CN108866337A - A method of processing metal sludge - Google Patents
A method of processing metal sludge Download PDFInfo
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- CN108866337A CN108866337A CN201810540421.1A CN201810540421A CN108866337A CN 108866337 A CN108866337 A CN 108866337A CN 201810540421 A CN201810540421 A CN 201810540421A CN 108866337 A CN108866337 A CN 108866337A
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- Prior art keywords
- filtrate
- metal
- film filtration
- filtration concentrated
- obtains
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- 238000000034 method Methods 0.000 title claims abstract description 47
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 40
- 239000002184 metal Substances 0.000 title claims abstract description 40
- 239000010802 sludge Substances 0.000 title claims abstract description 23
- 238000001914 filtration Methods 0.000 claims abstract description 79
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 55
- 238000000605 extraction Methods 0.000 claims abstract description 40
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 35
- 239000002002 slurry Substances 0.000 claims abstract description 33
- 239000010949 copper Substances 0.000 claims abstract description 28
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 24
- 230000008569 process Effects 0.000 claims abstract description 24
- 229910052802 copper Inorganic materials 0.000 claims abstract description 20
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 7
- 239000012528 membrane Substances 0.000 claims abstract description 5
- 238000001728 nano-filtration Methods 0.000 claims abstract description 5
- 239000000706 filtrate Substances 0.000 claims description 40
- 239000007788 liquid Substances 0.000 claims description 33
- 239000002699 waste material Substances 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 238000004519 manufacturing process Methods 0.000 claims description 22
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 20
- 229910001453 nickel ion Inorganic materials 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 18
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 16
- 239000003792 electrolyte Substances 0.000 claims description 16
- 239000012044 organic layer Substances 0.000 claims description 16
- 238000001556 precipitation Methods 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 claims description 12
- 238000000227 grinding Methods 0.000 claims description 12
- 235000014413 iron hydroxide Nutrition 0.000 claims description 12
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 claims description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 10
- 229910001431 copper ion Inorganic materials 0.000 claims description 10
- 239000011701 zinc Substances 0.000 claims description 10
- 229910052725 zinc Inorganic materials 0.000 claims description 10
- 229910021511 zinc hydroxide Inorganic materials 0.000 claims description 10
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 8
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 8
- 239000004571 lime Substances 0.000 claims description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 8
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 claims description 8
- 229940007718 zinc hydroxide Drugs 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 6
- 230000008021 deposition Effects 0.000 claims description 6
- 238000006073 displacement reaction Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 5
- 229910052602 gypsum Inorganic materials 0.000 claims description 4
- 239000010440 gypsum Substances 0.000 claims description 4
- 239000008267 milk Substances 0.000 claims description 4
- 210000004080 milk Anatomy 0.000 claims description 4
- 235000013336 milk Nutrition 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 230000001376 precipitating effect Effects 0.000 claims 1
- 238000004064 recycling Methods 0.000 claims 1
- 230000006641 stabilisation Effects 0.000 claims 1
- 238000011105 stabilization Methods 0.000 claims 1
- 239000011651 chromium Substances 0.000 abstract description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 abstract description 3
- 239000011575 calcium Substances 0.000 abstract description 3
- 229910052791 calcium Inorganic materials 0.000 abstract description 3
- 229910052804 chromium Inorganic materials 0.000 abstract description 3
- 229910052742 iron Inorganic materials 0.000 abstract description 3
- 229910052749 magnesium Inorganic materials 0.000 abstract description 3
- 239000011777 magnesium Substances 0.000 abstract description 3
- 230000009467 reduction Effects 0.000 abstract description 2
- 229910000570 Cupronickel Inorganic materials 0.000 abstract 1
- 238000007598 dipping method Methods 0.000 abstract 1
- 238000003672 processing method Methods 0.000 abstract 1
- 239000002253 acid Substances 0.000 description 6
- 238000000151 deposition Methods 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 239000010801 sewage sludge Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 239000013049 sediment Substances 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 239000008235 industrial water Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- FLTRNWIFKITPIO-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe] FLTRNWIFKITPIO-UHFFFAOYSA-N 0.000 description 2
- KOMIMHZRQFFCOR-UHFFFAOYSA-N [Ni].[Cu].[Zn] Chemical compound [Ni].[Cu].[Zn] KOMIMHZRQFFCOR-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- -1 metals ion Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Removal Of Specific Substances (AREA)
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
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 report that China Patent No. such as is in succession：CN.201410111803.4, open one kind " 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 includes the following steps：
S1, heavy metal dangerous waste pug is delivered to immersing-by-grinding machine grinding, is classified as 1 according to the ratio of useless pug and production cycle water：
After the ratio column mixing of 3-5, it is ground into heavy metal slurry, control 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 is obtained, 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, stillness of night 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,
Extracting operation is used to film filtration concentrated, the extracting operation includes the following steps：
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 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 is：Successively add into the raffinate two in filtrate three and step A1 respectively
After entering suitable hydrogen peroxide, any, tune pH value of solution to 3.8-4.8 in sodium carbonate or sodium hydroxide solution is added, it is stable
After being filtered, washed, iron hydroxide and chromium hydroxide precipitation are obtained.
