CN102634672A - Method for treating arsenic-containing waste copper slag - Google Patents
Method for treating arsenic-containing waste copper slag Download PDFInfo
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Abstract
The invention provides a method for treating arsenic-containing waste copper slag. The method comprises the following steps of: adding alkali and arsenic fixation roasting on the arsenic-containing waste copper slag from a copper electrolysis purification procedure to convert the arsenic into low-toxicity, water-soluble and nonvolatile arsenate, leaching the roasting slag into water to remove the arsenic, recovering copper and enriching antimony bismuth silver by virtue of acid leaching, and embedding calcium arsenate sediment converted from the arsenic in the water leaching solution; and comprehensively recovering valued metals such as copper, silver, antimony and bismuth in the black copper slag. The method is a safe and effective wet smelting method for recovering the valued metals in the black copper slag, and the arsenic and the copper are leached separately; the recovery rate of the copper in the black copper slag reaches 99.6 percent, and the removal rate of the arsenic reaches over 98 percent; over 95 percent of antimony and over 98 percent of bismuth enter the slag, and over 98 percent of silver also enters the acid leaching slag by adding trace chlorine radicals during acid leaching, so that the antimony, the bismuth and the silver are comprehensively recovered; and the method has the advantages of low equipment investment, short flow, low running cost and safe and reliable operating environment.
Description
Technical field
The invention belongs to non-ferrous metal wet process smelting technique field, relate to a kind of method of handling the black copper slag, be specifically related to the method that a kind of processing contains the arsenic waste copper slag.
Background technology
In the copper refining system electrolyte purification process, arsenic, antimony, bismuth are separated out on negative electrode with copper, and output composition complicacy contains the higher black copper slag of arsenic.The quantity of black copper slag is generally 1.0～1.5% of electrolytic copper amount, and its chemical ingredients is a copper content 50%～60%, arsenic content 5～10%, antimony content 0.4～0.7%, bi content 0.5～0.6%, silver content 500～800g/t.The processing of black copper slag is a difficult problem of nonferrous metallurgy always, and each enterprise has carried out secular effort, but lacks a kind of processing means of economic environmental protection always.
Known black copper slag treatment process mainly contains roasting method, pickling process, alkaline leaching etc.Roasting method produces the flue gas that contains poisonous arsenic oxide, contaminate environment.Pickling process is to place the acidic medium oxidation to leach the black copper slag, reclaims copper wherein with the copper sulfate form, reclaims most arsenic wherein with the white arsenic form; But white arsenic is the arsenide with hypertoxicity, and the pressure of safety and environmental protection aspect is very big in the organization of production; The arsenic organic efficiency of common alkaline leaching is lower, and alkaline consumption is high, and valuable metals such as silver, antimony, bismuth are difficult to comprehensive recovery.Therefore, when handling the black copper slag, objectionable impurities arsenic is distributed in the per pass operation of flow process, and the environment around the scene has been caused serious pollution.
Summary of the invention
In order to overcome the problem that exists in the above-mentioned prior art, the purpose of this invention is to provide the method that a kind of processing contains the arsenic waste copper slag, not only avoid in the waste copper slag treating processes arsenic to the pollution of environment, and can comprehensively reclaim the valuable metal in the waste copper slag.
