsenic slag, the method comprising:

acquiring basic parameters of arsenic slag;

determining the mixing components of a stabilizing agent according to the basic parameters of the arsenic slag, wherein the stabilizing agent is used for stabilizing the arsenic slag;

carrying out multiple stabilization experiments on the arsenic slag by using stabilizing agents prepared from mixing components with different proportions to obtain the leaching concentration of arsenic in the arsenic slag;

establishing a mathematical model according to the leaching concentration of the arsenic, the cost of each mixed material component and the proportion of each mixed material component;

and optimally solving the mathematical model to obtain the optimal stabilizing medicament.

2. The design method of stabilizing agent for treating arsenic slag as claimed in claim 1, wherein the basic parameters of arsenic slag include main occurrence state of arsenic, leaching toxicity of arsenic slag, pH value, arsenic content;

the step of obtaining the basic parameters of the arsenic slag comprises the following steps:

and carrying out X-ray photoelectron spectroscopy analysis and X-ray fluorescence spectroscopy analysis on the arsenic slag to obtain the main occurrence state of the arsenic, leaching toxicity of the arsenic slag, the pH value and the arsenic content.

3. The method of claim 1, wherein the mixture composition of the stabilizing agent comprises a main component and an auxiliary component;

the main component comprises at least one of ferrous sulfate monohydrate, ferrous sulfate tetrahydrate and ferrous sulfate heptahydrate, and the auxiliary component comprises at least one of reduced iron powder, manganese dioxide and electrolytic manganese slag.

4. The method for designing the stabilizing agent for treating the arsenic slag as claimed in claim 1, wherein the step of performing a plurality of stabilizing experiments on the arsenic slag by using the stabilizing agent prepared from mixing components with different proportions to obtain the leaching concentration of the arsenic in the arsenic slag comprises:

according to the mixing components of the stabilizing agent, the mixture design method is utilized to design the mixture ratio of each mixing component, so that a plurality of mixing components with different mixture ratios are obtained;

preparing according to a plurality of mixing components with different proportions to obtain a plurality of different stabilizing agents;

and carrying out multiple stabilization experiments on the arsenic slag by using a plurality of different stabilizing agents to obtain a plurality of leaching concentrations of arsenic in the arsenic slag.

5. The method for designing a stabilizing agent for arsenic slag according to claim 4, wherein the step of establishing a mathematical model based on the leaching concentration of arsenic, the cost of each of the mixed components and the ratio of each of the mixed components comprises:

establishing a regression model between the leaching concentration of arsenic in the arsenic slag and the mixture ratio of each mixture component according to the leaching concentration of arsenic in the arsenic slag obtained by the stabilization experiments for a plurality of times and the mixture ratio of each mixture component in the corresponding stabilizing agent;

and establishing a linear model between the cost of the stabilizing agent and the proportion of each mixing component according to the cost of each mixing component.

6. The method of claim 5, wherein the regression equation of the regression model is as follows:

wherein, Y_iIs the leaching concentration of arsenic, X₁、X₂…X_i、X_j、X_k…X_pIs the proportion of each mixing component, a_i、a_ij、a_ijk、a_12…pIs a regression model coefficient, and p is the number of compounding components.

7. The method of claim 5, wherein the step of optimally solving the mathematical model to obtain an optimal stabilizing agent comprises:

the regression model and the linear model are connected in parallel;

when the leaching concentration of arsenic in the arsenic slag is minimum and the cost of the stabilizing agent is minimum, the proportion of each mixed material component in the stabilizing agent is calculated;

and preparing according to the proportion of each mixed material component in the stabilizing agent to obtain the optimal stabilizing agent.

8. A method for treating arsenic slag, which comprises applying the stabilizing agent designed by the method for designing a stabilizing agent for treating arsenic slag according to any one of claims 1 to 6, wherein the method comprises:

crushing the arsenic slag to the particle size of less than or equal to 0.5 cm, and adding the crushed arsenic slag into a reaction container;

adding the stabilizing agent into the reaction vessel, and stirring for 10-30 minutes;

adding acid liquor into the reaction container, stirring, adding water, adjusting the pH value in the reaction container to 7.0-8.0, and stirring for 10-30 minutes;

and (3) maintaining the reaction vessel at 5-35 ℃ for 2-7 days.

9. The method of treating arsenic slag as claimed in claim 8, wherein the stabilizing agent is present in an amount of 20 to 35% by mass of the arsenic slag.

10. The method for treating arsenic slag as claimed in claim 8, wherein the acid solution comprises any one of sulfuric acid, nitric acid and hydrochloric acid, and the amount of water is controlled so that the liquid-solid ratio in the reaction vessel is in the range of 2-5: 10, respectively.

Technical Field

The invention relates to the field of data processing, in particular to a design method of a stabilizing agent for processing arsenic slag and a method for processing the arsenic slag.

