CN103449517B - Method for preparing white arsenic from arsenic-containing dust in evaporation-free manner - Google Patents

Method for preparing white arsenic from arsenic-containing dust in evaporation-free manner Download PDF

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Publication number
CN103449517B
CN103449517B CN201310377631.0A CN201310377631A CN103449517B CN 103449517 B CN103449517 B CN 103449517B CN 201310377631 A CN201310377631 A CN 201310377631A CN 103449517 B CN103449517 B CN 103449517B
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arsenic
acid
smoke dust
white
containing smoke
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CN201310377631.0A
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CN103449517A (en
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廖亚龙
彭志强
周娟
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Kunming University of Science and Technology
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Kunming University of Science and Technology
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Abstract

The invention relates to a method for preparing white arsenic from arsenic-containing dust in an evaporation-free manner, which belongs to the field of metallurgical engineering. The method comprises the following steps of: adding an oxidizing agent to oxidize trivalent arsenious acid into pentavalent arsenic acid during a process of leaching by water by virtue of the characteristics that arsenic acid is high in solubility in water and is low in solubility in water; purifying and removing impurities, then charging a reducing agent to reduce the pentavalent arsenic acid into the trivalent arsenious acid, cooling, and then crystallizing the arsenious acid into arsenic trioxide; and returning the filtrate obtained by filtering the cooled and crystallized product, leaching, drying the filter cake, thus obtaining the white arsenic product. According to the method, the characteristic of high solubility of pentavalent arsenic can be adequately utilized, and the high leaching rate of arsenic is realized with low water consumption and at a low reaction temperature, thus reducing water consumption and energy consumption.