To achieve these goals, the technical scheme that the present invention adopted is: a kind of processing contains the method for arsenic waste copper slag, specifically carries out according to the following steps:
Step 1: with black copper slag and alkali thorough mixing, the alkali coefficient of used alkali is 1.5～2.0, the ball mill ore grinding;
Step 2: in micro-oxidizing atmosphere, step 1 ore grinding after product is placed roasting kiln, 500 ℃～600 ℃ roasting temperatures 1.5 hours～2.5 hours, slag after the roasting;
Step 3: pulp water after the roasting of step 2 is soaked dearsenification; Liquid-solid ratio during water soaking dearsenication be 5～6
1; 60 ℃～65 ℃ of water soaking temperatures; 40 minutes～60 minutes water logging time; Make that the arsenic in the slag all changes in the leach liquor after the roasting, the water logging ore pulp;
Step 4: the water logging ore pulp in the sieve classification step 3 obtains granularity greater than the coarse fraction material grain of 0.2mm and the granularity fines level slip less than 0.2mm;
Step 5: the coarse fraction material grain in the step 4 returns the copper smelting system;
Fines level slip in the filtration step 4 obtains slag after infusion and the water logging;
Step 6: the infusion in the step 5 is sunk arsenic, and the adding coefficient of used lime is 1.5～2.0 during heavy arsenic, and 55 ℃～60 ℃ of heavy arsenic temperature, obtain liquid and heavy arsenic slag behind the heavy arsenic, heavy arsenic slag landfill disposal at heavy 1 hour～2 hours arsenic time;
Slag after the water logging in the step 5 is carried out acidleach; Liquid-solid ratio during acidleach be 8～10
1; Acid coefficient 1.1～1.3; 78～85 ℃ of extraction temperatures, bubbling air leached 2.5～3.5 hours, obtained copper sulfate leaching liquid and leached mud; Copper sulfate leaching liquid directly returns production system; Leached mud is used for further extracting valuable metal.
When slag after the water logging is carried out acidleach, add the chlorine root, add 0.1～0.8g chlorine root when the amount of used chlorine root is every liter of acidleach in the used liquid.
Treatment process of the present invention has thoroughly solved the open circuit problem of arsenic in the copper production process; Increased substantially the concentration ratio of silver, antimony, bismuth in the black copper slag; Flow process is novel succinct; Break through domestic enterprise's black copper slag and handled pyrogenic process or the wet processing that generally adopts, obtained the win-win of economic benefit and social environment benefit.Adopt the inventive method to handle the black copper slag and can satisfy the requirement of developing a circular economy, meet the environmental protection policy of the national comprehensive utilization of resources of advocating, reduce dangerous solid discharging of giving up and deposit.
Description of drawings
Fig. 1 is a process flow sheet of the present invention.
Embodiment
Below in conjunction with accompanying drawing and embodiment the present invention is elaborated.
The hydrometallurgy copper refining is produced in the electrolytic copper process; Cleaning section produces a large amount of arsenic black copper ashes that contain, and adopts methods such as roasting method, pickling process, alkaline leaching to handle the black copper slag usually, but these methods are when handling black copper slags; Perhaps produce deleterious arsenic oxide flue gas, contaminate environment; Perhaps produce the arsenide of hypertoxicity; Perhaps the arsenic recovery is lower, is difficult to comprehensively recovering valuable metal.In order to solve the problem that exists in the above-mentioned prior art; The invention provides the method that the processing as shown in Figure 1 of a kind of schema contains the arsenic waste copper slag; Can the arsenic in the black copper slag be converted into hypotoxic Tricalcium arsenate deposition down-hole landfill, the comprehensive simultaneously method that reclaims valuable metals such as wherein copper, silver, antimony, bismuth.This method is specifically carried out according to the following steps:
Step 1: at first with black copper slag and alkali thorough mixing, the alkali coefficient of used alkali is 1.5～2.0 (in alkali add-on and the black copper slag arsenic all convert the ratio of the theoretical amount of the required alkali of sodium arseniate into be the alkali coefficient), afterwards, sends into ore grinding in the ball mill;
Alkali adopts sodium hydroxide, yellow soda ash or calcium hydroxide.