Preferably, the heavy zinc in the step A2, which is handled, is：Toward disposing waste liquid in one plus sodium carbonate tune pH7.8-9.0, 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 useless pug and production
The weight ratio of recirculated water is 1：3 ratio arranges mixing, is ground into heavy metal slurry, control metal slurry discharge fineness is 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 includes the following steps：
S1, heavy metal dangerous waste pug is delivered to immersing-by-grinding machine grinding, the weight ratio according to useless pug and production cycle water is
1：After 3 ratio column mixing, it is ground into heavy metal slurry, control 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 is obtained, 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, stillness of night 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,
Extracting operation is used to film filtration concentrated, the extracting operation includes the following steps：
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 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 is：
Zn2++2OH-→Zn(OH)2↓
Wherein, siderochrome process is：It is sequentially added respectively into the raffinate two in filtrate three and step A1 appropriate
Hydrogen peroxide after, be added any in sodium carbonate or sodium hydroxide solution, adjust pH value of solution to 3.8-4.8, after stablizing by
After filter, washing, iron hydroxide and chromium hydroxide precipitation are obtained, the reaction equation of siderochrome process is：
CaCO3+2H+→H2O+CO2↑+Ca2+；
2Fe2++H2O2+2H+→2H2O+2Fe3+；
2Fe3++2Cr3++12OH-→Fe(OH)3↓+Cr(OH)3↓；
Wherein, the heavy zinc in step A2, which is handled, is：Toward disposing waste liquid in one plus sodium carbonate tune pH7.8-9.0, after stablizing, warp
After filtration washing, zinc hydroxide precipitation is obtained.
Wherein, being related to chemical principle in step S2 is：
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, the chemical principle for replacing reaction is：
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 are in step A1：
Extraction：2ROH+Cu2+→RO2Cu+2H+；Back extraction：RO2Cu+2H+→2ROH+Cu2+；
Strip liquor is once the equation of cyclone electrolytic cell deposition reaction：
Cathode reaction：Cu2++2e→Cu；Anode reaction：2OH--2e→O2↑+H2O；
Wherein, the extraction principle of extraction of nickel and back extraction principle equation are in step A2：Extraction：2ROH+Ni2+→
RO2Ni+2H+；Back extraction：RO2Ni+2H+→2ROH+Ni2+；
Equation of the strip liquor two through cyclone electrolytic cell deposition reaction be：
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 includes the following steps：
S1, heavy metal dangerous waste pug is delivered to immersing-by-grinding machine grinding, the weight ratio according to useless pug and production cycle water is
1：After 5 ratio column mixing, it is ground into heavy metal slurry, control 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 is obtained, 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, stillness of night 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,
Extracting operation is used to film filtration concentrated, the extracting operation includes the following steps：
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 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 is：
Zn2++2OH-→Zn(OH)2↓
Wherein, siderochrome process is：It is sequentially added respectively into the raffinate two in filtrate three and step A1 appropriate
Hydrogen peroxide after, be added any in sodium carbonate or sodium hydroxide solution, adjust pH value of solution to 3.8-4.8, after stablizing by
After filter, washing, iron hydroxide and chromium hydroxide precipitation are obtained, the reaction equation of siderochrome process is：
CaCO3+2H+→H2O+CO2↑+Ca2+；
2Fe2++H2O2+2H+→2H2O+2Fe3+；
2Fe3++2Cr3++12OH-→Fe(OH)3↓+Cr(OH)3↓；
Wherein, the heavy zinc in step A2, which is handled, is：Toward disposing waste liquid in one plus sodium carbonate tune pH7.8-9.0, after stablizing, warp
After filtration washing, zinc hydroxide precipitation is obtained.
Wherein, being related to chemical principle in step S2 is：
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, the chemical principle for replacing reaction is：
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 are in step A1：Extraction：2ROH+Cu2+→RO2Cu+
2H+；Back extraction：RO2Cu+2H+→2ROH+Cu2+；Strip liquor is once the equation of cyclone electrolytic cell deposition reaction：Cathode reaction：Cu2+
+2e→Cu；Anode reaction：2OH--2e→O2↑+H2O；
Wherein, the extraction principle of extraction of nickel and back extraction principle equation are in step A2：Extraction：2ROH+Ni2+→
RO2Ni+2H+；Back extraction：RO2Ni+2H+→2ROH+Ni2+；Equation of the strip liquor two through cyclone electrolytic cell deposition reaction be：Cathode is anti-
It answers：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 is characterized in that include the following steps：
S1, heavy metal dangerous waste pug is delivered to immersing-by-grinding machine grinding, is 1 according to the weight ratio of useless pug and production cycle water：3-5
Weight ratio mixing after, be ground into heavy metal slurry, control 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 is obtained, 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, the stillness of night 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 uses extracting operation, and the extracting operation includes the following steps：
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 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 is：Respectively
After sequentially adding suitable hydrogen peroxide into the raffinate two in filtrate three and step A1, sodium carbonate is added or sodium hydroxide is molten
It is any in liquid, adjust 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
For：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, is 1 according to the weight ratio of useless pug and production cycle water：3 weight ratio mixing, is ground into weight
Metal slurry, control 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.
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| CN114752766A (en) * | 2021-07-30 | 2022-07-15 | 中南大学 | A kind of method for selective separation of zinc, chromium and iron and recovery of polymetals in electroplating sludge |
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