CN105349770A - Processing method of copper electrolysis arsenic matte - Google Patents

Processing method of copper electrolysis arsenic matte Download PDF

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Publication number
CN105349770A
CN105349770A CN201510814533.8A CN201510814533A CN105349770A CN 105349770 A CN105349770 A CN 105349770A CN 201510814533 A CN201510814533 A CN 201510814533A CN 105349770 A CN105349770 A CN 105349770A
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China
Prior art keywords
speiss
liquid
cupric electrolysis
pulp
treatment process
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Pending
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CN201510814533.8A
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Chinese (zh)
Inventor
董存武
李宝平
叶剑鸣
张双泉
孟茂勇
孙正德
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Jinchuan Group Co Ltd
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Jinchuan Group Co Ltd
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Priority to CN201510814533.8A priority Critical patent/CN105349770A/en
Publication of CN105349770A publication Critical patent/CN105349770A/en
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/005—Preliminary treatment of scrap
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/02—Obtaining nickel or cobalt by dry processes

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Geology (AREA)
  • Electrolytic Production Of Metals (AREA)

Abstract

The invention relates to a processing method of copper electrolysis arsenic matte, in particular to a method for removing free acid in copper electrolysis arsenic matte through Ni-Co hydrometallurgy. The processing method is characterized in that the processing process sequentially comprises the steps that firstly, arsenic matte pulpifying and heating are carried out; secondly, lime milk is added into a pulpifying solution to react; thirdly, solid and liquid separation is carried out to obtain calcium residues and liquid obtained after acid removing of arsenic matte; and fourthly, pulpifying, washing and filtering are carried out on the calcium residues obtained in the third step, residue washing liquid is returned to the first step, and residues are conveyed to a nickel pyrogenic process melting system after washing. According to the processing method of copper electrolysis arsenic matte, the free acid in the copper electrolysis arsenic matte is removed through the measures such as hot water pulpifying, pH adjustment through lime milk and calcium residue washing, operation is simple, the metal recovery rate is high, and new impurities are not introduced; and the processing expense of the copper electrolysis arsenic matte acid removing can be obviously reduced, and the processing method is an economical and applicable method.