Step 2: the ore grinding after product with step 1 in micro-oxidizing atmosphere places the roasting roasting in kilns, 500～600 ℃ of maturing temperatures, roasting time 1.5～2.5 hours, slag after the roasting;
Step 3: slag after the roasting of step 2 is carried out water soaking dearsenication; Liquid-solid ratio during water soaking dearsenication be 5～6
1; Water soaking temperature is 60～65 ℃; 40～60 minutes water logging time made that the arsenic in the slag all changes in the leach liquor after the roasting, the water logging ore pulp; In the water logging process after the roasting copper in the slag, antimony, bismuth etc. do not get into the water logging ore pulp;
Step 4:, obtain granularity greater than the coarse fraction material grain of 0.2mm and granularity fines level slip less than 0.2mm with the water logging ore pulp sieve classification in the step 3;
Step 5: the coarse fraction material grain in the step 4 returns the copper smelting system;
With the fines level slurry filtration in the step 4, obtain slag after infusion and the water logging;
Step 6: the infusion in the step 5 is sunk arsenic, and the adding coefficient of used lime is 1.5～2.0 during heavy arsenic, 55～60 ℃ of heavy arsenic temperature; Heavy 1～2 hour arsenic time; Obtain liquid and heavy arsenic slag behind the heavy arsenic, the alkali in the liquid behind the heavy arsenic is returned step 1 continue to use, heavy arsenic slag landfill disposal;
Slag after the water logging in the step 5 is carried out acidleach; Liquid-solid during acidleach be 8～10
1; Acid coefficient 1.1～1.3; Add micro-chlorine root during acidleach, add 0.1～0.8g chlorine root, 78～85 ℃ of extraction temperatures when the amount of used chlorine root is every liter of acidleach in the used liquid; Bubbling air leached 2.5～3.5 hours, obtained copper sulfate leaching liquid and leached mud; Impurity in this copper sulfate leaching liquid is few, can directly return production system; Adding the chlorine root during acidleach can sink to the small amount of silver that gets in the leach liquor in the leached mud, and antimony bismuth silver concentration ratio is high in this leached mud, can further extract valuable metal.
The gordian technique of the inventive method is following several respects; The one, utilize arsenic under comparatively high temps, to be prone to generate hypotoxicity high price arsenate and both sexes characteristic with the oxygen reaction; Employing adds the solid arsenic roasting of alkali; Convert arsenic into non-volatile, hypotoxic water-soluble sodium arseniate, avoided the volatilization of arsenic in the roasting process, arsenic converts the Tricalcium arsenate landfill of indissoluble into the most at last; Low-cost high-efficiency solved impurity elements such as copper system of enterprise arsenic, antimony, bismuth in system circulation and to the influence of quality product, guaranteed the steady running of production system.The 2nd, take the lead at home adopting adding the solid arsenic roasting method of alkali and handling the black copper slag, make the open circuit hypotoxicity of arsenic, and separate with the leaching of copper, not only improve the recovery of metal, and improved production environment.The 3rd, the sodium carbonate roasting process can be destroyed the structure of copper-arsenic compound, reduces and leaches difficulty, improves the leaching yield of copper, and copper leaching rate can reach more than 98%, and the leached mud rate is little, antimony, bismuth enrichment multiple height.The 4th, it is very low that sulfuric acid leaches the copper-bath impurity content that obtains, but direct production goes out qualified mantoquita product.
The present invention is the wet method smelting process method of valuable metal in a kind of safe and effective recovery black copper slag, and the leaching of arsenic can be separated with the leaching of copper.And low equipment investment, flow process are lacked, working cost is lower, operation environment safety is reliable.
When adopting the inventive method to handle the black copper slag; The recovery of copper reaches 99.6% in the black copper slag; The arsenic extrusion rate reaches more than 98%, and antimony more than 95% and 98% above bismuth get in the slag, pass through to add micro-chlorine root during acidleach; Silver more than 98% also gets in the acid leaching residue, helps the comprehensive recovery of antimony, bismuth, silver.
