CN108866337B - A method of processing metal sludge - Google Patents

A method of processing metal sludge Download PDF

Info

Publication number
CN108866337B
CN108866337B CN201810540421.1A CN201810540421A CN108866337B CN 108866337 B CN108866337 B CN 108866337B CN 201810540421 A CN201810540421 A CN 201810540421A CN 108866337 B CN108866337 B CN 108866337B
Authority
CN
China
Prior art keywords
heavy metal
filtrate
film filtration
filtration concentrated
obtains
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.)
Active
Application number
CN201810540421.1A
Other languages
Chinese (zh)
Other versions
CN108866337A (en
Inventor
刘来宝
周旋
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.)
JIANGSU JIAYU RESOURCE UTILIZATION CO Ltd
Original Assignee
JIANGSU JIAYU RESOURCE UTILIZATION 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 JIANGSU JIAYU RESOURCE UTILIZATION CO Ltd filed Critical JIANGSU JIAYU RESOURCE UTILIZATION CO Ltd
Priority to CN201810540421.1A priority Critical patent/CN108866337B/en
Publication of CN108866337A publication Critical patent/CN108866337A/en
Application granted granted Critical
Publication of CN108866337B publication Critical patent/CN108866337B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/46—Sulfates
    • 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
    • C22B15/00—Obtaining copper
    • C22B15/0063—Hydrometallurgy
    • C22B15/0084—Treating solutions
    • 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
    • C22B19/00—Obtaining zinc or zinc oxide
    • C22B19/20—Obtaining zinc otherwise than by distilling
    • 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
    • C22B19/00—Obtaining zinc or zinc oxide
    • C22B19/30—Obtaining zinc or zinc oxide from metallic residues or scraps
    • 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
    • C22B23/04—Obtaining nickel or cobalt by wet processes
    • C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
    • 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
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
    • C22B3/30—Oximes
    • 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
    • C22B34/00—Obtaining refractory metals
    • C22B34/30—Obtaining chromium, molybdenum or tungsten
    • C22B34/32—Obtaining chromium
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/06—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese
    • C25C1/08—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese of nickel or cobalt
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Abstract

The present invention discloses a kind of method for handling metal sludge, it is ground including dipping machine, dilute sulfuric acid, adjust heavy metal slurry pH, it is detected after nanofiltration membrane film filtration concentrated, according to the copper in film filtration concentrated, nickel metal ion content selective reduction iron powder directly handles film filtration concentrated, metal agent for capturing is added to handle, and three kinds of processing modes of extraction, wherein extraction includes extracting copper, two step extracting operation of extraction of nickel, technical solution disclosed by the invention is not removing iron, chromium, calcium, cupro-nickel metal is directly extracted under the metal ions state such as magnesium, opposite Conventional processing methods, not only process flow is simple, easy to operate and extraction processing is high-efficient.

