CN105400955A - Method for removing copper ions in zinc sulfate solution - Google Patents

Method for removing copper ions in zinc sulfate solution Download PDF

Info

Publication number
CN105400955A
CN105400955A CN201510802755.8A CN201510802755A CN105400955A CN 105400955 A CN105400955 A CN 105400955A CN 201510802755 A CN201510802755 A CN 201510802755A CN 105400955 A CN105400955 A CN 105400955A
Authority
CN
China
Prior art keywords
zinc sulfate
solution
cupric
cupric ion
ammonium bisulfite
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201510802755.8A
Other languages
Chinese (zh)
Inventor
李才发
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hunan Lihong New Material Technology Co Ltd
Original Assignee
Hunan Lihong New Material Technology Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hunan Lihong New Material Technology Co Ltd filed Critical Hunan Lihong New Material Technology Co Ltd
Priority to CN201510802755.8A priority Critical patent/CN105400955A/en
Publication of CN105400955A publication Critical patent/CN105400955A/en
Pending legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/44Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B15/00Obtaining copper
    • C22B15/0063Hydrometallurgy
    • C22B15/0084Treating solutions
    • C22B15/0089Treating solutions by chemical methods
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B19/00Obtaining zinc or zinc oxide
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Geology (AREA)
  • Removal Of Specific Substances (AREA)

Abstract

The invention provides a method for removing copper ions in a zinc sulfate solution. According to the method, ammonium hydrogen sulfite is used as a reducing agent for removing the copper ions in the zinc sulfate solution, the PH value of the zinc sulfate solution is 4.0-4.5, and the concentration of the copper ions in the zinc sulfate solution is 1-10 g/L. The method specifically comprises the following steps that the zinc sulfate solution is added into a reaction tank and is heated up to 45-55 DEG C; ammonium hydrogen sulfite is added for reaction, the reaction time is 25-30 min, and the reaction temperature is 45-55 DEG C; the copper ions in the zinc sulfate solution are changed to be in a cuprous oxide form from a bivalence form and are separated from the zinc sulfate solution; solid-liquid separation is conducted after reaction is completed, and the zinc sulfate solution without the copper ions and copper-bearing filter residues are obtained.