Treatment process of the present invention will originate from the black copper slag of cupric electrolysis cleaning section and add the solid arsenic roasting of alkali; Convert arsenic into hypotoxicity, water-soluble, nonvolatile arsenate; Behind the fired slags water soaking dearsenication, copper enrichment antimony bismuth silver is reclaimed in the slag oxidation acidleach, and the arsenic in the infusion converts Tricalcium arsenate deposition landfill into; And comprehensively reclaim valuable metals such as copper in the black copper slag, silver, antimony, bismuth.The open circuit that makes arsenic separates with the leaching of copper, recovery rate of valuable metals is high, and environmental friendliness has thoroughly solved impurity elements such as arsenic, antimony, bismuth in the intrasystem circulation of cupric electrolysis with to the influence of quality product, has guaranteed production system steady running.
When adopting the inventive method roasting black copper slag, the fixed rate of arsenic reaches more than 99%, and copper leaching rate reaches more than 98%, slag rate low (about 3%), and antimony bismuth concentration ratio high (antimony bismuth total content reaches about 50% in the slag), the detrimental impurity that contains in the flue dust is seldom.Operational path of the present invention, low equipment investment, flow process is short, and operating environment is reliable, and the main agents lime source of consumption is wide, low price, investment and production cost are lower.
Embodiment 1
The black copper slag ingredient of certain electrolysis copper work output is Ni0.87%, Co0.0052%, Cu56.72%, Fe0.23%, Pb0.056%, Zn0.0034%, Mn0.022%, As5.18%, Sb0.37%, Bi0.56%, S4.23%, Ag538.75 (g/t), SiO
21.0%.With this black copper slag and sodium hydroxide thorough mixing, the alkali coefficient of used sodium hydroxide is 2.0, the ball mill ore grinding; Place roasting kiln 550 ℃ roasting temperature 2 hours the ore grinding after product in the micro-oxidizing atmosphere, fired slags; Slag after this roasting is carried out water soaking dearsenication; Liquid-solid ratio 5 during water soaking dearsenication
1; 60 ℃ of water soaking temperatures, 60 minutes water logging time; Make that the arsenic in the slag all changes in the leach liquor after the roasting, the water logging ore pulp; In the water logging process after the roasting copper in the slag, antimony, bismuth etc. do not get into the water logging ore pulp; With this water logging ore pulp sieve classification, obtain granularity greater than the coarse fraction material grain of 0.2mm and granularity fines level slip less than 0.2mm; Coarse fraction material grain returns the copper smelting system; Filter fines level slip and obtain slag after infusion and the water logging; With the heavy arsenic of this infusion, the adding coefficient of used lime is 1.5～2.0 during heavy arsenic, 60 ℃ of heavy arsenic temperature, and the heavy 2 hours arsenic time, obtain liquid and heavy arsenic slag behind the heavy arsenic, the alkali in the liquid behind the heavy arsenic is returned calcining process continue to use, heavy arsenic slag landfill disposal; Slag after the water logging is carried out acidleach; Liquid-solid ratio during acidleach be 8
1; Acid coefficient 1.2; Add the chlorine root during acidleach, add 0.45g chlorine root, 78 ℃ of extraction temperatures when the amount of used chlorine root is every liter of acidleach in the used liquid; Bubbling air leached 3 hours, obtained copper sulfate leaching liquid and leached mud; This copper sulfate leaching liquid is directly returned production system; This leached mud is further extracted valuable metal.
Comparative Examples 1
The black copper slag ingredient of certain electrolysis copper work output is Ni0.97%, Co0.0048%, Cu56.52%, Fe0.43%, Pb0.036%, Zn0.0054%, Mn0.032%, As5.32%, Sb0.17%, Bi0.36%, S4.43%, Ag538.95 (g/t), SiO
21.2%.This black copper slag is carried out dearsenification by the method for embodiment 1 to be handled.
Table 1 is the typical composition table of infusion after the black copper slag alkali roasting in embodiment 1 and the Comparative Examples 1.
