CN105154679A - Treatment method for separating copper and arsenic in arsenic filter cakes - Google Patents
Treatment method for separating copper and arsenic in arsenic filter cakes Download PDFInfo
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- CN105154679A CN105154679A CN201510606648.8A CN201510606648A CN105154679A CN 105154679 A CN105154679 A CN 105154679A CN 201510606648 A CN201510606648 A CN 201510606648A CN 105154679 A CN105154679 A CN 105154679A
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Abstract
The invention discloses a treatment method for separating copper and arsenic in arsenic filter cakes. The method comprises the following steps: (1) drying, grinding and sieving raw residues of the arsenic filter cakes; (2) mixing the sieved residues with water and pulping; (3) adding copper chloride into a solution; (4) placing the solution in a water bath stirrer at 80-85 DEG C and simultaneously introducing air and reacting for 6 hours; and (5) reacting for 1-3 hours, then adding sodium sulfide into the solution, introducing the generated sodium sulfide into leaching residues, wherein a leaching solution is an arsenic-containing solution. According to the treatment method for separating copper and arsenic of the arsenic filter cakes, the purpose of separating copper and arsenic can be effectively achieved; the leaching residue is returned to the smelting process and is used; then the leaching solution is oxidized; the pH is regulated; ferrous sulfate is used for depositing arsenic to generate scorodite crystals. The method effectively reaches high recovery rate of copper and harmless treatment of arsenic in the arsenic filter cakes with low cost.
Description
Technical field
The invention belongs to the process of arsenic-containing solid wastes, be specifically related to the treatment process that in a kind of arsenic filter cake, copper arsenic is separated.
Background technology
Nonferrous smelting is one of most important arsenic source of pollution, and global the sector discharges nearly 100,000 tons of arsenic every year.Wherein the arsenic of about 90% is from non-ferrous metal metallurgy industries such as copper, lead, zinc, and the arsenic filter cake produced in Copper making process is also the important sources that arsenic pollutes.Arsenic filter cake is by the flue gas produced in Flash Microcontroller through sulfuric acid scrubbing, and arsenic wherein and other heavy metals enter in dirty acid solution, a kind of material that output obtains after sulfidizing.Its slag is strongly-acid, and higher containing arsenic, copper amount, other non-ferrous metal content are less, and Some Domestic smeltery still adopts directly stores up and sell mode process arsenic filter cake.
At present, the treatment technology method of arsenic filter cake is mainly divided into pyrogenic process and wet method.Pyrogenic process adopts the methods such as oxidizing roasting, reducing roasting and vacuum baking to process, and arsenic is directly with As
2o
3form reclaims.This method is ripe, and flow process is relatively short, and cost is lower; But at the As of process drying regime
2o
3time, operating environment is poor, very easily causes the secondary pollution of environment, and the arsenic rate of recovery is low, and product purity is low.Wet method has pressure leaching process, prepares cupric arsenate, ferric sulfate method, alkaline leaching etc.Pressure leaching process is in acid system, and adopt pressure leaching method that arsenic and copper are all leached in solution, leach liquor can obtain white arsenic product through reduction.The method is high to equipment requirements, and arsenical copper leaching yield is the highest only reaches about 90%.The method preparing cupric arsenate is that employing is leached, oxidative synthesis technique processes arsenic filter cake, although cupric arsenate may be used for preparing wood preservative, cupric arsenate is still highly toxic substance, is forbidden by government.Ferric sulfate method is under the condition of high pressure, utilizes ferric sulfate to leach red arsenic, and each metal ion species is separated in this process.Owing to adopting high top pressure operation in production process, equipment and operational condition more complicated, therefore cost is also higher.Alkaline leaching is the wet method dearsenicating method based on NaOH, and raw material sources are convenient, and working method is simple, and without the need to changing original smelting technology method, but the shortcoming of the method is when to be arsenic concentration higher, the consumption of alkali, cost is higher, and does not have the alkali reclaiming method simple, cost is low at present.
Therefore, the rationalization process of arsenic filter cake is disposed is the problem that one, China needs solution badly.
Summary of the invention
The object of the invention is for the deficiencies in the prior art part, according to the characteristic of arsenic filter cake, invented the copper arsenic method for separating and processing of a kind of economy, flow process is simple, copper arsenic separation rate is high arsenic filter cake.