Description

A method of processing metal sludge
Technical field
The present invention relates to metal sludge processing, the method for specifically a kind of processing metal sludge.
Background technique
Can generate a large amount of metallic dust and compound in metal production process, above-mentioned dust and compound with Recirculated water deposits in water treatment sludge and forms metal sludge, and due to heavy metal ion and compounds content in metal sludge Exceeded direct emission not only causes serious environmental pollution, threatens the balance of the ecosystem, and for Health Impact compared with Greatly.
It is most important for environmental protection, green production accordingly, with respect to the processing of metal sludge, and due to Heavy Metals in Sludge Content is high, broad categories, and causing the processing of heavy metal sewage sludge, not only treatment process is cumbersome, and generates with treatment process secondary Pollutant is also more serious.
It is based on, the difficulty and necessity of heavy metal sewage sludge processing, a series of techniques about heavy metal sewage sludge processing change Into patent document reported in succession such as China Patent No. are as follows: CN.201410111803.4, it is open a kind of " to utilize Copper making spent acid The method of copper zinc-nickel is recycled from heavy metal sewage sludge ", the technical solution extraction efficiency is more low, and sludge extraction is not enough, Cause in waste liquid or waste residue extracted still containing a large amount of heavy metal ion such as metallic nickel etc..
And prior art is in the elementary processes such as extracting copper, nickel, need in advance by extract liquor metallic iron, chromium, The metal ions such as calcium, magnesium remove, not only processing step is many and diverse, high production cost, and " three wastes " yield in treatment process also compared with It is high.
In view of the shortcomings of the prior art, not there is a kind of implementation effective means solution so far.
Summary of the invention
(1) the technical issues of solving
In view of the deficiency of the prior art, the present invention provides a kind of method for handling metal sludge.
(2) technical solution
In order to achieve the above object, the present invention is achieved by the following technical programs:
A method of processing metal sludge, comprising the following steps:
S1, heavy metal dangerous waste pug is delivered to immersing-by-grinding machine grinding, according to heavy metal dangerous waste pug and production cycle water After ratio than being classified as 1:3-5 arranges mixing, it is ground into heavy metal slurry, control heavy metal slurry discharge fineness is more than 100 mesh；
S2, it is slowly added to configured 30% dilute sulfuric acid into the heavy metal slurry in step S1, adjusts heavy metal slurry pH To 0.5-1, after stirring at normal temperature is reacted 2 hours, lime milk solution is added into heavy metal slurry, adjusts heavy metal slurry pH to 2.0- 2.5, filter residue one and filtrate one are obtained after filtering, and into filter residue one plus lime slurry tune pH to 7.0 is obtained after filtration washing To filter residue two and filtrate two, filter residue two is recycled as gypsum product, and filtrate two recycles as production cycle water；
S3, the filtrate in step S2 is obtained to film filtration concentrated and clear liquid, clear liquid conduct after nanofiltration membrane Production cycle water recycles, and detects to the metal ion in film filtration concentrated；
Wherein, the testing result in step S3 is shown in film filtration concentrated, when not containing nickel ion and low copper ion, Displacement reaction directly is carried out toward the film filtration concentrated middle suitable reduced iron powder of addition, reaction is finished, and reaction solution is filtered, and is filtered Slag three and filtrate three, filter residue three are copper sponge, and filtrate three obtains iron hydroxide and chromium hydroxide is heavy after siderochrome process It forms sediment；
Wherein, the testing result in step S3 show contain in film filtration concentrated nickel ion and nickel ion concentration compared with When low, directly toward metal agent for capturing, while liquid feeding alkali tune film filtration concentrated pH to 5.0-8.0 is added in film filtration concentrated, surely After fixed, filtration washing obtains filter residue four and filtrate four, and filter residue four is metal enrichment object, and filtrate four is returned as production cycle water It receives and utilizes；
