CN112280992B - Recovery method of lead acid leaching mud - Google Patents
Recovery method of lead acid leaching mud Download PDFInfo
- Publication number
- CN112280992B CN112280992B CN202011173370.7A CN202011173370A CN112280992B CN 112280992 B CN112280992 B CN 112280992B CN 202011173370 A CN202011173370 A CN 202011173370A CN 112280992 B CN112280992 B CN 112280992B
- Authority
- CN
- China
- Prior art keywords
- lead
- reaction
- mud
- filtrate
- ammonium chloride
- 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
Links
- 239000002253 acid Substances 0.000 title claims abstract description 78
- 238000002386 leaching Methods 0.000 title claims abstract description 64
- 238000000034 method Methods 0.000 title claims abstract description 61
- 238000011084 recovery Methods 0.000 title claims abstract description 31
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 106
- 238000006243 chemical reaction Methods 0.000 claims abstract description 105
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 70
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 70
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 67
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 53
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 50
- 230000023556 desulfurization Effects 0.000 claims abstract description 50
- 239000012452 mother liquor Substances 0.000 claims abstract description 31
- 230000008929 regeneration Effects 0.000 claims abstract description 29
- 238000011069 regeneration method Methods 0.000 claims abstract description 29
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 24
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 24
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 24
- 238000002156 mixing Methods 0.000 claims abstract description 24
- 239000011505 plaster Substances 0.000 claims abstract description 23
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 15
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 15
- 229910000464 lead oxide Inorganic materials 0.000 claims abstract description 15
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000706 filtrate Substances 0.000 claims description 65
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 50
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 50
- 229920002401 polyacrylamide Polymers 0.000 claims description 33
- 238000001514 detection method Methods 0.000 claims description 30
- 238000000926 separation method Methods 0.000 claims description 30
- 238000005406 washing Methods 0.000 claims description 30
- 239000007788 liquid Substances 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 238000001914 filtration Methods 0.000 claims description 24
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 claims description 24
- 238000003825 pressing Methods 0.000 claims description 22
- 150000002500 ions Chemical class 0.000 claims description 18
- 230000035484 reaction time Effects 0.000 claims description 18
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 15
- 229910017604 nitric acid Inorganic materials 0.000 claims description 15
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 claims description 14
- 238000004064 recycling Methods 0.000 claims description 12
- 229910052602 gypsum Inorganic materials 0.000 claims description 10
- 239000010440 gypsum Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 10
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 7
- 239000005695 Ammonium acetate Substances 0.000 claims description 7
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 7
- 235000019257 ammonium acetate Nutrition 0.000 claims description 7
- 229940043376 ammonium acetate Drugs 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 238000000746 purification Methods 0.000 claims description 7
- 238000010008 shearing Methods 0.000 claims description 7
- ORZHVTYKPFFVMG-UHFFFAOYSA-N xylenol orange Chemical compound OC(=O)CN(CC(O)=O)CC1=C(O)C(C)=CC(C2(C3=CC=CC=C3S(=O)(=O)O2)C=2C=C(CN(CC(O)=O)CC(O)=O)C(O)=C(C)C=2)=C1 ORZHVTYKPFFVMG-UHFFFAOYSA-N 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 6
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 5
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 5
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 claims description 3
- KEQXNNJHMWSZHK-UHFFFAOYSA-L 1,3,2,4$l^{2}-dioxathiaplumbetane 2,2-dioxide Chemical compound [Pb+2].[O-]S([O-])(=O)=O KEQXNNJHMWSZHK-UHFFFAOYSA-L 0.000 claims description 2
- 229910052924 anglesite Inorganic materials 0.000 claims description 2
- 238000005554 pickling Methods 0.000 claims 1
- 238000003860 storage Methods 0.000 abstract description 11
- 239000006227 byproduct Substances 0.000 abstract description 6
- 239000003795 chemical substances by application Substances 0.000 abstract description 5
- 230000003009 desulfurizing effect Effects 0.000 abstract description 5
- 239000000243 solution Substances 0.000 description 56
- 239000012535 impurity Substances 0.000 description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000005189 flocculation Methods 0.000 description 9
- 230000016615 flocculation Effects 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000010926 purge Methods 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000010413 mother solution Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052925 anhydrite Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- -1 for example Polymers 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000002699 waste material 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
- C22B13/00—Obtaining lead
- C22B13/04—Obtaining lead by wet processes
- C22B13/045—Recovery from waste materials
-
- 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
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Geochemistry & Mineralogy (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a recovery method of lead mud after acid leaching, belongs to the technical field of lead acid storage batteries, and solves the problems that the lead mud after acid leaching in the prior art is high in desulfurization cost and byproducts cannot be treated. According to the recovery method, the mother liquor ammonium chloride is used as a desulfurizing agent to carry out a desulfurization reaction on lead slime to be treated, the ammonium sulfate solution obtained by desulfurization carries out a regeneration reaction on calcium hydroxide, the regenerated ammonia water reacts with the lead plaster obtained by desulfurization to obtain lead oxide plaster and regenerated ammonium chloride, the lead oxide plaster is used for a plaster mixing procedure of a battery, and the regenerated ammonium chloride is used as the mother liquor ammonium chloride, so that recovery of lead slime subjected to acid leaching is completed. The recovery method of the invention can be used for recovering lead mud after acid leaching.