The typical composition (g/L) of infusion after the table 1 liang group sample alkali roasting
The composition of liquid is as shown in table 2 behind the corresponding heavy arsenic behind the heavy arsenic of two kinds of infusions of composition shown in the table 1.
The composition (g/L) of liquid behind the corresponding heavy arsenic behind the heavy arsenic of two kinds of infusions of composition shown in table 2 table 1
Annotate: the Tricalcium arsenate slag contains arsenic and is respectively 19.09 % and 18.42%.
The typical composition of slag after the water logging is as shown in table 3 after the black copper slag alkali roasting in embodiment 1 and the Comparative Examples 1.
The typical composition of slag after the water logging after the table 3 liang group sample alkali roasting
The typical composition of slag pickling liquor is as shown in table 4 after the black copper slag alkali roasting water logging in embodiment 1 and the Comparative Examples 1.
The typical composition (g/L) of slag pickling liquor after the table 4 liang group sample roasting water logging
The typical composition of slag acid leaching residue is as shown in table 5 after the black copper slag alkali roasting water logging in embodiment 1 and the Comparative Examples 1.
The typical composition (g/L) of slag acid leaching residue after the table 5 liang group sample roasting water logging
Can find out from table 1, table 2, table 3, table 4 and table 5, when adopting the inventive method that the different black copper slag of component content is handled, after the solid arsenic roasting of black copper slag; Gu the arsenic rate is all greater than 99%, the water soaking dearsenication rate is respectively 99.56% and 99.28%, and copper, antimony, bismuth etc. do not get into infusion basically in the water logging; The copper leaching rate of acidleach is respectively 99.78% and 99.80%; Pickling liquor contains assorted low, can directly advance the copper sulfate production system, and the acid leaching residue rate is respectively 2.66% and 2.94%.Explain that economic targets such as leaching yield, the recovery are the same, thereby have proved the safety of the inventive method when adopting the inventive method to handle the different material that composition slightly distinguishes.
Embodiment 2
The black copper slag ingredient of certain electrolysis copper work output is: Ni1.36%, Co0.015%, Cu41.48%, Fe0.066%, Pb0.064%, Zn0.0038%, Mn0.0041%, As4.05%, Sb0.69%, Bi0.60%, S8.02%, Ag 666.25 (g/t).With this black copper slag and yellow soda ash thorough mixing, the alkali coefficient of all yellow soda ash is 1.5, the ball mill ore grinding; In micro-oxidizing atmosphere, the ore grinding after product was placed 600 ℃ of roasting temperatures of roasting kiln 1.5 hours, slag after the roasting; Slag after the roasting is carried out water soaking dearsenication; Liquid-solid ratio during water soaking dearsenication be 6
1; 65 ℃ of water soaking temperatures; 40 minutes water logging time made that the arsenic in the slag all changes in the leach liquor after the roasting, the water logging ore pulp; In the water logging process after the roasting copper in the slag, antimony, bismuth etc. do not get into the water logging ore pulp; With this water logging ore pulp sieve classification, obtain granularity greater than the coarse fraction material grain of 0.2mm and granularity fines level slip less than 0.2mm; This coarse fraction material grain is returned the copper smelting system; Filter fines level slip, obtain slag after infusion and the water logging; With the heavy arsenic of infusion, the adding coefficient of used lime is 2.0 during heavy arsenic, 55 ℃ of heavy arsenic temperature, and the heavy 1 hour arsenic time, obtain liquid and heavy arsenic slag behind the heavy arsenic, the alkali in the liquid behind the heavy arsenic is returned calcining process continue to use, heavy arsenic slag landfill disposal; Slag after the water logging is carried out acidleach; Liquid-solid ratio during acidleach be 10
1; Acid coefficient 1.3; Add micro-chlorine root during acidleach, add 0.8g chlorine root, 85 ℃ of extraction temperatures when the amount of used chlorine root is every liter of acidleach in the used liquid; Bubbling air leached 2.5 hours, obtained copper sulfate leaching liquid and leached mud; This copper sulfate leaching liquid directly returns production system; This leached mud further extracts valuable metal.