Wherein, when the testing result in step S3 shows film filtration concentrated middle nickel ion and higher content of copper ion, To it is film filtration concentrated use extracting operation, the extracting operation the following steps are included:
A1, extracting copper: the M5640 copper dedicated extractant enough toward film filtration concentrated middle addition, after being extracted, being separated, Obtain organic layer one and raffinate one, organic layer obtains strip liquor one after back extraction, strip liquor after cyclone electrolytic cell deposition, Metallic copper and lean electrolyte one are obtained, it is spare that lean electrolyte one is re-used as strip liquor one；
A2, extraction of nickel: after the raffinate one in step A1 is adjusted pH to 2.0-2.5, it is dedicated that enough HBL110 nickel is added Extractant after being extracted, being separated, obtains organic layer two and raffinate two, and organic layer two obtains strip liquor two after being stripped, back extraction Liquid two obtains metallic nickel and lean electrolyte two after cyclone electrolytic cell deposits, and it is spare that lean electrolyte two is re-used as strip liquor two, institute Raffinate two is stated after siderochrome process, filtering, obtains iron hydroxide, chromium hydroxide precipitation, and disposes waste liquid one, processing Waste liquid is handled once heavy zinc, after filtration washing, is obtained zinc hydroxide precipitation and is disposed waste liquid two, described to dispose waste liquid two again It is spare as filtrate one in step S3.
Preferably, the siderochrome process are as follows: successively add into the raffinate two in filtrate three and step A2 respectively After entering suitable hydrogen peroxide, any one in sodium carbonate or sodium hydroxide solution is added, adjusts pH value of solution to 3.8-4.8, stablizes After being filtered, washed, iron hydroxide and chromium hydroxide precipitation are obtained.
Preferably, the heavy zinc processing in the step A2 are as follows: add sodium carbonate tune pH7.8-9.0 in one toward disposing waste liquid, surely After fixed, after filtration washing, zinc hydroxide precipitation is obtained.
Preferably, heavy metal dangerous waste pug is delivered to immersing-by-grinding machine grinding in the step S1, according to heavy metal dangerous waste mud Expect to mix with the ratio column that the weight ratio of production cycle water is 1:3, is ground into heavy metal slurry, controls heavy metal slurry discharge fineness More than 100 mesh.
Preferably, the weight of the dedicated extractant of M5640 copper and film filtration concentrated weight proportion are 4- in the step A1 15:1。
Preferably, the weight proportion of the weight of the dedicated extractant of HBL110 nickel and raffinate one is 4- in the step A2 15:1。
Beneficial effect
The present invention provides a kind of method for handling metal sludge, treatment process disclosed by the invention has below beneficial to effect Fruit:
1, full technique is to carry out environmentally friendly processing, efficent use of resources at normal temperatures and pressures；
2, advanced mill leaching technology is used, discharge fineness is more evenly, (processing step S1) easy to operate；
3, advanced membrane filtration technique is used, metal is enriched in strong acid environment, while having recycled acid solution, is subtracted Lack production acid cleaning, 3 times of enriched in metals ion or more, reduces process treating capacity；
4, advanced abstraction technique is used, compared with traditional extraction technique, this technique is not removing the gold such as iron, chromium, calcium, magnesium Belong to and directly being extracted under ionic condition, compared to P204, P507 extraction process is used, is less likely to cause secondary pollution, reduces auxiliary material and disappear Consumption, improves metal recovery rate；
5, advanced eddy flow electrodeposition technology is used, electrodeposition overall process closed operation non-exhaust emission improves product weight Amount, Chan Pin , Nie≤99.5% of Tong≤99.9%；
6, rear process also uses film filtering, and the liquid that preceding process generates reaches industrial water standard through film filtering, and water follows Ring uses, without sewage discharge；
7, industrial water, which is recycled, saves water, and 2 tons of water/ton butt hazardous waste sludge, whole year can save water 40,000 tons, Meet national energy-saving consumption reduction policy.
Detailed description of the invention