Description
Technical Field
The invention belongs to the technical field of lead-acid storage batteries, and particularly relates to a recovery method of lead mud after acid leaching.
Background
The production of lead-acid storage batteries generally comprises the steps of casting plates, ball milling, plate coating, acid spraying, surface drying, solidification, sheet separation and brushing, assembly, acidification formation, cleaning, packaging and the like. A large amount of lead mud can be produced in the coating plate and/or acid leaching step.
In the prior art, the lead acid leaching mud is treated by the following two methods. According to the method, acid-leaching lead mud is directly converted into lead ingots according to a certain proportion and then used for a casting plate and/or ball milling process, and the waste of the acid-leaching lead mud can be caused due to the fact that the proportion of the acid-leaching lead mud converted into the lead ingots is not high, so that the production cost of the battery is increased; meanwhile, lead is harmful to the environment and the human health, and in the transportation process of lead mud coated with acid, if the lead mud is improperly treated, the lead mud is very likely to pollute the environment or harm the human health. In another method, sodium hydroxide is adopted to carry out sulfur removal on lead mud drenching acid, so that lead sulfate is converted into lead oxide and then recycled.
Disclosure of Invention
In view of the analysis, the invention aims to provide a recovery method of lead mud after acid leaching, which solves the problems of high desulfurization cost and no byproduct treatment of the lead mud after acid leaching in the prior art.
The aim of the invention is mainly realized by the following technical scheme:
The invention provides a recovery method of lead mud for acid leaching, which adopts mother liquor ammonium chloride as a desulfurizing agent to carry out desulfurization reaction on lead mud to be treated, ammonium sulfate solution obtained by desulfurization carries out regeneration reaction with calcium hydroxide, ammonia water obtained by regeneration reacts with lead plaster obtained by desulfurization to obtain lead oxide lead plaster and regenerated ammonium chloride, the lead oxide lead plaster is used for a paste mixing procedure of a battery, and the regenerated ammonium chloride is used as mother liquor ammonium chloride, so that the recovery of the lead mud for acid leaching is completed.
Further, the recovery method of the lead acid leaching mud comprises the following steps:
step S1: carrying out filter pressing separation on lead mud subjected to acid leaching by adopting a filter press to obtain lead mud to be treated and filtrate, and conveying the obtained filter pressing lead mud to a reaction kettle;
Step S2: mixing, shearing and stirring mother liquor ammonium chloride and lead slime to be treated for desulfurization reaction, and carrying out filter pressing separation to obtain desulfurized lead slime and ammonium sulfate solution;
Step S3: mixing and stirring ammonium sulfate solution and calcium hydroxide for regeneration reaction, and carrying out solid-liquid separation to obtain gypsum (high-purity gypsum) and ammonia water;
Step S4: mixing and stirring the regenerated ammonia water and the lead plaster obtained by desulfurization for reaction, and carrying out solid-liquid separation to obtain lead oxide lead plaster and regenerated ammonium chloride, thereby completing the recovery of lead acid leaching mud.
Further, after the step S1 and before the step S2, the method further includes the following steps:
and detecting the lead sulfate content in the lead slime to be treated obtained by press filtration.
Further, the detecting includes the steps of:
Taking part of lead mud to be treated (2+/-0.2 g) as a detection sample, placing the detection sample into a conical flask, adding diluted nitric acid (the mass ratio of the diluted nitric acid to the lead mud to be treated is 1:7-8, 15+/-0.5 ml) to boil, filtering (for example, naturally filtering) to obtain primary filtrate and primary filter residue, washing the primary filter residue with water (for example, pure water) once until no lead ions exist, transferring the primary filter residue and filter paper into the conical flask, adding 80-100 ml (for example, 100 ml) of 20% ammonium acetate solution to boil for 3-6 min (for example, 5 min), cooling and filtering to obtain secondary filtrate and secondary filter residue, carrying out secondary washing with water (for example, pure water) until no lead ions exist, combining the primary filtrate and the secondary filtrate, adding 9-10.5 ml (for example, 10 ml) of 20% hexamethyl tetra ammonium and 2-5 drops xylenol orange, calculating the mass ratio of lead sulfate to lead mud in the detection sample according to the quality of lead mud to EDTA in the detection sample.
