CN116411169A - Comprehensive utilization method of leadless hot galvanizing scum - Google Patents
Comprehensive utilization method of leadless hot galvanizing scum Download PDFInfo
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- CN116411169A CN116411169A CN202310390151.1A CN202310390151A CN116411169A CN 116411169 A CN116411169 A CN 116411169A CN 202310390151 A CN202310390151 A CN 202310390151A CN 116411169 A CN116411169 A CN 116411169A
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- zinc
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- 238000000034 method Methods 0.000 title claims abstract description 38
- 238000005246 galvanizing Methods 0.000 title claims abstract description 27
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 122
- 239000011701 zinc Substances 0.000 claims abstract description 121
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 120
- 229910052751 metal Inorganic materials 0.000 claims abstract description 56
- 239000002184 metal Substances 0.000 claims abstract description 55
- 239000007788 liquid Substances 0.000 claims abstract description 42
- 239000002245 particle Substances 0.000 claims abstract description 39
- 239000002699 waste material Substances 0.000 claims abstract description 35
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 30
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000005266 casting Methods 0.000 claims abstract description 26
- 238000002386 leaching Methods 0.000 claims abstract description 22
- 239000000843 powder Substances 0.000 claims abstract description 22
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 21
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 15
- 238000000227 grinding Methods 0.000 claims abstract description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000011084 recovery Methods 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 238000007885 magnetic separation Methods 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 9
- 239000002002 slurry Substances 0.000 claims abstract description 7
- 238000004064 recycling Methods 0.000 claims abstract description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 73
- 229910052742 iron Inorganic materials 0.000 claims description 34
- 239000000243 solution Substances 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 238000011282 treatment Methods 0.000 claims description 22
- 238000000926 separation method Methods 0.000 claims description 19
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 14
- 238000004537 pulping Methods 0.000 claims description 14
- 239000006148 magnetic separator Substances 0.000 claims description 12
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 8
- 239000010413 mother solution Substances 0.000 claims description 8
- 238000001556 precipitation Methods 0.000 claims description 7
- 239000011780 sodium chloride Substances 0.000 claims description 7
- 229910001415 sodium ion Inorganic materials 0.000 claims description 7
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 7
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 5
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- 239000003792 electrolyte Substances 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- IPCXNCATNBAPKW-UHFFFAOYSA-N zinc;hydrate Chemical compound O.[Zn] IPCXNCATNBAPKW-UHFFFAOYSA-N 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 abstract description 10
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052801 chlorine Inorganic materials 0.000 abstract description 9
- 230000008901 benefit Effects 0.000 abstract description 3
- 125000004122 cyclic group Chemical group 0.000 abstract 1
- 230000008569 process Effects 0.000 description 15
- 150000003752 zinc compounds Chemical class 0.000 description 10
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 10
- PTENJNIBULCQNG-UHFFFAOYSA-N N.[Cl].[Zn] Chemical compound N.[Cl].[Zn] PTENJNIBULCQNG-UHFFFAOYSA-N 0.000 description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 238000006298 dechlorination reaction Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000011592 zinc chloride Substances 0.000 description 5
- 235000005074 zinc chloride Nutrition 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000002920 hazardous waste Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- -1 and finally Substances 0.000 description 2
- 238000009854 hydrometallurgy Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 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
- C22B7/007—Wet processes by acid leaching
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D7/00—Casting ingots, e.g. from ferrous metals
- B22D7/005—Casting ingots, e.g. from ferrous metals from non-ferrous metals
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/005—Preliminary treatment of scrap
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/30—Obtaining zinc or zinc oxide from metallic residues or scraps
-
- 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
- C25C1/16—Electrolytic production, recovery or refining of metals by electrolysis of solutions of zinc, cadmium or mercury
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/06—Operating or servicing
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/12—Halides
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
- C30B7/14—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions the crystallising materials being formed by chemical reactions in the solution
-
- 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)
- Metallurgy (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Geology (AREA)
- Electrochemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Electrolytic Production Of Metals (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a comprehensive utilization method of lead-free hot galvanizing scum, which comprises the following steps: s1, magnetic separation: s2, grinding and winnowing: inputting the nonferrous materials into a Raymond mill for grinding, collecting zinc-containing powder with small granularity through a 50-mesh sieve, and independently collecting residual metal zinc particles with large granularity; s3, leaching and electrolysis: adding the zinc-containing powder into a slurrying tank, slurrying by using electrolytic waste liquid, liquid ammonia and 20% hydrochloric acid, leaching the slurrying liquid after slurrying, filtering the leached slurry, electrolyzing the filtered liquid, and obtaining an electrolytic zinc plate on an electrode after electrolysis, wherein the electrolytic waste liquid is returned to the slurrying tank for slurrying; s4, casting: casting the zinc particles obtained in the step S2 and the electrolytic zinc plate obtained in the step S3; s5, recycling ammonium chloride. The method has the advantages of high zinc recovery rate, little influence by chlorine content, cyclic utilization of resources and no generation of secondary dangerous waste.