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention, Technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described embodiment is the present invention one Divide embodiment, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not making Every other embodiment obtained, shall fall within the protection scope of the present invention under the premise of creative work.
Fig. 1 is integrated artistic flow diagram of the present invention.
Specific embodiment
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention, Technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described embodiment is the present invention one Divide embodiment, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not making Every other embodiment obtained, shall fall within the protection scope of the present invention under the premise of creative work.
Embodiment 1:
A method of processing metal sludge, comprising the following steps:
S1, heavy metal dangerous waste pug is delivered to immersing-by-grinding machine grinding, according to heavy metal dangerous waste pug and production cycle water After the ratio column mixing that weight ratio is 1:3, it is ground into heavy metal slurry, control heavy metal slurry discharge fineness is more than 100 mesh；
S2, it is slowly added to configured 30% dilute sulfuric acid into the heavy metal slurry in step S1, adjusts heavy metal slurry pH To 0.5, after stirring at normal temperature is reacted 2 hours, lime milk solution is added into heavy metal slurry, adjusts heavy metal slurry pH to 2.0- 2.5, filter residue one and filtrate one are obtained after filtering, and into filter residue one plus lime slurry tune pH to 7.0 is obtained after filtration washing To filter residue two and filtrate two, filter residue two is recycled as gypsum product, and filtrate two recycles as production cycle water；
S3, the filtrate in step S2 is obtained to film filtration concentrated and clear liquid, clear liquid conduct after nanofiltration membrane Production cycle water recycles, and detects to the metal ion in film filtration concentrated；
Wherein, the testing result in step S3 is shown in film filtration concentrated, when not containing nickel ion and low copper ion, Displacement reaction directly is carried out toward the film filtration concentrated middle suitable reduced iron powder of addition, reaction is finished, and reaction solution is filtered, and is filtered Slag three and filtrate three, filter residue three are copper sponge, and filtrate three obtains iron hydroxide and chromium hydroxide is heavy after siderochrome process It forms sediment；
Wherein, the testing result in step S3 show contain in film filtration concentrated nickel ion and nickel ion concentration compared with When low, directly toward metal agent for capturing, while liquid feeding alkali tune film filtration concentrated pH to 5.0-8.0 is added in film filtration concentrated, surely After fixed, filtration washing obtains filter residue four and filtrate four, and filter residue four is metal enrichment object, and filtrate four is returned as production cycle water It receives and utilizes；
Wherein, when the testing result in step S3 shows film filtration concentrated middle nickel ion and higher content of copper ion, To it is film filtration concentrated use extracting operation, the extracting operation the following steps are included:
A1, extracting copper: toward the film filtration concentrated middle dedicated extraction of M5640 copper that film filtration concentrated 15 times of weight is added Agent after being extracted, being separated, obtains organic layer one and raffinate one, and organic layer obtains strip liquor one, strip liquor one after back extraction After cyclone electrolytic cell deposits, metallic copper and lean electrolyte one are obtained, it is spare that lean electrolyte one is re-used as strip liquor one；
A2, extraction of nickel: after the raffinate one in step A1 is adjusted pH to 2.0-2.5, film filtration concentrated 10 times of weights are added The dedicated extractant of HBL110 nickel of amount after being extracted, being separated, obtains organic layer two and raffinate two, organic layer two is after being stripped Strip liquor two is obtained, strip liquor two obtains metallic nickel and lean electrolyte two, the double new work of lean electrolyte after cyclone electrolytic cell deposits Spare for strip liquor two, the raffinate two obtains iron hydroxide, chromium hydroxide precipitation after siderochrome process, filtering, with And dispose waste liquid one, it disposes waste liquid after the processing of heavy zinc, filtration washing, obtains zinc hydroxide precipitation and dispose waste liquid two, It is described to dispose waste liquid two to be re-used as filtrate one in step S3 spare；The reaction equation of heavy zinc processing are as follows:
Zn2++2OH-→Zn(OH)2↓
Wherein, siderochrome process are as follows: sequentially added respectively into the raffinate two in filtrate three and step A2 appropriate Hydrogen peroxide after, any one in sodium carbonate or sodium hydroxide solution is added, adjusts pH value of solution to 3.8-4.8, after stablizing by After filter, washing, iron hydroxide and chromium hydroxide precipitation, the reaction equation of siderochrome process are obtained are as follows:
CaCO3+2H+→H2O+CO2↑+Ca2+；
2Fe2++H2O2+2H+→2H2O+2Fe3+；
2Fe3++2Cr3++12OH-→Fe(OH)3↓+Cr(OH)3↓；
Wherein, the heavy zinc processing in step A2 are as follows: toward disposing waste liquid in one plus sodium carbonate tune pH7.8-9.0, after stablizing, pass through After filtration washing, zinc hydroxide precipitation is obtained.
Wherein, it is related to chemical principle in step S2 are as follows:
CuR+H2SO4→Cu2++SO4 2-+R2-+2H+；
NiR+H2SO4→Ni2++SO4 2-+R2-+2H+；
ZnR+H2SO4→Zn2++SO4 2-+R2-+2H+；
CrR+nH2SO4→Cr3+/6++nSO4 2-+R3-/6-+2nH+；
Wherein, the testing result in step S3 is shown in film filtration concentrated, when not containing nickel ion and low copper ion, Displacement reaction directly is carried out toward the film filtration concentrated middle suitable reduced iron powder of addition, replaces the chemical principle of reaction are as follows:
Cu2++Fe→Cu↓+Fe2+；
In above-mentioned reaction equation, R represents various acid groups or alkali.
Wherein, the extraction of extracting copper and back extraction principle equation in step A1 are as follows:
Extraction: 2ROH+Cu2+→RO2Cu+2H+；Back extraction: RO2Cu+2H+→2ROH+Cu2+；
Equation of the strip liquor once cyclone electrolytic cell deposition reaction are as follows:
Cathode reaction: Cu2++2e→Cu；Anode reaction: 2OH--2e→O2↑+H2O；
Wherein, the extraction principle of extraction of nickel and back extraction principle equation in step A2 are as follows: extraction: 2ROH+Ni2+→ RO2Ni+2H+；Back extraction: RO2Ni+2H+→2ROH+Ni2+；
Equation of the strip liquor two through cyclone electrolytic cell deposition reaction are as follows:
Cathode reaction: Ni2++2e→Ni；Anode reaction: 2OH--2e→O2↑+H2O；
Above-mentioned RO indicates extractant combination functional group.
Embodiment 2:
A method of processing metal sludge, comprising the following steps:
S1, heavy metal dangerous waste pug is delivered to immersing-by-grinding machine grinding, according to heavy metal dangerous waste pug and production cycle water After the ratio column mixing that weight ratio is 1:5, it is ground into heavy metal slurry, control heavy metal slurry discharge fineness is more than 100 mesh；
S2, it is slowly added to configured 30% dilute sulfuric acid into the heavy metal slurry in step S1, adjusts heavy metal slurry pH To 0.5, after stirring at normal temperature is reacted 2 hours, lime milk solution is added into heavy metal slurry, adjusts heavy metal slurry pH to 2.0- 2.5, filter residue one and filtrate one are obtained after filtering, and into filter residue one plus lime slurry tune pH to 7.0 is obtained after filtration washing To filter residue two and filtrate two, filter residue two is recycled as gypsum product, and filtrate two recycles as production cycle water；
S3, the filtrate in step S2 is obtained to film filtration concentrated and clear liquid, clear liquid conduct after nanofiltration membrane Production cycle water recycles, and detects to the metal ion in film filtration concentrated；
Wherein, the testing result in step S3 is shown in film filtration concentrated, when not containing nickel ion and low copper ion, Displacement reaction directly is carried out toward the film filtration concentrated middle suitable reduced iron powder of addition, reaction is finished, and reaction solution is filtered, and is filtered Slag three and filtrate three, filter residue three are copper sponge, and filtrate three obtains iron hydroxide and chromium hydroxide is heavy after siderochrome process It forms sediment；
Wherein, the testing result in step S3 show contain in film filtration concentrated nickel ion and nickel ion concentration compared with When low, directly toward metal agent for capturing, while liquid feeding alkali tune film filtration concentrated pH to 5.0-8.0 is added in film filtration concentrated, surely After fixed, filtration washing obtains filter residue four and filtrate four, and filter residue four is metal enrichment object, and filtrate four is returned as production cycle water It receives and utilizes；
Wherein, when the testing result in step S3 shows film filtration concentrated middle nickel ion and higher content of copper ion, To it is film filtration concentrated use extracting operation, the extracting operation the following steps are included:
A1, extracting copper: toward the film filtration concentrated middle dedicated extraction of M5640 copper that film filtration concentrated 15 times of weight is added Agent after being extracted, being separated, obtains organic layer one and raffinate one, and organic layer obtains strip liquor one, strip liquor one after back extraction After cyclone electrolytic cell deposits, metallic copper and lean electrolyte one are obtained, it is spare that lean electrolyte one is re-used as strip liquor one；
A2, extraction of nickel: after the raffinate one in step A1 is adjusted pH to 2.0-2.5, film filtration concentrated 10 times of weights are added The dedicated extractant of HBL110 nickel of amount after being extracted, being separated, obtains organic layer two and raffinate two, organic layer two is after being stripped Strip liquor two is obtained, strip liquor two obtains metallic nickel and lean electrolyte two, the double new work of lean electrolyte after cyclone electrolytic cell deposits Spare for strip liquor two, the raffinate two obtains iron hydroxide, chromium hydroxide precipitation after siderochrome process, filtering, with And dispose waste liquid one, it disposes waste liquid after the processing of heavy zinc, filtration washing, obtains zinc hydroxide precipitation and dispose waste liquid two, It is described to dispose waste liquid two to be re-used as filtrate one in step S3 spare；The reaction equation of heavy zinc processing are as follows:
Zn2++2OH-→Zn(OH)2↓
Wherein, siderochrome process are as follows: sequentially added respectively into the raffinate two in filtrate three and step A2 appropriate Hydrogen peroxide after, any one in sodium carbonate or sodium hydroxide solution is added, adjusts pH value of solution to 3.8-4.8, after stablizing by After filter, washing, iron hydroxide and chromium hydroxide precipitation, the reaction equation of siderochrome process are obtained are as follows:
CaCO3+2H+→H2O+CO2↑+Ca2+；
2Fe2++H2O2+2H+→2H2O+2Fe3+；
2Fe3++2Cr3++12OH-→Fe(OH)3↓+Cr(OH)3↓；
Wherein, the heavy zinc processing in step A2 are as follows: toward disposing waste liquid in one plus sodium carbonate tune pH7.8-9.0, after stablizing, pass through After filtration washing, zinc hydroxide precipitation is obtained.
Wherein, it is related to chemical principle in step S2 are as follows:
CuR+H2SO4→Cu2++SO4 2-+R2-+2H+；
NiR+H2SO4→Ni2++SO4 2-+R2-+2H+；
ZnR+H2SO4→Zn2++SO4 2-+R2-+2H+；
CrR+nH2SO4→Cr3+/6++nSO4 2-+R3-/6-+2nH+；
Wherein, the testing result in step S3 is shown in film filtration concentrated, when not containing nickel ion and low copper ion, Displacement reaction directly is carried out toward the film filtration concentrated middle suitable reduced iron powder of addition, replaces the chemical principle of reaction are as follows:
Cu2++Fe→Cu↓+Fe2+；
In above-mentioned reaction equation, R represents various acid groups or alkali.
Wherein, the extraction of extracting copper and back extraction principle equation in step A1 are as follows:
Extraction: 2ROH+Cu2+→RO2Cu+2H+；Back extraction: RO2Cu+2H+→2ROH+Cu2+；
Equation of the strip liquor once cyclone electrolytic cell deposition reaction are as follows:
Cathode reaction: Cu2++2e→Cu；Anode reaction: 2OH--2e→O2↑+H2O；
Wherein, the extraction principle of extraction of nickel and back extraction principle equation in step A2 are as follows:
Extraction: 2ROH+Ni2+→RO2Ni+2H+；Back extraction: RO2Ni+2H+→2ROH+Ni2+；
Equation of the strip liquor two through cyclone electrolytic cell deposition reaction are as follows:
Cathode reaction: Ni2++2e→Ni；Anode reaction: 2OH--2e→O2↑+H2O；
Above-mentioned ROIndicate extractant combination functional group.
The above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations, although with reference to the foregoing embodiments Invention is explained in detail, those skilled in the art should understand that: it still can be to aforementioned each implementation Technical solution documented by example is modified or equivalent replacement of some of the technical features；And these modification or Replacement, the spirit and scope for technical solution of various embodiments of the present invention that it does not separate the essence of the corresponding technical solution.

Claims (6)

1. a kind of method for handling metal sludge, which comprises the following steps:
S1, heavy metal dangerous waste pug is delivered to immersing-by-grinding machine grinding, according to the weight of heavy metal dangerous waste pug and production cycle water After the weight ratio mixing for 1:3-5, it is ground into heavy metal slurry, control heavy metal slurry discharge fineness is more than 100 mesh；
S2, it is slowly added to configured 30% dilute sulfuric acid into the heavy metal slurry in step S1, adjusts heavy metal slurry pH extremely After stirring at normal temperature is reacted 2 hours, lime milk solution is added into heavy metal slurry, adjusts heavy metal slurry pH to 2.0- by 0.5-1 2.5, filter residue one and filtrate one are obtained after filtering, and into filter residue one plus lime slurry tune pH to 7.0 is obtained after filtration washing To filter residue two and filtrate two, filter residue two is recycled as gypsum product, and filtrate two recycles as production cycle water；
S3, the filtrate in step S2 is obtained to film filtration concentrated and clear liquid after nanofiltration membrane, clear liquid is as production Circulating water reclamation utilizes, and detects to the metal ion in film filtration concentrated；
Wherein, the testing result in step S3 is shown in film filtration concentrated, when not containing nickel ion and low copper ion, directly Displacement reaction is carried out toward the film filtration concentrated middle suitable reduced iron powder of addition, reaction is finished, and reaction solution is filtered, and filter residue three is obtained With filtrate three, filter residue three is copper sponge, and filtrate three obtains iron hydroxide and chromium hydroxide precipitation after siderochrome process；
Wherein, the testing result in step S3 is shown when containing nickel ion and lower nickel ion concentration in film filtration concentrated, Directly toward in film filtration concentrated plus metal agent for capturing, while liquid feeding alkali tune film filtration concentrated pH to 5.0-8.0, after stabilization, Filtration washing obtains filter residue four and filtrate four, and filter residue four is metal enrichment object, and filtrate four is as production cycle water recycling benefit With；
Wherein, when the testing result in step S3 shows film filtration concentrated middle nickel ion and higher content of copper ion, to film Filtering and concentrating liquid use extracting operation, the extracting operation the following steps are included:
A1, extracting copper: the M5640 copper dedicated extractant enough toward film filtration concentrated middle addition obtains after being extracted, being separated Organic layer one and raffinate one, organic layer obtain strip liquor one after back extraction, and strip liquor obtains after cyclone electrolytic cell deposition Metallic copper and lean electrolyte one, it is spare that lean electrolyte one is re-used as strip liquor one；
A2, extraction of nickel: after the raffinate one in step A1 is adjusted pH to 2.0-2.5, enough dedicated extractions of HBL110 nickel are added Agent after being extracted, being separated, obtains organic layer two and raffinate two, and organic layer two obtains strip liquor two, strip liquor two after being stripped After cyclone electrolytic cell deposits, metallic nickel and lean electrolyte two are obtained, it is spare that lean electrolyte two is re-used as strip liquor two, the extraction Extraction raffinate two obtains iron hydroxide, chromium hydroxide precipitation after siderochrome process, filtering, and disposes waste liquid one, disposes waste liquid It once the processing of heavy zinc, after filtration washing, obtains zinc hydroxide precipitation and disposes waste liquid two, described dispose waste liquid two is re-used as Filtrate one is spare in step S3.
2. the method for processing metal sludge according to claim 1, is characterized in that, the siderochrome process are as follows: respectively After sequentially adding suitable hydrogen peroxide into the raffinate two in filtrate three and step A2, sodium carbonate is added or sodium hydroxide is molten Any one in liquid adjusts pH value of solution to obtain iron hydroxide and chromium hydroxide after stablizing after being filtered, washed to 3.8-4.8 Precipitating.
3. the method for processing metal sludge according to claim 1, is characterized in that, the heavy zinc processing in the step A2 Are as follows: toward disposing waste liquid in one plus sodium carbonate tune pH7.8-9.0 after filtration washing, obtains zinc hydroxide precipitation after stablizing.
4. the method for processing metal sludge according to claim 1, is characterized in that, by heavy metal dangerous waste in the step S1 Pug is delivered to immersing-by-grinding machine grinding, mixes according to heavy metal dangerous waste pug with the weight ratio that the weight ratio of production cycle water is 1:3, It is ground into heavy metal slurry, control heavy metal slurry discharge fineness is more than 100 mesh.
5. the method for processing metal sludge according to claim 1, is characterized in that, M5640 copper is dedicated in the step A1 The weight of extractant and film filtration concentrated weight proportion are 4-15:1.
6. the method for processing metal sludge according to claim 1, is characterized in that, HBL110 nickel is dedicated in the step A2 The weight of extractant and the weight proportion of raffinate one are 4-15:1.
CN201810540421.1A 2018-05-30 2018-05-30 A method of processing metal sludge Active CN108866337B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810540421.1A CN108866337B (en) 2018-05-30 2018-05-30 A method of processing metal sludge