Further, diluted nitric acid is obtained by diluting concentrated nitric acid with water (for example, pure water), and the volume ratio of the concentrated nitric acid to the water is 1:3.5 to 4.5 (e.g., 1:4).
Further, the two washes until no lead ions are detected by the following method: the washing liquid is detected by adopting 20% dilute sulfuric acid, and if no white precipitate is precipitated in the washing liquid, the washing is proved to be carried out until no lead ions are generated.
Further, in the step S1, the obtained filtrate is used in an acid leaching process of a lead-acid battery.
Further, in the step S2, the mass ratio of the ammonium chloride in the mother solution ammonium chloride to the lead sulfate in the lead slime to be treated is 2-3:1, wherein the mass fraction of the ammonium chloride in the mother solution is 5-20%.
Further, in the above step S2, the reaction temperature of the desulfurization reaction is 20 to 80 ℃ (e.g., 20 ℃, 33 ℃, 42 ℃, 59 ℃, 71 ℃ and 80 ℃), and the reaction time of the desulfurization reaction is 1 to 3 hours (e.g., 1 hour, 1.4 hours, 2.2 hours, 2.7 hours and 3.0 hours).
Further, in the step S3, the method further comprises the following steps before mixing and stirring the ammonium sulfate solution and the calcium hydroxide:
step a: sequentially adding polymeric ferric sulfate and polyacrylamide into the ammonium sulfate solution obtained in the step S2, stirring for 5-30 min at normal temperature, and filtering and separating to obtain a purified solid and a purified filtrate;
step b: detecting the lead ion content of the purified filtrate;
If the lead ion content of the purified filtrate is less than or equal to the threshold value (e.g., 20 ppm), judging that the purification of the ammonium sulfate solution obtained in the step S2 is completed, and taking the purified ammonium sulfate solution as the ammonium sulfate solution in the step S3;
If the lead ion content of the purge filtrate is greater than a threshold (e.g., 20 ppm), then step a is repeated until the lead ion content of the purge filtrate is less than or equal to the threshold.
Further, the polymeric ferric sulfate accounts for 0.01 to 0.1 percent of the ammonium sulfate solution by mass, and the polyacrylamide accounts for 0.1 to 0.5 percent of the ammonium sulfate solution by mass.
Further, the polymeric ferric sulfate is added in a plurality of times, and the addition amount of each time is gradually reduced, for example, the polymeric ferric sulfate is added in three times, the first addition amount is 50% of the total polymeric ferric sulfate, the second addition amount is 30% of the total polymeric ferric sulfate, and the third addition amount is 20% of the total polymeric ferric sulfate.
Further, the polyacrylamide is added in several times, and the addition amount of each time is gradually reduced, for example, the polyacrylamide is added in three times, the first addition amount is 50% of the total amount of the polyacrylamide, the second addition amount is 30% of the total amount of the polyacrylamide, and the third addition amount is 20% of the total amount of the polyacrylamide.
Further, in the step S3, the molar ratio of the calcium hydroxide to the ammonium sulfate is 1 to 1.1:1.
Further, in the above step S3, the reaction temperature of the regeneration reaction is 20 to 40 ℃ (e.g., 20 ℃, 25 ℃, 35 ℃ and 40 ℃), and the reaction time of the regeneration reaction is 1 to 5 hours (e.g., 1 hour, 1.5 hours, 2.0 hours, 2.9 hours, 3.4 hours, 4.1 hours and 5 hours).
Further, in the above step S4, the reaction temperature of the reaction is 20 to 60 ℃ (e.g., 20 ℃, 31 ℃, 44 ℃, 56 ℃ and 60 ℃), and the reaction time of the reaction is 1 to 3 hours (e.g., 1 hour, 1.4 hours, 2.2 hours, 2.7 hours and 3.0 hours).
Compared with the prior art, the invention has at least one of the following beneficial effects:
a) According to the recovery method of the lead acid leaching mud, the mother liquor ammonium chloride is used as a desulfurizing agent, and the lead sulfate in the lead acid leaching mud and the mother liquor ammonium chloride are subjected to desulfurization reaction, regeneration reaction of ammonium sulfate obtained by desulfurization and calcium hydroxide and reaction of ammonia water obtained by regeneration and lead plaster obtained by desulfurization in sequence, so that the lead sulfate can be converted into lead oxide plaster for a plaster mixing procedure of a battery, the mother liquor ammonium chloride is reacted and circulated to obtain regenerated ammonium chloride, and the regenerated ammonium chloride can be used as the mother liquor ammonium chloride again, thereby realizing the recovery and utilization of the lead acid leaching mud and the ammonium chloride. In the recycling process, the consumable product basically only comprises calcium hydroxide, and the price of the calcium hydroxide is far lower than that of sodium hydroxide, so that the desulfurization cost of lead mud in acid leaching can be greatly reduced, and the recycling cost of the lead-acid storage battery is greatly reduced.