The composition of pulp water immersion liquid after the roasting of black copper slag is as shown in table 6 in the present embodiment.
The composition (g/L) of pulp water immersion liquid after the roasting of black copper slag among table 6 embodiment 2
The composition of slag pickling liquor after the water logging is as shown in table 7 in the present embodiment.
The composition of slag pickling liquor (g/L) after the water logging among table 7 embodiment 2
The composition of leached mud after the acidleach is as shown in table 8 in the present embodiment.
The composition of leached mud (g/L) after the acidleach among table 8 embodiment 2
Table 6, table 7 and table 8 show that treatment process of the present invention is at revolution roasting in kilns black copper slag, and material has wriggling in the roasting process, the dearsenification better effects if.Whole flow process copper leaching rate reaches more than 98%, and the arsenic extrusion rate is more than 99%, total slag rate about 3%, and arsenic is with Tricalcium arsenate form open circuit, and 90% antimony and 98% above bismuth get in the slag.
Embodiment 3
With black copper slag and calcium hydroxide thorough mixing, the alkali coefficient of used calcium hydroxide is 1.75, the ball mill ore grinding; In micro-oxidizing atmosphere, the ore grinding after product was placed 500 ℃ of roasting temperatures of roasting kiln 2.5 hours, slag after the roasting; Slag after the roasting is carried out water soaking dearsenication; Liquid-solid ratio during water soaking dearsenication be 5.5
1; 62.5 ℃ of water soaking temperatures; 50 minutes water logging time made that the arsenic in the slag all changes in the leach liquor after the roasting, the water logging ore pulp; In the water logging process after the roasting copper in the slag, antimony, bismuth etc. do not get into the water logging ore pulp; With water logging ore pulp sieve classification, obtain granularity greater than the coarse fraction material grain of 0.2mm and granularity fines level slip less than 0.2mm; Coarse fraction material grain returns the copper smelting system; Filter fines level slip, obtain slag after infusion and the water logging; With the heavy arsenic of infusion, the adding coefficient of used lime is 1.8 during heavy arsenic, 57.5 ℃ of heavy arsenic temperature, and the heavy 1.5 hours arsenic time, obtain liquid and heavy arsenic slag behind the heavy arsenic, the alkali in the liquid behind the heavy arsenic is returned calcining process continue to use, heavy arsenic slag landfill disposal; Slag after the acidleach water logging; Liquid-solid ratio during acidleach be 9
1; Acid coefficient 1.1; Add micro-chlorine root during acidleach, add 0.1g chlorine root, 81 ℃ of extraction temperatures when the amount of used chlorine root is every liter of acidleach in the used liquid; Bubbling air leached 3.5 hours, obtained copper sulfate leaching liquid and leached mud; Copper sulfate leaching liquid directly returns production system; Leached mud further extracts valuable metal.
Embodiment 4
With black copper slag and sodium hydroxide thorough mixing, the alkali coefficient of used sodium hydroxide is 1.6, the ball mill ore grinding; In micro-oxidizing atmosphere, the ore grinding after product was placed 510 ℃ of roasting temperatures of roasting kiln 1.6 hours, slag after the roasting; Slag after the roasting is carried out water soaking dearsenication; Liquid-solid ratio during water soaking dearsenication be 5.1
1; 61 ℃ of water soaking temperatures; 45 minutes water logging time made that the arsenic in the slag all changes in the leach liquor after the roasting, the water logging ore pulp; In the water logging process after the roasting copper in the slag, antimony, bismuth etc. do not get into the water logging ore pulp; With water logging ore pulp sieve classification, obtain granularity greater than the coarse fraction material grain of 0.2mm and granularity fines level slip less than 0.2mm; Coarse fraction material grain returns the copper smelting system; Filter fines level slip, obtain slag after infusion and the water logging; With the heavy arsenic of infusion, the adding coefficient of used lime is 1.6 during heavy arsenic, 56 ℃ of heavy arsenic temperature, and the heavy 1.1 hours arsenic time, obtain liquid and heavy arsenic slag behind the heavy arsenic, the alkali in the liquid behind the heavy arsenic is returned calcining process continue to use, heavy arsenic slag landfill disposal; Slag after the acidleach water logging; Liquid-solid ratio during acidleach be 8.5
1; Acid coefficient 1.12; Add micro-chlorine root during acidleach, add 0.2g chlorine root, 80 ℃ of extraction temperatures when the amount of used chlorine root is every liter of acidleach in the used liquid; Bubbling air leached 2.6 hours, obtained copper sulfate leaching liquid and leached mud; Copper sulfate leaching liquid directly returns production system; Leached mud further extracts valuable metal.