Description

Remove the method for cupric ion in solution of zinc sulfate
Technical field
The present invention relates to a kind of chemical technology field, particularly a kind of method removing cupric ion in solution of zinc sulfate.
Background technology
At present, the ordinary method removing cupric ion in solution of zinc sulfate is a lot, as zinc powder reduction method, extraction process etc.Zinc powder reduction method adds in the solution of zinc sulfate of copper ions by zinc powder, copper ions in solution of zinc sulfate removed by displacement.Extraction process is by adding phosphoric acid dibutyl ester in the solution of zinc sulfate of copper ions, copper ions in solution of zinc sulfate is extracted by phosphoric acid dibutyl ester.
The treating processes of aforesaid method is very complicated, and cost is very high, and effect is not very good, also can produce reluctant copper-cadmium slag.
Summary of the invention
The object of the invention is to overcome the above-mentioned deficiency of prior art and a kind of method removing cupric ion in solution of zinc sulfate is provided.
Technical scheme of the present invention is: a kind of method removing cupric ion in solution of zinc sulfate, it is employing ammonium bisulfite removes in solution of zinc sulfate cupric ion as reductive agent, pH value in solution of zinc sulfate is 4.0 ~ 4.5, and in solution of zinc sulfate, the concentration of cupric ion is 1 ~ 10g/L.
Its concrete steps are as follows:
A, solution of zinc sulfate is added in retort;
B, the solution of zinc sulfate in retort is warming up to 45 ~ 55 DEG C;
C, in retort, add ammonium bisulfite, reduce bivalent cupric ion in solution of zinc sulfate with ammonium bisulfite as reductive agent, 1m 3solution of zinc sulfate add the ammonium bisulfite of 5.1 ~ 49.9Kg, the mol ratio of ammonium bisulfite and cupric ion is 3.2 ~ 3.3, reaction times is 25 ~ 30min, temperature of reaction is 45 ~ 55 DEG C, make cupric ion in solution of zinc sulfate become Red copper oxide form by divalence, be separated from solution of zinc sulfate;
The chemical equation of ammonium bisulfite and solution of zinc sulfate is as follows:
6(NH4)HSO3+2CuSO4=3(NH4)2SO4+3H2O+5SO2↑+Cu2O
Reducing heavy copper with other reductive agent is liquid and gas soluble in water unlike the reduzate of ammonium bisulfite;
D, reaction carry out solid-liquid separation after terminating, and obtain solution of zinc sulfate and the cupric filter residue of removing cupric ion, and the solution of zinc sulfate of removing cupric ion enters subsequent processing purifying regeneration and produces zinc series product;
E, the cupric filter residue feeding washery slag tank will acquired in step D, in washery slag tank, add water, the solid-to-liquid ratio of cupric filter residue and water is 1:3, then adds the vitriol oil and regulates pH value to 3.5 ~ 4.0, carry out solid-liquor separation after stirring 25 ~ 30min, obtain the copper sludge filter residue that cupric is of high grade.
The present invention compared with prior art has following features:
1, adopt ammonium bisulfite to remove cupric ion in solution of zinc sulfate as reductive agent, copper removal effective, the residual copper concentration of solution of zinc sulfate all lower than 0.05g/L, can output copper grade higher than the Red copper oxide of 80%, be beneficial to the recovery of copper;
2, the copper removal operating time is short, and compared with the method for the copper removal industrially used with other, its cost is low, is easy to combine with existing zinc wet process, comprehensively achieves economic benefit and environmental benefit.
Below in conjunction with embodiment, detailed construction of the present invention is further described.
Embodiment
Embodiment one, a kind of method removing cupric ion in solution of zinc sulfate, it is employing ammonium bisulfite removes in solution of zinc sulfate cupric ion as reductive agent, and the pH value in solution of zinc sulfate is 4.0, and in solution of zinc sulfate, the concentration of cupric ion is 1g/L.
Its concrete steps are as follows:
A, solution of zinc sulfate is added in retort;
B, the solution of zinc sulfate in retort is warming up to 45 DEG C;
C, in retort, add ammonium bisulfite, reduce bivalent cupric ion in solution of zinc sulfate with ammonium bisulfite as reductive agent, 1m 3solution of zinc sulfate add the ammonium bisulfite of 5.1Kg, the mol ratio of ammonium bisulfite and cupric ion is 3.2, and the reaction times is 25min, and temperature of reaction is 45 DEG C, make cupric ion in solution of zinc sulfate become Red copper oxide form by divalence, be separated from solution of zinc sulfate;
The chemical equation of ammonium bisulfite and solution of zinc sulfate is as follows:
6(NH4)HSO3+2CuSO4=3(NH4)2SO4+3H2O+5SO2↑+Cu2O
Reducing heavy copper with other reductive agent is liquid and gas soluble in water unlike the reduzate of ammonium bisulfite;
D, reaction carry out solid-liquid separation after terminating, and obtain solution of zinc sulfate and the cupric filter residue of removing cupric ion, and the solution of zinc sulfate of removing cupric ion enters subsequent processing purifying regeneration and produces zinc series product;
E, the cupric filter residue feeding washery slag tank will acquired in step D, in washery slag tank, add water, the solid-to-liquid ratio of cupric filter residue and water is 1:3, then adds the vitriol oil and regulates pH value to 3.5, carry out solid-liquor separation, obtain the copper sludge filter residue that cupric is of high grade after stirring 25min.
After testing, adopt the present invention to remove cupric ion in solution of zinc sulfate, in the solution of zinc sulfate processed, cupric ion is 0.03g/L, and copper sludge filter residue cupric 81%, copper removal effect is very good.
Embodiment two, a kind of method removing cupric ion in solution of zinc sulfate, it is employing ammonium bisulfite removes in solution of zinc sulfate cupric ion as reductive agent, and the pH value in solution of zinc sulfate is 4.25, and in solution of zinc sulfate, the concentration of cupric ion is 5g/L.
Its concrete steps are as follows:
A, solution of zinc sulfate is added in retort;
B, the solution of zinc sulfate in retort is warming up to 50 DEG C;
C, in retort, add ammonium bisulfite, reduce bivalent cupric ion in solution of zinc sulfate with ammonium bisulfite as reductive agent, 1m 3solution of zinc sulfate add the ammonium bisulfite of 25.3Kg, the mol ratio of ammonium bisulfite and cupric ion is 3.25, and the reaction times is 28min, and temperature of reaction is 50 DEG C, make cupric ion in solution of zinc sulfate become Red copper oxide form by divalence, be separated from solution of zinc sulfate;
The chemical equation of ammonium bisulfite and solution of zinc sulfate is as follows:
6(NH4)HSO3+2CuSO4=3(NH4)2SO4+3H2O+5SO2↑+Cu2O
Reducing heavy copper with other reductive agent is liquid and gas soluble in water unlike the reduzate of ammonium bisulfite;
D, reaction carry out solid-liquid separation after terminating, and obtain solution of zinc sulfate and the cupric filter residue of removing cupric ion, and the solution of zinc sulfate of removing cupric ion enters subsequent processing purifying regeneration and produces zinc series product;
E, the cupric filter residue feeding washery slag tank will acquired in step D, in washery slag tank, add water, the solid-to-liquid ratio of cupric filter residue and water is 1:3, then adds the vitriol oil and regulates pH value to 3.75, carry out solid-liquor separation, obtain the copper sludge filter residue that cupric is of high grade after stirring 30min.
After testing, adopt the present invention to remove cupric ion in solution of zinc sulfate, in the solution of zinc sulfate processed, cupric ion is 0.04g/L, and copper sludge filter residue cupric 81%, copper removal effect is very good.
Embodiment three, a kind of method removing cupric ion in solution of zinc sulfate, it is employing ammonium bisulfite removes in solution of zinc sulfate cupric ion as reductive agent, and the pH value in solution of zinc sulfate is 4.5, and in solution of zinc sulfate, the concentration of cupric ion is 10g/L.
Its concrete steps are as follows:
A, solution of zinc sulfate is added in retort;
B, the solution of zinc sulfate in retort is warming up to 55 DEG C;
C, in retort, add ammonium bisulfite, reduce bivalent cupric ion in solution of zinc sulfate with ammonium bisulfite as reductive agent, 1m 3solution of zinc sulfate add the ammonium bisulfite of 49.9Kg, the mol ratio of ammonium bisulfite and cupric ion is 3.3, and the reaction times is 30min, and temperature of reaction is 55 DEG C, make cupric ion in solution of zinc sulfate become Red copper oxide form by divalence, be separated from solution of zinc sulfate;
The chemical equation of ammonium bisulfite and solution of zinc sulfate is as follows:
6(NH4)HSO3+2CuSO4=3(NH4)2SO4+3H2O+5SO2↑+Cu2O
Reducing heavy copper with other reductive agent is liquid and gas soluble in water unlike the reduzate of ammonium bisulfite;
D, reaction carry out solid-liquid separation after terminating, and obtain solution of zinc sulfate and the cupric filter residue of removing cupric ion, and the solution of zinc sulfate of removing cupric ion enters subsequent processing purifying regeneration and produces zinc series product;
E, the cupric filter residue feeding washery slag tank will acquired in step D, in washery slag tank, add water, the solid-to-liquid ratio of cupric filter residue and water is 1:3, then adds the vitriol oil and regulates pH value to 4.0, carry out solid-liquor separation, obtain the copper sludge filter residue that cupric is of high grade after stirring 30min.
After testing, adopt the present invention to remove cupric ion in solution of zinc sulfate, in the solution of zinc sulfate processed, cupric ion is 0.035g/L, and copper sludge filter residue cupric 81.2%, copper removal effect is very good.