B) According to the recovery method of the lead acid leaching mud, which is provided by the invention, in the recovery and utilization process of the lead acid leaching mud, no by-product is generated basically, and the treatment of the by-product is not needed, so that the whole recovery and utilization process can be effectively simplified.
C) According to the recovery method of lead acid leaching mud, impurities such as metal impurities (antimony, barium and residual lead and iron dissolved in mother liquor) exist in the ammonium sulfate solution obtained in the step S2, the quality of gypsum is influenced by the impurities, firstly, the ammonium sulfate solution obtained in the step S2 is purified by adopting polymeric ferric sulfate, and in the ammonium sulfate solution obtained in the step S2, the polymeric ferric sulfate provides a large number of macromolecular complexes and hydrophobic hydroxide polymers, so that the adsorption effect is good, and impurities in the ammonium sulfate solution can be adsorbed, and meanwhile, the polymeric ferric sulfate has large surface area, high surface energy, compact structure and certain strength and large adsorption quantity to the impurities; then, the ammonium sulfate solution purified by the polymeric ferric sulfate is further purified by polyacrylamide, and the polyacrylamide has good flocculation property, so that the friction resistance between the liquids can be reduced, and the flocculation of the polymeric ferric sulfate can further grow up, thereby being convenient for subsequent separation.
D) According to the recovery method of lead acid leaching mud, in the initial stage of adding the polymeric ferric sulfate, the impurities in the ferric sulfate solution obtained in the step S2 are more, and the part of the polymeric ferric sulfate added at first can adsorb most of the impurities and is basically close to the state of adsorption saturation; the added polymeric ferric sulfate can further adsorb impurities among the floccules formed by the polymeric ferric sulfate added at the previous time, thereby playing a role in improving the purification degree.
E) According to the recovery method of lead acid leaching mud, the polyacrylamide added for the first time can be wrapped outside the flocculation of the polymeric ferric sulfate, so that the flocculation volume of the polymeric ferric sulfate is increased, the polyacrylamide added for the second time can be wrapped outside the polyacrylamide added for the first time, the polymeric ferric sulfate is further increased, and the like, so that subsequent separation is further promoted, and the influence of the addition of the polymeric ferric sulfate and the polyacrylamide on an ammonium sulfate solution is reduced.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention may be realized and attained by the structure particularly pointed out in the written description and drawings.
Drawings
The drawings are only for the purpose of illustrating the invention and are not to be construed as limiting the invention, like reference numerals referring to like parts throughout the several views.
Fig. 1 is a flow chart of a recovery method of lead acid leaching mud provided by the invention.
Detailed Description
The following detailed description of the preferred invention is provided in connection with the accompanying drawings, which form a part hereof, and together with the description serve to explain the principles of the invention.
The invention provides a recovery method of lead mud for acid leaching, which is shown in figure 1, wherein mother liquor ammonium chloride is used as a desulfurizing agent to carry out desulfurization reaction on lead mud to be treated, ammonium sulfate solution obtained by desulfurization carries out regeneration reaction on calcium hydroxide, ammonia water obtained by regeneration reacts with lead plaster (lead chloride) obtained by desulfurization to obtain lead oxide lead plaster and regenerated ammonium chloride, the lead oxide lead plaster is used for a paste combining procedure of a battery, and the regenerated ammonium chloride is used as mother liquor ammonium chloride, so that the recovery of the lead mud for acid leaching is completed.
It should be noted that both the mother liquor ammonium chloride and regenerated ammonium chloride are ammonium chloride, and that "mother liquor" and "regenerated" are merely to distinguish ammonium chloride in different steps.
Compared with the prior art, the recovery method of the lead acid leaching mud adopts the mother liquor ammonium chloride as the desulfurizing agent, and sequentially passes through the desulfurization reaction of lead sulfate in the lead acid leaching mud and the mother liquor ammonium chloride, the regeneration reaction of ammonium sulfate obtained by desulfurization and calcium hydroxide, and the reaction of ammonia water obtained by regeneration and lead paste obtained by desulfurization, so that the lead sulfate can be converted into lead oxide paste for the paste mixing process of a battery, the mother liquor ammonium chloride is reacted and circulated to obtain the regenerated ammonium chloride, and the regenerated ammonium chloride can be used as the mother liquor ammonium chloride again, thereby realizing the recovery and utilization of the lead acid leaching mud and the ammonium chloride. In the recycling process, the consumable product basically only comprises calcium hydroxide, and the price of the calcium hydroxide is far lower than that of sodium hydroxide, so that the desulfurization cost of lead mud in acid leaching can be greatly reduced, and the recycling cost of the lead-acid storage battery is greatly reduced.