Embodiment 5
With black copper slag and yellow soda ash thorough mixing, the alkali coefficient of used yellow soda ash is 1.9, the ball mill ore grinding; In micro-oxidizing atmosphere, the ore grinding after product was placed 580 ℃ of roasting temperatures of roasting kiln 2.4 hours, slag after the roasting; Slag after the roasting is carried out water soaking dearsenication; Liquid-solid ratio during water soaking dearsenication be 5.9
1; Water soaking temperature is 64 ℃; 55 minutes water logging time made that the arsenic in the slag all changes in the leach liquor after the roasting, the water logging ore pulp; In the water logging process after the roasting copper in the slag, antimony, bismuth etc. do not get into the water logging ore pulp; Sieve classification water logging ore pulp obtains granularity greater than the coarse fraction material grain of 0.2mm and the granularity fines level slip less than 0.2mm; Coarse fraction material grain returns the copper smelting system; Filter fines level slip, obtain slag after infusion and the water logging; With the heavy arsenic of infusion, the adding coefficient of used lime is 1.7 during heavy arsenic, 59 ℃ of heavy arsenic temperature, and the heavy 1.9 hours arsenic time, obtain liquid and heavy arsenic slag behind the heavy arsenic, the alkali in the liquid behind the heavy arsenic is returned calcining process continue to use, heavy arsenic slag landfill disposal; Slag after the acidleach water logging; Liquid-solid ratio during acidleach be 9.5
1; Acid coefficient 1.25; Add micro-chlorine root during acidleach, add 0.7g chlorine root, 84 ℃ of extraction temperatures when the amount of used chlorine root is every liter of acidleach in the used liquid; Bubbling air leached 3.4 hours, obtained copper sulfate leaching liquid and leached mud; Copper sulfate leaching liquid directly returns production system; Leached mud further extracts valuable metal.
Embodiment 6
With black copper slag and calcium hydroxide thorough mixing, the alkali coefficient of used calcium hydroxide is 1.8, ball mill, ore grinding; In micro-oxidizing atmosphere, the ore grinding after product was placed 520 ℃ of roasting temperatures of roasting kiln 1.8 hours, slag after the roasting; Slag after the roasting is carried out water soaking dearsenication; Liquid-solid ratio during water soaking dearsenication be 5.4
1; 63 ℃ of water soaking temperatures; 58 minutes water logging time made that the arsenic in the slag all changes in the leach liquor after the roasting, the water logging ore pulp; In the water logging process after the roasting copper in the slag, antimony, bismuth etc. do not get into the water logging ore pulp; Sieve classification water logging ore pulp obtains granularity greater than the coarse fraction material grain of 0.2mm and the granularity fines level slip less than 0.2mm; Coarse fraction material grain returns the copper smelting system; Filter fines level slip, obtain slag after infusion and the water logging; With the heavy arsenic of infusion, the adding coefficient of used lime is 1.9 during heavy arsenic, 58 ℃ of heavy arsenic temperature, and the heavy 1.3 hours arsenic time, obtain liquid and heavy arsenic slag behind the heavy arsenic, the alkali in the liquid behind the heavy arsenic is returned calcining process continue to use, heavy arsenic slag landfill disposal; Slag after the water logging is carried out acidleach; Liquid-solid ratio during acidleach be 8.3
1; Acid coefficient 1.28; Add micro-chlorine root during acidleach, add 0.6g chlorine root, 83 ℃ of extraction temperatures when the amount of used chlorine root is every liter of acidleach in the used liquid; Bubbling air leached 2.8 hours, obtained copper sulfate leaching liquid and leached mud; Copper sulfate leaching liquid directly returns production system; Leached mud further extracts valuable metal.
Claims (5)
1. a processing contains the method for arsenic waste copper slag; The arsenic waste copper slag that contains that originates from the cupric electrolysis cleaning section is added the solid arsenic roasting of alkali; Convert arsenic into hypotoxicity, water-soluble, nonvolatile arsenate; Behind the fired slags water soaking dearsenication, copper enrichment antimony bismuth silver is reclaimed in acidleach, and the arsenic in the infusion converts Tricalcium arsenate deposition landfill into; And comprehensively reclaim valuable metals such as copper in the black copper slag, silver, antimony, bismuth.
2. processing as claimed in claim 1 contains the method for arsenic waste copper slag, it is characterized in that, this method is specifically carried out according to the following steps:
Step 1: with black copper slag and alkali thorough mixing, the alkali coefficient of used alkali is 1.5～2.0, the ball mill ore grinding;
Step 2: in micro-oxidizing atmosphere, step 1 ore grinding after product is placed roasting kiln, 500 ℃～600 ℃ roasting temperatures 1.5 hours～2.5 hours, slag after the roasting;
Step 3: pulp water after the roasting of step 2 is soaked dearsenification; Liquid-solid ratio during water soaking dearsenication be 5～6
1; 60 ℃～65 ℃ of water soaking temperatures; 40 minutes～60 minutes water logging time; Make that the arsenic in the slag all changes in the leach liquor after the roasting, the water logging ore pulp;
Step 4: the water logging ore pulp in the sieve classification step 3 obtains granularity greater than the coarse fraction material grain of 0.2mm and the granularity fines level slip less than 0.2mm;
Step 5: the coarse fraction material grain in the step 4 returns the copper smelting system;
Fines level slip in the filtration step 4 obtains slag after infusion and the water logging;
Step 6: the infusion in the step 5 is sunk arsenic, and the adding coefficient of used lime is 1.5～2.0 during heavy arsenic, and 55 ℃～60 ℃ of heavy arsenic temperature, obtain liquid and heavy arsenic slag behind the heavy arsenic, heavy arsenic slag landfill disposal at heavy 1 hour～2 hours arsenic time;
Slag after the water logging in the step 5 is carried out acidleach; Liquid-solid ratio during acidleach be 8～10
1; Acid coefficient 1.1～1.3; 78～85 ℃ of extraction temperatures, bubbling air leached 2.5～3.5 hours, obtained copper sulfate leaching liquid and leached mud; Copper sulfate leaching liquid directly returns production system; Leached mud is used for further extracting valuable metal.
3. processing as claimed in claim 2 contains the method for arsenic waste copper slag, it is characterized in that, the alkali that adopts in the said step 1 is sodium hydroxide, yellow soda ash or calcium hydroxide.
4. processing as claimed in claim 2 contains the method for arsenic waste copper slag, it is characterized in that, in the step 6 behind the heavy arsenic alkali in the liquid return step 1 and continue to use.
5. processing as claimed in claim 2 contains the method for arsenic waste copper slag, it is characterized in that, when in the said step 6 slag after the water logging being carried out acidleach, adds the chlorine root, adds 0.1g～0.8g chlorine root when the amount of used chlorine root is every liter of acidleach in the used liquid.
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