Arsenic filter cake raw material is produced by dirty acid sludge sodium sulphite process in Copper making process, most of sulfide structural instability, and sulphur content is high, and also has a small amount of sulphur elemental form to exist.The volatilization of white arsenic and sulphur simple substance can be caused, contaminate environment with pyrogenic attack.Technique former slag used is acid, although can reach good copper arsenic separating effect with traditional alkaline leaching dearsenification, alkali consumption is too large, and cost is higher.Therefore, applicants have invented a kind of wet-method for leaching, effective, low cost reach the high-recovery of copper and the harmless treatment of arsenic in arsenic filter cake.
In leaching process, copper arsenic is separated and mainly carries out following several reaction:
3Cu
2++As
2S
3+4H
2O＝3CuS+HAsO
2+6H
+
3Cu
2++4S+4H
2O＝3CuS+SO
4 2-+8H
+
2As
2S
3+3O
2+2H2O＝4HAsO
2+6S
Cu
2++S
2-＝CuS
By adjustment control Cu, As, S tri-kinds of elements at the ratio of solution Leaching Systems and content, the process of the several reaction of further control, Cu is precipitated with the form of CuS, and As is existed in solution with arsenic acid and arsenus acid form by replacement(metathesis)reaction, thus reaches the effect of copper arsenic separation.
The object of the invention realizes in the following way:
A copper arsenic method for separating and processing for arsenic filter cake, comprises the following steps:
(1) arsenic filter cake material is carried out dry, grind, sieve;
(2) material is mixed with water size mixing;
(3) added by soluble copper salt in the slurry that step (2) mixes up, stirring and dissolving is even;
(4) by the agitation leach reaction under aerobic conditions of the mixed slurry of step (3);
(5) the sulfocompound heavy copper further that sulfonium ion can be provided is added after Leaching reaction;
(6) leach liquor is used for the recovery of arsenic.
Described arsenic filter cake material is the dirt acid produced in Copper making process, through the product of sodium sulphite process; Arsenic filter cake comprises the composition of following mass percent: arsenic 12.01% ~ 19.5%, copper 15.10% ~ 20.00%, sulphur 25.30% ~ 48.21%.In described arsenic filter cake material, the existing forms of arsenic and mass percent are: pozzuolite compound 0.5% ~ 3.0%, arsenic oxide 9.2% ~ 17.2%, arsenate 0.1% ~ 1.5%, the existing forms of copper and mass percent are: soluble copper 5.6% ~ 9.31%, cupric sulfide 7.50% ~ 10.56%.
Arsenic filter cake in step (1) is dried to water ratio lower than 5% under 105 DEG C of conditions, and crosses 100 eye mesh screens, and screen over-size is less than 25%.
The liquid-solid ratio that water described in step (2) and arsenic filter cake mixing of materials are sized mixing is 8:1 ~ 12:1ml/g, and wherein optimum liquid-solid volume mass is than being 10:1ml/g.
In step (3), soluble copper salt comprises one or more in cupric chloride, Salzburg vitriol, cupric nitrate.
In soluble copper salt and former slag, the summation of soluble copper with the mass ratio of arsenic in arsenic filter cake is in step (3): Cu: As=3:8 ~ 7:8, wherein optimum quality is than being 5:8.
Extract technology condition in step (4) is: temperature is 75 ~ 90 DEG C, and mixing speed is 200r/min ~ 400r/min, and the flow passing into air is 30 ~ 60L/min, and extraction time is 5 ~ 7h; Wherein optimum temperature is 80 DEG C, and optimized rotating speed is 300r/min, and passing into air flow quantity optimum is 40L/min, and extraction time optimum is 6h.
Sulfocompound comprises in step (5): one or more in sodium sulphite, Sodium sulfhydrate, potassium sulphide, and the sulfocompound time added in solution is after Leaching reaction 1 ~ 3 hour.
In the sulfonium ion that sulfocompound added in step (5) provides and now solution, the ratio of cupric ion is S: Cu=2:1 ~ 4:1, and wherein optimum quality is than being 3:1.
In step (5), leached mud returns Copper making operation; Leach liquor again through overregulating pH, arsenious oxidation, finally add ferrous sulfate sink arsenic reaction, obtain scorodite crystals.
Raw material of the present invention is the arsenic filter cake waste residue that in present Copper making process, dirty acid obtains through sodium persulfide process, by adding soluble copper and red arsenic generation replacement(metathesis)reaction in cupric ion and raw material, generate copper sulfide precipitation, arsenic becomes arsenate ion and arsenite ion exists in solution, and the arsenic oxide in former slag is also dissolved in solution by the Oxidation Leaching of certain condition.After one section of leaching terminates, obtain the filter residue of arsenic solution and enrichment cupric sulfide.Arsenic solution adds sulfocompound more wherein provides sulfonium ion to precipitate unnecessary cupric ion, and because pH is still acid and the solubility product constant of cupric sulfide is less than red arsenic, sulfonium ion reacts with the arsenic in solution hardly.Solution through overregulating pH, arsenious oxidising process, finally adds a certain proportion of ferrous sulfate in solution again, through the heavy arsenic reaction of certain condition, obtains scorodite crystals and two sections of filtrates.Filtrate is by the process of drainage sunk well operation.