Description
Technical Field
The invention relates to the technical field of hot galvanizing dross treatment, in particular to a comprehensive utilization method of lead-free hot galvanizing dross.
Background
The hot galvanizing treatment of the metal surface is an important steel anticorrosion means, and the total capacity of the national hot galvanizing product reaches about two hundred million tons. Oxide impurities, chloride impurities and the like with small density continuously float on the surface of molten metal zinc in the hot galvanizing process to form scum, and the accumulation of the scum can influence the product quality of a plated part and needs to be fished out in time. The hot dip zinc dross is leached out to be toxic and corrosive, and the zinc-containing waste HW23 in the national hazardous waste directory (2021 edition) cannot be buried at will. Based on the hot galvanizing, the zinc ingot No. 0 is adopted as the raw material, the content of harmful metal elements such as lead, cadmium and the like is extremely low, and the lead-free hot galvanizing scum is comprehensively utilized and becomes a main means for processing the lead-free hot galvanizing scum.
The comprehensive utilization method of the leadless hot galvanizing scum at the present stage mainly comprises particle-powder separation, zinc wet smelting and the like. The separation of the grain powder is to grind the scum in a ball mill by utilizing the characteristic that the simple substance zinc in the scum exists mainly in a grain state, separate zinc compounds such as zinc oxide, zinc chloride and the like in a powder state, then recycle granular metallic zinc after multi-stage screening, and carry out other treatments or utilization on the zinc compounds. In the utilization process, the separation of the metal zinc particles and other powders is difficult to control, and transition grinding, scattering and crushing all cause the metal zinc to fall off and enter the powders, so that the recovery rate of the metal zinc is lower. Meanwhile, the separated powder is usually not collected timely, so that materials are accumulated in the mill, phenomena such as expansion of the mill and the like occur, and the energy consumption of the mill is increased.
The zinc hydrometallurgy, such as the publication No. CN104805301A, is named as a method for producing zinc ingots by using hot-dip zinc slag hydrometallurgy waste residue in zero discharge, adopts a sulfuric acid method to leach and electrolyze to obtain metallic zinc, but the control requirement on the chlorine content in electrolyte in the process is very high and is usually less than or equal to 0.2%, otherwise, the phenomenon of burning plates occurs to influence production, and therefore, the process of dechlorination is usually needed before the scum leaching. The dechlorination treatment is usually realized by adding sodium carbonate and the like, zinc chloride in the scum reacts with the sodium carbonate to generate sodium chloride which is soluble in water and zinc carbonate sediment which is difficult to be soluble in water, and chlorine element in the zinc scum enters into solution to realize zinc ash dechlorination. However, the method introduces a large amount of sodium ion impurities into the solution, and in order to achieve the dechlorination efficiency of more than 80%, the liquid-solid ratio in the dechlorination process is generally not less than 5:1, and the consumption of alkaline washing water (namely the sodium carbonate-containing solution) is large. In addition, when the concentration of chloride ions in alkaline washing water is more than 150g/L, the alkaline washing water is discharged from an alkaline washing system for subsequent treatment, otherwise, the alkaline washing chlorine removal efficiency is affected, the treatment cost of the chlorine washing wastewater is high, and the chlorine element cannot be effectively recovered.
Disclosure of Invention
The invention aims to solve the technical problem of providing a comprehensive utilization method of lead-free hot galvanizing scum, which has high zinc recovery rate, is little influenced by chlorine content, and is free from secondary dangerous waste.