Meanwhile, in the recycling process of the lead acid leaching mud, no by-product is generated basically, and the treatment of the by-product is not needed, so that the whole recycling process can be simplified effectively.
Specifically, the recovery method of the lead acid leaching mud comprises the following steps:
step S1: carrying out filter pressing separation on lead mud subjected to acid leaching by adopting a filter press to obtain lead mud to be treated and filtrate, and conveying the obtained filter pressing lead mud to a reaction kettle;
Step S2: mixing, shearing and stirring mother liquor ammonium chloride and lead slime to be treated for desulfurization reaction, and carrying out filter pressing separation to obtain desulfurized lead slime and ammonium sulfate solution;
The reaction takes place as follows:
PbSO4+2NH4Cl→PbCl2+(NH4)2SO4
Step S3: mixing and stirring ammonium sulfate solution and calcium hydroxide for regeneration reaction, and carrying out solid-liquid separation to obtain gypsum (high-purity gypsum) and ammonia water;
The reaction takes place as follows:
(NH4)2SO4+Ca(OH)2→CaSO4+2NH3·H2O
Step S4: mixing and stirring the regenerated ammonia water and the lead plaster obtained by desulfurization for reaction, and carrying out solid-liquid separation to obtain lead oxide lead plaster and regenerated ammonium chloride, thereby completing the recovery of lead acid leaching mud.
In order to determine the lead sulfate content in the filter-pressed lead slime so as to accurately add the corresponding sodium chloride, the method further comprises the following steps after the step S1 and before the step S2:
and detecting the lead sulfate content in the lead slime to be treated obtained by press filtration.
Specifically, the detection includes the following steps:
Taking part of lead mud to be treated (2+/-0.2 g) as a detection sample, placing the detection sample into a conical flask, adding diluted nitric acid (the mass ratio of the diluted nitric acid to the lead mud to be treated is 1:7-8, 15+/-0.5 ml) to boil, filtering (for example, naturally filtering) to obtain primary filtrate and primary filter residue, washing the primary filter residue with water (for example, pure water) once until no lead ions exist, transferring the primary filter residue and filter paper into the conical flask, adding 80-100 ml (for example, 100 ml) of 20% ammonium acetate solution to boil for 3-6 min (for example, 5 min), cooling and filtering to obtain secondary filtrate and secondary filter residue, carrying out secondary washing with water (for example, pure water) until no lead ions exist, combining the primary filtrate and the secondary filtrate, adding 9-10.5 ml (for example, 10 ml) of 20% hexamethyl tetra ammonium and 2-5 drops xylenol orange, calculating the mass ratio of lead sulfate to lead mud in the detection sample according to the quality of lead mud to EDTA in the detection sample.
The diluted nitric acid is obtained by diluting concentrated nitric acid with water (for example, pure water), and the volume ratio of the concentrated nitric acid to the water is 1:3.5 to 4.5 (e.g., 1:4).
It should be noted that, the above two washes to lead-free ion were judged by the following method: the washing liquid is detected by adopting 20% dilute sulfuric acid, and if no white precipitate is precipitated in the washing liquid, the washing is proved to be carried out until no lead ions are generated.
In consideration of the fact that the main component in the filtrate generated in the filter pressing separation process is dilute sulfuric acid, dilute sulfuric acid is needed to be adopted in the acid leaching process of the lead-acid storage battery, in order to realize the recycling of the obtained filtrate, the overall value of the recovery method of the acid leaching lead mud is improved, and in the step S1, the obtained filtrate is used in the acid leaching process of the lead-acid storage battery.
In order to ensure the desulfurization effect of the lead slime to be treated in the step S2, the mass ratio of the ammonium chloride in the mother liquor ammonium chloride to the lead sulfate in the lead slime to be treated is 2-3:1, wherein the mass fraction of the ammonium chloride in the mother liquor is 5-20%.
