Method for preparing iron oxide red by roasting cyanidation tailings containing arsenic
阅读说明：本技术 用含砷焙烧氰化尾渣制备铁红的方法 (Method for preparing iron oxide red by roasting cyanidation tailings containing arsenic ) 是由 陈运法 王永良 叶树峰 涂玉波 于 2018-06-01 设计创作，主要内容包括：一种用含砷焙烧氰化尾渣制备铁红的方法,包括以下步骤：将含砷焙烧氰化尾渣磨矿至细度小于0.048mm的部分占90％以上；将含砷焙烧氰化尾渣和强化剂加入多级逆流浸出装置中,通过多级逆流浸出方法浸出其中的铁和砷,反应完毕得到浸出液和浸出渣；调节浸出液pH至0.5～3,加入铁粉将其中的Fe<Sup>3+</Sup>全部还原为Fe<Sup>2+</Sup>,反应完毕后固液分离；将得到的液体调节pH至1～7,加入氧化剂将其中的砷全部转化为砷渣,过滤；将过滤得到的液体调节pH至3～7,加入氧化剂并搅拌,使溶液中的铁离子沉淀,过滤得到氢氧化铁；焙烧氢氧化铁得到铁红。本发明采用湿法工艺,清洁环保,不仅可以实现铁资源的利用,还可以将砷、氰根等进行无害化处置,具有良好的经济效益和广阔的应用前景。(A method for preparing iron oxide red from arsenic-containing roasted cyanidation tailings comprises the following steps of grinding the arsenic-containing roasted cyanidation tailings until the part with the fineness smaller than 0.048mm accounts for more than 90%, adding the arsenic-containing roasted cyanidation tailings and an enhancer into a multistage countercurrent leaching device, leaching iron and arsenic in the arsenic-containing roasted cyanidation tailings by a multistage countercurrent leaching method to obtain a leaching solution and leaching residues after reaction, adjusting the pH of the leaching solution to 0.5-3, adding iron powder to reduce all Fe 3+ in the leaching solution to Fe 2+ , performing solid-liquid separation after the reaction is finished, adjusting the pH of the obtained liquid to 1-7, adding an oxidant to convert all arsenic in the arsenic residues into arsenic residues, filtering the arsenic residues, adjusting the pH of the filtered liquid to 3-7, adding the oxidant and stirring to precipitate iron ions in the solution, filtering to obtain iron hydroxide, and roasting the iron oxide red to obtain the iron oxide red.)
1. The method for preparing iron oxide red by using arsenic-containing roasted cyanidation tailings is characterized by comprising the following steps of:
(1) Grinding the arsenic-containing roasted cyanidation tailings until the part with the fineness of less than 0.048mm accounts for more than 90%;
(2) Adding the arsenic-containing roasted cyanidation tailings obtained by grinding in the step (1) and a reinforcing agent into a multistage countercurrent leaching device, leaching iron and arsenic in the arsenic-containing roasted cyanidation tailings by a multistage countercurrent leaching method, supplementing water, acid and the reinforcing agent according to needs in the stage leaching process, and obtaining leachate and leaching slag after the reaction is finished;
(3) Adjusting the pH value of the leachate obtained in the step (2) to 0.5-3, adding iron powder to reduce all Fe 3+ in the leachate to Fe 2+, and carrying out solid-liquid separation after the reaction is finished;
(4) adjusting the pH value of the liquid obtained in the step (3) to 1-7, adding an oxidant to convert all arsenic in the liquid into arsenic slag, and filtering;
(5) Adjusting the pH of the liquid obtained in the step (4) to 3-7, adding an oxidant, stirring to precipitate iron ions in the solution, and filtering to obtain ferric hydroxide;
(6) Roasting the ferric hydroxide obtained in the step (5) to obtain iron oxide red.
2. The method for preparing iron oxide red by using arsenic-containing roasted cyanidation tailings according to claim 1,
in the step (2), the enhancer is one or a combination of more than two of FeSO 4, Na 2 SO 3, Na 2 S 2 O 3, NaHS, Na 2 S 2 O 5, Na 2 S 2 O 4, H 2 S, Na 2 S, CaS, H 2 SO 3, Al, Zn, Fe, Mg or Na, and the adding amount of the enhancer is 1-30% of the mass of the arsenic-containing roasted cyanidation tailings.