Background

Arsenic (Arsenic, element symbol As) is a metal species often associated with non-ferrous metals (e.g., copper, lead, zinc, antimony, gold, etc.), and Arsenic slag is mainly derived from the non-ferrous metals industry. The wet treatment is a main way for producing arsenic slag, and a lime neutralization method or a lime iron salt method for treating waste acid and waste water containing arsenic can produce a large amount of alkaline arsenate arsenic slag. In addition, alkaline arsenic residues such as neutralization residues, primary arsenic alkali residues and secondary arsenic alkali residues are also generated in the coarse antimony refining dearsenification process. The stability of the alkaline arsenic slag in the environment is poor, the alkaline arsenic slag generally shows higher As leaching concentration (>100mg/L), the randomly piled alkaline arsenic slag has great harm to the storage surrounding environment and human health, and safe and harmless treatment is urgently needed.

The arsenic slag is stabilized, namely, the arsenic and other heavy metals in the arsenic slag are converted into stable forms or fixed in a compact inclusion with certain strength through physical, chemical or synergistic action of the arsenic slag and the heavy metals, so that the mobility of the arsenic and other heavy metals is reduced, and the pollution risk of the arsenic slag to the environment is reduced. At present, aiming at the stabilization treatment of high-concentration arsenic slag, the adopted stabilizing additives mainly comprise chemical stabilizers such as ferrous salt, ferric salt, calcium salt and sulfide, and curing gelling agents such as cement, fly ash, blast furnace slag and smelting water-quenched slag. Accordingly, arsenic slag stabilization is classified into mineralization stabilization, gelation solidification stabilization, and both combined stabilization. Compared with the latter two, the mineralization stabilization phase has the advantages of small dosage of medicament, small weight gain/capacity increase ratio, good treatment effect and the like, and becomes a preferred process for stabilizing the high-concentration arsenic slag.

The key of mineralization stabilization is stabilization of the medicament, and due to the synergistic effect among multi-component medicaments, the development of composite stabilization medicaments becomes a trend. The currently published patents on the mineralization and stabilization of arsenic slag mainly provide an arsenic slag stabilizing medicament and a stabilizing treatment method, and lack a specific and mature stabilizing medicament formula design method. The mature stabilizing medicament formula design method is the key for influencing the stabilizing performance of the designed stabilizing medicament and has important guiding significance for the actual application of the stabilizing medicament.

Disclosure of Invention

In view of the above problems, the present invention provides a method for designing a stabilizing agent for treating arsenic slag and a method for treating arsenic slag. The specific scheme is as follows:

in a first aspect, the disclosed embodiments provide a method for designing a stabilizing agent for treating arsenic slag, the method comprising:

acquiring basic parameters of arsenic slag;

determining the mixing components of a stabilizing agent according to the basic parameters of the arsenic slag, wherein the stabilizing agent is used for stabilizing the arsenic slag;

carrying out multiple stabilization experiments on the arsenic slag by using stabilizing agents prepared from mixing components with different proportions to obtain the leaching concentration of arsenic in the arsenic slag;

establishing a mathematical model according to the leaching concentration of the arsenic, the cost of each mixed material component and the proportion of each mixed material component;

and optimally solving the mathematical model to obtain the optimal stabilizing medicament.

According to a specific embodiment of the present disclosure, the basic parameters of the arsenic slag include the main occurrence state of arsenic, leaching toxicity of arsenic slag, pH value, and arsenic content;

the step of obtaining the basic parameters of the arsenic slag comprises the following steps:

and carrying out X-ray photoelectron spectroscopy analysis and X-ray fluorescence spectroscopy analysis on the arsenic slag to obtain the main occurrence state of the arsenic, leaching toxicity of the arsenic slag, the pH value and the arsenic content.

According to a specific embodiment of the present disclosure, the compounding ingredients of the stabilizing agent include a main ingredient and an auxiliary ingredient;

the main component comprises at least one of ferrous sulfate monohydrate, ferrous sulfate tetrahydrate and ferrous sulfate heptahydrate, and the auxiliary component comprises at least one of reduced iron powder, manganese dioxide and electrolytic manganese slag.

According to a specific embodiment of the present disclosure, the step of performing multiple stabilization experiments on the arsenic slag by using stabilizing agents prepared from mixing components with different ratios to obtain the leaching concentration of arsenic in the arsenic slag includes:

according to the mixing components of the stabilizing agent, the mixture design method is utilized to design the mixture ratio of each mixing component, so that a plurality of mixing components with different mixture ratios are obtained;

preparing according to a plurality of mixing components with different proportions to obtain a plurality of different stabilizing agents;

and carrying out multiple stabilization experiments on the arsenic slag by using a plurality of different stabilizing agents to obtain a plurality of leaching concentrations of arsenic in the arsenic slag.