Description

A kind of method exempting from the white arsenic of Evaporation preparation of arsenic-containing smoke dust
Technical field
The present invention relates to a kind of method exempting from the white arsenic of Evaporation preparation of arsenic-containing smoke dust, belong to metallurgical engineering field.
Background technology
Arsenic and compound thereof are general all toxic, and its toxicity is notorious, almost widely known.But arsenic and compound thereof industrially but have a wide range of applications field and superior using function.Be used as alloy addition and produce plumbous bullet processed, type metal, brass (condenser), accumulator grid, wear resistant alloy, High Strength Construction Steel and corrosion-resisting steel etc.Dezincify can be prevented containing a certain amount of arsenic in brass.High purity arsenic is the raw material producing gaas compound semiconductor, indium arsenide etc., is also the doped element of semiconductor material germanium and silicon.The compound of arsenic is also for the manufacture of agricultural chemicals, sanitas, dyestuff and pharmaceutical preparation etc.
Arsenic content in the earth's crust is also little, but it grows on trees at occurring in nature, mainly exists with the form of sulfide mineral.All containing the sulfide of a certain amount of arsenic in which kind of metallic sulfide ores, the heavy metals such as general and copper, lead, zinc, tin, tungsten, molybdenum, mercury and the association of gold and silver precious metal ore or symbiosis, the concentrate with metal enters smeltery and chemical plant.Arsenic pollute be present in nonferrous metallurgy and chemical industry mining, mineral ore dressing processing be separated, smelt and to purify and in the process such as chemical industry deep processing, in recent years, environmental pollution becomes the focus of social concerns, particularly heavy metal and arsenic pollution.The improvement of arsenic has become the bottleneck of restriction metallurgical industry development.
Arsenic-containing smoke dust in metallurgical or chemical industry contains other valuable metals toward contact, after generally taking to extract arsenic wherein, valuable constituent is returned technical process.The extraction process of arsenic in flue dust, generally has following several method.With acid or water close to boiling temperature under leach, purification after evaporation concentration prepare white arsenic product (Huang Gansheng, Quan Changrong. wet-extraction for arsenic novel process explore [J]. non-ferrous metal (Smelting Part), 1994 (3): 3 ~ 4).Due to As 2o 3in water, solubleness is little, prepares white arsenic need to solve the problem that energy consumption is large, cost is high further with the method for evaporation concentration.
Summary of the invention
For overcoming the deficiencies in the prior art, the invention provides a kind of method exempting from the white arsenic of Evaporation preparation of arsenic-containing smoke dust, the characteristic that pentavalent arsenic solubleness is high can be made full use of, under low water consumption and low reaction temperatures, realize the high leaching yield of arsenic, decrease water consumption and energy consumption.
Technical scheme of the present invention is: utilize that the solubleness of arsenic acid in water is large, arsenus acid dissolves low, adds the arsenic acid that the arsenus acid of trivalent is oxidized to pentavalent by oxygenant in the process gone out with water logging.Pass into the arsenus acid that the arsenic acid of pentavalent is reduced to trivalent by reductive agent after purification and impurity removal, after cooling, arsenus acid crystallization is white arsenic.Concrete steps comprise as follows:
(1) heat water to 60 ~ 90 DEG C, under the state stirred, add arsenic-containing smoke dust, hydrogen peroxide and diluted acid successively in water, the pH value that diluted acid controls mixing solutions is 1 ~ 3, filters after reaction 0.5 ~ 3h, obtains the filter cake containing valuable metal and the solution containing arsenic acid;
(2) to being 4 ~ 7 containing the pH value adding ammoniacal liquor regulator solution in the solution of arsenic acid, be stirring reaction 0.5 ~ 2h under the condition of 40 ~ 70 DEG C at solution temperature, reaction terminates rear filtration, the filtrate obtained and filter cake, and filter cake is the material (recoverable) containing valuable metals such as copper;
(3) pass into containing SO in the filtrate of preparing to step (2) 2---gas carry out reduction reaction, after being cooled to 20 ~ 25 DEG C after completion of the reaction filter, namely filter cake obtains white arsenic product after 60 ~ 80 DEG C of drying 8 ~ 24h.
Described arsenic-containing smoke dust is As 2o 3the flue dust of > 30 wt%.
In described step (1), the solid-to-liquid ratio of arsenic-containing smoke dust and water is 1:2 ~ 8g/ml.
Described diluted acid is the one in the sulfuric acid of concentration 10 ~ 20wt%, hydrochloric acid or nitric acid.
The concentration of described hydrogen peroxide is 25 ~ 30wt%, and add-on is 1.8 ~ 3.0 times of arsenic weight in arsenic-containing smoke dust.
Described ammoniacal liquor is industrial ammonia, and industrial ammonia is the aqueous solution containing ammonia 25% ~ 28%.
Described containing SO 2---gas in SO 2---volume be greater than 5%, SO in the gas passed into 2weight be arsenic in solution
0.8 ~ 1.5 times of weight.
Describedly to pass into containing SO 2---the speed of gas be 150 ~ 170L/h.
Principle of the present invention is: utilize that the solubleness of arsenic acid in water is large, arsenus acid dissolves low, adds the arsenic acid that the arsenus acid of trivalent is oxidized to pentavalent by oxygenant in the process gone out with water logging.Pass into the arsenus acid that the arsenic acid of pentavalent is reduced to three by reductive agent after purification and impurity removal, after cooling, arsenus acid crystallization is white arsenic.The filtrate that the product of crystallisation by cooling filters returns leaching, obtains white arsenic product after filtration cakes torrefaction.