In order to solve the technical problems, the technical scheme of the invention is as follows: the comprehensive utilization method of the leadless hot galvanizing scum comprises the following steps:
s1, magnetic separation: magnetically separating hot galvanizing scum by adopting a magnetic separator, collecting the magnetically separated ferrous metal, and enabling non-ferrous materials to enter S2;
s2, grinding and winnowing: inputting the nonferrous materials into a Raymond mill for grinding, wherein the rotation speed of a central shaft in the Raymond mill is 60-85 r/min, and the air quantity is 10000-23000 m 3 Per hour, the total pressure is 3.2 to 4.5kpa, and the air quantity of the residual air pipe is 15000 to 45000m 3 And (h) a 50-mesh sieve is used for a discharge hole, zinc-containing powder with small granularity passes through the 50-mesh sieve to be collected, and the residual metal zinc particles with large granularity are collected independently;
s3, leaching and electrolysis: adding the zinc-containing powder into a slurrying tank, slurrying by using electrolytic waste liquid, liquid ammonia and 20% hydrochloric acid, wherein the volume ratio of the electrolytic waste liquid to the liquid ammonia to the 20% hydrochloric acid is 1:0.2 to 0.3: 0.05-0.1, wherein the pH value in the slurrying tank is 4-6, the stirring speed in the slurrying tank is 150-300 r/min, and the temperature in the slurrying tank is 60-70 ℃; leaching the slurry after pulping, wherein ph=5-6, the leaching temperature is 60-70 ℃, the leaching speed is 50-200 r/min, and the leaching time is 12-24 h; filtering the leached slurry, electrolyzing the filtered liquid with ph=5-6.5, electrolysis temperature of 60-80 deg.c, electrolysis time of 12-24 hr and current densityThe degree is 200-300A/m 2 The voltage is 3.0-3.2 v; an electrolytic zinc plate is obtained on the electrode after electrolysis, and the electrolytic waste liquid returns to the slurrying tank for slurrying;
s4, casting: casting the zinc particles obtained in the step S2 and the electrolytic zinc plate obtained in the step S3, wherein the mass ratio of the zinc particles to the electrolytic zinc plate is 1: 2-4, and the casting temperature is 420-450 ℃; during casting, zinc particles and electrolytic zinc plates are alternately placed in a casting furnace from bottom to top, the zinc particles can be prevented from being oxidized under the electrolytic zinc plates by casting for 0.5 to 1.5 hours, layered placement promotes uniform heating, local oxidation is prevented, and after the zinc particles are completely melted, zinc water in the casting furnace is poured into a die and cooled and cast into regenerated zinc ingots;
s5, ammonium chloride recovery: s3, recycling the electrolysis waste liquid for 5-8 times, and when the concentration of chloride ions in the solution reaches 200-240 g/L, pulping the electrolysis waste liquid; the electrolytic waste liquid is subjected to zinc precipitation treatment by adopting sodium sulfide, the dosage of the sodium sulfide is 1.5-2.0 times of the zinc ion content in the electrolytic waste liquid, then three-effect evaporation treatment is carried out, the treated mother liquid returns to S3 for pulping again, and the precipitated ammonium chloride crystal is packaged independently.
As the preferable technical scheme, in S1, a two-stage dry magnetic separator is adopted to carry out magnetic separation on hot galvanizing scum; the feeding speed of the first-stage magnetic separator is 60-100 m/min, and the magnetic field strength is 4000 gauss; the feeding speed of the second-stage magnetic separator is 80-100 m/min, and the magnetic field strength is 5000 gauss.
As a preferable technical scheme, the iron-containing metal selected by S1 magnetism is sent into 20% hydrochloric acid for reaction, and the mass ratio of the iron-containing metal to the 20% hydrochloric acid is 1: 7-10; after all the iron-containing metal reacts, sending part of the metal zinc particles obtained in the step S2 into the reaction solution for iron separation treatment; after the treatment is finished, carrying out solid-liquid separation on the reaction solution, carrying out magnetic attraction separation on the separated metal zinc particles and iron powder, and independently collecting the magnetically sucked metal iron and using the rest metal zinc particles for S4 casting.