According to a specific embodiment of the present disclosure, the step of establishing a mathematical model according to the leaching concentration of arsenic, the cost of each of the mixed components, and the ratio of each of the mixed components includes:

establishing a regression model between the leaching concentration of arsenic in the arsenic slag and the mixture ratio of each mixture component according to the leaching concentration of arsenic in the arsenic slag obtained by the stabilization experiments for a plurality of times and the mixture ratio of each mixture component in the corresponding stabilizing agent;

and establishing a linear model between the cost of the stabilizing agent and the proportion of each mixing component according to the cost of each mixing component.

According to a specific embodiment of the present disclosure, the regression equation of the regression model is:

wherein, Y_iIs the leaching concentration of arsenic, X₁、X₂…X_i、X_j、X_k…X_pIs the proportion of each mixing component, a_i、a_ij、a_ijk、a_12…pIs a regression model coefficient, and p is the number of compounding components.

According to a specific embodiment of the present disclosure, the step of optimally solving the mathematical model to obtain an optimal stabilizing agent includes:

the regression model and the linear model are connected in parallel;

when the leaching concentration of arsenic in the arsenic slag is minimum and the cost of the stabilizing agent is minimum, the proportion of each mixed material component in the stabilizing agent is calculated;

and preparing according to the proportion of each mixed material component in the stabilizing agent to obtain the optimal stabilizing agent.

In a second aspect, the present disclosure also provides a method for treating arsenic slag, which applies the stabilizing agent designed by the method for designing a stabilizing agent for treating arsenic slag according to any one of the first aspect, and the method includes:

crushing the arsenic slag to the particle size of less than or equal to 0.5 cm, and adding the crushed arsenic slag into a reaction container;

adding the stabilizing agent into the reaction vessel, and stirring for 10 to 30 minutes;

adding acid liquor into the reaction container, stirring, adding water, adjusting the pH value in the reaction container to 7.0-8.0, and stirring for 10-30 minutes;

and (3) maintaining the reaction vessel at 5-35 ℃ for 2-7 days.

According to an embodiment of the present disclosure, the stabilizing agent is 20% to 35% by mass of the arsenic slag.

According to a specific embodiment of the present disclosure, the acid solution includes any one of sulfuric acid, nitric acid, and hydrochloric acid, and the amount of water is controlled such that a liquid-solid ratio in the reaction container is 2-5: 10, respectively.

According to the design method of the stabilizing agent for treating the arsenic slag and the method for treating the arsenic slag, which are provided by the embodiment of the disclosure, the high-efficiency and economical stabilizing agent applied to stabilizing the high-concentration arsenic slag is successfully developed by using the mixed material design, the empirical defect that a formula is determined by a person in the prior art by simply depending on a simple subjective proportioning design is overcome, and the formula design of the stabilizing agent is more scientific and reasonable; the stabilizing agent is matched with acid to synergistically stabilize the high-concentration arsenic slag, the adding amount of the agent is small, the acid leaching concentration of the treated arsenic slag is lower than 1.2mg/L, and the pH of the water leaching leachate is between 7.0 and 12.0, so that the requirements specified in the hazardous waste landfill pollution control standard (GB 18598-; meanwhile, the treatment process is simple, the operability is strong, the arsenic slag treatment cost is low, and the engineering application is easy to realize.

Drawings

In order to more clearly illustrate the technical solution of the present invention, the drawings required to be used in the embodiments will be briefly described below, and it should be understood that the following drawings only illustrate some embodiments of the present invention, and therefore should not be considered as limiting the scope of the present invention. Like components are numbered similarly in the various figures.

FIG. 1 is a schematic flow chart illustrating a method for designing a stabilizing agent for treating arsenic slag according to an embodiment of the disclosure;

FIG. 2 shows an As3d XPS spectrum of a sample of calcium arsenic slag from a design method of a stabilizing agent for treating arsenic slag according to an embodiment of the present disclosure;

FIG. 3 illustrates an overall plot diagram based on a three-component simplex gravity-center blend design for a design method of a stabilizing agent for treating arsenic slag provided by an embodiment of the present disclosure;

FIG. 4 is a schematic flow chart illustrating a method for treating arsenic slag provided by the embodiment of the disclosure.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments.

The components of embodiments of the present invention generally described and illustrated in the figures herein may be arranged and designed in a wide variety of different configurations. Thus, the following detailed description of the embodiments of the present invention, presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without making any creative effort, shall fall within the protection scope of the present invention.

Hereinafter, the terms "including", "having", and their derivatives, which may be used in various embodiments of the present invention, are only intended to indicate specific features, numbers, steps, operations, elements, components, or combinations of the foregoing, and should not be construed as first excluding the existence of, or adding to, one or more other features, numbers, steps, operations, elements, components, or combinations of the foregoing.