The advantage that the present invention possesses and effect:
(1) the high characteristic of pentavalent arsenic solubleness can be made full use of, under low water consumption and low reaction temperatures, realize arsenic
High leaching yield, decrease water consumption and energy consumption;
(2) filtrate after purification of leaching liquor removal of impurities adds smeltery's relieving haperacidity flue gas and pentavalent arsenic acid is reduced to trivalent arsenic acid,
Crystallisation by cooling, crystallized product filters, the white arsenic of dry rear preparation.Process, without the need to carrying out evaporation concentration operation, saves a large amount of energy consumptions.
(3) harmful material of arsenic-containing smoke dust metallurgical process produced is converted into white arsenic product and has reclaimed having in flue dust
Valency metal, realizes resource comprehensive recycle, decreases in commercial run the amount being discharged into arsenic in environment, is conducive to environment protection.
Embodiment
Below in conjunction with embodiment, the invention will be further described.
Embodiment one: the method exempting from the white arsenic of Evaporation preparation of the arsenic-containing smoke dust of present embodiment is:
(1) heat water to 85 DEG C, add containing As in water successively under the state stirred 2o 339.6wt%, Pb18.6wt%, H 2flue dust, the concentration of the plumbous metallurgical process generation of O 8wt% are 30wt% hydrogen peroxide (add-on is 2.3 times of arsenic weight in arsenic-containing smoke dust) and diluted acid (sulfuric acid of concentration 10wt%), the pH value controlling mixing solutions is 1.5 reaction 3h, then filter, obtain mainly containing the filter cake of valuable metal and the solution containing arsenic acid;
(2) to being 5 containing the pH value adding ammoniacal liquor regulator solution in the solution of arsenic acid, be stirring reaction 2h under the condition of 70 DEG C at solution temperature, reaction terminates rear filtration, the filtrate obtained and filter cake, and filter cake is the material (recoverable) containing valuable metals such as copper;
(3) pass into containing SO in the filtrate of preparing to step (2) 2---gas (SO in gas 2---volume 8%, SO in the gas passed into 2weight be 1.5 times of the weight of arsenic in solution, pass into containing SO 2---the speed of gas be 160L/h) carry out reduction reaction, filter after being cooled to 24 DEG C after completion of the reaction, namely filter cake obtains white arsenic product after 80 DEG C of dry 20h, As 2o 3content is 99.2%.
Embodiment two: the method exempting from the white arsenic of Evaporation preparation of the arsenic-containing smoke dust of present embodiment is:
(1) heat water to 90 DEG C, under the state stirred, in water, add As successively 2o 3the arsenic-containing smoke dust of 38 wt%, concentration are 28wt% hydrogen peroxide (add-on is 1.8 times of arsenic weight in arsenic-containing smoke dust) and diluted acid (concentration 15wt% hydrochloric acid), the pH value controlling mixing solutions is 1 reaction 2h, then filter, obtain mainly containing the filter cake of valuable metal and the solution containing arsenic acid;
(2) to being 4 containing the pH value adding ammoniacal liquor regulator solution in the solution of arsenic acid, be stirring reaction 1h under the condition of 40 DEG C at solution temperature, reaction terminates rear filtration, the filtrate obtained and filter cake, and filter cake is the material (recoverable) containing valuable metals such as copper;
(3) pass into containing SO in the filtrate of preparing to step (2) 2---gas (SO in gas 2---volume 7%, SO in the gas passed into 2weight be 1 times of the weight of arsenic in solution, pass into containing SO 2---the speed of gas be 150L/h) carry out reduction reaction, filter after being cooled to 25 DEG C after completion of the reaction, namely filter cake obtains white arsenic product after 60 DEG C of dry 24h, As 2o 3content is 99.5%.
Embodiment three: the method exempting from the white arsenic of Evaporation preparation of the arsenic-containing smoke dust of present embodiment is:
(1) heat water to 60 DEG C, under the state stirred, in water, add As successively 2o 3the arsenic-containing smoke dust of 41 wt%, concentration are 25wt% hydrogen peroxide (add-on is 3.0 times of arsenic weight in arsenic-containing smoke dust) and diluted acid (nitric acid of concentration 20wt%), the pH value controlling mixing solutions is 3 reaction 0.5h, then filter, obtain mainly containing the filter cake of valuable metal and the solution containing arsenic acid;
(2) to being 7 containing the pH value adding ammoniacal liquor regulator solution in the solution of arsenic acid, be stirring reaction 0.5h under the condition of 60 DEG C at solution temperature, reaction terminates rear filtration, the filtrate obtained and filter cake, and filter cake is the material (recoverable) containing valuable metals such as copper;
(3) pass into containing SO in the filtrate of preparing to step (2) 2---gas (SO in gas 2---volume 6%, SO in the gas passed into 2weight be 0.8 times of the weight of arsenic in solution, pass into containing SO 2---the speed of gas be 170L/h) carry out reduction reaction, filter after being cooled to 20 DEG C after completion of the reaction, namely filter cake obtains white arsenic product after 70 DEG C of dry 8h, As 2o 3content is 99.4%.
Above the specific embodiment of the present invention is explained in detail, but the present invention is not limited to above-mentioned embodiment, in the ken that those of ordinary skill in the art possess, various change can also be made under the prerequisite not departing from present inventive concept.