As a preferable technical scheme, the residual reaction solution after solid-liquid separation is sent to S3 for pulping, and when the residual reaction solution is added in S3, liquid ammonia is added at the same time, and the volume ratio of the added liquid ammonia to the residual reaction solution is 2-6: 1.
as a preferable technical scheme, the method further comprises S6, sodium chloride recovery: when the concentration of sodium ions in the S5 mother solution reaches 10-12 g/L, carrying out high-temperature concentration filtration on the mother solution, and returning the filtrate obtained by the high-temperature concentration filtration to S3 for pulping to use as an electrolyte waste liquid.
Due to the adoption of the technical scheme, the invention has the following beneficial effects: (1) The zinc element in the dross can be obtained by respectively grinding and separating out metal zinc particles and extracting the electrolytic zinc plate by a zinc compound wet method, the zinc recovery rate is high, the obtained zinc is directly metal zinc, the zinc can be directly recast and utilized, the process is simple, and the energy consumption is lower; (2) The zinc element in the zinc compound is recovered by adopting a zinc-ammonia-chlorine wet method system, the process is less influenced by chlorine content, and the operation is simple and convenient; (3) The electrolytic waste liquid can be recycled, all impurity components such as iron, sodium and the like can be independently recovered, resources are recycled, and no secondary dangerous waste is generated.
Detailed Description
The invention is further illustrated by the following examples. In the following detailed description, exemplary embodiments of the invention are described by way of illustration only. It is needless to say that the person skilled in the art realizes that the described embodiments may be modified in various different ways without departing from the spirit and scope of the invention. Accordingly, the description is illustrative in nature and is not intended to limit the scope of the claims.
The comprehensive utilization method of the leadless hot galvanizing scum comprises the following steps.
S1, magnetic separation: and (2) magnetically separating hot galvanizing scum by using a magnetic separator, collecting the magnetically separated ferrous metal, and enabling non-ferrous materials to enter S2. In the hot galvanizing process, a small amount of metal iron is doped into the dross, and the iron-containing metal is separated independently through magnetic separation in the embodiment, so that the influence of the metal iron on the subsequent process is avoided.
Preferably, in the step S1, a two-stage dry magnetic separator is adopted to carry out magnetic separation on hot galvanizing scum; the feeding speed of the first-stage magnetic separator is 60-100 m/min, and the magnetic field strength is 4000 gauss; the feeding speed of the second-stage magnetic separator is 80-100 m/min, and the magnetic field strength is 5000 gauss. Through two magnetic separations, the iron-containing metal can be completely separated, and continuous operation is facilitated.
S2, grinding and winnowing: inputting the nonferrous materials into a Raymond mill for grinding, wherein the Raymond mill is a known technology capable of grinding metals with the Mohs hardness below seven, and the structural principle is not repeated here; wherein the central shaft rotating speed in the Raymond mill of the embodiment is 60-85 r/min, and the air quantity is 10000-23000 m 3 Per hour, the total pressure is 3.2 to 4.5kpa, and the air quantity of the residual air pipe is 15000 to 45000m 3 And (h) a 50-mesh sieve is used for the discharge hole, zinc-containing powder with small granularity passes through the 50-mesh sieve to be collected, and the residual metal zinc particles with large granularity are singly collected. The step utilizes the difference of physical properties (such as specific gravity and brittleness) of the metal zinc particles and zinc compounds to realize the large-scale separation of the metal zinc particles, and only a small part of zinc powder is screened out and collected along with zinc oxide, zinc chloride and other zinc compounds to form zinc-containing powder.
S3, leaching and electrolysis: adding the zinc-containing powder into a slurrying tank, slurrying by using electrolytic waste liquid, liquid ammonia and 20% hydrochloric acid, wherein the volume ratio of the electrolytic waste liquid to the liquid ammonia to the 20% hydrochloric acid is 1:0.2 to 0.3: 0.05-0.1, pH=4-6 in the slurrying tank, stirring speed in the slurrying tank is 150-300 r/min, and temperature in the slurrying tank is 60-70 ℃. By continuously stirring and pulping, the simple substance zinc and zinc compound in the zinc-containing powder are prepared by using dichloro diammine zinc (Zn (NH) 3 )Cl 2 ) The zinc dichlorodiammine is kept high in solubility by temperature control.