Furthermore, the terms "first," "second," "third," and the like are used solely to distinguish one from another and are not to be construed as indicating or implying relative importance.

Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which various embodiments of the present invention belong. The terms (such as those defined in commonly used dictionaries) should be interpreted as having a meaning that is consistent with their contextual meaning in the relevant art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein in various embodiments of the present invention.

Example 1

Fig. 1 is a schematic flow chart illustrating a method for designing a stabilizing agent for treating arsenic slag according to an embodiment of the present disclosure. As shown in fig. 1, the method includes:

s101, obtaining basic parameters of arsenic slag;

specifically, the arsenic slag treated in the embodiment of the disclosure refers to alkaline arsenic slag with an As content of more than 1% and an As leaching concentration of more than 100mg/L, and includes arsenic-calcium slag, arsenic-alkaline slag leaching slag, and the like. The basic parameters of the arsenic slag were obtained by XRF (X-Ray Fluorescence Spectroscopy) analysis and XPS (X-Ray Photoelectron Spectroscopy). The basic parameters in the arsenic slag mainly include main occurrence state, leaching toxicity, pH, arsenic content and the like of arsenic.

S102, determining mixing components of a stabilizing agent according to basic parameters of the arsenic slag, wherein the stabilizing agent is used for stabilizing the arsenic slag;

in specific implementation, the stabilizing agent is mainly used for oxidizing As (III) in the arsenic slag into As (V) and then generating a stable complex to reduce the leaching toxicity of the arsenic slag. The main component of the stabilizing agent is generally selected from cheap and common ferrous salts, such as ferrous sulfate monohydrate, ferrous sulfate tetrahydrate, ferrous sulfate heptahydrate and the like; the auxiliary component is at least one of reduced iron powder, manganese dioxide and electrolytic manganese slag. Generally, the method is considered in various aspects such as the occurrence state of arsenic in the arsenic slag to be stabilized, the comprehensive cost of the stabilizer, the dosage of the stabilizer, the synergistic effect among components and the like, and can be further verified and screened through a stabilization experiment.

S103, carrying out multiple stabilization experiments on the arsenic slag by using stabilizing agents prepared from mixing components with different proportions to obtain the leaching concentration of arsenic in the arsenic slag;

specifically, based on the selected mixing components in S102, a formula design method is adopted for formula design, different formulas of the mixing component distribution ratios are obtained through simple physical mixing, and the leaching concentration of arsenic in the arsenic slag is obtained according to a batch stabilization experiment of the high-concentration arsenic slag; and the proportions of the different mixture components and the arsenic leaching concentration in each test are recorded.

S104, establishing a mathematical model according to the leaching concentration of the arsenic, the cost of each mixed material component and the proportion of each mixed material component;

in specific implementation, the As leaching concentration is set As response Y1, the component proportion is X1, X2, X3, … and Xi, a regression model is established between Y1 and X1, X2, X3, … and Xi through a Scheffe polynomial function, and then a linear model is established between Y2 and X1, X2, X3, … and Xi of the stabilizing agent cost.

And S105, carrying out optimal solution on the mathematical model to obtain an optimal stabilizing medicament.

Specifically, the regression equation is planned and solved by minimizing the As leaching concentration and the cost of the stabilizing agent, and the optimal stabilizing agent which is efficient and economical is determined by jointly optimizing the acid leaching As leaching concentration and the cost of the stabilizing agent.

Further, after the optimal stabilizing agent is determined, a verification experiment should be performed, not only for the regression model, but also for the obtained optimal stabilizing agent. Specifically, the stabilizing agent obtained by compounding under the optimal formula is used for stabilizing arsenic slag, and the reasonability and effectiveness of a regression model and the optimal formula are verified according to the leaching experiment result.

The method successfully develops the efficient and economic stabilizing agent applied to stabilizing the high-concentration arsenic slag by using the mixed material design, overcomes the empirical defect that the prior art personnel determine the formula by simply depending on simple subjective proportioning design, and ensures that the formula design method of the stabilizing agent is more scientific and reasonable.

According to a specific embodiment of the present disclosure, the basic parameters of the arsenic slag include the main occurrence state of arsenic, leaching toxicity of arsenic slag, pH value, and arsenic content;

in specific implementation, the main occurrence state of arsenic in the arsenic slag is the key influencing the stabilizing effect, the As (III) is generally difficult to stabilize, and the main component in the stabilizing agent is determined according to the main occurrence state of arsenic; the dosage of the stabilizing agent can be determined by parameters of leaching toxicity, pH value and arsenic content of the arsenic slag.