Claims (7)

1. the method exempting from the white arsenic of Evaporation preparation of arsenic-containing smoke dust, is characterized in that comprising the following steps:
(1) heat water to 60 ~ 90 DEG C, under the state stirred, add arsenic-containing smoke dust, hydrogen peroxide and diluted acid successively in water, the pH value that diluted acid controls mixing solutions is 1 ~ 3, filters after reaction 0.5 ~ 3h, obtains the filter cake containing valuable metal and the solution containing arsenic acid;
(2) to being 4 ~ 7 containing the pH value adding ammoniacal liquor regulator solution in the solution of arsenic acid, be stirring reaction 0.5 ~ 2h under the condition of 40 ~ 70 DEG C at solution temperature, reaction terminates rear filtration, the filtrate obtained and the filter cake containing copper;
(3) pass into containing SO in the filtrate of preparing to step (2) 2---gas carry out reduction reaction, after being cooled to 20 ~ 25 DEG C after completion of the reaction filter, namely filter cake obtains white arsenic after 60 ~ 80 DEG C of drying 8 ~ 24h.
2. the method exempting from the white arsenic of Evaporation preparation of arsenic-containing smoke dust according to claim 1, is characterized in that: described arsenic-containing smoke dust is As 2o 3the flue dust of > 30 wt%.
3. the method exempting from the white arsenic of Evaporation preparation of arsenic-containing smoke dust according to claim 1, is characterized in that: in described step (1), the solid-to-liquid ratio of arsenic-containing smoke dust and water is 1:2 ~ 8g/ml.
4. the method exempting from the white arsenic of Evaporation preparation of arsenic-containing smoke dust according to claim 1, is characterized in that: described diluted acid is the sulfuric acid of concentration 10 ~ 20wt%, hydrochloric acid or nitric acid.
5. the method exempting from the white arsenic of Evaporation preparation of arsenic-containing smoke dust according to claim 1, is characterized in that: the concentration of described hydrogen peroxide is 25 ~ 30wt%, and add-on is 1.8 ~ 3.0 times of arsenic weight in arsenic-containing smoke dust.
6. the method exempting from the white arsenic of Evaporation preparation of arsenic-containing smoke dust according to claim 1, is characterized in that: described containing SO 2---gas in SO 2---volume be greater than 5%, SO in the gas passed into 2weight be 0.8 ~ 1.5 times of the weight of arsenic in solution.
7. the method exempting from the white arsenic of Evaporation preparation of arsenic-containing smoke dust according to claim 6, is characterized in that: described in pass into containing SO 2---the speed of gas be 150 ~ 170L/h.
CN201310377631.0A 2013-08-27 2013-08-27 Method for preparing white arsenic from arsenic-containing dust in evaporation-free manner Expired - Fee Related CN103449517B (en)

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CN106268179B (en) * 2016-08-25 2018-09-07 长沙有色冶金设计研究院有限公司 A kind of energy saving technique and system of synthetical recovery sulfuric acid purification spent acid
CN106834676B (en) * 2016-12-21 2017-11-14 中南大学 A kind of method that valuable metal and arsenic recycling harmlessness disposing are reclaimed from arsenic-containing smoke dust
CN106834718B (en) * 2016-12-21 2017-11-14 中南大学 A kind of arsenic-containing smoke dust comprehensive utilization and the method for arsenic harmlessness disposing
CN106834711B (en) * 2016-12-21 2017-11-14 中南大学 A kind of method for reclaiming in the flue dust from tellurium containing arsenic and preparing high purity tellurium
CN106834707B (en) * 2016-12-21 2019-03-26 中南大学 A kind of method that arsenic-containing material synthetical recovery and arsenic resource utilize
CN106801151B (en) * 2017-01-22 2019-05-07 中国恩菲工程技术有限公司 The method of flyash reduction melting enriched germanium
CN107523702B (en) * 2017-08-23 2019-03-19 中南大学 A kind of method that the pressure oxidation of sodium salt system prepares sodium pyroantimonate

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CN1101010A (en) * 1994-06-10 1995-04-05 大厂矿务局来宾冶炼厂 Wet method for preparation of sodium arsenate from fume containing arsenic

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