And leaching the slurry after pulping, wherein ph=5-6, the leaching temperature is 60-70 ℃, the leaching speed is 50-200 r/min, and the leaching time is 12-24 h. The solution in which zinc dichlorodiammine is mainly dissolved is separated by this step. Filtering the leached slurry, wherein the filtered solution is a filtrate mainly dissolved with zinc dichlorodiammine; electrolyzing the filtered liquid at the electrolysis temperature of 60-80 ℃ for 12-24 h with the current density of 200-300A/m, wherein ph=5-6.5 2 The voltage is 3.0-3.2 v; electrolytic electrode is obtainedAnd (3) forming a solution with the main component of ammonium chloride by the electrolytic waste liquid to the electrolytic zinc plate, and returning the solution to the slurrying tank for slurrying.
The zinc-ammonia-chlorine wet method system is formed, and zinc element in the zinc compound is recovered. Based on the disorder of zinc and iron element aggregation during the dross formation process, the iron-containing metal selected by the S1 magnet forms a mixture with metallic zinc and a small amount of zinc compound. Preferably, the iron-containing metal magnetically selected in the embodiment S1 is fed into 20% hydrochloric acid for reaction, and the mass ratio of the iron-containing metal to the 20% hydrochloric acid is 1: 7-10. The mixture is uniformly fed into 20% hydrochloric acid for reaction, so that metallic iron, metallic zinc and zinc compounds are all in the form of chloride in the reaction solution.
After all the iron-containing metal reacts, part of the metal zinc particles obtained in the step S2 are sent into the reaction solution for iron precipitation treatment. The step utilizes the characteristic that the reducibility of zinc is stronger than that of iron to replace iron element from ferrous chloride, and simultaneously utilizes the advantage of larger surface area of metallic zinc particles to improve the replacement efficiency of metallic iron. After the treatment is finished, the reaction solution forms a solution mainly dissolved with zinc chloride, the solid-liquid separation is carried out on the reaction solution, the separated metal zinc particles and iron powder are subjected to magnetic attraction separation, the magnetically sucked metal iron is pure iron, the pure iron can be singly collected, and the rest metal zinc particles are used for S4 fusion casting.
Preferably, the residual reaction solution after solid-liquid separation is sent to S3 for pulping, and when the residual reaction solution is added in S3, liquid ammonia is added at the same time, and the volume ratio of the added liquid ammonia to the residual reaction solution is 2-6: 1.
according to the embodiment, before grinding, the iron-containing metal is firstly separated, so that the influence of the grinding separation of the metal zinc particles caused by the fact that the metal iron with higher hardness enters a grinding procedure can be avoided, and the accurate separation of the metal zinc particles and zinc-containing powder is ensured. The zinc-ammonia-chlorine wet system based on zinc-containing powder is used, iron-containing metal is also subjected to wet separation by hydrochloric acid, and finally, metal zinc and metal iron can be respectively and independently separated, and zinc chloride solution can be matched with the zinc-ammonia-chlorine wet system to enter leaching and electrolysis circulation, so that the energy consumption in the whole process is low, and resources such as iron and the like can be independently separated and recovered, so that secondary dangerous waste is avoided.
S4, casting: casting the zinc particles obtained in the step S2 and the electrolytic zinc plate obtained in the step S3, wherein the mass ratio of the zinc particles to the electrolytic zinc plate is 1: 2-4, and the casting temperature is 420-450 ℃; during casting, zinc particles and electrolytic zinc plates are alternately placed in a casting furnace from bottom to top, the surface area of the zinc particles is large, oxidation of the zinc particles can be avoided under the electrolytic zinc plates, layered placement promotes uniform heating, and local oxidation is prevented; pouring the molten zinc in the casting furnace into a mould after complete melting, and cooling and casting to obtain regenerated zinc ingots.
S5, ammonium chloride recovery: and S3, the electrolysis waste liquid is mainly ammonium chloride solution, and is recycled for 5-8 times, and when the chloride ion concentration in the solution reaches 200-240 g/L, the electrolysis waste liquid is not pulpified. The electrolytic waste liquid is subjected to zinc precipitation treatment by adopting sodium sulfide, namely, a small amount of zinc ions remained in the electrolytic waste liquid are separated out in a zinc sulfide precipitation mode by adopting sodium sulfide, wherein the dosage of the sodium sulfide is 1.5-2.0 times of the content of the zinc ions in the electrolytic waste liquid; and (3) carrying out triple-effect evaporation treatment after zinc precipitation treatment, and independently packaging the precipitated ammonium chloride crystals, wherein the treated mother solution is a solution with the ammonium chloride content greatly reduced, and returning to S3 for pulping again.
Based on the zinc precipitation treatment, sodium ions are doped in the solution, and the process also comprises S6 and sodium chloride recovery: when the concentration of sodium ions in the S5 mother solution reaches 10-12 g/L, the mother solution is concentrated and filtered at high temperature, namely, most of sodium chloride is separated out and filtered at high temperature by utilizing the principle that the solubility of sodium chloride is small along with the change of temperature and the solubility of ammonium chloride is obviously increased along with the rise of temperature. The filtrate of high-temperature concentration and filtration is ammonium chloride solution containing a small amount of sodium ions, and the concentration of the sodium ions is always kept at a lower concentration level, so that the concentration and the catalytic action of the ammonia ions in the zinc-ammonia-chlorine wet system are not influenced. Therefore, in this embodiment, the filtrate obtained by high-temperature concentration filtration is returned to S3 as the electrolyte waste liquid for slurrying. Therefore, the embodiment can generate the ammonium chloride crystal product, and meanwhile, the residual ammonium chloride can still participate in leaching and electrolysis circulation, sodium chloride can also be separately separated and collected, resources can be recycled, and no secondary hazardous waste is generated.
In the embodiment, the scum is firstly subjected to magnetic separation for removing iron, so that the influence of metal iron on the accurate separation of metal zinc particles and zinc-containing powder can be avoided, the metal zinc particles and the zinc-containing powder can be separated from the non-iron materials after magnetic separation through grinding, the zinc-containing powder can be used for obtaining an electrolytic zinc plate through slurrying, leaching and electrolysis, and finally, zinc in the scum is extracted and cast by directly obtaining the metal zinc particles and the electrolytic zinc plate, so that the zinc recovery rate is high, the process is simple, and the energy consumption is lower. The zinc-containing powder of the embodiment mainly adopts a zinc-ammonia-chlorine wet method system to extract and recycle zinc elements, and has little influence on the chlorine content in the process and simple and convenient operation. The iron-containing metal treatment and the electrolysis waste liquid treatment can be used for independently extracting and collecting metallic iron, excessive ammonium chloride and the like, extracting and treating doped sodium and the like, and the produced residual reaction solution, mother solution and the like can be matched with a zinc-ammonia-chlorine wet method system to participate in leaching and electrolysis circulation, so that the process circulation is good, and no secondary hazardous waste is generated.
The foregoing has shown and described the basic principles, main features and advantages of the present invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined in the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (5)
1. The comprehensive utilization method of the leadless hot galvanizing scum is characterized by comprising the following steps:
s1, magnetic separation: magnetically separating hot galvanizing scum by adopting a magnetic separator, collecting the magnetically separated ferrous metal, and enabling non-ferrous materials to enter S2;
s2, grinding and winnowing: inputting the nonferrous materials into a Raymond mill for grinding, wherein the rotation speed of a central shaft in the Raymond mill is 60-85 r/min, and the air quantity is 10000-23000 m 3 Per hour, the total pressure is 3.2 to 4.5kpa, and the air quantity of the residual air pipe is 15000 to 45000m 3 And (h) a 50-mesh sieve is used for a discharge hole, zinc-containing powder with small granularity passes through the 50-mesh sieve to be collected, and the residual metal zinc particles with large granularity are collected independently;
s3, leaching and electrolysis: adding the zinc-containing powder into a slurrying tank, slurrying by using electrolytic waste liquid, liquid ammonia and 20% hydrochloric acid, wherein the volume ratio of the electrolytic waste liquid to the liquid ammonia to the 20% hydrochloric acid is 1:0.2 to 0.3: 0.05-0.1, wherein the pH value in the slurrying tank is 4-6, the stirring speed in the slurrying tank is 150-300 r/min, and the temperature in the slurrying tank is 60-70 ℃; leaching the slurry after pulping, wherein ph=5-6, the leaching temperature is 60-70 ℃, the leaching speed is 50-200 r/min, and the leaching time is 12-24 h; filtering the leached slurry, electrolyzing the filtered liquid with ph=5-6.5, electrolytic temperature of 60-80 deg.c, electrolytic time of 12-24 hr and current density of 200-300A/m 2 The voltage is 3.0-3.2 v; an electrolytic zinc plate is obtained on the electrode after electrolysis, and the electrolytic waste liquid returns to the slurrying tank for slurrying in the step;
s4, casting: casting the zinc particles obtained in the step S2 and the electrolytic zinc plate obtained in the step S3, wherein the mass ratio of the zinc particles to the electrolytic zinc plate is 1: 2-4, and the casting temperature is 420-450 ℃; during casting, zinc particles and electrolytic zinc plates are alternately placed in a casting furnace from bottom to top, the zinc particles can be prevented from being oxidized under the electrolytic zinc plates by casting for 0.5 to 1.5 hours, layered placement promotes uniform heating, local oxidation is prevented, and after the zinc particles are completely melted, zinc water in the casting furnace is poured into a die and cooled and cast into regenerated zinc ingots;
s5, ammonium chloride recovery: s3, recycling the electrolysis waste liquid for 5-8 times, and when the concentration of chloride ions in the solution reaches 200-240 g/L, pulping the electrolysis waste liquid; the electrolytic waste liquid is subjected to zinc precipitation treatment by adopting sodium sulfide, the dosage of the sodium sulfide is 1.5-2.0 times of the zinc ion content in the electrolytic waste liquid, then three-effect evaporation treatment is carried out, the treated mother liquid returns to S3 for pulping again, and the precipitated ammonium chloride crystal is packaged independently.
2. The comprehensive utilization method of the lead-free hot galvanizing dross according to claim 1, which is characterized in that: s1, magnetically separating hot galvanizing scum by adopting a two-stage dry magnetic separator; the feeding speed of the first-stage magnetic separator is 60-100 m/min, and the magnetic field strength is 4000 gauss; the feeding speed of the second-stage magnetic separator is 80-100 m/min, and the magnetic field strength is 5000 gauss.
3. The comprehensive utilization method of the lead-free hot galvanizing dross according to claim 1, which is characterized in that: s1, feeding the magnetically selected ferrous metal into 20% hydrochloric acid for reaction, wherein the mass ratio of the ferrous metal to the 20% hydrochloric acid is 1: 7-10; after all the iron-containing metal reacts, sending part of the metal zinc particles obtained in the step S2 into the reaction solution for iron separation treatment; after the treatment is finished, carrying out solid-liquid separation on the reaction solution, carrying out magnetic attraction separation on the separated metal zinc particles and iron powder, and independently collecting the magnetically sucked metal iron and using the rest metal zinc particles for S4 casting.
4. The comprehensive utilization method of the lead-free hot galvanizing scum according to claim 3, which is characterized in that: and (3) feeding the residual reaction solution after solid-liquid separation into S3 for pulping, and adding liquid ammonia when the residual reaction solution is added in S3, wherein the volume ratio of the added liquid ammonia to the residual reaction solution is 2-6: 1.
5. the comprehensive utilization method of the lead-free hot galvanizing dross according to claim 1, which is characterized in that: and S6, sodium chloride recovery: when the concentration of sodium ions in the S5 mother solution reaches 10-12 g/L, carrying out high-temperature concentration filtration on the mother solution, and returning the filtrate obtained by the high-temperature concentration filtration to S3 for pulping to use as an electrolyte waste liquid.
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| CN117926346A (en) * | 2024-03-22 | 2024-04-26 | 清华大学 | Process for producing electrodeposited zinc by leaching zinc-containing paint slag in ammonium chloride solution |
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| CN113186394A (en) * | 2020-12-15 | 2021-07-30 | 云南宇菲工程设计有限责任公司 | Method for producing metal zinc by treating high-lead zinc-containing material by ammonia-ammonium method |
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| CN104005051A (en) * | 2014-04-29 | 2014-08-27 | 戴兴征 | Method for extracting electrodeposited zinc from zinc oxide powder in ammonium chloride solution system |
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