3. the method for preparing iron oxide red by using arsenic-containing roasted cyanidation tailings according to claim 1,
in the step (2), the temperature of each stage of leaching operation is 50-150 ℃, and the time is 2-12 hours.
4. The method for preparing iron oxide red by using arsenic-containing roasted cyanidation tailings according to claim 1,
In the step (2), the acid is one or a combination of more than two of sulfuric acid, nitric acid, hydrochloric acid, sulfurous acid, acetic acid or oxalic acid; the concentration of the acid in the solution after the acid is added is 10-50%.
5. The method for preparing iron oxide red by using arsenic-containing roasted cyanidation tailings according to claim 1,
In the step (2), the multistage countercurrent leaching stages are two stages, three stages, four stages, five stages or six stages.
6. The method for preparing iron oxide red by using arsenic-containing roasted cyanidation tailings according to claim 1,
in the step (3), the substance for adjusting the pH is one or the combination of more than two of NaOH, Ca (OH) 2, CaO, Na 2 CO 3 or ammonia water.
7. the method for preparing iron oxide red by using arsenic-containing roasted cyanidation tailings according to claim 1,
In the step (3), the reaction temperature is 20-60 ℃.
8. The method for preparing iron oxide red by using arsenic-containing roasted cyanidation tailings according to claim 1,
In the steps (4) and (5), the oxidant is one or a combination of more than two of hydrogen peroxide, peracetic acid, sodium dichromate, chromic acid, nitric acid, potassium permanganate, ammonium persulfate, sodium hypochlorite, calcium hypochlorite, potassium chlorate, potassium perchlorate, sodium chlorate, sodium perchlorate, sodium percarbonate, sodium perborate, potassium perborate, manganese dioxide, bromine, iodine, chlorine, oxygen or ozone; in the step (4), the addition amount of the oxidant is 1-10 times of the amount of the arsenic substance.
9. the method for preparing iron oxide red by using arsenic-containing roasted cyanidation tailings according to claim 1,
In the step (5), the substance for adjusting pH is an acid as described in claim 4.
10. The method for preparing iron oxide red by using arsenic-containing roasted cyanidation tailings according to claim 1,
In the step (6), the roasting temperature is 600-1000 ℃, and the roasting time is 1-5 h.
Technical Field
The invention belongs to the technical field of hydrometallurgy, and particularly relates to a method for preparing iron oxide red by using arsenic-containing roasted cyanidation tailings.
Background
The arsenic-containing roasting cyanidation tailings are solid wastes generated after gold concentrate is roasted to prepare acid and cyaniding to extract gold, and according to incomplete statistics, the quantity of cyanidation tailings discharged by gold smelting enterprises in China per year exceeds 2000 million tons, and the accumulated stockpiling quantity reaches more than 1.2 hundred million tons. Because the cyanidation tailings contain a large amount of cyanide and heavy metals such as arsenic, lead and the like, the cyanidation tailings bring huge risks to the ecological environment and are inorganic cyanidation solid wastes in national hazardous waste lists.
The method mainly comprises the steps of Fe 2 O 3, generally containing 20-60% of iron, particularly tailings with high iron content, and having a great recycling value for iron.
Besides valuable metal elements, some tailings also contain a large amount of arsenic, which not only causes environmental pollution, but also influences the secondary resource utilization of the slag. For example, arsenic enters molten iron along with the iron making process, the thermoplasticity of iron is seriously affected, and cracks are easy to appear when the iron is heavily pressed. Therefore, before secondary resource utilization of the burned slag, it is usually necessary to remove arsenic from the burned slag. In order to prevent the adverse effect of arsenic on the subsequent resource utilization, arsenic entering the cinder is usually removed by a chemical method, and then is enriched and recycled or is subjected to harmless disposal. At present, a sulfuric acid leaching method, an alkaline leaching method, a copper sulfate replacement method, an iron sulfate method and the like are mainly used. The wet process has the advantages of high efficiency, low energy consumption, small environmental pollution and good working conditions, but the process flow is complex and the treatment cost is relatively high.
Therefore, with the increasing attention of China to environmental protection and the increasing shortage of resources, the method has very important significance in developing and utilizing the resources of the arsenic-containing roasted cyaniding tailings and reducing the harm of the cyaniding tailings to the environment.
Disclosure of Invention
In view of the shortcomings of the prior art, the present invention is directed to a method for preparing iron oxide red from arsenic-containing roasted cyanidation tailings, so as to solve at least one of the above problems.
the invention is realized by the following technical scheme:
A method for preparing iron oxide red by using arsenic-containing roasting and cyaniding tailings comprises the following steps of (1) grinding the arsenic-containing roasting and cyaniding tailings until the part with the fineness of less than 0.048mm accounts for more than 90 percent of the arsenic-containing roasting and cyaniding tailings, 2) adding the arsenic-containing roasting and cyaniding tailings and an enhancer obtained by grinding in the step (1) into a multistage countercurrent leaching device, leaching iron and arsenic in the arsenic-containing roasting and cyaniding tailings by a multistage countercurrent leaching method, supplementing water, acid and the enhancer according to needs in the stage leaching process, obtaining a leaching solution and leaching residues after the reaction is finished, 3) adjusting the pH of the leaching solution obtained in the step (2) to 0.5-3, adding iron powder to reduce Fe 3+ in the leaching solution into Fe 2+ completely, performing solid-liquid separation after the reaction is finished, 4) adjusting the pH of the liquid obtained in the step (3) to 1-7, adding an oxidant to convert arsenic in the arsenic residues into arsenic residues completely, filtering, 5) adjusting the pH of the liquid obtained in the step (4) to 3-7, adding the oxidant and stirring to precipitate iron hydroxide ions in the step (5) to obtain iron oxide red.
preferably, in the step (2), the enhancer is one or a combination of more than two of FeSO 4, Na 2 SO 3, Na 2 S 2 O 3, NaHS, Na 2 S 2 O 5, Na 2 S 2 O 4, H 2 S, Na2S, CaS, H 2 SO 3, Al, Zn, Fe, Mg or Na, and the adding amount of the enhancer is 1-30% of the mass of the arsenic-containing roasted cyaniding tailings.
Preferably, in the step (2), the temperature of each stage of leaching operation is 50-150 ℃ and the time is 2-12 h.
preferably, in the step (2), the acid is one or a combination of two or more of sulfuric acid, nitric acid, hydrochloric acid, sulfurous acid, acetic acid or oxalic acid; the concentration of the acid in the solution after the acid is added is 10-50%.
preferably, in the step (2), the multistage countercurrent leaching stage number is two, three, four, five or six.
preferably, in the step (3), the substance for adjusting the pH is one or a combination of more than two of NaOH, Ca (OH) 2, CaO, Na 2 CO 3 or ammonia water.
Preferably, in the step (3), the reaction temperature is 20-60 ℃.
Preferably, the oxidizing agent in steps (4) and (5) is one or a combination of two or more of hydrogen peroxide, peracetic acid, sodium dichromate, chromic acid, nitric acid, potassium permanganate, ammonium persulfate, sodium hypochlorite, calcium hypochlorite, potassium chlorate, potassium perchlorate, sodium chlorate, sodium perchlorate, sodium percarbonate, sodium perborate, potassium perborate, manganese dioxide, bromine, iodine, chlorine, oxygen, or ozone; in the step (4), the addition amount of the oxidant is 1-10 times of the amount of the arsenic substance.
preferably, in step (5), the substance for adjusting the pH is an acid as described in step (2).
Preferably, in the step (6), the roasting temperature is 600-1000 ℃, and the roasting time is 1-5 h.
according to the technical scheme, the method for preparing the iron oxide red by using the arsenic-containing roasted cyanidation tailings has the following beneficial effects:
(1) leaching most of iron, arsenic and cyanide in the solution into the solution by a multistage reinforced countercurrent acid leaching process, wherein most of cyanide is decomposed in the process, and the cyanide and arsenic in the obtained leaching slag are basically and completely removed;
(2) For the leachate containing iron and arsenic, arsenic precipitate is subjected to harmless treatment in a mode of iron-arsenic co-oxidation precipitation, so that environmental pollution is avoided;
(3) The whole process flow is mainly a hydrometallurgical means, eliminates the harm of cyanide in the treatment process, realizes the harmless treatment of arsenic and the full utilization of iron resources, does not cause secondary pollution to the environment, and has certain economic benefit.
Drawings
FIG. 1 is a flow chart of a method for preparing iron oxide red by roasting cyanidation tailings containing arsenic in an embodiment of the invention.
Detailed Description
In order that the objects, technical solutions and advantages of the present invention will become more apparent, the present invention will be further described in detail with reference to the accompanying drawings in conjunction with the following specific embodiments.
A method for preparing iron oxide red from arsenic-containing roasted cyanidation tailings comprises the following steps of grinding the arsenic-containing roasted cyanidation tailings until the part with the fineness smaller than 0.048mm accounts for more than 90%, adding the arsenic-containing roasted cyanidation tailings and an enhancer into a multistage countercurrent leaching device, leaching iron and arsenic in the arsenic-containing roasted cyanidation tailings by a multistage countercurrent leaching method to obtain a leaching solution and leaching residues after reaction, adjusting the pH of the leaching solution to 0.5-3, adding iron powder to reduce all Fe 3+ in the leaching solution to Fe 2+, performing solid-liquid separation after the reaction is finished, adjusting the pH of the obtained liquid to 1-7, adding an oxidant to convert all arsenic in the arsenic residues into arsenic residues, filtering the arsenic residues, adjusting the pH of the filtered liquid to 3-7, adding the oxidant and stirring to precipitate iron ions in the solution, filtering to obtain iron hydroxide, and roasting the iron oxide red to obtain the iron oxide red.
Specifically, the invention provides a method for preparing iron oxide red by roasting cyanidation tailings containing arsenic, which comprises the following steps: (1) grinding the arsenic-containing roasted cyanidation tailings until the part with the fineness of less than 0.048mm accounts for more than 90%; (2) adding the arsenic-containing roasted cyanidation tailings obtained by grinding in the step (1) and a reinforcing agent into a multistage countercurrent leaching device, leaching iron and arsenic in the arsenic-containing roasted cyanidation tailings by a multistage countercurrent leaching method, supplementing water, acid and the reinforcing agent according to needs in the stage leaching process, and obtaining leachate and leaching slag after the reaction is finished; (3) adjusting the pH value of the leachate obtained in the step (2) to 0.5-3, adding iron powder to reduce all Fe3+ in the leachate to Fe2+, and carrying out solid-liquid separation after the reaction is finished; (4) adjusting the pH value of the liquid obtained in the step (3) to 1-7, adding an oxidant to convert all arsenic in the liquid into arsenic slag, and filtering; (5) adjusting the pH of the liquid obtained in the step (4) to 3-7, adding an oxidant, stirring to precipitate iron ions in the solution, and filtering to obtain ferric hydroxide; (6) roasting the ferric hydroxide obtained in the step (5) to obtain iron oxide red.
In the step (2), the enhancer is one or a combination of more than two of FeSO 4, Na 2 SO 3, Na 2 5 2 O 3, NaHS, Na 2 S 2 O 5, Na 2 S 2 O 4, H 2 S, Na 2 S, CaS, H 2 SO 3, Al, Zn, Fe, Mg or Na, and the adding amount of the enhancer is 1-30% of the mass of the arsenic-containing roasted cyanided tailings.
in the step (2), the temperature of each stage of leaching operation is 50-150 ℃, and the time is 2-12 hours.
In the step (2), the acid is one or a combination of more than two of sulfuric acid, nitric acid, hydrochloric acid, sulfurous acid, acetic acid or oxalic acid; the concentration of the acid in the solution after the acid is added is 10-50%.
in the step (2), the multistage countercurrent leaching stages are two stages, three stages, four stages, five stages or six stages.
In the step (3), the substance for adjusting the pH is one or the combination of more than two of NaOH, Ca (OH) 2, CaO, Na 2 CO 3 or ammonia water.
in the step (3), the reaction temperature is 20-60 ℃.
in the steps (4) and (5), the oxidant is one or a combination of more than two of hydrogen peroxide, peracetic acid, sodium dichromate, chromic acid, nitric acid, potassium permanganate, ammonium persulfate, sodium hypochlorite, calcium hypochlorite, potassium chlorate, potassium perchlorate, sodium chlorate, sodium perchlorate, sodium percarbonate, sodium perborate, potassium perborate, manganese dioxide, bromine, iodine, chlorine, oxygen or ozone; in the step (4), the addition amount of the oxidant is 1-10 times of the amount of the arsenic substance.
In the step (5), the substance for adjusting the pH is the acid in the step (2).
in the step (6), the roasting temperature is 600-1000 ℃, and the roasting time is 1-5 h.
the method for preparing iron oxide red by using arsenic-containing roasted cyanidation tailings is further described in detail by combining specific examples and attached drawings.
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