The step of obtaining the basic parameters of the arsenic slag comprises the following steps:

and carrying out X-ray photoelectron spectroscopy analysis and X-ray fluorescence spectroscopy analysis on the arsenic slag to obtain the main occurrence state of the arsenic, leaching toxicity of the arsenic slag, the pH value and the arsenic content.

Specifically, XRF analysis is carried out on the arsenic slag to obtain the composition of each element in the arsenic slag, so that the proportion of the mixed material in the stabilizing agent is more reasonably selected; XPS analysis can obtain the proportion of each occurrence state of arsenic in the arsenic slag, thereby more reasonably selecting the mixed material components in the stabilizing agent.

According to a specific embodiment of the present disclosure, the compounding ingredients of the stabilizing agent include a main ingredient and an auxiliary ingredient;

the main component comprises at least one of ferrous sulfate monohydrate, ferrous sulfate tetrahydrate and ferrous sulfate heptahydrate, and the auxiliary component comprises at least one of reduced iron powder, manganese dioxide and electrolytic manganese slag.

Specifically, the main component of the stabilizing agent is selected from cheap and common ferrous salts, such as ferrous sulfate monohydrate, ferrous sulfate tetrahydrate, ferrous sulfate heptahydrate and the like. The auxiliary component is selected from at least one of reduced iron powder, manganese dioxide and electrolytic manganese slag, and is generally considered in various aspects such as the occurrence state of arsenic in arsenic slag to be stabilized, the comprehensive cost of stabilizing agents, the dosage of the stabilizing agents, the synergistic effect among components and the like, and can be further verified and screened through stabilizing experiments. The cheap and efficient ferrous sulfate is widely applied to the stabilization of arsenic in the arsenic slag; the iron content of the reduced iron powder of unit mass is several times of that of most common iron salts, so that the reduced iron powder is more suitable for providing Fe in the long run and can bring the great advantage of low capacity-increasing ratio for the stabilization of the high-concentration arsenic slag; the manganese dioxide has good synergistic effect with iron-containing substances in the aspect of arsenic stabilization, and the excellent oxidation performance of the manganese dioxide can greatly improve the stabilization performance of the composite stabilization agent.

According to a specific embodiment of the present disclosure, the step of performing multiple stabilization experiments on the arsenic slag by using stabilizing agents prepared from mixing components with different ratios to obtain the leaching concentration of arsenic in the arsenic slag includes:

according to the mixing components of the stabilizing agent, the mixture design method is utilized to design the mixture ratio of each mixing component, so that a plurality of mixing components with different mixture ratios are obtained;

in specific implementation, in a specific embodiment, a simplex gravity center mixing formula design method with upper and lower boundary constraints is adopted for developing the stabilizing medicine. When the mixing design is carried out, the dosage proportion of the main components is more than that of other components; meanwhile, the sum of the mixture ratio of each mixing component is 1.

Preparing according to a plurality of mixing components with different proportions to obtain a plurality of different stabilizing agents;

specifically, different stabilizing agents are prepared according to different mixing component proportion formulas. In the laboratory where stabilization is performed, the amounts of different stabilizing agents should be the same.

And carrying out multiple stabilization experiments on the arsenic slag by using a plurality of different stabilizing agents to obtain a plurality of leaching concentrations of arsenic in the arsenic slag.

In specific implementation, a certain amount of arsenic slag is taken and divided into a plurality of parts with the same mass, and different stabilizing agents with the same mass are added into each part; and carrying out a stabilization experiment to obtain the leaching concentration of arsenic in the arsenic-free slag. The mixture ratio of the mixed components in each stabilizing agent is recorded, and the corresponding arsenic leaching concentration is recorded at the same time.

According to a specific embodiment of the present disclosure, the step of establishing a mathematical model according to the leaching concentration of arsenic, the cost of each of the mixed components, and the ratio of each of the mixed components includes:

establishing a regression model between the leaching concentration of arsenic in the arsenic slag and the mixture ratio of each mixture component according to the leaching concentration of arsenic in the arsenic slag obtained by the stabilization experiments for a plurality of times and the mixture ratio of each mixture component in the corresponding stabilizing agent;

specifically, assuming that the leaching concentration of As is response Y1, the component ratios are X1, X2, X3, … and Xi, a regression model is established between Y1 and X1, X2, X3, … and Xi through a Scheffe polynomial function, and constraint conditions are imposed on each mixed component, wherein the constraint conditions are X1+ X2+ … + Xi ═ 1.

And establishing a linear model between the cost of the stabilizing agent and the proportion of each mixing component according to the cost of each mixing component.

In specific implementation, a linear model is established between the monovalent stabilizing agent cost Y2 of each mixing material component and X1, X2, X3, … and Xi.