Description

A kind for the treatment of process of cupric electrolysis speiss
Technical field
A treatment process for cupric electrolysis speiss, relates to a kind of method removing cupric electrolysis speiss Free Acid of nickel cobalt hydrometallurgy.
Background technology
Cupric electrolysis speiss forms by liquid after cupric electrolysis purification system decopper(ing) is concentrated, and its main component is NiSO 4and H 2sO 4, wherein free H 2sO 4content be 15%-17%.The method removing cupric electrolysis speiss Free Acid the most frequently used is neutralisation, and neutralizing agent is the alkaline rich nickel materials such as thick nickelous carbonate, thick nickel hydroxide.
With the expansion of copper products production capacity, the quantum of output of cupric electrolysis speiss increases suddenly, and because thick nickelous carbonate, the slightly rich nickel materials of nickel hydroxide alkalescence are under-supply, neutralizing agent is just by sodium carbonate (Na 2cO 3) and liquid caustic soda (NaOH) supplement, cause depickling expense suddenly to increase, tied up enterprise getting profit space and profit norm.
Summary of the invention
Object of the present invention is exactly the deficiency existed for above-mentioned prior art, provides a kind of simple to operate, treatment process that can reduce the cupric electrolysis speiss of cupric electrolysis speiss depickling expense.
The object of the invention is to be achieved through the following technical solutions.
A treatment process for cupric electrolysis speiss, is characterized in that the step of its treating processes comprises successively:
(1) speiss pulp, heating;
(2) milk of lime reaction is added in pulp liquid;
(3) solid-liquid separation obtains liquid after calcium slag and speiss depickling;
(4) by the calcium slag that step (3) obtains, carry out pulp, washing, filtration, wash heat liquid returns step (1), washes rear slag and delivers to nickel pyrometallurgical smelting system.
The treatment process of a kind of cupric electrolysis speiss of the present invention, is characterized in that the main component of its cupric electrolysis speiss is NiSO 4and H 2sO 4, its Chemical Composition comprises: ω h2SO4=15%-17%, ω ni=17%-19%, ω co≤ 0.5%, ω cu≤ 0.5%, ω fe≤ 0.5%, ω pb≤ 0.01%, ω zn≤ 0.5%, ω ca=0.5%-0.6%, ω mg=0.5%-1.0%, ω na≤ 0.1%, m ni/ m ca=25-40.
The treatment process of a kind of cupric electrolysis speiss of the present invention, is characterized in that the liquid-solid envelope-bulk to weight ratio of speiss pulp in its step (1) is V/m=2-2.8/1.
The treatment process of a kind of cupric electrolysis speiss of the present invention, is characterized in that in its step (1), speiss slurrying temperature is 80 DEG C-95 DEG C.
The treatment process of a kind of cupric electrolysis speiss of the present invention, is characterized in that in its step (2), milk of lime adds at the end pulp liquid pH2.0-2.5.
The treatment process of a kind of cupric electrolysis speiss of the present invention, is characterized in that the pH of liquid after speiss depickling in its step (2) is 3.5-4.5.
The treatment process of a kind of cupric electrolysis speiss of the present invention, is characterized in that the liquid-solid envelope-bulk to weight ratio of calcium slag pulp in its step (4) is V/m=4-6/1.
The present invention's milk of lime removes the principle of cupric electrolysis speiss Free Acid:
The main component Ca (OH) of milk of lime 2with the sulfuric acid (H in speiss 2sO 4) form micro-soluble material calcium sulfate (CaSO in aqueous 4), because of CaSO 4solubility with temperature raises (>=40 DEG C) and reduces, for avoiding CaSO 4(s) → Ca 2++ SO 4 2-balance moves to right, determination operation temperature 80 DEG C-95 DEG C.
Correlated response equation is:
Ca(OH) 2+H 2SO 4→CaSO 4(s)+H 2O
CaSO 4(s) → Ca 2++ SO 4 2-(reversible reaction)
The major ingredient of the present invention's cupric electrolysis speiss used is NiSO 4and H 2sO 4, its chemical constitution is: ω h2SO4=15%-17%, ω ni=17%-19%, ω co≤ 0.5%, ω cu≤ 0.5%, ω fe≤ 0.5%, ω pb≤ 0.01%, ω zn≤ 0.5%, ω ca=0.5%-0.6%, ω mg=0.5%-1.0%, ω na≤ 0.1%, nickel calcium mass ratio m ni/ m ca=25-40.
The treatment process of a kind of cupric electrolysis speiss of the present invention, the free acid in cupric electrolysis speiss is removed by the measure such as adjust pH, calcium wash heat to wash with hot water pulp, milk of lime, simple to operate, metal yield is high and do not introduce new impurity, significantly can reduce cupric electrolysis speiss depickling processing costs, be an economic and practical method.
Embodiment
A treatment process for cupric electrolysis speiss, comprises the following steps:
(1) speiss pulp: the hot water of cupric electrolysis speiss and 80 DEG C-95 DEG C is pressed liquid-solid ratio (V/m=2.0-2.8/1) pulp in steel basin;
(2) pH adjusted by milk of lime: in step a pulp liquid, slowly add milk of lime to pH2.0-2.5, continues reaction 1.5h-2.0h:
(3) use pressure filter separating calcium slag, obtain liquid after speiss depickling;
(4) calcium wash heat is washed: by step b calcium slag hot water by liquid-solid ratio (V/m=4-6/1) pulp, filters, and then use the hot water injection of 80 DEG C-95 DEG C to filter press filtrate in white, wash heat liquid returns step a reuse, washes rear slag and delivers to nickel pyrometallurgical smelting system.
Embodiment 1
By 7.0 tons of cupric electrolysis speiss and 20m 3tap water is pulp in stirring tank, temperature 80 DEG C, stirs, and slowly adds milk of lime to pulp liquid pH2.0, continues reaction 2.0h, use pressure filter separating calcium slag, obtains liquid after speiss depickling; Then calcium slag is pressed liquid-solid ratio V/m=5/1 pulp with hot water in washery slag still, filter, use hot water injection to filter press filtrate in white, wash heat liquid is back to pulp cupric electrolysis speiss, washes rear slag and delivers to nickel pyrometallurgical smelting system.
Milk of lime deacidification technique index: nickel yield: 96.51%, slag rate: 27.65%, neutralizing agent consumption: 0.68tCaO/t nickel, liquid pH3.5, nickel calcium mass ratio m after depickling ni/ m ca: 97.4.
Embodiment 2
By 10.0 tons of cupric electrolysis speiss and 20m 3the pulp in stirring tank of wash heat liquid, temperature 91 DEG C, stirs, and slowly adds milk of lime to pulp liquid pH2.5, continues reaction 1.8h, use pressure filter separating calcium slag, obtains liquid after speiss depickling; Then calcium slag is pressed liquid-solid ratio V/m=6/1 pulp with hot water in washery slag still, filter, use hot water injection to filter press filtrate in white, filtrate recycle, in pulp cupric electrolysis speiss, is washed rear slag and is delivered to nickel pyrometallurgical smelting system.
Milk of lime deacidification technique index: nickel yield: 95.75%, slag rate: 26.82%, neutralizing agent consumption: 0.69tCaO/t nickel, liquid pH4.5, nickel calcium mass ratio m after depickling ni/ m ca: 92.2.
Embodiment 3
By 8.5 tons of cupric electrolysis speiss and 20m 3the pulp in stirring tank of wash heat liquid, temperature 95 DEG C, stirs, and slowly adds milk of lime to pulp liquid pH2.0, continues reaction 1.5h, use pressure filter separating calcium slag, obtains liquid after speiss depickling; Then calcium slag is pressed liquid-solid ratio V/m=4/1 pulp with hot water in washery slag still, filter, use hot water injection to filter press filtrate in white, filtrate recycle, in pulp cupric electrolysis speiss, is washed rear slag and is delivered to nickel pyrometallurgical smelting system.
Milk of lime deacidification technique index: nickel yield: 96.44%, slag rate: 27.37%, neutralizing agent consumption: 0.68tCaO/t nickel, liquid pH3.5, nickel calcium mass ratio m after speiss depickling ni/ m ca: 95.9.

