CN115092957B - Method for cooperatively disposing arsenic alkali slag leaching slag by adopting pyrometallurgy of antimony concentrate - Google Patents
Method for cooperatively disposing arsenic alkali slag leaching slag by adopting pyrometallurgy of antimony concentrate Download PDFInfo
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
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Abstract
The invention discloses a sulfate acid tin dioxide composite material and a method for preparing the same and cooperatively disposing arsenic alkali slag leaching slag by pyrometallurgy of antimony concentrate. Will contain Sn 4+ Alkaline substances are adopted to adjust the solution to form colloidal solution, and the colloidal solution is aged, solid-liquid separated and dried to obtain tin oxide particles; the tin oxide particles are soaked in sulfuric acid and activated and baked in sequence to obtain sulfate acidic SnO 2 The composite material is used for the synergistic pyrometallurgy of antimony concentrate and arsenic alkali slag leaching slag, and can promote the volatilization of complex antimony and arsenic components in arsenic slag to Sb by utilizing the high strong acidity and high oxidability of the composite material 2 O 3 And As 2 O 3 The method has the advantages of high efficiency, low cost, simple process and convenient operation, and really realizes the resource utilization of the arsenic alkali residue leaching slag.
Description
Technical Field
The invention relates to a sulfate acid tin dioxide composite material, and also relates to a preparation method of the sulfate acid tin dioxide composite material and application thereof in the synergic resource treatment of arsenic alkali residue leaching residues in the pyrometallurgy of antimony concentrate, belonging to the technical field of solid waste treatment of the arsenic alkali residue leaching residues.
Background
At present, smelting processes of antimony mainly comprise 3 processes of volatilizing roasting (smelting), reducing smelting and alkaline refining. In the volatilizing roasting (smelting) process, antimony and arsenic are respectively oxidized into Sb 2 O 3 And As 2 O 3 They volatilize into furnace gas in the form of steam, and are cooled and collected to obtain powdery intermediate product antimony oxide (commonly called as antimony oxide); in the reduction smelting process, sb 2 O 3 And As 2 O 3 Is reduced into elemental antimony and arsenic, and the arsenic enters into crude antimony; in the alkaline refining process, sodium carbonate blast is generally adopted to remove arsenic in crude antimony, and the main reactions are as follows:
2As+O 2 +2Na 2 CO 3 ＝2Na 2 AsO 4 +2CO 2
4Sb+3O 2 +6Na 2 CO 3 ＝4Na 2 SbO 3 +6CO 2
slag floating on the surface of the antimony liquid formed in the process can be raked out, and the slag which is alkaline and contains arsenic is called arsenic alkali slag. According to statistics, 130-140 kg of arsenic caustic sludge can be produced every 1t of refined antimony production, and the environment and human body are greatly threatened. In view of the fact that the arsenic caustic sludge not only contains metallic antimony which can be recycled, but also has the characteristic of highly toxic sodium arsenate, the arsenic caustic sludge is difficult to directly carry out secondary smelting and cannot be directly discarded. It is necessary to treat and recycle the arsenic caustic sludge. The domestic recycling of the arsenic alkali slag is mainly carried out from two aspects, namely, the recycling of antimony in the arsenic alkali slag and the comprehensive utilization of arsenic in the arsenic alkali slag. At present, the treatment mode of arsenic alkali residues at home and abroad mainly comprises the following steps: and (5) performing fire treatment and wet treatment. The advantage of the pyrogenic process for treating arsenic alkali slag is that the treating capacity is large, the production efficiency is high, the equipment of an antimony smelting system can be utilized, and the investment is saved. The pyrogenic process has the obvious disadvantages at the same time: 1. raw materials and products have high arsenic content, poor operation environment and serious damage to the health of staff; 2. repeatedly refining high-arsenic crude antimony, wherein the returned slag generated by refining contains higher arsenic and cannot be treated, so that malignant circulation of arsenic is formed; 3. the perfection and the tightness of the cooling dust collection system are not high in the pyrogenic treatment process, and the environmental risk is huge. At present, the academic and industrial views are consistent that arsenic is removed from arsenic-containing hazardous waste by mainly adopting a wet leaching method for arsenic alkali residues. The main components of the arsenic alkali slag are arsenate/arsenite, antimonate/antimonite and sodium carbonate/sodium hydroxide, and simultaneously, the arsenic alkali slag also contains a large amount of impurity components such as silicon, aluminum, fluorine, chlorine and the like. In the process of the selective leaching process of the arsenic alkali residue, soluble arsenic, antimony and alkali components enter the leaching solution, various indissolvable components and newly formed precipitates are reserved in the leaching residue to become main components of the leaching residue, and the XRF result analysis of the leaching residue of the arsenic alkali residue obtained by the existing leaching process is shown in the following table 1.1, wherein the main elements of the leaching residue of the arsenic alkali residue are Sb, as and partial silicate elements thereof. The leaching residue maintains a high pH in an aqueous leaching environment. In the sulfuric acid leaching system, part of the arsenic-containing component is released into the solution system again. If the arsenic-containing leaching residues are not treated, a large amount of arsenic can enter the environment again under the action of wind power, water power and the like when the arsenic-containing leaching residues are contacted with the atmosphere, rainwater and the like, so that serious secondary pollution is caused. Therefore, it is important to recycle and reuse antimony in the leaching residue and to perform further harmless treatment in the context of recycling and reduction.
Table 1 representative arsenic caustic sludge leaching elemental composition (XRF analysis)
In the prior art, the harm of leaching slag cannot be reduced by simple landfill, secondary pollution is easy to cause, so that the leaching slag cannot be simply landfilled, and harmful substances in the leaching slag must be treated and then landfilled, so that the toxicity of the harmful substances is reduced or isolated. Common disposal methods for the arsenic alkali leaching slag mainly comprise treatment methods such as stabilization and solidification, a pyrogenic process and a wet process of the leaching slag, but the common disposal methods are used for directly stabilizing the leaching slag, so that the recycling of antimony resources in the leaching slag and the harmless disposal requirements of the arsenic alkali slag are not facilitated. On the basis of arsenic alkaline residue leaching, the leaching residue is continuously treated by a wet method, so that the cost of recycling and reducing the leaching residue is greatly increased, the link of wastewater disposal is increased, and the efficiency of leaching residue disposal is reduced.
The leached residue is an important product of the selective leaching of arsenic alkali residue, and contains high content of metallic antimony and partial indissolvable arsenic-containing components. If the treatment is improper, the problems of resource waste, environmental pollution and the like are caused. The novel disposal technology is explored and sought and applied to industrial practice, the problem of safe disposal of leaching residues is solved, and the method has important significance for guaranteeing environmental health and life safety and promoting green sustainable development of the antimony smelting industry.
Disclosure of Invention
Aiming at the technical problems that the prior art means is difficult to recycle and effectively and circularly treat the arsenic caustic sludge leaching slag, the first aim of the invention is to provide a sulfate acid SnO 2 The composite material has strong acid center and high oxidation activity, and can promote the volatilization of complex antimony and arsenic components in arsenic alkali residue leaching residue to Sb under high temperature condition 2 O 3 And As 2 O 3 The high-efficiency conversion is carried out, thereby realizing the high-efficiency and low-cost recovery of arsenic and antimony in the arsenic alkaline residue leaching slag and achieving the purpose of recycling the arsenic alkaline residue leaching slag.
A second object of the present invention is to provide a sulfate acid SnO 2 The preparation method of the composite material has the advantages of simple steps, mild reaction conditions and low cost, and is beneficial to large-scale production.
The third purpose of the invention is to provide a method for cooperatively recycling and disposing arsenic alkali residue leaching slag by adopting the pyrometallurgy of antimony concentrateAccording to the method, the antimony concentrate and arsenic alkali slag leaching slag are cooperatively treated by adopting a pyrometallurgy method, and the sulfate acid tin oxide composite material is utilized, so that the aim of efficiently recycling antimony in the antimony concentrate is achieved, and meanwhile, the complex antimony and arsenic components in the arsenic slag can be efficiently promoted to volatile Sb 2 O 3 And As 2 O 3 The method has the advantages of high efficiency, low cost, simple process, convenient operation and meeting the industrial production. Compared with the existing hydrometallurgical technology, the pyrometallurgical technology has the advantages of relatively simple operation, high productivity, preferential removal of arsenic and separation from other valuable metals, thereby avoiding complex separation steps and wastewater discharge.
In order to achieve the technical aim, the invention provides a sulfate acid SnO 2 A process for producing a composite material comprising reacting a Sn-containing material 4+ Alkaline substances are adopted to adjust the solution to form colloidal solution, and the colloidal solution is aged, solid-liquid separated and dried to obtain tin oxide particles; the tin oxide particles are soaked in sulfuric acid and activated and baked in sequence to obtain sulfate acidic SnO 2 A composite material.
Sulfate acid SnO of the present invention 2 The preparation process of the composite material comprises the steps of firstly obtaining tin oxide particles by utilizing a precipitation method, drying and dehydrating the tin oxide particles to expose more strong L acid centers due to strong adsorption action of the super strong L acid centers on water molecules, so that more sulfate ions can be coordinately adsorbed, and after sulfate radical impregnation, through activation roasting, water can be dissociated and desorbed to generate protonic acid centers, and sulfate radical acidic SnO can be produced 2 The material shows a regular and effective mesoporous pore structure and has larger specific surface and pore volume, thereby endowing the material with high catalytic activity.
Sulfate acid SnO of the present invention 2 The composite material is characterized in that sulfate radicals are loaded on the surfaces of tin oxide particles, and the electronic cloud intensity on Sn-O bonds is offset by utilizing the coordination adsorption of the surfaces of the tin oxide with the sulfate radicals, so that the activity of an L acid center is enhanced.
As a preferred embodiment, the Sn-containing compound contains 4+ Sn in solution of (a) 4+ The mass percentage concentration of (2) is 0.2-3%. If Sn is 4+ Too low a concentration will result in subsequent Sn-O being SO 4 2- The coverage of induced electron cloud distribution deviation is small, and the acidity of the generated L acid center is weak. And Sn is 4+ Too high a concentration, on adsorption of SO 4 2- The s=o bond induces a decrease in the efficiency of electron cloud distribution shift of Mn-O, affecting the acidity of the overall L acid center. Sn (Sn) 4+ Mainly provided by readily soluble tin salts, such as tin tetrachloride and the like.
As a preferable embodiment, the conditions of the drying treatment are as follows: the temperature is 150-200 ℃ and the time is 3.0-4.0 h. The roasting process mainly converts tin hydroxide into tin dioxide, and simultaneously removes the combined water, so that more L acid centers can be exposed, and the subsequent sulfuric acid modification is facilitated. If the temperature is too low, the tin hydroxide conversion is incomplete and fewer L acid centers are exposed, such as if the temperature is too high, the reactivity of the tin hydroxide is destroyed.
As a preferable scheme, the condition of the sulfuric acid soaking is as follows: the liquid-solid ratio is 10-20 mL to 1g, the sulfuric acid concentration is 0.5-1 mol/L, and the soaking time is 30-60 min. The tin dioxide is soaked in dilute sulfuric acid under proper conditions, so that the tin dioxide surface layer can react with sulfuric acid to generate tin sulfate, and the tin sulfate is adsorbed on the tin dioxide surface in situ. If the sulfuric acid concentration is too high or the soaking time is too long, the dissolution of tin dioxide is easy to cause, and if the sulfuric acid concentration is too low or the soaking time is too short, more high-activity tin sulfate components are difficult to generate on the surface of tin dioxide.
As a preferable mode, the conditions of the activation baking are as follows: the temperature is 450-550 ℃ and the time is 2-6 h. If the activation temperature is too high, the sulfate component is lost, the structure of the acid center is destroyed, and if the activation temperature is too low, the activation of the strong acid center on the metal oxide is not favored.
As a preferred embodiment, the alkaline substance is ammonia, sodium hydroxide or potassium hydroxide, etc., preferably ammonia, which is conventional industrial ammonia. By means of alkaline substancesRegulation of Sn content 4+ The pH of the solution is 7 to 9, and a colloidal solution can be obtained.
As a preferred embodiment, the aging time is 8 to 16 hours. The tin hydroxide colloidal phase is converted to a crystalline precipitate by aging.
The invention also provides a sulfate acid SnO 2 A composite material obtainable by the process.
The invention also provides a method for cooperatively recycling the arsenic alkaline residue leaching residue in the pyrometallurgy of the antimony concentrate, which comprises the steps of leaching the arsenic alkaline residue leaching residue containing the antimony concentrate, the binding agent, the reducing agent and the sulfate acid SnO 2 The raw materials of the composite material are sequentially mixed, ground, pressed into blocks, dried and roasted, and antimony oxide and arsenic oxide are recovered in roasting flue gas.
The key of the technical scheme of the invention is as follows: realizes the treatment of the arsenic alkaline residue leaching residue with high efficiency and low cost, and carries out the recycling and high-consumption utilization of the arsenic and antimony components in the arsenic alkaline residue leaching residue. By combining the volatilization behavior and technical principle of the arsenic-antimony components in the antimony smelting process flow in the prior art based on the change behavior of the arsenic-antimony components in the pyrometallurgy process of the arsenic-alkali slag leaching slag. Mixing the arsenic alkali residue leaching slag and the antimony concentrate according to a certain mixing ratio to form pellet ore, and carrying out pyrogenic treatment roasting to realize enrichment, removal and collection of arsenic and antimony. Has important significance for the antimony smelting process and the arsenic alkali residue disposal process flow. In addition, more importantly, the special sulfate acid SnO is added in the pyrometallurgy process 2 The composite material has high strong acid and strong oxidation active center, and can promote stable and difficult-to-volatilize arsenic-antimony components in arsenic alkali slag leaching slag to be converted into volatile Sb 2 O 3 And As 2 O 3 Sulfate acid SnO 2 SO on the surface of the composite material 4 2- Can cause SnO 2 The electron cloud intensity on the Sn-O bond on the surface deviates, the electronegativity of O is far greater than that of S, and the electron cloud on S and metal also deviates to O, so that the generation of strong acid center is caused, and the arsenic and antimony in leaching slag can be converted into volatile medium by virtue of the characteristics of strong oxidizing property and high acidity.The antimony in the arsenic alkali slag in the prior art is Sb after entering and exiting the slag through water 2 O 3 And Sb (Sb) 2 O 4 In the form of (a), arsenic is mainly present As a higher oxide 2 O 5 In addition, arsenic and antimony exist in the form of arsenic and antimonate. The higher oxides of arsenic and antimony are essentially non-volatile and therefore require the addition of a reducing agent to reduce to a lower valence state during the calcination process to reduce the arsenic and antimony components to As 2 O 3 And Sb (Sb) 2 O 3 The main reactions of the volatile removal are as follows: sb (Sb) 2 O 4 +CO＝Sb 2 O 3 +CO 2 ；Sb 2 O 4 +C＝Sb 2 O 3 +CO；2Sb 2 O 4 +C＝2Sb 2 O 3 +CO 2 ；Sb 2 O 4 +2C＝2Sb+2CO 2 ；4Sb+3O 2 ＝2Sb 2 O 3 ；As 2 O 5 +C＝As 2 O 3 +CO 2 ；As 2 O 5 +2CO＝As 2 O 3 +2CO 2 ；
At present, 95% of antimony smelting adopts a pyrometallurgical process, the volatilization rate of antimony reaches more than 97%, and the reaction is as follows:
2Sb 2 S 3 +9O 2 ＝2Sb 2 O 3 +6SO 2
gaseous Sb 2 O 3 Along with the discharge of furnace gas, antimony oxide and non-volatilized Sb can be obtained through condensation and dust collection 2 O 3 Can be further oxidized to become nonvolatile Sb 2 O 4 Is left in the smelting slag. At the same time, in order to reduce this loss, a certain amount of reducing component is added during the roasting of the antimony concentrate to prevent its high-intensity oxidation. The inventor finds that the leaching residue roasting and the antimony concentrate pyrogenic process have certain correlation in principle theory through the theoretical and practical exploration processes, and lays a key foundation for collaborative roasting. At present, no relevant research reports and industrial application for the synergic roasting of leaching residues and antimony concentrate exist. The method is beneficial to efficiently and low-cost disposal of arsenic alkali residue leaching residues, and realizesThe arsenic and antimony components in the arsenic alkali residue leaching slag are utilized in high-resource and high-consumption way in industry. Has important significance for upgrading antimony smelting and disposing arsenic alkali residue.
As a preferable scheme, the mass ratio of the arsenic alkali residue leaching slag to the antimony concentrate is 0.5-1:1. If the ratio of the arsenic alkali slag leached slag is too high, the volatilization effect of arsenic and antimony is not complete, and because the leached slag contains high-content aluminosilicate, silicate is molten and hardened in a porcelain boat to influence the development of a process, the ratio of antimony concentrate is too high, the melting influence effect cannot be generated in the roasting process, the volatilization rate effect of arsenic and antimony is not obvious under the medium-temperature condition, and the higher volatilization effect of arsenic and antimony needs to be obtained by increasing the temperature. The problems can be well overcome by carrying out collaborative pyrometallurgy on the two materials according to a proper proportion, the melting temperature of antimony concentrate can be reduced by the arsenic alkali slag leaching slag, the antimony concentrate can effectively prevent the caking of the arsenic alkali slag leaching slag, and the integral arsenic-antimony volatilization rate is increased.
As a preferable scheme, the mass of the reducing agent is 20-30% of the total mass of the arsenic alkali slag leaching slag and the antimony concentrate. The reducing agent is conventionally used in the process of smelting antimony concentrate by a pyrogenic process, the consumption of the reducing agent is in the range, the volatilization efficiency of arsenic and antimony is improved along with the increase of the reducing agent, but the effect of the excessively high reducing agent on improving the volatilization efficiency of arsenic and antimony is not obvious, and the use cost is increased. As a more preferable scheme, the reducing agent is at least one of active carbon, high-purity coal and coking coal. The reducing agent mainly plays a role in reducing arsenic and antimony.
As a preferable scheme, the mass percentage of the binder in the raw materials is 5-10%. As a more preferable scheme, the binder is at least one of bentonite, sodium humate, sodium lignin sulfonate and water glass. The function of the binder is to improve the binding properties between minerals and facilitate the preparation of the agglomerate.
As a preferred embodiment, the sulfate acid SnO in the feedstock 2 The mass percentage content of the composite material is 0.5-1.5%. Sulfate acid SnO 2 The amount of the composite material is within this range, along with sulfuric acidRoot acidic SnO 2 The addition of the composite material is beneficial to improving the volatilization efficiency of arsenic and antimony, but the excessive sulfate acid SnO 2 The effect of the composite material for improving the volatilization efficiency of arsenic and antimony is not obvious, but the use cost is increased.
As a preferable mode, the conditions of the calcination are: the temperature is 800-900 ℃. The calcination time is generally determined by complete volatilization of arsenic and antimony. In combination with a reducing agent and sulfate acid SnO 2 Under the condition of the composite material, the high-efficiency volatilization of arsenic and antimony can be realized under the medium-high temperature condition.
As a preferable scheme, the arsenic caustic sludge leaching slag and the antimony concentrate are crushed and ground to a granularity smaller than-40 meshes, so that important conditions are provided for the mineral surface to fully contact with high-temperature heat.
As a preferable scheme, a proper amount of water is added into the raw materials, so that the physical mixing is uniform, and the water content in the mixed raw materials is ensured to be 5% -8%; after being uniformly mixed, the mixed materials are placed in the air for 12-15 hours for natural drying, and the dried materials are ground.
As a preferable scheme, the briquetting process adopts a hydraulic sampler at 10-20 kg cm -2 Making into pellet under pressure of the above formula, the size of the raw pellet is
As a preferable scheme, the raw pellets are dried for 3 hours in a hot air drying oven at 110 ℃ in the drying process, so that the finished raw pellets are obtained.
Sulfate acid SnO provided by the invention 2 The preparation method of the composite material comprises the following steps: adding a certain amount of deionized water into tin tetrachloride solid to prepare a solution with tin ion mass fraction of 0.2-3%, fully stirring, slowly adding industrial ammonia water (concentration is about 25%) until the pH of the solution is 7-9 and the solution is colloidal, aging for 8-16 h, filtering and washing to obtain a corresponding tin hydroxide intermediate medium product, adding the tin hydroxide solid into a baking oven with the temperature of 150-200 ℃ to bake for 3.0-4.0 h, and taking the baked solid sample as liquid-solidThe ratio is 10-20: 1 is placed in sulfuric acid with the dosage of 0.5-1 mol/L for soaking for 30-60 min, a filtered sample is placed in a muffle furnace for activation roasting at the temperature of 450-550 ℃ for 2-6 h, the temperature is too high, sulfur components in the composite material are lost, the structure of an acid center is damaged, and the activation of a strong acid center on a metal oxide is not facilitated if the temperature is too low.
The invention provides a method for cooperatively recycling arsenic alkali slag leaching residues in pyrometallurgy of antimony concentrate, which comprises the following steps: the arsenic alkali residue leaching slag and the antimony concentrate are crushed and ground to the granularity smaller than-40 meshes, important conditions are provided for fully contacting high-temperature heat on the surface of the mineral, and the crushed and ground arsenic alkali residue leaching slag and the antimony concentrate are mixed according to the mass ratio of 0.5-1:1. Adding bentonite and reducing agent into the mixed ore, gradually adding water, mixing and stirring, wherein the content of the added bentonite is 5-10% of the total amount, the dosage of the added reducing agent is 20-30% of the total amount, adding water to ensure that the water content is 5-8%, and adding sulfate acid SnO 2 The composite material accounts for 0.5 to 1.5 percent of the total weight. After being evenly mixed, the mixture is placed in air for 12 to 15 hours for natural drying, and the materials are ground after the drying. Placing the materials in a hydraulic sampling machine at 10-20 kg cm -2 Making into agglomerate under pressure of the above formula, the size of the obtained agglomerate isDrying the raw ore in a hot air drying box at 100-120 ℃ for 2-4 hours to obtain a finished product antimony concentrate-arsenic caustic sludge leaching slag mixed ore, and sending the finished product ore to a resistance furnace for high-temperature volatilization and arsenic removal and antimony treatment at 800-900 ℃ until the volatilization of arsenic and antimony is completed.
Compared with the prior art, the technical scheme of the invention has the beneficial technical effects that:
sulfate acid SnO provided by the invention 2 The composite material comprises high-strength oxidizing and strong-acidity active tin sulfate components on the surfaces of tin dioxide particles, and can efficiently promote complex antimony and arsenic components which are difficult to volatilize in arsenic alkali slag leaching slag waste residues to volatile Sb under high temperature conditions 2 O 3 And As 2 O 3 The conversion is carried out, thereby realizing the high-efficiency and low-cost recovery of arsenic and antimony in the arsenic alkali residue leaching slag and realizing the resource utilization of the arsenic alkali residue leaching slag.
Sulfate acid SnO provided by the invention 2 The preparation method of the composite material has simple steps, mild reaction conditions and low cost, and is beneficial to large-scale production.
The method for cooperatively recycling the arsenic alkali slag leaching slag in the fire smelting of the antimony concentrate realizes the cooperative fire smelting of the antimony concentrate and the arsenic alkali slag leaching slag, and the sulfate radical acidic tin oxide composite material is utilized in the fire smelting process, so that the aim of efficiently recycling antimony in the antimony concentrate is fulfilled, and meanwhile, the complex antimony and arsenic components in the arsenic slag can be efficiently promoted to volatile Sb 2 O 3 And As 2 O 3 The method has the advantages of high efficiency, low cost, simple process, convenient operation and meeting the industrial production. Compared with the existing hydrometallurgical technology, the pyrometallurgical technology has the advantages of relatively simple operation, high productivity, preferential removal of arsenic and separation from other valuable metals, thereby avoiding complex separation steps and wastewater discharge.
Detailed Description
The following specific examples are intended to further illustrate the present invention, but not to limit the scope of the claims.
Example 1
50g of stannic chloride solid is weighed, 1L of deionized water is added to prepare a solution with the mass fraction of 5% (tin ion concentration of about 2.2%), after full stirring, 25% ammonia water is slowly added until the pH of the solution is about 8, and the solution is in a colloid state. The corresponding tin hydroxide intermediate medium product is obtained through ageing for 12 hours, filtering and washing, the obtained tin hydroxide solid is added into a baking oven at 200 ℃ and baked for 4.0 hours, the baked solid sample is placed into sulfuric acid with the liquid-solid ratio of 10:1 of 0.5-1 mol/L for soaking for 30-60 minutes, the filtered sample is divided into three parts after rapid filtering, and the three parts are respectively placed into a muffle furnace for activation baking at the temperature of 350-550 ℃ for 4 hours, and the baked solid sample is taken out for subsequent use.
Sulfate acid SnO prepared 2 The composite material was subjected to Hammett indicator amine titration to determine the acid strength of the solid catalyst, the indicator used being in fact a weak base, which when it meets the acid centre is adsorbed to react with the acid centre. Expressed by the following formula:
by H 0 The acid strength coefficient of the composite is measured. When H is 0 The smaller the value of (2), the stronger the acid strength, whereas the weaker the acid strength. Sulfate acidic SnO formed under several different conditions 2 The acidity of the composite material is subjected to experimental analysis, and the soaking time, the acid soaking concentration and the roasting time have certain influence on the acid strength of the composite material. The concrete steps are as follows: the acid strength of the composite material can be enhanced to a certain extent by increasing the soaking time and the concentration of the soaking acid and the roasting temperature. An increase in the concentration of immersion acid results in more SO 4 2- Can cause SnO 2 The electron cloud intensity on sn—o bonds on the surface shifts, and the electron cloud on S and metal also shifts to O, resulting in the generation of strong acid centers. Too high or too low a firing temperature, the acid centers are not easily activated or the activation is affected. And the formation of strong acid center is favorable for volatilizing and recycling arsenic and antimony components in the arsenic alkali residue leaching slag. Sulfate acid SnO with different acid strength coefficients generated according to different conditions 2 The roasting at 800 ℃ is carried out according to the doping ratio of 0.5% (see the specific operation of example 2, the doping ratio of antimony concentrate to leaching slag is 1.5:1, the content of reducing agent is 20% and bentonite is 5%), the experimental results are shown in table 2, the stronger the acidity coefficient is, the sufficient acidity and oxidation performance is, and the volatilization of arsenic and antimony is realized directly at a lower temperature, which is a huge breakthrough for industrial application.
TABLE 1 sulfate acidic SnO formed under different conditions 2 Acidity coefficient of composite material
TABLE 2 sulfate acid SnO under different conditions 2 Arsenic and antimony volatilization rate of leaching residue
Example 2
Taking cold water Jiang Xi mine arsenic alkali slag leaching slag as a test research object, crushing and grinding the arsenic alkali slag leaching slag and antimony concentrate to a granularity smaller than-40 meshes, weighing 500g of the arsenic alkali slag leaching slag after crushing and grinding, and mixing the antimony concentrate and the arsenic alkali slag leaching slag according to a certain proportion: 0.5-2.0:1. 5 percent of bentonite and 5 to 30 percent of reducing agent are added into the mixed ore; pouring tap water to make the water content of the tap water 5%. 5g of tin hydroxide calcined product (sulfate acid SnO having an acid strength coefficient of-13.26 prepared in example 1) was taken 2 Composite material), the acid composite material is added to be 0.2 to 1.0 percent of the total amount. After being evenly mixed, the mixture is placed in air for 12 hours for natural drying, and the materials are ground after the drying. Placing the materials in a hydraulic sampling machine at 20kg cm -2 Making into agglomerate under pressure of the above formula, the size of the obtained agglomerate isDrying the raw pellets in a hot air drying box at 110 ℃ for 3 hours to obtain the finished antimony concentrate-arsenic alkali leaching slag mixed pellets. And feeding the finished product agglomerate into a resistance furnace for high-temperature volatilization arsenic and antimony removal treatment at 600-1000 ℃. And the volatilization removal rate of the arsenic and antimony components is calculated according to the quality before and after the reaction. The test results are shown in the following table 3, the single leaching slag is roasted, the arsenic and antimony volatilization effect is incomplete, the single leaching slag roasting can lead to silicate melting and hardening in a porcelain boat, the development of the process is affected, the antimony concentrate roasting process can not produce the effect of melting, the arsenic and antimony volatilization rate effect is not obvious under the condition of medium and high temperature, and the higher the temperature is, the slag isThe better the arsenic and antimony volatilizing effect. The synergistic mode increases the volatilization rate of the whole arsenic and antimony, and realizes the synergistic roasting of the leaching slag of the arsenic alkali slag and the antimony concentrate. Test data show that the doping amount of the antimony concentrate is higher than the yield of the leaching slag, and under the same condition, the volatilization rate of arsenic and antimony is further improved along with the increase of the doping ratio of the antimony concentrate and the leaching slag. Meanwhile, the test result proves that the consumption of the reducing agent and the sulfate tin dioxide composite material can influence the arsenic-antimony volatilization effect of the overall synergistic mode. With the increase of the consumption of the reducing agent and the sulfate tin dioxide composite material, the volatilization rate of arsenic and antimony is further improved. The temperature can also influence the overall arsenic-antimony volatilization effect, and the higher the temperature is, the better the volatilization effect is. More importantly, the antimony concentrate and the leaching slag complement each other in the whole. The antimony concentrate provides non-melting conditions for the leaching slag, and the high content of sodium in the leaching slag reduces the melting point of the whole system, so that the high-efficiency volatilization of arsenic and antimony components can be realized at a certain temperature. The synergistic mode greatly reduces the energy consumption of the energy consumption process, realizes the green sustainable development of antimony smelting, and the roasted product can be directly used as cement for disposal. Has critical strategic significance for antimony smelting.
TABLE 3 volatilization rates of arsenic and antimony in leaching residues by synergistic treatment through pyrogenic process under different conditions
Claims (6)
1. A method for cooperatively recycling and disposing arsenic alkali slag leaching residues by adopting pyrometallurgy of antimony concentrate is characterized by comprising the following steps: leaching slag containing antimony concentrate, arsenic alkali slag, binder, reducing agent and sulfate acid SnO 2 The raw materials of the composite material are sequentially mixed, ground, pressed into clusters, dried and roasted, and antimony oxide and arsenic oxide are recovered in roasting flue gas;
the sulfate acidSnO 2 The composite material is prepared by the following steps: will contain Sn 4+ Alkaline substances are adopted to adjust the solution to form colloidal solution, and the colloidal solution is aged, solid-liquid separated and dried to obtain tin oxide particles; the tin oxide particles are soaked in sulfuric acid and activated and baked in sequence to obtain sulfate acidic SnO 2 A composite material; the conditions of the drying treatment are as follows: the temperature is 150-200 ℃ and the time is 3.0-4.0 h; the conditions of the sulfuric acid soaking are as follows: the liquid-solid ratio is 10-20 mL to 1g, the sulfuric acid concentration is 0.5-1 mol/L, and the soaking time is 30-60 min.
2. The method for cooperatively recycling and disposing arsenic alkali residue leaching slag by adopting pyrometallurgy of antimony concentrate according to claim 1, which is characterized in that: the Sn-containing alloy 4+ Sn in solution of (a) 4+ The mass percentage concentration of (2) is 0.2-3%.
3. The method for cooperatively recycling and disposing arsenic alkali residue leaching slag by adopting pyrometallurgy of antimony concentrate according to claim 1, which is characterized in that: the conditions of the activation roasting are as follows: the temperature is 450-550 ℃ and the time is 2-6 h.
4. The method for cooperatively recycling and disposing arsenic alkali residue leaching slag by adopting pyrometallurgy of antimony concentrate according to claim 1, which is characterized in that:
the mass ratio of the arsenic caustic sludge leaching slag to the antimony concentrate is 0.5-1:1;
the mass of the reducing agent is 20-30% of the total mass of arsenic alkali slag leaching slag and antimony concentrate;
the reducing agent is at least one of active carbon, high-purity coal and coking coal.
5. The method for cooperatively recycling and disposing arsenic alkali residue leaching slag by adopting pyrometallurgy of antimony concentrate according to claim 1, which is characterized in that:
the mass percentage content of the binder in the raw materials is 5-10%;
the binder is at least one of bentonite, sodium humate, sodium lignin sulfonate and sodium silicate;
sulfate acid SnO in the raw materials 2 The mass percentage content of the composite material is 0.5-1.5%.
6. The method for cooperatively recycling and disposing arsenic alkali residue leaching slag by adopting pyrometallurgy of antimony concentrate according to claim 1, which is characterized in that: the roasting conditions are as follows: the temperature is 800-900 ℃.
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