According to a specific embodiment of the present disclosure, the regression equation of the regression model is:

wherein, Y_iIs the leaching concentration of arsenic, X₁、X₂…X_i、X_j、X_k…X_pIs the proportion of each mixing component, a_i、a_ij、a_ijk、a_12…pIs a regression model coefficient, and p is the number of compounding components.

Specifically, a_iIs a linear mixed system regression model coefficient, a_ijIs a coefficient of a regression model of a binary mixed system_ijkIs a coefficient of a regression model of a ternary mixed system_12…pIs a regression model coefficient of a p-element mixed system.

According to a specific embodiment of the present disclosure, the step of optimally solving the mathematical model to obtain an optimal stabilizing agent includes:

the regression model and the linear model are connected in parallel;

in specific implementation, a regression equation in the regression model and a linear equation in the linear model are combined.

When the leaching concentration of arsenic in the arsenic slag is minimum and the cost of the stabilizing agent is minimum, the proportion of each mixed material component in the stabilizing agent is calculated;

specifically, the regression equation and the linear equation that are simultaneously solved are optimally solved to obtain the values of X1, X2, X3, …, and Xi when Y1 and Y2 simultaneously obtain the minimum value. The values of X1, X2, X3, … and Xi are the mixture ratio of the mixture components.

And preparing according to the proportion of each mixed material component in the stabilizing agent to obtain the optimal stabilizing agent.

In one embodiment, the acidic wastewater treatment product of antimony smelter, arsenic-calcium slag, is the object of study. The main occurrence state of arsenic in arsenic slag is the key to influence the stabilization effect, and the stabilization of As (III) is generally difficult to be performed by As (V). As shown in tables 1, 2 and 2, As in the calcium arsenic slag is mainly As (iii), and therefore, the oxidation performance of the stabilizer is an important factor affecting the stabilization of the calcium arsenic slag. Based on the principle of medicament development with low price, high efficiency and small dosage, cheap and high-efficiency ferrous sulfate monohydrate (FeSO 4. H2O) is selected As a main component, and reduced iron powder (ZVI) with high iron content and capable of greatly reducing dosage and manganese dioxide (MnO2) with oxidizability and adsorbability to As are selected As auxiliary components for compounding. The stabilizing effect of stabilizing agents with different formulas on arsenic-calcium slag is examined through stabilizing experiments.

TABLE 1 elemental composition of arsenic calcium slag (XRF analysis)

TABLE 2 basic physicochemical characteristics of arsenic-calcium slag

The stabilization test method is as follows: 100g of arsenic-calcium slag is taken, 30g of composite agent is uniformly added according to the proportion of 30 wt%, the mixture is solidified and uniformly mixed, then 6mL of concentrated sulfuric acid with the mass fraction of 98% is added to adjust the pH value, 50mL of water is added, the mixture is fully stirred for 5min, finally the mixture is placed in a ventilated place for natural curing for 7d, and the leaching concentration of As is measured by adopting a leaching toxicity test-sulfuric acid-nitric acid method.

Mathematical modeling and determination of stabilized pharmaceutical formulations is as follows: the medicament is developed by adopting a simplex gravity center mixing formula design method with upper and lower boundary constraints. In view of the relatively low cost and good stabilization effect of FeSO 4. H2O, FeSO 4. H2O should be used as the main component in an amount larger than that of the other components. Therefore, the restraint conditions of each component are respectively 40 percent to 80 percent of X1, 10 percent to 50 percent of X2 and 10 percent to 50 percent of X3. The point distribution Design formula is obtained according to Design Expert 10.0 data processing software or Minitab statistical software, the component proportions are respectively X1, X2 and X3, and the constraint condition is X1+ X2+ X3 is 1. The stabilization experiment was carried out according to the given protocol, and the As leaching concentration after 7d of curing was determined As the response value Y1, and the agent cost As the response value Y2. Wherein the price of FeSO4 & H2O is 700 yuan/ton, the price of reduced iron powder is 4000 yuan/ton, and the price of MnO2 is 800 yuan/ton. The polynomial model of the compounding design is represented by the following equation:

by establishing a mathematical model and utilizing an intuitive analysis method and a planning analysis method, the optimal formula for efficiently stabilizing the arsenic-calcium slag is determined.

As shown in table 3 and fig. 3, visual analysis shows that when X1 is 0.666667, X2 is 0.166667, and X3 is 0.166667 in the composition design point A8, the minimum As leaching concentration response value Y1 is 0.06 mg/L. Polynomial fitting is carried out on the experimental data by using Design Expert data processing software or Minitab statistical software, and the obtained final fitting equation is as follows:

Y1＝3.23725*X1+10.50807*X2+13.93153*X3-21.20828*X1*X2-27.34024*X1*X3-27.39024*X2*X3；

Y2＝700*X1+4000*X2+800*X3。

table 3 mixing design layout and corresponding response values

As shown in table 4, it is reasonable to predict the sum of squares R2-0.8804, adjust the sum of squares R2-0.9378, and make the difference between the two less than 0.2; and analysis of variance showed p <0.0001, much less than 0.05, indicating that the relationship between the variables of the regression equation is significant.