Claims (7)

1. a treatment process for cupric electrolysis speiss, is characterized in that the step of its treating processes comprises successively:
(1) speiss pulp, heating;
(2) milk of lime reaction is added in pulp liquid;
(3) solid-liquid separation obtains liquid after calcium slag and speiss depickling;
(4) by the calcium slag that step (3) obtains, carry out pulp, washing, filtration, wash heat liquid returns step (1), washes rear slag and delivers to nickel pyrometallurgical smelting system.
2. the treatment process of a kind of cupric electrolysis speiss according to claim 1, is characterized in that the main component of its cupric electrolysis speiss is NiSO 4and H 2sO 4, its Chemical Composition comprises: ω h2SO4=15%-17%, ω ni=17%-19%, ω co≤ 0.5%, ω cu≤ 0.5%, ω fe≤ 0.5%, ω pb≤ 0.01%, ω zn≤ 0.5%, ω ca=0.5%-0.6%, ω mg=0.5%-1.0%, ω na≤ 0.1%, m ni/ m ca=25-40.
3. the treatment process of a kind of cupric electrolysis speiss according to claim 1, is characterized in that the liquid-solid envelope-bulk to weight ratio of speiss pulp in its step (1) is V/m=2-2.8/1.
4. the treatment process of a kind of cupric electrolysis speiss according to claim 1, is characterized in that in its step (1), speiss slurrying temperature is 80 DEG C-95 DEG C.
5. the treatment process of a kind of cupric electrolysis speiss according to claim 1, is characterized in that in its step (2), milk of lime adds at the end pulp liquid pH2.0-2.5.
6. the treatment process of a kind of cupric electrolysis speiss according to claim 1, is characterized in that (in (2), after speiss depickling, the pH of liquid is 3.5-4.5 to its step.
7. the treatment process of a kind of cupric electrolysis speiss according to claim 1, is characterized in that the liquid-solid envelope-bulk to weight ratio of calcium slag pulp in its step (4) is V/m=4-6/1.
CN201510814533.8A 2015-11-23 2015-11-23 Processing method of copper electrolysis arsenic matte Pending CN105349770A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105714119A (en) * 2016-04-08 2016-06-29 金川集团股份有限公司 Method for recovering nickel from calcium-magnesium slag through ion exchange solution

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN87103814A (en) * 1987-05-23 1988-12-14 张铨 Electrolytic process is POV nickel from the nickel plating waste residue
JP2005015272A (en) * 2003-06-26 2005-01-20 Nippon Steel Corp Recovery method of nickel salt from nickel-containing waste solution sludge
RU2007116650A (en) * 2007-05-02 2008-11-10 Дмитрий Борисович Басков (RU) METHOD FOR PROCESSING SOLUTIONS CONTAINING NICKEL AND METAL IMPURITIES
CN102040252A (en) * 2009-10-16 2011-05-04 中科铜都粉体新材料股份有限公司 Method for producing battery-level refined nickel sulfate with electrolyte
CN102627333A (en) * 2012-04-24 2012-08-08 中南大学 Method for refined nickel sulfate
CN103397185A (en) * 2013-06-24 2013-11-20 中南大学 Method for calcium removal during iron precipitation of nickel sulfate solution containing iron and free sulfuric acid

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN87103814A (en) * 1987-05-23 1988-12-14 张铨 Electrolytic process is POV nickel from the nickel plating waste residue
JP2005015272A (en) * 2003-06-26 2005-01-20 Nippon Steel Corp Recovery method of nickel salt from nickel-containing waste solution sludge
RU2007116650A (en) * 2007-05-02 2008-11-10 Дмитрий Борисович Басков (RU) METHOD FOR PROCESSING SOLUTIONS CONTAINING NICKEL AND METAL IMPURITIES
CN102040252A (en) * 2009-10-16 2011-05-04 中科铜都粉体新材料股份有限公司 Method for producing battery-level refined nickel sulfate with electrolyte
CN102627333A (en) * 2012-04-24 2012-08-08 中南大学 Method for refined nickel sulfate
CN103397185A (en) * 2013-06-24 2013-11-20 中南大学 Method for calcium removal during iron precipitation of nickel sulfate solution containing iron and free sulfuric acid

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105714119A (en) * 2016-04-08 2016-06-29 金川集团股份有限公司 Method for recovering nickel from calcium-magnesium slag through ion exchange solution
CN105714119B (en) * 2016-04-08 2018-06-29 金川集团股份有限公司 A kind of method for recycling nickel from nickeliferous calcium and magnesium slag with ion exchanged soln

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Application publication date: 20160224