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810540421.1A CN108866337B (en) 2018-05-30 2018-05-30 A method of processing metal sludge

Publications (2)

Publication Number Publication Date
CN108866337A CN108866337A (en) 2018-11-23
CN108866337B true CN108866337B (en) 2019-08-16

Family

ID=64335910

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810540421.1A Active CN108866337B (en) 2018-05-30 2018-05-30 A method of processing metal sludge

Country Status (1)

Country Link
CN (1) CN108866337B (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109680155B (en) * 2018-12-26 2020-07-31 北京科技大学 Method for harmless disposal and resource utilization of stainless steel dust and sludge containing nickel and chromium
CN111841895A (en) * 2020-06-24 2020-10-30 紫金矿业集团股份有限公司 Method for recovering valuable metal minerals from sulfide ore mine beneficiation sludge
CN114752766A (en) * 2021-07-30 2022-07-15 中南大学 Method for selectively separating zinc, chromium and iron and recovering multiple metals in electroplating sludge

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101830581A (en) * 2009-03-09 2010-09-15 深圳市金达莱环保股份有限公司 Method for treating heavy metal industrial sewage
CN101871046A (en) * 2010-06-29 2010-10-27 青川县天运金属开发有限公司 Method for recycling heavy metal pollution wastes
CN105256141B (en) * 2015-10-26 2017-12-19 广西银亿再生资源有限公司 A kind of electric plating sludge resource processing and the method for comprehensive reutilization
CN105506291A (en) * 2015-12-11 2016-04-20 苏州华周胶带有限公司 Method for recycling heavy metals in electroplating sludge
WO2018047147A1 (en) * 2016-09-12 2018-03-15 Attero Recycling Pvt. Ltd. Process for recovering pure cobalt and nickel from spent lithium batteries
CN107460315B (en) * 2017-08-24 2019-10-25 中国有色集团刚果矿业有限公司 A method of using copper, cobalt in nanofiltration membrane concentration and separation-neutralization precipitation recycling copper raffinate

Also Published As

Publication number Publication date
CN108866337A (en) 2018-11-23

Similar Documents

Publication Publication Date Title
CN101838736B (en) Wet separation method for valuable metals in purified liquid cobalt slags of wet zinc smelting system
CN101845562B (en) Improved device and method for producing electrolytic manganese metal by two-ore method
CN102173547B (en) Resource recycling process for nickel-containing sludge in electroplating enterprises
JP6070898B2 (en) Method and facility for recovering valuable components from waste dry batteries
CN102851707B (en) The technique of a kind of alkaline leaching remanufacture electrolytic zinc powder and lead powder from smelting ash
CN106868307B (en) A kind of comprehensive utilization process of pyrite cinder arsenic removal enrichment gold and silver
CN103556180B (en) Reclaim from copper-cadmium slag copper, cadmium method and from rich cadmium solution of zinc sulfate, reclaim the device of cadmium
CN106048217B (en) The comprehensive reutilization method of oxide powder and zinc
CN101497458B (en) Method for preparing sodium stannate using circuit board tin-stripping wastewater
CN107002176A (en) The recovery method of high-purity scandium
CN108866337B (en) A method of processing metal sludge
JP2015206077A (en) Method and apparatus for separating and recovering resource from waste dry cell and recovered substance
CN106745193A (en) The method that iron content zinc-containing sludge recovery prepares zinc hydroxide and dyestuff level iron oxide red
CN102358645B (en) Fully-closed circulation treatment method for water used by electrolytic manganese metal production
WO2020196046A1 (en) Method for manufacturing nickel and cobalt-containing solution from hydroxide containing nickel and cobalt
CN102912133A (en) Method for classifying and purifying heavy metals in electroplating sludge
CN109811132A (en) A method of comprehensive reutilization carbon, iron, aluminium, zinc, lead from blast furnace gas mud
CN108517425A (en) A kind of method of calcium ions and magnesium ions in reduction electrolytic manganese qualifying liquid
CN101122034A (en) Method for extracting high-grade metal zinc powder from zinc-containing material
CN103482680A (en) Process for producing nano zinc oxide by using crude zinc oxide
CN104609683A (en) Chrome tanning sludge heavy metal chromium regeneration method
CN104451159A (en) Process for recycling metals from electroplating wastewater
CN104152701B (en) The method that tin is reclaimed from tin refinement slag
CN109321745A (en) Utilize the method for Treatment of Metal Surface waste preparation nickel plate
CN107604163A (en) A kind of technique of no scorification processing electroplating sludge

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
CB03 Change of inventor or designer information

Inventor after: Liu Laibao

Inventor after: He Haifeng

Inventor after: Zhou Xuan

Inventor before: Liu Laibao

Inventor before: Zhou Xuan

CB03 Change of inventor or designer information
GR01 Patent grant
GR01 Patent grant