TABLE 4 response Y1(As leach concentration) ANOVA TABLE

And (3) planning and solving a regression equation by minimizing the As leaching concentration and the stabilizing agent cost, wherein when X1 is 0.634, X2 is 0.104 and X3 is 0.262, the As leaching concentration and the agent cost are minimum values, namely Y1 is 0.108mg/L and Y2 is 1069.957 yuan/ton respectively.

And (3) verifying the formula: compounding the medicament according to the optimal formula obtained in the last step, and verifying the reasonability of the optimal formula through a stabilization experiment and a leaching test. The results show that the As leaching concentration (M1-0.13 mg/L and M2-0.15 mg/L) in two groups of experimental data is in good agreement with the predicted value, and the formula obtained by optimization is proved to be reasonable in design. By reducing the addition amount (20 percent and 25 percent) of the compound medicament, the dosage of the stabilizing medicament can be further reduced to 25 percent under the condition of being lower than the control limit value of 1.2mg/L in the hazardous waste landfill pollution control standard (GB 18598-2019), and the leaching concentration of As is 0.65 mg/L.

In the embodiment, on the basis of the optimal formula obtained in the embodiment, the electrolytic manganese slag is adopted to replace the component MnO2, the composition of each element in the electrolytic manganese slag is shown in Table 5, the replacement proportion is respectively 0, 25%, 50%, 75% and 100%, and the stabilized object is the acidic wastewater treatment product of certain antimony smelting plant, namely the # arsenic-calcium slag.

TABLE 5 electrolytic manganese slag elemental composition (XRF analysis)

Stabilization test method: 100g of arsenic-calcium slag is taken, 30g of compound medicament is added, the mixture is solidified and uniformly mixed, then 6mL of concentrated sulfuric acid with the mass fraction of 98% is added to adjust the pH value, 50mL of water is added, the mixture is fully stirred for 10min, finally the mixture is placed in a ventilated place for natural curing for 7d, the leaching concentration of As is measured by adopting a leaching toxicity test-sulfuric acid-nitric acid method, and the stabilization experiment result is shown in Table 6.

TABLE 6 stabilization test results

The optimal formula obtained by the embodiment takes the residue 2# leaching residue obtained after the secondary arsenic alkaline residue water leaching of certain antimony smelting plant as a research object, and the element composition and the basic physicochemical characteristics of the 2# leaching residue are shown in the table 7 and

shown in Table 8.

TABLE 72 # Leaching slag elemental composition (XRF analysis)

TABLE 82 basic physicochemical properties of leached residues

Stabilization test method: taking 150g of leaching residue (which is not dried and has the particle size of less than 1cm), respectively adding 20 wt% (30g), 25 wt% (37.5g) and 30 wt% (45g) of compound agents, adding 6mL of 98% concentrated sulfuric acid to adjust the pH, adding 25mL of water, stirring for 5min, finally placing in a ventilated place for natural curing for 7d, and determining the leaching concentration of As by adopting a leaching toxicity test-sulfuric acid-nitric acid method.

The results of the experiment are shown in Table 9.

TABLE 9 stabilization test results

The method successfully develops the efficient and economic stabilizing agent applied to stabilizing the high-concentration arsenic slag by using the mixed material design, overcomes the empirical defect that the prior art personnel determine the formula by simply depending on simple subjective proportioning design, and ensures that the formula design of the stabilizing agent is more scientific and reasonable; the stabilizing agent is matched with acid to synergistically stabilize the high-concentration arsenic slag, the adding amount of the agent is small, the acid leaching concentration of the treated arsenic slag is lower than 1.2mg/L, and the pH of the water leaching leachate is between 7.0 and 12.0, so that the requirements specified in the hazardous waste landfill pollution control standard (GB 18598-; meanwhile, the treatment process is simple, the operability is strong, the arsenic slag treatment cost is low, and the engineering application is easy to realize.

Example 2

FIG. 4 is a schematic flow chart illustrating a method for treating arsenic slag according to an embodiment of the disclosure. As shown in fig. 4, the method applies the stabilizing agent designed by the design method for treating the arsenic slag shown in fig. 1 to 3, and comprises the following steps:

s401, crushing the arsenic slag to a particle size of less than or equal to 0.5 cm, and adding the crushed arsenic slag into a reaction container;

specifically, the arsenic slag is crushed to the particle size of less than or equal to 0.5 cm, which is beneficial to fully contacting the arsenic slag with the stabilizing agent and making the arsenic slag more likely to react with the stabilizing agent.