Claims (1)

1. remove the method for cupric ion in solution of zinc sulfate for one kind, it is characterized in that: it is employing ammonium bisulfite removes in solution of zinc sulfate cupric ion as reductive agent, pH value in solution of zinc sulfate is 4.0 ~ 4.5, and in solution of zinc sulfate, the concentration of cupric ion is 1 ~ 10g/L;
Its concrete steps are as follows:
A, solution of zinc sulfate is added in retort;
B, the solution of zinc sulfate in retort is warming up to 45 ~ 55 DEG C;
C, in retort, add ammonium bisulfite, reduce bivalent cupric ion in solution of zinc sulfate with ammonium bisulfite as reductive agent, 1m 3solution of zinc sulfate add the ammonium bisulfite of 5.1 ~ 49.9Kg, the mol ratio of ammonium bisulfite and cupric ion is 3.2 ~ 3.3, reaction times is 20 ~ 30min, temperature of reaction is 45 ~ 55 DEG C, make cupric ion in solution of zinc sulfate become Red copper oxide form by divalence, be separated from solution of zinc sulfate;
The chemical equation of ammonium bisulfite and solution of zinc sulfate is as follows:
6(NH4)HSO3+2CuSO4=3(NH4)2SO4+3H2O+5SO2↑+Cu2O
Reducing heavy copper with other reductive agent is liquid and gas soluble in water unlike the reduzate of ammonium bisulfite;
D, reaction carry out solid-liquid separation after terminating, and obtain solution of zinc sulfate and the cupric filter residue of removing cupric ion, and the solution of zinc sulfate of removing cupric ion enters subsequent processing purifying regeneration and produces zinc series product;
E, the cupric filter residue feeding washery slag tank will acquired in step D, in washery slag tank, add water, the solid-to-liquid ratio of cupric filter residue and water is 1:3, then adds the vitriol oil and regulates pH value to 3.5 ~ 4.0, carry out solid-liquor separation after stirring 25 ~ 30min, obtain the copper sludge filter residue that cupric is of high grade.
CN201510802755.8A 2015-11-19 2015-11-19 Method for removing copper ions in zinc sulfate solution Pending CN105400955A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201510802755.8A CN105400955A (en) 2015-11-19 2015-11-19 Method for removing copper ions in zinc sulfate solution

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201510802755.8A CN105400955A (en) 2015-11-19 2015-11-19 Method for removing copper ions in zinc sulfate solution

Publications (1)

Publication Number Publication Date
CN105400955A true CN105400955A (en) 2016-03-16

Family

ID=55466708

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510802755.8A Pending CN105400955A (en) 2015-11-19 2015-11-19 Method for removing copper ions in zinc sulfate solution

Country Status (1)

Country Link
CN (1) CN105400955A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106191441A (en) * 2016-08-05 2016-12-07 来宾华锡冶炼有限公司 A kind of method preparing solution of zinc sulfate removing impurities agent

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2280168A (en) * 1941-08-22 1942-04-21 Jr William B Stoddard Process of preparing cuprous oxide
CN1054956A (en) * 1990-03-12 1991-10-02 烟台市古现化工厂 A kind of method of producing Red copper oxide
JP2006069879A (en) * 2004-09-06 2006-03-16 Fuji Photo Film Co Ltd Method of manufacturing cuprous oxide particles, and cuprous oxide particles
CN102390861A (en) * 2011-08-17 2012-03-28 金川集团有限公司 Method for preparing cuprous oxide powder
CN103112883A (en) * 2012-12-10 2013-05-22 浙江理工大学 Method for preparing superfine cuprous oxide powder
CN104591257A (en) * 2015-01-12 2015-05-06 广东光华科技股份有限公司 Preparation method of cubic micro/nano cuprous oxide powder

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2280168A (en) * 1941-08-22 1942-04-21 Jr William B Stoddard Process of preparing cuprous oxide
CN1054956A (en) * 1990-03-12 1991-10-02 烟台市古现化工厂 A kind of method of producing Red copper oxide
JP2006069879A (en) * 2004-09-06 2006-03-16 Fuji Photo Film Co Ltd Method of manufacturing cuprous oxide particles, and cuprous oxide particles
CN102390861A (en) * 2011-08-17 2012-03-28 金川集团有限公司 Method for preparing cuprous oxide powder
CN103112883A (en) * 2012-12-10 2013-05-22 浙江理工大学 Method for preparing superfine cuprous oxide powder
CN104591257A (en) * 2015-01-12 2015-05-06 广东光华科技股份有限公司 Preparation method of cubic micro/nano cuprous oxide powder

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
杨加定: ""电镀污泥中铜、镍、铬、锌的回收利用研究"", 《化学工程与装备》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106191441A (en) * 2016-08-05 2016-12-07 来宾华锡冶炼有限公司 A kind of method preparing solution of zinc sulfate removing impurities agent
CN106191441B (en) * 2016-08-05 2017-11-03 来宾华锡冶炼有限公司 A kind of method for preparing solution of zinc sulfate removing impurities agent

Similar Documents

Publication Publication Date Title
CN102627333B (en) Method for refined nickel sulfate
CN109055757B (en) Method for recovering manganese dioxide and lead in anode slag of electrolytic manganese or electrolytic zinc
KR102188441B1 (en) Method for preparing a solution containing nickel and cobalt
KR102282701B1 (en) Lithium recovery method
AU2012330140A1 (en) Method for producing high-purity cobalt sulfate aqueous solution
CN103224259A (en) Method for refining crude nickel sulphate and recycling valuable metals
CN105568269A (en) Preparation method of cyanide-free gold plating reagent sodium gold sulfite
WO2017121343A1 (en) Process for recovering lithium from industrial wastewater
CN102701263B (en) Method for preparing copper sulfate in mode that stanniferous copper slag is leached in selective mode and free of evaporation
CN102443700B (en) Method for recovering nickel from nickel-laterite leaching solution and device
CN105349803A (en) Method for separating tungsten and molybdenum from molybdenum-contained phosphotungstic acid/phosphowolframate solution
CN106630313A (en) Reduction circulation process method for recycling zinc elements in iron-containing waste acid
CN103771526A (en) Method for preparing high-purity manganese sulfate with industrial manganese sulfate as raw material
CN104787952B (en) A kind of from containing the technique reclaiming chromium hexavalent chromium wastewater
CN112553481A (en) Production method of electrolytic manganese
CN109338103B (en) Method for extracting vanadium from calcified roasted clinker by countercurrent acid leaching
CN103572064B (en) Method for enriching lead and recovering rare earth from rare earth lead slag
WO2008125728A3 (en) Method for the treatment and reuse of a stripper solution
JP5867727B2 (en) Separation method of rare earth elements
CN102442657A (en) Washing technology for refinement of wet-process phosphoric acid by solvent extraction method
JP6337708B2 (en) Method for separating nickel from nickel sludge
WO2013139228A1 (en) Method for preparing magnesium metal powder
CN103014338A (en) Method for processing poor organic phase after solvent extraction indium extracting
CN105400955A (en) Method for removing copper ions in zinc sulfate solution
KR20180064753A (en) Methods for waste water treatment of Nitrogen trifluoride(NF3) process

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20160316

WD01 Invention patent application deemed withdrawn after publication