Compared with prior art, the present invention has following advantage:
1. arsenic filter cake copper arsenic separating technology of the present invention, the separation rate of copper arsenic is high, and the leaching yield of arsenic can reach more than 98%; The rate of recovery of copper can reach more than 99%, and in the sulfuration copper ashes produced, arsenic content is less than 0.5%, can directly return Copper making operation.The form of arsenic in leach liquor with pentavalent arsenic after Oxidation Leaching exists in solution, and easilier precipitates with stable scorodite crystals form, can realize the stabilization of arsenic.
2. arsenic filter cake material is strongly-acid, and traditional alkaline leaching can consume the alkali reagents such as a large amount of sodium hydroxide, and cost can a large amount of improve, and the process of alkali lye after leaching also is a difficult problem.The effect utilizing red arsenic and the replacement(metathesis)reaction of cupric ion under acidic oxidation condition can reach copper arsenic to be separated.In solution, add alkaline sulfocompound, sulfonium ion can be provided to make in solution cupric ion precipitation further, reduce reaction required time and regulate pH to provide condition for follow-up molysite sinks arsenic.
3. these processing condition require not strict, and technical process is short, and production unit is simple, operates more convenient, high financial profit, practical.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet of the inventive method.
Embodiment
Below by embodiment, the present invention is described in further detail, but protection scope of the present invention is not limited to described content.
Embodiment 1: the copper arsenic method for separating and processing of a kind of arsenic filter cake of the present invention, concrete operations are as follows:
Embodiment 1 is raw materials used comes from certain copper smelting plant, first by raw material arsenic filter cake, (component of the principal element mass percent comprised is: S42.10%, As18.20%, Cu17.10%, Bi0.82%, Pb0.41%, main thing phase mass percent component is: pozzuolite compound 1.2%, arsenate 0.75%, arsenic oxide 15.04%, processable copper 7.23%, cupric sulfide 8.94%) oven dry, ore grinding, sieve after get 50g, add water 500ml in proportion, after mixing, add CuCl by Cu: As=5:8 again
2medicament 3g.Heating in water bath control temperature 80 ± 5 DEG C, passes into air with 40L/min simultaneously, and stirs with the speed of 300r/min.After 3h is carried out in reaction, add Na
2s solid 1.6g, continues heated and stirred 3h.When leaching process just starts, solution is blue, and along with the carrying out of leaching process, solution colour shoals gradually until be water white transparency.After leaching, the principal element mass percent of slag is: S59.30%, As0.45%, Cu33.16%, Bi0.68%, Pb0.30%, the dominant phase mass percent of leached mud is: pozzuolite compound 0.14%, arsenate 0.13%, arsenic oxide 0.12%, processable copper 0.29%, cupric sulfide 32.38%.Because the valuable metal such as antimony, bismuth is not leached substantially, based on cupric sulfide in filter residue, and some sulfide and some valuable metals, can directly return smelting procedure and recycle.
It is 28.35g that 50g material remains the quantity of slag after Oxidation Leaching, and leaching yield is 43.3%.In leached mud, the content of arsenic is only 0.45%, and the leaching yield of arsenic reaches 98.6%, and the content of copper in leached mud is 33.16%, and the leaching yield of copper is 0.1%.Leached mud can return smelting procedure and utilize.
Through Oxidation Leaching, obtain the arsenic solution 500ml of about 17.5g/L, simultaneously add 15mlH at 100: 3 by volume
2o
2solution, is oxidized to pentavalent arsenic remaining trivalent arsenic.Finally add FeSO according to the mol ratio of Fe: As=1.5: 1
4, 90 ~ 95 DEG C of agitation leachs 3 ~ 5 hours.Generation celandine green precipitates.Filter, celandine green is precipitated as ferric arsenate crystal, ferric arsenate crystal arsenic content 32.15%, iron-holder 29.31%.Two sections of filtrates can be discharged by drainage procedure.
Embodiment 2: the copper arsenic method for separating and processing of a kind of arsenic filter cake of the present invention, concrete operations are as follows:
Embodiment 2 is raw materials used comes from certain copper smelting plant, first by raw material arsenic filter cake, (component of the principal element mass percent comprised is: S31.2%, As13.5%, Cu17.60%, Bi0.72%, Pb0.23%, main thing phase mass percent component is: pozzuolite compound 0.95%, arsenate 0.55%, arsenic oxide 10.84%, processable copper 8.51%, cupric sulfide 9.57%) oven dry, ore grinding, sieve after get 50g, add water 600ml in proportion, after mixing, add CuCl by Cu: As=5:8 again
2medicament 2.25g.Heating in water bath control temperature 80 ± 5 DEG C, passes into air with 20L/min simultaneously, and stirs with the speed of 300r/min.After 2h is carried out in reaction, add Na
2s solid 0.88g, continues heated and stirred 3h.When leaching process just starts, solution is blue, and along with the carrying out of leaching process, solution colour shoals gradually until be water white transparency.After leaching, the principal element mass percent of slag is: S45.60%, As0.68%, Cu31.08%, Bi0.67%, Pb0.20%, the dominant phase mass percent of leached mud is: pozzuolite compound 0.21%, arsenate 0.18%, arsenic oxide 0.15%, processable copper 0.12%, cupric sulfide 30.5%.Because the valuable metal such as antimony, bismuth is not leached substantially, based on cupric sulfide in filter residue, and some sulfide and some valuable metals, can directly return smelting procedure and recycle.
It is 29.95g that 50g material remains the quantity of slag after Oxidation Leaching, and leaching yield is 40.1%.In leached mud, the content of arsenic is only 0.68%, and the leaching yield of arsenic is 97.5%, and the content of copper in leached mud is 30.5%, and the leaching yield of copper is 0.25%.Leached mud can return smelting procedure and utilize.
Through Oxidation Leaching, obtain the arsenic solution 500ml of about 13g/L, simultaneously add 15mlH at 100: 3 by volume
2o
2solution, is oxidized to pentavalent arsenic remaining trivalent arsenic.The mol ratio of last Fe: As=1.5: 1 adds FeSO
4, 90 ~ 95 DEG C of agitation leachs 3 ~ 5 hours.Generation celandine green precipitates.Filter, celandine green is precipitated as ferric arsenate crystal, ferric arsenate crystal arsenic content 29.95%, iron-holder 27.20%.Two sections of filtrates can be discharged by drainage procedure.
Embodiment 3: the copper arsenic method for separating and processing of a kind of arsenic filter cake of the present invention, concrete operations are as follows:
Embodiment 3 is raw materials used comes from certain copper smelting plant, first by raw material arsenic filter cake, (component of the principal element mass percent comprised is: S42.10%, As18.20%, Cu17.10%, Bi0.82%, Pb0.41%, main thing phase mass percent component is: pozzuolite compound 1.2%, arsenate 0.75%, arsenic oxide 15.04%, processable copper 7.23%, cupric sulfide 8.94%) oven dry, ore grinding, sieve after get 50g, add water 500ml in proportion, after mixing, add CuSO by Cu: As=7:8 again
4medicament 4.2g.Heating in water bath control temperature 85 ± 5 DEG C, and stir with the speed of 200r/min.After 1h is carried out in reaction, add Na
2s solid 1.7g, continues heated and stirred 5h.When leaching process just starts, solution is blue, and along with the carrying out of leaching process, solution colour shoals gradually until be water white transparency.After leaching, the principal element mass percent of slag is: S60.02%, As0.98%, Cu33.84%, Bi0.7%, Pb0.37%, the dominant phase mass percent of leached mud is: pozzuolite compound 0.22%, arsenate 0.35%, arsenic oxide 0.13%, processable copper 0.21%, cupric sulfide 33.14%.Because the valuable metal such as antimony, bismuth is not leached substantially, based on cupric sulfide in filter residue, and some sulfide and and some valuable metals, can directly return smelting procedure and recycle.
It is 28.1g that 50g material remains the quantity of slag after Oxidation Leaching, and leaching yield is 43.8%.In leached mud, the content of arsenic is 0.98%, and the leaching yield of arsenic reaches 96.9%, and the content of copper in leached mud is 33.84%, and the leaching yield of copper is 0.5%.Leached mud can return smelting procedure and utilize.
Through Oxidation Leaching, obtain the arsenic solution 500ml of about 17.3g/L, add NaOH and regulate pH to 4 ~ 5, simultaneously add 15mlH at 100: 3 by volume
2o
2solution, is oxidized to pentavalent arsenic remaining trivalent arsenic.The mol ratio of last Fe: As=1.5: 1 adds FeSO
4, 90 ~ 95 DEG C of agitation leachs 3 ~ 5 hours.Generation celandine green precipitates.Filter, celandine green is precipitated as ferric arsenate crystal, ferric arsenate crystal arsenic content 30.31%, iron-holder 27.01%.Two sections of filtrates can be discharged by drainage procedure.
Embodiment 4: the copper arsenic method for separating and processing of a kind of arsenic filter cake of the present invention, concrete operations are as follows:
Embodiment 4 is raw materials used comes from certain copper smelting plant, first by raw material arsenic filter cake, (component of the principal element mass percent comprised is: S42.10%, As18.20%, Cu17.10%, Bi0.82%, Pb0.41%, main thing phase mass percent component is: pozzuolite compound 1.2%, arsenate 0.75%, arsenic oxide 15.04%, processable copper 7.23%, cupric sulfide 8.94%) oven dry, ore grinding, sieve after get 50g, add water 500ml in proportion, after mixing, add CuCl by Cu: As=3:8 again
2medicament 1.8g.Heating in water bath control temperature 80 ± 5 DEG C, stirs with 400r/min speed.After 2h is carried out in reaction, add NaHS solid 0.6g, continue heated and stirred 3h.When leaching process just starts, solution is blue, and along with the carrying out of leaching process, solution colour shoals gradually until colourless.After leaching, the principal element mass percent of slag is: S57.91%, As1.07%, Cu32.22%, Bi0.7, Pb0.35%, the dominant phase mass percent of leached mud is: pozzuolite compound 0.3%, arsenate 0.45%, arsenic oxide 0.14%, processable copper 0.39%, cupric sulfide 30.2%.The valuable metal such as antimony, bismuth is not leached substantially, based on cupric sulfide in filter residue, and some sulfide and some valuable metals.
It is 27.89g that 50g material remains the quantity of slag after Oxidation Leaching, and leaching yield is 44.22%.In leached mud, the content of arsenic is 1.07%, and the leaching yield of arsenic reaches 96.72%, and the content of copper in leached mud is 32.22%, and the leaching yield of copper is 0.13%, and leached mud can return smelting procedure and utilize.
Through Oxidation Leaching, obtain the arsenic solution 500ml of about 17.3g/L, add NaOH and regulate pH to 4 ~ 5, simultaneously add 15mlH at 100: 3 by volume
2o
2solution, is oxidized to pentavalent arsenic remaining trivalent arsenic.The mol ratio of last Fe: As=1.5: 1 adds FeSO
4, 90 ~ 95 DEG C of agitation leachs 3 ~ 5 hours.Generation celandine green precipitates.Filter, celandine green is precipitated as ferric arsenate crystal, ferric arsenate crystal arsenic content 24.96%, iron-holder 25.2%.
Embodiment 5: the copper arsenic method for separating and processing of a kind of arsenic filter cake of the present invention, concrete operations are as follows:
Embodiment 5 is raw materials used comes from certain copper smelting plant, first by raw material arsenic filter cake, (component of the principal element mass percent comprised is: S42.10%, As18.20%, Cu17.10%, Bi0.82%, Pb0.41%, main thing phase mass percent component is: pozzuolite compound 1.2%, arsenate 0.75%, arsenic oxide 15.04%, processable copper 7.23%, cupric sulfide 8.94%) oven dry, ore grinding, sieve after get 50g, add water 500ml in proportion, after mixing, add CuCl by Cu: As=5:8 again
2medicament 3g.Heating in water bath control temperature 80 ± 5 DEG C, and carry out stirring 6h with the speed of 400r/min.After leaching, the principal element mass percent of slag is: S58.3%, As1.25%, Cu29.87%, Bi0.72%, Pb0.39%, the dominant phase mass percent of leached mud is: pozzuolite compound 0.52%, arsenate 0.35%, arsenic oxide 0.1%, processable copper 0.58%, cupric sulfide 28.74%.The valuable metal such as antimony, bismuth is not leached substantially, based on cupric sulfide in filter residue, and some sulfide and some valuable metals.
It is 29.8g that 50g material remains the quantity of slag after Oxidation Leaching, and leaching yield is 40.4%.In leached mud, the content of arsenic is 1.25%, and the leaching yield of arsenic reaches 95.9%, and copper leaching rate is 1.93%, and the content of copper in leached mud is 28.87%.
Through Oxidation Leaching, obtain the arsenic solution 500ml of about 17.3g/L, simultaneously add 15mlH at 100: 3 by volume
2o
2solution, is oxidized to pentavalent arsenic remaining trivalent arsenic.Finally add FeSO according to the mol ratio of Fe: As=1.5: 1
4, 90 ~ 95 DEG C of agitation leachs 3 ~ 5 hours.Generation celandine green precipitates.Filter, celandine green is precipitated as ferric arsenate crystal, ferric arsenate crystal arsenic content 30.15%, iron-holder 29.31%.Two sections of filtrates can be discharged by drainage procedure.
Embodiment 6: the copper arsenic method for separating and processing of a kind of arsenic filter cake of the present invention, concrete operations are as follows:
Embodiment 6 is raw materials used comes from certain copper smelting plant, first by raw material arsenic filter cake, (component of the principal element mass percent comprised is: S42.10%, As18.20%, Cu17.10%, Bi0.82%, Pb0.41%, main thing phase mass percent component is: pozzuolite compound 1.2%, arsenate 0.75%, arsenic oxide 15.04%, processable copper 7.23%, cupric sulfide 8.94%) dry, ore grinding, 50g is got after sieving, add water 500ml in proportion, heating in water bath control temperature 80 ± 5 DEG C, pass into air with 40L/min simultaneously, and carry out stirring 6 hours with the speed of 300r/min.When leaching process just starts, solution is blue, and along with the carrying out of leaching process, solution colour shoals gradually until for light blue.After leaching, the principal element mass percent of slag is: S53.71%, As2.81%, Cu26.84%, Bi0.7%, Pb0.37%, the dominant phase mass percent of leached mud is: pozzuolite compound 2.62%, arsenate 0.45%, arsenic oxide 0.33%, processable copper 0.38%, cupric sulfide 24.94%.Because the valuable metal such as antimony, bismuth is not leached substantially, based on cupric sulfide in filter residue, and some sulfide and some valuable metals.
It is 32.1g that 50g material remains the quantity of slag after Oxidation Leaching, and total leaching yield is 35.8%.In leached mud, the content of arsenic is 2.81%, and the leaching yield of arsenic reaches 89.08%, and the content of copper in leached mud is 29.84%, and the leaching yield of copper is 0.2%.
This example is that arsenic filter cake slag directly leaches, and does not add the material of any type of cupric and sulphur, from found that arsenic leaching yield is only 89.08%.Owing to not adding cupric ion in solution, part arsenic can not with copper generation replacement(metathesis)reaction, cause arsenic leaching yield to decline, do not reach copper arsenic be separated requirement.
Embodiment 7: the copper arsenic method for separating and processing of a kind of arsenic filter cake of the present invention, concrete operations are as follows:
Embodiment 7 is raw materials used comes from certain copper smelting plant, first by raw material arsenic filter cake, (component of the principal element mass percent comprised is: S42.10%, As18.20%, Cu17.10%, Bi0.82%, Pb0.41%, main thing phase mass percent component is: pozzuolite compound 1.2%, arsenate 0.75%, arsenic oxide 15.04%, processable copper 7.23%, cupric sulfide 8.94%) oven dry, ore grinding, sieve after get 50g, add water 500ml in proportion, after mixing, add CuCl by Cu: As=1:8 again
2medicament 0.6g.Heating in water bath control temperature 80 ± 5 DEG C, passes into air with 40L/min simultaneously, and stirs with the speed of 300r/min.After 3h is carried out in reaction, add Na
2s solid 0.5g, continues heated and stirred 3h.When leaching process just starts, solution is blue, and along with the carrying out of leaching process, solution colour shoals gradually until be water white transparency.After leaching, the principal element mass percent of slag is: S56.30%, As2.51%, Cu30.44%, Bi0.78%, Pb0.35%, the dominant phase mass percent of leached mud is: pozzuolite compound 0.94%, arsenate 0.33%, arsenic oxide 0.42%, processable copper 0.25%, cupric sulfide 32.15%.Because the valuable metal such as antimony, bismuth is not leached substantially, based on cupric sulfide in filter residue, and some sulfide and some valuable metals.
It is 31.7g that 50g material remains the quantity of slag after Oxidation Leaching, and leaching yield is 36.6%.In leached mud, the content of arsenic is 2.51%, and the leaching yield of arsenic reaches 91.23%, and the content of copper in leached mud is 30.44%, and the leaching yield of copper is 0.12%.
Through Oxidation Leaching, obtain the arsenic solution 500ml of about 17.5g/L, simultaneously add 15mlH at 100: 3 by volume
2o
2solution, is oxidized to pentavalent arsenic remaining trivalent arsenic.Finally add FeSO according to the mol ratio of Fe: As=1.5: 1
4, 90 ~ 95 DEG C of agitation leachs 3 ~ 5 hours.Generation celandine green precipitates.Filter, celandine green is precipitated as ferric arsenate crystal, ferric arsenate crystal arsenic content 28.75%, iron-holder 29.34%.Two sections of filtrates can be discharged by drainage procedure.
Embodiment 8: the copper arsenic method for separating and processing of a kind of arsenic filter cake of the present invention, concrete operations are as follows:
Embodiment 8 is raw materials used comes from certain copper smelting plant, first by raw material arsenic filter cake, (component of the principal element mass percent comprised is: S42.10%, As18.20%, Cu17.10%, Bi0.82%, Pb0.41%, main thing phase mass percent component is: pozzuolite compound 1.2%, arsenate 0.75%, arsenic oxide 15.04%, processable copper 7.23%, cupric sulfide 8.94%) oven dry, ore grinding, sieve after get 50g, add water 500ml in proportion, after mixing, add CuCl by Cu: As=9:8 again
2medicament 5.4g.Heating in water bath control temperature 80 ± 5 DEG C, passes into air with 40L/min simultaneously, and stirs with the speed of 300r/min.After 3h is carried out in reaction, add Na
2s solid 3.1g, continues heated and stirred 4h.When leaching process just starts, solution is blue, and along with the carrying out of leaching process, solution colour shoals gradually until for colourless.After leaching, the principal element mass percent of slag is: S62.9%, As0.97%, Cu38.12%, Bi0.52%, Pb0.32%, the dominant phase mass percent of leached mud is: pozzuolite compound 0.22%, arsenate 0.2%, arsenic oxide 0.16%, processable copper 0.46%, cupric sulfide 35.94%.Because the valuable metal such as antimony, bismuth is not leached substantially, based on cupric sulfide in filter residue, and some sulfide and some valuable metals.
It is 36.5g that 50g material remains the quantity of slag after Oxidation Leaching, and total leaching yield is 27%.In leached mud, the content of arsenic is 0.81%, and the leaching yield of arsenic reaches 97.1%, and the content of copper in leached mud is 38.12%, and the leaching yield of copper is 0.2%.
Through Oxidation Leaching, obtain the arsenic solution 500ml of about 17.5g/L, simultaneously add 15mlH at 100: 3 by volume
2o
2solution, is oxidized to pentavalent arsenic remaining trivalent arsenic.Finally add FeSO according to the mol ratio of Fe: As=1.5: 1
4, 90 ~ 95 DEG C of agitation leachs 3 ~ 5 hours.Generation celandine green precipitates.Filter, celandine green is precipitated as ferric arsenate crystal, ferric arsenate crystal arsenic content 30.18%, iron-holder 31.44%.Two sections of filtrates can be discharged by drainage procedure.
From this example, strengthen copper arsenic than the effect that can reach the separation of copper arsenic equally, but copper-containing compound and sulfocompound add-on are too much, cause reagent waste.
The experiment condition of each example and the analysis of experimental result contrast as shown in table 1.
Table 1.
Claims (10)
1. a copper arsenic method for separating and processing for arsenic filter cake, is characterized in that, comprise the following steps:
(1) arsenic filter cake material is carried out dry, grind, sieve;
(2) material is mixed with water size mixing;
(3) added by soluble copper salt in the slurry that step (2) mixes up, stirring and dissolving is even;
(4) by the agitation leach reaction under aerobic conditions of the mixed slurry of step (3);
(5) the sulfocompound heavy copper further that sulfonium ion can be provided is added after Leaching reaction;
(6) leach liquor is used for the recovery of arsenic.
2. the copper arsenic method for separating and processing of a kind of arsenic filter cake according to claim 1, is characterized in that: described arsenic filter cake material is the dirt acid produced in Copper making process, through the product of sodium sulphite process; Arsenic filter cake comprises the composition of following mass percent: arsenic 12.01% ~ 19.5%, copper 15.10% ~ 20.00%, sulphur 25.30% ~ 48.21%; In described arsenic filter cake material, the existing forms of arsenic and mass percent are: pozzuolite compound 0.5% ~ 3.0%, arsenic oxide 9.2% ~ 17.2%, arsenate 0.1% ~ 1.5%, the existing forms of copper and mass percent are: soluble copper 5.6% ~ 9.31%, cupric sulfide 7.50% ~ 10.56%.
3. the copper arsenic method for separating and processing of a kind of arsenic filter cake according to claim 1 and 2, is characterized in that: in step (1), arsenic filter cake is dried to water ratio lower than 5% under 105 DEG C of conditions, and crosses 100 eye mesh screens, and screen over-size is less than 25%.
4. the copper arsenic method for separating and processing of a kind of arsenic filter cake according to claim 1 and 2, it is characterized in that: the liquid-solid volume mass that in step (2), water and arsenic filter cake mixing of materials are sized mixing is than being 8:1 ~ 12:1ml/g, and wherein optimum liquid-solid volume mass is than being 10:1ml/g.
5. the copper arsenic method for separating and processing of a kind of arsenic filter cake according to claim 1, is characterized in that: step (3) soluble copper salt comprise in cupric chloride, Salzburg vitriol, cupric nitrate one or more.
6. the copper arsenic method for separating and processing of a kind of arsenic filter cake according to claim 1 or 5, it is characterized in that: in soluble copper salt and former slag, the summation of soluble copper with the mass ratio of arsenic in arsenic filter cake is in step (3): Cu: As=3:8 ~ 7:8, wherein optimum quality is than being 5:8.
7. the copper arsenic method for separating and processing of a kind of arsenic filter cake according to claim 1, it is characterized in that: the extract technology condition in step (4) is: temperature is 75 ~ 90 DEG C, mixing speed is 200r/min ~ 400r/min, the flow passing into air is 30 ~ 60L/min, and extraction time is 5 ~ 7h; Wherein optimum temperature is 80 DEG C, and optimized rotating speed is 300r/min, and passing into air flow quantity optimum is 40L/min, and extraction time optimum is 6h.
8. the copper arsenic method for separating and processing of a kind of arsenic filter cake according to claim 1, it is characterized in that: sulfocompound comprises in step (5): one or more in sodium sulphite, Sodium sulfhydrate, potassium sulphide, the sulfocompound time added in solution is after Leaching reaction 1 ~ 3 hour.
9. the copper arsenic method for separating and processing of a kind of arsenic filter cake according to claim 1 or 8, it is characterized in that: in the sulfonium ion that sulfocompound added in step (5) provides and now solution, the ratio of cupric ion is S: Cu=2:1 ~ 4:1, wherein optimum quality is than being 3:1.
10. the copper arsenic method for separating and processing of a kind of arsenic filter cake according to claim 1, is characterized in that: in step (5), leached mud returns Copper making operation; Leach liquor again through conciliation pH, arsenious oxidation, finally add ferrous sulfate sink arsenic reaction, obtain scorodite crystals.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105603218A (en) * | 2015-12-28 | 2016-05-25 | 长沙赛恩斯环保科技有限公司 | Method for enriching and recovering bismuth in copper smelting process |
| CN105603217A (en) * | 2015-12-28 | 2016-05-25 | 中南大学 | Method for enriching and recovering antimony in contaminated acid vulcanization residue |
| CN107012340A (en) * | 2017-03-30 | 2017-08-04 | 郴州金山冶金化工有限公司 | The technique that a kind of Whote-wet method extracts arsenic from arsenones waste residue |
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| CN110468282A (en) * | 2019-09-20 | 2019-11-19 | 北方铜业股份有限公司 | The alkali of arsenic-containing material soaks arsenic removing method |
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| CN114317962A (en) * | 2021-11-22 | 2022-04-12 | 长沙有色冶金设计研究院有限公司 | Method for separating copper from sulfuric acid leaching solution containing copper ions |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85104205A (en) * | 1985-05-28 | 1986-05-10 | 沈阳矿冶研究所 | The arsenic filter cake method of comprehensive utilization |
| CN101372360A (en) * | 2008-10-14 | 2009-02-25 | 江苏科技大学 | Method for preparing copper arsenate from arsenic filter cake |
| CN101386915A (en) * | 2008-08-13 | 2009-03-18 | 湖南宏大锑铅有限公司 | Method for recovering simple substance arsenic from arsenic sulfide slag |
-
2015
- 2015-09-22 CN CN201510606648.8A patent/CN105154679B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85104205A (en) * | 1985-05-28 | 1986-05-10 | 沈阳矿冶研究所 | The arsenic filter cake method of comprehensive utilization |
| CN101386915A (en) * | 2008-08-13 | 2009-03-18 | 湖南宏大锑铅有限公司 | Method for recovering simple substance arsenic from arsenic sulfide slag |
| CN101372360A (en) * | 2008-10-14 | 2009-02-25 | 江苏科技大学 | Method for preparing copper arsenate from arsenic filter cake |
Non-Patent Citations (1)
| Title |
|---|
| 刘松林等: ""硫化砷渣的资源化处理技术现状"", 《磷肥与复肥》 * |
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