S402, adding the stabilizing agent into the reaction container, and stirring for 10-30 minutes;

in specific implementation, after the stabilizing agent is added into the reaction vessel, the arsenic slag and the stabilizing agent can be fully reacted by stirring, and the reaction process is accelerated. In the present embodiment, the stirring time is 10 to 30 minutes, and the stirring time may be flexibly set as necessary.

S403, adding acid liquor into the reaction container, stirring, adding water, adjusting the pH value in the reaction container to 7.0-8.0, and stirring for 10-30 minutes;

specifically, by adding an acid solution to the reaction vessel, a large amount of acid solution can be introducedH of (A) to (B)⁺On one hand, the release of As in the arsenic slag from a solid phase to a liquid phase is promoted, so that the As is easier to react with a stabilizing agent; on the other hand, the pH value is adjusted to 7.0-8.0, and the adsorption and coprecipitation between Fe and As are more facilitated in a weak alkaline environment.

S404, placing the reaction container at 5-35 ℃, and maintaining for 2-7 days.

In specific implementation, the reaction vessel is maintained for 2 to 7 days, so that the stabilizing medicament can fully play a role; meanwhile, the phenomenon that the As after adsorption and precipitation is changed back to an ionic state in a short time to influence an experimental result is avoided.

According to an embodiment of the present disclosure, the stabilizing agent is 20% to 35% by mass of the arsenic slag.

Specifically, aiming at the high-concentration alkaline arsenic slag with the As content of more than 1 percent and the As leaching concentration of more than 100mg/L, the dosage of the stabilizing agent in the formula design process is 20-35 percent of the mass of the arsenic slag. Specifically, the specific amount can be determined according to a dose gradient stabilization experiment of the main component.

According to a specific embodiment of the present disclosure, the acid solution includes any one of sulfuric acid, nitric acid, and hydrochloric acid, and the amount of water is controlled such that a liquid-solid ratio in the reaction container is 2-5: 10, respectively.

The treatment object of the embodiment of the disclosure is high-concentration alkaline arsenic slag, and a large amount of H is introduced by hydrolysis release of Fe (II) and acid addition⁺On one hand, the release of As in the arsenic slag from a solid phase to a liquid phase is promoted, so that the As is easier to react with a stabilizing agent; on one hand, the pH value is adjusted to 7.0-8.0, and the adsorption and coprecipitation between Fe and As are more facilitated in a weak alkaline environment. And Fe (II) and zero-valent iron (reduced iron powder) in the stabilizing agent induce molecular oxygen to generate active oxygen species (ROSs) including superoxide radical (O)₂-), hydrogen peroxide (H)₂O₂) And hydroxyl radical (. OH), with MnO₂Exhibit excellent oxidation properties for As, and these oxidizing agents greatly promote the oxidation of As (III) to As (V). Finally, the As (V) and Fe (III) and OH-generate stable Fe-O-As complex basic ferric arsenate (FeAsO) under the mutual action₄·xFe(OH)₃) Thereby reducing the leaching toxicity of the arsenic slag.

In the embodiments provided in the present application, it should be understood that the disclosed apparatus and method can be implemented in other ways. The apparatus embodiments described above are merely illustrative and, for example, the flowchart and block diagrams in the figures illustrate the architecture, functionality, and operation of possible implementations of apparatus, methods and computer program products according to various embodiments of the present invention. In this regard, each block in the flowchart or block diagrams may represent a module, segment, or portion of code, which comprises one or more executable instructions for implementing the specified logical function(s). It should also be noted that, in alternative implementations, the functions noted in the block may occur out of the order noted in the figures. For example, two blocks shown in succession may, in fact, be executed substantially concurrently, or the blocks may sometimes be executed in the reverse order, depending upon the functionality involved. It will also be noted that each block of the block diagrams and/or flowchart illustration, and combinations of blocks in the block diagrams and/or flowchart illustration, can be implemented by special purpose hardware-based systems which perform the specified functions or acts, or combinations of special purpose hardware and computer instructions.

In addition, each functional module or unit in each embodiment of the present invention may be integrated together to form an independent part, or each module may exist separately, or two or more modules may be integrated to form an independent part.

The functions, if implemented in the form of software functional modules and sold or used as a stand-alone product, may be stored in a computer readable storage medium. Based on such understanding, the technical solution of the present invention or a part of the technical solution that contributes to the prior art in essence can be embodied in the form of a software product, which is stored in a storage medium and includes instructions for causing a computer device (which may be a smart phone, a personal computer, a server, or a network device, etc.) to execute all or part of the steps of the method according to the embodiments of the present invention. And the aforementioned storage medium includes: a U-disk, a removable hard disk, a Read-Only Memory (ROM), a Random Access Memory (RAM), a magnetic disk or an optical disk, and other various media capable of storing program codes.

The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention.