CN115092957A - Sulfate acid tin dioxide composite material and preparation method thereof and method for cooperatively treating arsenic-alkali residue leaching residue through pyrometallurgy of antimony concentrate - Google Patents
Sulfate acid tin dioxide composite material and preparation method thereof and method for cooperatively treating arsenic-alkali residue leaching residue through pyrometallurgy of antimony concentrate Download PDFInfo
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Abstract
The invention discloses a sulfate acid tin dioxide composite material and a preparation method thereof, and a method for treating arsenic-alkali residue leaching residue by cooperation of pyrometallurgy of antimony concentrate. Will contain Sn 4+ The solution is adjusted to form a colloidal solution by adopting an alkaline substance, and the colloidal solution is aged, subjected to solid-liquid separation and dried to obtain tin oxide particles; the tin oxide particles are sequentially soaked in sulfuric acid and activated and roasted to obtain sulfate radical acidic SnO 2 The composite material is used for the cooperative pyrometallurgical smelting of antimony concentrate and arsenic alkaline residue leaching residue, and can promote the volatile Sb of complex antimony and arsenic components in arsenic residue by utilizing the high strong acidity and the high oxidizability of the composite material 2 O 3 And As 2 O 3 The method has the advantages of high conversion efficiency, realization of antimony and arsenic removal from the arsenic alkali residue leaching residue with high efficiency and low cost, real realization of resource utilization of the arsenic alkali residue leaching residue, and quick, high-efficiency and low costThe method is simple in process and convenient to operate, and industrial production is met.
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 of the sulfate acid tin dioxide composite material in antimony concentrate pyrometallurgy cooperative recycling treatment of arsenic alkali residue leaching residue, belonging to the technical field of solid waste treatment of arsenic alkali residue leaching residue.
Background
At present, the smelting process of antimony mainly comprises 3 processes of volatilization roasting (smelting), reduction smelting and alkaline refining. During the volatilizing roasting (smelting), antimony and arsenic are oxidized into Sb respectively 2 O 3 And As 2 O 3 Volatilizing the antimony into furnace gas in the form of steam, cooling, collecting dust and the like to obtain a powdery intermediate product, namely antimony oxide (commonly called antimony oxide); in the reduction smelting process, Sb 2 O 3 And As 2 O 3 Is reduced into simple substance antimony and arsenic which can enter into crude antimony; in the alkaline refining process, arsenic in the crude antimony is usually removed by blowing sodium carbonate, 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
the slag floating on the surface of the antimony liquid formed in the process can be raked off, and the alkaline and arsenic-containing dross is called arsenic alkali slag. According to statistics, 130-140 kg of arsenic alkali residue can be produced every 1t of refined antimony, and great potential threat is caused to the environment and human bodies. As the arsenic alkali slag not only contains metal antimony which can be recycled, but also has the characteristic of extremely toxic sodium arsenate, the arsenic alkali slag is difficult to directly carry out secondary smelting and cannot be directly discarded. It is necessary to treat and recycle the arsenic alkali residue. The domestic resource utilization of the arsenic alkali residue is mainly carried out from two aspects, namely the recovery of antimony in the arsenic alkali residue and the comprehensive utilization of arsenic in the arsenic alkali residue. At present, the domestic and foreign treatment modes of arsenic alkali residues mainly comprise: pyrogenic and wet processes. The advantages of the pyrometallurgical treatment of arsenic-alkali slag are high treatment capacity, high production efficiency, and low investment, and can utilize the equipment of antimony smelting system. The pyrogenic process treatment process has obvious disadvantages at the same time: 1. the raw materials and products have high arsenic content and poor operating environment, and the health of workers is seriously damaged; 2. the high-arsenic crude antimony is repeatedly refined, the return slag generated by refining contains higher arsenic and cannot be treated, and the vicious circle of arsenic is formed; 3. the integrity and the tightness of a cooling dust collecting system are not high in the pyrogenic process treatment process, and the environmental risk is huge. At present, the academic and industrial consistent view is that the arsenic alkaline residue is mainly subjected to dearsenification from arsenic-containing hazardous waste by a wet leaching method. The arsenic alkali slag mainly comprises arsenate/arsenite, antimonite/antimonite and sodium carbonate/sodium hydroxide, and also comprises a large amount of impurity components such as silicon, aluminum, fluorine, chlorine and the like. In the process of the arsenic alkali residue selective leaching process, easily soluble arsenic, antimony and alkali components enter a leaching solution, various difficultly soluble components and newly formed precipitates are retained in leaching residues to become main components of the leaching residues, XRF (X-ray fluorescence) result analysis of the leaching residues obtained by the existing leaching process is shown in the following table 1.1, and main elements of the arsenic alkali residue leaching residues are Sb, As and partial silicate elements thereof. The leached residue is kept at a high pH value in an aqueous solution leaching environment. In the sulfuric acid leaching system, part of arsenic-containing components are released into the solution system again. If the arsenic-containing leaching residues are not treated, a large amount of arsenic enters 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, rain water and the like, and serious secondary pollution is caused. Therefore, it is important to recycle antimony from the leaching residue and to perform further harmless treatment in the context of recycling and reduction.
TABLE 1 representative arsenic caustic leach residue elemental composition (XRF analysis)
In the prior art, the damage of leaching slag cannot be reduced by simple landfill, and secondary pollution is easily caused, so that the leaching slag cannot be simply buried, and harmful substances in the leaching slag must be treated and then buried to reduce or isolate the toxicity of the leaching slag. The common treatment method for the arsenic alkali residue leaching residue mainly comprises treatment methods of stabilization and solidification, pyrogenic process, wet process and the like of the leaching residue, but the leaching residue is directly subjected to stabilization treatment, which is not favorable for the recycling of antimony resources in the leaching residue and the harmless treatment requirement of the arsenic alkali residue. On the basis of arsenic alkaline residue leaching, the leaching residue is continuously treated by a wet method, so that the cost of leaching residue recovery and reduction is greatly increased, the link of wastewater treatment is increased, and the efficiency of leaching residue treatment is reduced.
The leaching residue is an important product for selectively leaching the arsenic-alkali residue, and contains high-content metallic antimony and part of insoluble arsenic-containing components. If the treatment is improper, the problems of resource waste, environmental pollution and the like are caused. A new disposal technology is explored and applied to industrial practice, the problem of safe disposal of leaching slag is solved by disposal, 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 problem that the arsenic alkali residue leaching residue is difficult to recycle and efficiently and circularly treated by the prior art, the invention aims to provide sulfate acid SnO 2 The composite material has strong acid centers and high oxidation activity, and can promote the volatile Sb of complex antimony and arsenic components in arsenic-alkali residue leaching residue and waste residue under the condition of high temperature 2 O 3 And As 2 O 3 The high-efficiency transformation is carried out, so that the high-efficiency and low-cost recovery of arsenic and antimony in the arsenic-alkali residue leaching residue can be realized, and the purpose of resource utilization of the arsenic-alkali residue leaching residue is achieved.
The second purpose of the invention is to provide 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 treating arsenic alkaline residue leaching residue by cooperation of pyrometallurgical co-recycling of antimony concentrate, wherein the antimony concentrate and the arsenic alkaline residue leaching residue are cooperatively treated by pyrometallurgical co-processing, and the sulfate acid tin oxide composite material is utilized, so that the purpose of efficiently recovering antimony from the antimony concentrate is achieved, and simultaneously, the complex antimony arsenic component in the arsenic residue can be efficiently promoted to volatile Sb 2 O 3 And As 2 O 3 The transformation is carried out, antimony and arsenic are removed from the arsenic alkali residue leaching residue at high efficiency and low cost, the resource utilization of the arsenic alkali residue leaching residue is really realized, the method is rapid, high-efficiency and low-cost, the process is simple, the operation is convenient, and the industrial production is met. And compared with the existing hydrometallurgy technology, the pyrometallurgical technology has relatively simple operation and high production rate, and arsenic is preferentially removed and separated from other valuable metals, so that the complicated separation steps and wastewater discharge are avoided.
In order to achieve the technical purpose, the invention provides sulfate acid SnO 2 The preparation method of the composite material is to mix Sn with the composite material 4+ The solution is adjusted to form a colloidal solution by adopting an alkaline substance, and the colloidal solution is aged, subjected to solid-liquid separation and dried to obtain tin oxide particles; the tin oxide particles are sequentially soaked in sulfuric acid and activated and roasted to obtain sulfate radical 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 using a precipitation method, wherein the superstrong L acid centers in the tin oxide particles have stronger adsorption effect on water molecules, and are dried and dehydrated to facilitate exposure of more strong L acid centers, so that more sulfuric acid can be coordinated and adsorbedThe radical ions are impregnated with sulfate radicals, and then activated and roasted to enable water to be dissociated and desorbed to generate protonic acid centers and enable the sulfate radicals to be acidic SnO 2 The material shows a regular and effective mesoporous pore channel 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 prepared by loading sulfate radicals on the surfaces of tin oxide particles, and shifting the strength of an electron cloud on a Sn-O bond by utilizing coordination adsorption of the surfaces of the sulfate tin oxide particles, so that the activity of an L acid center is enhanced.
As a preferable mode, the Sn-containing compound 4+ Sn in solution (2) 4+ The mass percentage concentration of (A) is 0.2-3%. If Sn 4+ Too low a concentration may result in subsequent SO-induced Sn-O 4 2- The coverage area for inducing the distribution and the deviation of the electron cloud is small, and the acidity of the generated L acid center is weak. And Sn 4+ Too high concentration of SO in the adsorption of 4 2- The efficiency of inducing the shift of the electron cloud distribution of Mn — O by the S ═ O bond decreases, affecting the acidity of the overall L acid center. Sn (tin) 4+ Mainly provided by readily soluble tin salts, such as tin tetrachloride and the like.
As a preferable scheme, the drying treatment conditions 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 conversion of tin hydroxide is incomplete and the exposed L acid sites are low, and if the temperature is too high, the reactivity of tin hydroxide is destroyed.
As a preferred scheme, the sulfuric acid soaking conditions are as follows: the liquid-solid ratio is 10-20 mL:1g, the concentration of sulfuric acid is 0.5-1 mol/L, and the soaking time is 30-60 min. The tin dioxide is soaked by 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 tin dioxide is likely to be dissolved, and if the sulfuric acid concentration is too low or the soaking time is too short, it is difficult to generate a large amount of highly active tin sulfate component on the surface of the tin dioxide.
As a preferred embodiment, the conditions of the activation roasting 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 and 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 facilitated.
Preferably, the alkaline substance is ammonia, sodium hydroxide or potassium hydroxide, preferably ammonia, which is conventional industrial ammonia. Regulating Sn content by alkaline substances 4+ The pH of the solution is 7-9, and a colloidal solution can be obtained.
As a preferable scheme, the aging time is 8-16 hours. The tin hydroxide is colloidally converted to a crystalline precipitate by aging.
The invention also provides sulfate acid SnO 2 A composite material obtained by the preparation method.
The invention also provides a method for treating arsenic-alkali residue leaching residue by virtue of cooperation of pyrometallurgy of antimony concentrate and recycling, which comprises the steps of carrying out pyrometallurgy on antimony concentrate, arsenic-alkali residue leaching residue, a binder, a reducing agent and sulfate radical acid SnO 2 The raw materials including the composite material are sequentially mixed, ground, pressed into balls, dried and roasted, and antimony oxide and arsenic oxide are recovered from roasting flue gas.
The key point of the technical scheme of the invention is as follows: the arsenic-antimony components in the arsenic-alkali residue leaching residue are recycled. Based on the change behavior of the arsenic and antimony components in the pyrometallurgical process of the arsenic alkali slag leaching slag, the volatilization behavior and the technical principle of the arsenic and antimony components in the antimony smelting process flow in the prior art are combined. And mixing the arsenic alkali residue leaching slag and the antimony concentrate according to a certain mixing ratio to form pellets, and roasting by a pyrogenic process to realize arsenic and antimony enrichment, removal and collection. Has important significance for antimony smelting process and arsenic alkali slag disposal process flow. In addition, it is more important to add special sulfate acid SnO during pyrometallurgical processes 2 A composite material having a high strong acid andthe strong oxidation active center can promote the stable and difficultly volatilized arsenic and antimony components in the arsenic alkali residue leaching residue to be converted into easily volatilized Sb 2 O 3 And As 2 O 3 Sulfuric acid radical acidic SnO 2 SO on the surface of composite materials 4 2- Can cause SnO 2 The electron cloud intensity on the Sn-O bond on the surface shifts, the electronegativity of O is far greater than that of S, the electron cloud on S and metal also shifts to O, so that a strong acid center is generated, and the arsenic and antimony in the leaching residue can be converted into a volatile medium by virtue of the characteristics of strong oxidizing property and high acidity. Sb is antimony in arsenic alkali slag after the arsenic alkali slag is leached and fed in and out through water in the prior art 2 O 3 And Sb 2 O 4 In the form of the main higher oxides As 2 O 5 In addition, arsenic and antimony are present as 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 the arsenic and antimony components to As during calcination 2 O 3 And Sb 2 O 3 Volatilization removal is carried out, and the main reaction is as follows: 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 With the discharge of furnace gas, antimony oxide and non-volatile Sb can be obtained by condensation and dust collection 2 O 3 Can be further oxidized to becomeNon-volatile Sb 2 O 4 And remain 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, preventing its high-intensity oxidation. The inventor finds out that the leaching slag roasting and antimony concentrate pyrogenic process have certain correlation in principle and theory through the theoretical and practical exploration processes, and the key foundation is laid for the synergistic roasting. At present, no relevant research report and industrial application aiming at the synergistic roasting of leaching slag and antimony concentrate exist. The method is beneficial to treating the arsenic alkali residue leaching residue with high efficiency and low cost, and realizes the industrial high-absorption and utilization of the arsenic and antimony components in the arsenic alkali residue leaching residue. Has important significance for upgrading antimony smelting and treating arsenic alkaline residue.
As a preferable scheme, the mass ratio of the arsenic alkali residue leaching residue to the antimony concentrate is 0.5-1: 1. If the proportion of the leaching slag of the arsenic alkali slag is too high, the volatilization effect of arsenic and antimony is not complete, and the leaching slag contains high-content aluminosilicate, which can cause the silicate to melt and harden in a porcelain boat, thus affecting the development of the process, while the proportion of antimony concentrate is too high, the effect of melting can not be generated in the roasting process, and under the condition of medium temperature, the volatilization rate effect of arsenic and antimony is not obvious, and higher volatilization effect of arsenic and antimony can be obtained by increasing the temperature. The arsenic-alkali slag leaching residue and the antimony concentrate are subjected to synergistic pyrometallurgy according to a proper proportion, so that the problems can be well overcome, the melting temperature of the antimony concentrate can be reduced by the arsenic-alkali slag leaching residue, the antimony concentrate can effectively prevent the arsenic-alkali slag leaching residue from being solidified, and the overall 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 residue leaching residue and the antimony concentrate. The reducing agent is a reducing agent which is conventionally used in the pyrometallurgical process of antimony concentrate, the using amount of the reducing agent is in the range, the increase of the reducing agent is beneficial to improving the volatilization efficiency of arsenic and antimony, 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. In a more preferred embodiment, the reducing agent is at least one of activated carbon, high-purity coal and coking coal. The reducing agent mainly plays a role in reducing arsenic and antimony.
Preferably, the mass percentage of the binder in the raw materials is 5-10%. In a more preferred embodiment, the binder is at least one of bentonite, sodium humate, sodium lignosulfonate, and water glass. The function of the binder is to improve the binding performance between minerals and facilitate the preparation of agglomerates.
As a preferable scheme, sulfate acid SnO in the raw material 2 The mass percentage content of the composite material is 0.5-1.5%. Sulfate acid SnO 2 The dosage of the composite material is in the range, and SnO is acidic along with sulfate radical 2 The increase of the composite material is beneficial to improving the volatilization efficiency of arsenic and antimony, but the overhigh sulfate acid SnO 2 The effect of the composite material for improving the volatilization efficiency of the arsenic and the antimony is not obvious, and the use cost is increased.
As a preferable scheme, the roasting conditions are as follows: the temperature is 800-900 ℃. The calcination time is generally determined by the complete volatilization of arsenic and antimony. Reducing agent and sulfate acid SnO are used in combination 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 alkali slag leaching residue and the antimony concentrate are crushed and ground to the granularity of less than minus 40 meshes, so that important conditions are provided for the full contact of the mineral surface with high-temperature heat.
As a preferred scheme, a proper amount of water is also added into the raw materials, so that the physical uniform mixing is facilitated, and the water content in the mixed raw materials is ensured to be 5-8%; after the materials are uniformly mixed, the mixed materials are placed in the air for 12-15 hours for natural drying, and are ground after drying.
As a preferable scheme, a hydraulic sampling machine is selected in the briquetting process at 10-20 kg-cm -2 Under pressure of (2) to form briquettes of size
As a preferable scheme, in the drying process, the green pellets are dried in a hot air drying oven for 3 hours at 110 ℃ to obtain finished green pellets.
The sulfate acid SnO provided by the invention 2 The preparation method of the composite material comprises the following specific steps: adding a certain amount of deionized water into a tin tetrachloride solid to prepare a solution with the mass fraction of tin ions of 0.2-3%, stirring fully, slowly adding industrial ammonia water (the concentration is about 25%) until the pH value of the solution is within the range of 7-9 and the solution state 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 drying oven at the temperature of 150-200 ℃ to bake for 3.0-4.0 h, and mixing the baked solid sample according to the liquid-solid ratio of 10-20: 1 is placed in 0.5-1 mol/L sulfuric acid for soaking for 30-60 min, a filter sample is placed in a muffle furnace for activation roasting at the temperature of 450-550 ℃ for 2-6 h after rapid filtration, the temperature is too high, sulfur components in the composite material are lost, the structure of an acid center is damaged, and the temperature is too low, so that the activation of a strong acid center on a metal oxide is not facilitated.
The invention provides a method for treating arsenic alkaline residue leaching residue by antimony concentrate pyrometallurgy and cooperative recycling, which comprises the following steps: crushing and grinding the arsenic alkali slag leaching residue and the antimony concentrate until the granularity is smaller than-40 meshes, providing important conditions for the surface of the mineral to fully contact with high-temperature heat, and mixing the arsenic alkali slag leaching residue and the antimony concentrate according to the mass ratio of 0.5-1: 1. Adding bentonite and a 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 amount. After being uniformly mixed, the mixture is placed in the air for 12-15 hours for natural drying, and the material is ground after drying. Placing the material in a hydraulic sample making machine at 10-20 kg-cm -2 Is pressed into briquettes with the size of the produced briquettes
Drying the raw briquettes in a hot air drying oven at 100-120 ℃ for 2-4 h to obtain finished product antimony concentrate-arsenic alkali residue leaching residue mixed briquettes, and drying the finished product briquettesAnd (4) conveying the mixture to a resistance furnace for high-temperature volatilization dearsenification and antimony treatment at 800-900 ℃ until the arsenic and antimony are volatilized.
Compared with the prior art, the technical scheme of the invention has the following beneficial technical effects:
the sulfate acid SnO provided by the invention 2 The composite material contains active tin sulfate components with high oxidizing property and strong acidity on the surfaces of tin dioxide particles, and can efficiently promote the difficult-to-volatilize complex antimony-arsenic components in arsenic-alkali residue leaching residue waste residues to volatile Sb under the high-temperature condition 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 residue and realizing the resource utilization of the arsenic alkali residue leaching residue.
The sulfate acid SnO provided by the invention 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 method for treating arsenic alkaline residue leaching residue by antimony concentrate pyrometallurgy and recycling cooperation realizes the cooperation pyrometallurgy of antimony concentrate and arsenic alkaline residue leaching residue, and can efficiently promote the complex antimony and arsenic components in the arsenic residue to volatile Sb by utilizing sulfate acid tin oxide composite material in the pyrometallurgy process while achieving the purpose of efficiently recovering antimony in the antimony concentrate 2 O 3 And As 2 O 3 The transformation is carried out, antimony and arsenic removal of arsenic and alkali residue leaching residue are efficiently and cheaply achieved, resource utilization of arsenic and alkali residue leaching residue is really achieved, the method is fast, efficient and low in cost, the process is simple, the operation is convenient, and industrial production is met. And compared with the existing hydrometallurgy technology, the pyrometallurgical technology has relatively simple operation and high production rate, and arsenic is preferentially removed and separated from other valuable metals, so that the complicated separation steps and wastewater discharge are avoided.
Detailed Description
The following specific examples are intended to further illustrate the present disclosure, but not to limit the scope of the claims.
Example 1
50g of tin tetrachloride solid is weighed, 1L of deionized water is added to prepare a solution with the mass fraction of 5% (the concentration of tin ions is about 2.2%), after the solution is fully stirred, 25% of ammonia water is slowly added until the pH value of the solution is about 8 and the solution is colloidal. Aging for 12h, filtering and washing to obtain a corresponding tin hydroxide intermediate medium product, adding the obtained tin hydroxide solid into a 200 ℃ oven, baking for 4.0h, placing the baked solid sample into 0.5-1 mol/L sulfuric acid according to the liquid-solid ratio of 10:1, soaking for 30-60 min, rapidly filtering, dividing the filtered sample into three parts, respectively placing the three parts into a muffle furnace, performing activation baking for 4h at the temperature of 350-550 ℃, and taking out for subsequent use.
Prepared sulfate acid SnO 2 The composite material was tested for acid strength by amine titration using a Hammett indicator, which is actually a weak base that is adsorbed to react with the acid sites when it encounters them. Represented by the formula:
with H 0 The acid strength coefficient of the composite material is measured. When H is present 0 The smaller the value of (A), the stronger the acid strength, and conversely, the weaker the acid strength. Sulfate acid SnO formed under several different conditions 2 The acidity of the composite material is experimentally analyzed, 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 expression is as follows: the acid strength of the composite material can be enhanced to a certain extent by increasing the soaking time, the concentration of the soaking acid and the roasting temperature. The increase in the concentration of the pickling acid results in more SO 4 2- Can cause SnO 2 The electron cloud on the Sn-O bond on the surface shifts in intensity, and the electron cloud on S and metal also shifts to O, resulting in the generation of strong acid centers. If the calcination temperature is too high or too low, the acid center is not easily activated or the activation is affected. And the formation of the strong acid center is beneficial to the volatilization and recovery of the arsenic and antimony components in the arsenic-alkali residue leaching residue. Sulfur with different acid strength coefficients generated according to different conditionsAcid radical acidic SnO 2 And roasting at 800 ℃ according to the mixing ratio of 0.5% (see example 2 for specific operation, antimony concentrate: leaching slag mixing ratio 1.5:1, reducing agent content 20%, and bentonite 5%), and the experimental results are shown in table 2. As can be seen from table 2, the stronger the acidity coefficient is, the sufficient acidity and oxidation performance are, and the volatilization of arsenic and antimony is directly realized at a lower temperature, which is a great breakthrough for industrial application.
TABLE 1 sulfate acid SnO formed in different conditions 2 Acidity index of composite material
TABLE 2 sulfate acid SnO under different conditions 2 Volatilization rate of arsenic and antimony in leaching residue
Example 2
Taking arsenic alkaline residue leaching residue of a cold water river tin mine as a test research object, crushing and grinding the arsenic alkaline residue leaching residue and antimony concentrate until the granularity is smaller than-40 meshes, weighing 500g of arsenic alkaline residue leaching residue after crushing and grinding is completed, and mixing the antimony concentrate and the arsenic alkaline residue leaching residue according to a certain proportion, wherein the proportion is as follows: 0.5-2.0: 1. Adding 5 percent of bentonite and 5 to 30 percent of reducing agent into the mixed ore; tap water was poured to make the water content 5%. 5g of a calcined tin hydroxide (sulfate acid SnO having an acid Strength index of-13.26 prepared in example 1) was sampled 2 Composite material) is added, and the acid composite material is added to account for 0.2-1.0 percent of the total amount. After being mixed evenly, the mixture is placed in the air for 12 hours for natural drying, and the material is ground after drying. Placing the materials in a hydraulic sample making machine at 20 kg-cm -2 Under a pressure of (2) to form briquettes of size
Drying the raw pellets in a hot air drying oven at 110 ℃ for 3h to obtain finished antimony concentrate-arsenic caustic sludge leaching residue mixed agglomerates. And conveying the finished pellets into a resistance furnace for high-temperature volatilization dearsenification and antimony treatment at 600-1000 ℃. And calculating the volatilization removal rate of the arsenic and antimony components according to the mass before and after the reaction. The test results are shown in the following table 3, the leaching residue is roasted alone, the leaching residue with incomplete arsenic and antimony volatilization effects contains high-content aluminosilicate, the roasting of the leaching residue alone can cause silicate melting and hardening in a porcelain boat, and the development of the process is influenced, while the roasting process of antimony concentrate can not generate melting influence effects, under the conditions of medium and high temperature, the arsenic and antimony volatilization rate effect is not obvious, and the higher the temperature is, the better the arsenic and antimony volatilization effect of the leaching residue is. And in a synergistic mode, the overall arsenic-antimony volatilization rate is increased, and the synergistic roasting of arsenic alkaline residue leaching slag and antimony concentrate is realized. Test data show that the doping amount of the antimony concentrate is higher than the yield of the leached 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 to the leached slag. Meanwhile, the test result proves that the dosage of the reducing agent and the sulfate tin dioxide composite material can influence the volatilization effect of the arsenic and the antimony in an integral synergistic mode. As the use amount of the reducing agent and the sulfate stannic oxide composite material is increased, the volatilization rate of arsenic and antimony is further improved. The temperature also influences the overall arsenic and antimony volatilization effect, and the higher the temperature is, the better the volatilization effect is. More importantly, the antimony concentrate and the leaching slag supplement each other in the whole. The antimony concentrate provides a non-melting condition for the leaching slag, and the high sodium content of the leaching slag reduces the melting point of the whole system, so that the antimony concentrate can realize high-efficiency volatilization of arsenic and antimony components at a certain temperature. And in a synergistic mode, the energy consumption of the energy consumption process is greatly reduced, the green sustainable development of antimony smelting is realized, and the roasted product can be directly used as cement for disposal. Has key strategic significance for antimony smelting.
TABLE 3 volatilization rate of arsenic and antimony from leaching residue by pyrogenic process under different conditions
Claims (10)
1. Sulfate acid SnO 2 The preparation method of the composite material is characterized by comprising the following steps: will contain Sn 4+ The solution is adjusted to form a colloidal solution by adopting an alkaline substance, and the colloidal solution is aged, subjected to solid-liquid separation and dried to obtain tin oxide particles; the tin oxide particles are sequentially soaked in sulfuric acid and activated and roasted to obtain sulfate radical acidic SnO 2 A composite material.
2. A sulfate acidic SnO according to claim 1 2 The preparation method of the composite material is characterized by comprising the following steps: the Sn is contained 4+ Sn in solution of 4+ The mass percentage concentration of (A) is 0.2-3%.
3. A sulfate acidic SnO according to claim 1 2 The preparation method of the composite material is characterized by comprising the following steps: the drying treatment conditions are as follows: the temperature is 150-200 ℃ and the time is 3.0-4.0 h.
4. A sulfate acidic SnO according to claim 1 2 The preparation method of the composite material is characterized by comprising the following steps: the sulfuric acid soaking conditions are as follows: the liquid-solid ratio is 10-20 mL:1g, the concentration of sulfuric acid is 0.5-1 mol/L, and the soaking time is 30-60 min.
5. A sulfate acidic SnO according to claim 1 2 The preparation method of the composite material is characterized by comprising the following steps: the conditions of the activating roasting are as follows: the temperature is 450-550 ℃, and the time is 2-6 h.
6. Sulfate acid SnO 2 A composite material characterized by: the preparation method of any one of claims 1 to 5.
7. Antimony concentrate pyrometallurgical cooperative recycling treatmentThe method for leaching the arsenic alkali residue is characterized by comprising the following steps: leaching slag containing antimony concentrate and arsenic caustic sludge, a binder, a reducing agent and sulfate acid SnO as claimed in claim 6 2 The raw materials including the composite material are sequentially mixed, ground, pressed into balls, dried and roasted, and antimony oxide and arsenic oxide are recovered from roasting flue gas.
8. The method for pyro-smelting cooperative recycling of arsenic alkali residue leaching residue of antimony concentrate according to claim 7, characterized by comprising the following steps:
the mass ratio of the arsenic alkali residue leaching residue to the antimony concentrate is 0.5-1: 1;
the mass of the reducing agent is 20-30% of the total mass of the arsenic alkali residue leaching residue and the antimony concentrate;
the reducing agent is at least one of active carbon, high-purity coal and coking coal.
9. The method for cooperative recycling of arsenic alkali slag leaching residue in antimony concentrate pyrometallurgy according to claim 7, wherein the method comprises the following steps:
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 lignosulfonate and water glass;
acid SnO sulfate radical in the raw material 2 The mass percentage content of the composite material is 0.5-1.5%.
10. The method for cooperative recycling of arsenic alkali slag leaching residue in antimony concentrate pyrometallurgy according to claim 7, wherein the method comprises the following steps: the roasting conditions are as follows: the temperature is 800-900 ℃.
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