In order to control the reaction rate of the desulfurization reaction and to secure the desulfurization effect of the lead slime to be treated, in the above step S2, the reaction temperature of the desulfurization reaction is 20 to 80 ℃ (e.g., 20 ℃, 33 ℃, 42 ℃, 59 ℃, 71 ℃ and 80 ℃), and the reaction time of the desulfurization reaction is 1 to 3 hours (e.g., 1 hour, 1.4 hours, 2.2 hours, 2.7 hours and 3.0 hours). This is because, by limiting the reaction temperature of the desulfurization reaction to the above range, the reaction rate of the desulfurization reaction can be appropriately increased, and the severe progress of the desulfurization reaction can be ensured, thereby improving the reaction safety of the desulfurization reaction; the reaction time of the desulfurization reaction is limited to the above range, and the reaction efficiency can be appropriately improved and the reaction time of the desulfurization reaction can be reduced on the basis of ensuring the sufficient reaction of the desulfurization reaction.
In order to purify impurities in the mother liquor, in the step S3, the step of mixing and stirring the ammonium sulfate solution and the calcium hydroxide further comprises the following steps:
step a: sequentially adding polymeric ferric sulfate and polyacrylamide into the ammonium sulfate solution obtained in the step S2, stirring for 5-30 min at normal temperature, and filtering and separating to obtain a purified solid and a purified filtrate;
step b: detecting the lead ion content of the purified filtrate;
If the lead ion content of the purified filtrate is less than or equal to the threshold value (e.g., 20 ppm), judging that the purification of the ammonium sulfate solution obtained in the step S2 is completed, and taking the purified ammonium sulfate solution as the ammonium sulfate solution in the step S3;
If the lead ion content of the purge filtrate is greater than a threshold (e.g., 20 ppm), then step a is repeated until the lead ion content of the purge filtrate is less than or equal to the threshold.
The ammonium sulfate solution obtained in the step S2 is purified by adopting the method, because impurities, such as metal impurities (antimony, barium and residual lead and iron dissolved in mother liquor) exist in the ammonium sulfate solution obtained in the step S2, the existence of the impurities can influence the quality of the generated gypsum, firstly, the ammonium sulfate solution obtained in the step S2 is purified by adopting the polymeric ferric sulfate, and in the ammonium sulfate solution obtained in the step S2, the polymeric ferric sulfate provides a large amount of macromolecular complexes and hydrophobic hydroxide polymers, so that the ammonium sulfate solution has better adsorption effect, thereby being capable of adsorbing the impurities in the ammonium sulfate solution, and meanwhile, the polymeric ferric sulfate has large flocculation surface area, high surface energy, compact structure and certain strength and large adsorption amount of the impurities; then, the ammonium sulfate solution purified by the polymeric ferric sulfate is further purified by polyacrylamide, and the polyacrylamide has good flocculation property, so that the friction resistance between the liquids can be reduced, and the flocculation of the polymeric ferric sulfate can further grow up, thereby being convenient for subsequent separation.
In order to ensure the purification effect of the polymeric ferric sulfate and the polyacrylamide on the ammonium sulfate solution, the polymeric ferric sulfate accounts for 0.01 to 0.1 percent of the ammonium sulfate solution in mass percent, and the polyacrylamide accounts for 0.1 to 0.5 percent of the ammonium sulfate solution in mass percent.
As for the manner of adding the polymeric ferric sulfate, for example, the polymeric ferric sulfate is added in a plurality of times with each addition gradually decreasing, for example, the polymeric ferric sulfate is added in three times, the first addition amount is 50% of the total polymeric ferric sulfate, the second addition amount is 30% of the total polymeric ferric sulfate, and the third addition amount is 20% of the total polymeric ferric sulfate. This is because, at the initial stage of adding the polymeric ferric sulfate, the impurity in the ferric sulfate solution obtained in step S2 is relatively large, and a part of the polymeric ferric sulfate added first can adsorb most of the impurity, and the state is substantially close to the adsorption saturation state; the added polymeric ferric sulfate can further adsorb impurities among the floccules formed by the polymeric ferric sulfate added at the previous time, thereby playing a role in improving the purification degree.
Also, as for the manner of adding polyacrylamide, for example, polyacrylamide is added in several times with gradually decreasing addition amount each time, for example, polyacrylamide is added in three times, the first addition amount is 50% of the total amount of polyacrylamide, the second addition amount is 30% of the total amount of polyacrylamide, and the third addition amount is 20% of the total amount of polyacrylamide. This is because the first added polyacrylamide can be wrapped outside the flocculation of the polymeric ferric sulfate, so that the flocculation volume of the polymeric ferric sulfate is increased, the second added polyacrylamide can be wrapped outside the first added polyacrylamide, so that the polymeric ferric sulfate is further increased, and the like, so that the subsequent separation is further promoted, and the influence of the addition of the polymeric ferric sulfate and the polyacrylamide on the ammonium sulfate solution is reduced.
In order to ensure the regeneration effect of the ammonium sulfate solution in the step S3, the molar ratio of the calcium hydroxide to the ammonium sulfate is 1 to 1.1:1. that is, the amount of calcium hydroxide added is in excess relative to the ammonium sulfate, which enables substantially all of the ammonium sulfate in the ammonium sulfate solution to be regenerated and converted to gypsum and ammonia.
In order to control the reaction rate of the regeneration reaction and to secure the regeneration effect of the ammonium sulfate solution, in the above step S3, the reaction temperature of the regeneration reaction is 20 to 40 ℃ (e.g., 20 ℃, 25 ℃, 35 ℃ and 40 ℃), and the reaction time of the regeneration reaction is 1 to 5 hours (e.g., 1 hour, 1.5 hours, 2.0 hours, 2.9 hours, 3.4 hours, 4.1 hours and 5 hours). This is because, by limiting the reaction temperature of the regeneration reaction to the above range, the reaction rate of the regeneration reaction can be appropriately increased, and the vigorous progress of the regeneration reaction can be ensured, thereby improving the reaction safety of the regeneration reaction; the reaction time of the regeneration reaction is limited to the above range, and the reaction efficiency can be appropriately improved and the reaction time of the regeneration reaction can be reduced while ensuring the sufficient reaction of the regeneration reaction.
Similarly, in order to control the reaction rate of the reaction in the step S4 and to ensure sufficient ammonia water obtained by regeneration and lead paste obtained by desulfurization, the reaction temperature of the reaction in the above step S4 is 20 to 60 ℃ (e.g., 20 ℃,31 ℃, 44 ℃, 56 ℃ and 60 ℃), and the reaction time of the reaction is 1 to 3 hours (e.g., 1 hour, 1.4 hours, 2.2 hours, 2.7 hours and 3.0 hours). This is because, by limiting the reaction temperature of the reaction in step S4 to the above-described range, the reaction rate of the reaction can be appropriately increased, and the vigorous progress of the reaction can be ensured, thereby improving the reaction safety of the above-described reaction; the reaction time of the reaction in step S4 is limited to the above range, and the reaction efficiency can be appropriately improved and the reaction time can be reduced while ensuring sufficient reaction.
Example 1
The embodiment provides a method for recycling lead acid leaching mud, which comprises the following steps:
step A: carrying out filter pressing separation on lead mud subjected to acid leaching by adopting a filter press to obtain lead mud to be treated and filtrate, wherein the obtained filtrate is used for an acid leaching process of a lead-acid storage battery, and the obtained filter pressing lead mud is conveyed to a reaction kettle;
And (B) step (B): taking 2g of lead mud to be treated as a detection sample, placing the detection sample into a conical flask, adding 15ml of diluted nitric acid, heating to boil, naturally filtering to obtain primary filtrate and primary filter residue, washing the primary filter residue with pure water for one time until no lead ions exist, transferring the primary filter residue and filter paper into the conical flask, adding 100ml of 20% ammonium acetate solution, heating to boil for 5min, cooling, filtering to obtain secondary filtrate and secondary filter residue, washing the secondary filter residue with pure water for the second time until no lead ions exist, combining the primary washing liquid, the secondary washing liquid, the primary filtrate and the secondary filtrate, adding 10ml of 20% hexamethylenetetramine and 2-5 drops of xylenol orange, titrating with 0.1mol/l EDTA, calculating the quality of lead sulfate in the detection sample, and calculating the quality of lead sulfate in the lead mud in acid leaching according to the mass ratio of the detection sample to the lead mud to be detected;
step C: the mass ratio is 2: mixing, shearing and stirring mother liquor ammonium chloride and lead slime to be treated for desulfurization reaction at a reaction temperature of 20 ℃ for 1.5 hours, and performing filter pressing separation to obtain desulfurization lead slime and ammonium sulfate solution;
step D: sequentially adding 0.01% of polymeric ferric sulfate and 0.2% of polyacrylamide into the ammonium sulfate solution, stirring for 10min at normal temperature, and filtering and separating to obtain a purified solid and a purified filtrate;
Step E: detecting the lead ion content of the purified filtrate, wherein the lead ion content of the purified filtrate is equal to 20ppm, and the purification of the ammonium sulfate solution is completed;
step F: according to the molar ratio of the calcium hydroxide to the ammonium sulfate of 1:1, mixing and stirring the purified ammonium sulfate solution and calcium hydroxide for a regeneration reaction, wherein the reaction temperature is 25 ℃, and the reaction time is 2h for solid-liquid separation to obtain high-purity gypsum and ammonia water;
step E: mixing and stirring the regenerated ammonia water and the lead plaster obtained by desulfurization for reaction, wherein the reaction temperature is 30 ℃, the reaction time of the reaction is 3 hours, and the solid-liquid separation is carried out to obtain lead oxide lead plaster and regenerated ammonium chloride, wherein the lead oxide lead plaster is used for a paste mixing procedure of a battery, and the regenerated ammonium chloride is used as mother liquor ammonium chloride, so that the recovery of lead mud after acid leaching is completed.
Example two
The embodiment provides a method for recycling lead acid leaching mud, which comprises the following steps:
step A: carrying out filter pressing separation on lead mud subjected to acid leaching by adopting a filter press to obtain lead mud to be treated and filtrate, wherein the obtained filtrate is used for an acid leaching process of a lead-acid storage battery, and the obtained filter pressing lead mud is conveyed to a reaction kettle;
And (B) step (B): taking 2g of lead mud to be treated as a detection sample, placing the detection sample into a conical flask, adding 14ml of diluted nitric acid, heating to boil, naturally filtering to obtain primary filtrate and primary filter residue, washing the primary filter residue with pure water for one time until no lead ions exist, transferring the primary filter residue and filter paper into the conical flask, adding 95ml of 20% ammonium acetate solution, heating to boil for 3min, cooling, filtering to obtain secondary filtrate and secondary filter residue, washing the secondary filter residue with pure water for the second time until no lead ions exist, combining the primary washing liquid, the secondary washing liquid, the primary filtrate and the secondary filtrate, adding 9ml of 20% hexamethylenetetramine and 2-5 drops of xylenol orange, titrating with 0.1mol/l EDTA, calculating the quality of lead sulfate in the detection sample, and calculating the quality of lead sulfate in the lead mud in acid leaching according to the mass ratio of the detection sample to the lead mud to be detected;
Step C: the mass ratio is 2.5: mixing, shearing and stirring mother liquor ammonium chloride and lead slime to be treated for desulfurization reaction at 45 ℃ for 2.5 hours, and performing filter pressing separation to obtain desulfurization lead slime and ammonium sulfate solution;
step D: sequentially adding 0.05% of polymeric ferric sulfate and 0.4% of polyacrylamide into the ammonium sulfate solution, stirring at normal temperature for 20min, and filtering and separating to obtain a purified solid and a purified filtrate;
Step E: detecting the lead ion content of the purified filtrate, wherein the lead ion content of the purified filtrate is less than 20ppm, and the purification of the ammonium sulfate solution is completed;
Step F: according to the molar ratio of the calcium hydroxide to the ammonium sulfate of 1: mixing and stirring the purified ammonium sulfate solution and calcium hydroxide for a regeneration reaction, wherein the reaction temperature is 20 ℃, and the reaction time is 5h for solid-liquid separation to obtain high-purity gypsum and ammonia water;
Step E: mixing and stirring the regenerated ammonia water and the lead plaster obtained by desulfurization for reaction, wherein the reaction temperature is 60 ℃, the reaction time of the reaction is 1h, and the solid-liquid separation is carried out to obtain lead oxide lead plaster and regenerated ammonium chloride, wherein the lead oxide lead plaster is used for a paste mixing procedure of a battery, and the regenerated ammonium chloride is used as mother liquor ammonium chloride, so that the recovery of lead mud after acid leaching is completed.
Example III
The embodiment provides a method for recycling lead acid leaching mud, which comprises the following steps:
step A: carrying out filter pressing separation on lead mud subjected to acid leaching by adopting a filter press to obtain lead mud to be treated and filtrate, wherein the obtained filtrate is used for an acid leaching process of a lead-acid storage battery, and the obtained filter pressing lead mud is conveyed to a reaction kettle;
And (B) step (B): taking 2g of lead mud to be treated as a detection sample, placing the detection sample into a conical flask, adding 16ml of diluted nitric acid, heating to boil, naturally filtering to obtain primary filtrate and primary filter residue, washing the primary filter residue with pure water for one time until no lead ions exist, transferring the primary filter residue and filter paper into the conical flask, adding 97ml of 20% ammonium acetate solution, heating to boil for 3min, cooling, filtering to obtain secondary filtrate and secondary filter residue, washing the secondary filter residue with pure water for the second time until no lead ions exist, combining the primary washing liquid, the secondary washing liquid, the primary filtrate and the secondary filtrate, adding 10ml of 20% hexamethylenetetramine and 2-5 drops of xylenol orange, titrating with 0.1mol/l EDTA, calculating the quality of lead sulfate in the detection sample, and calculating the quality of lead sulfate in the lead mud in acid leaching according to the mass ratio of the detection sample to the lead mud to be detected;
step C: the mass ratio is 2: mixing, shearing and stirring mother liquor ammonium chloride and lead slime to be treated for desulfurization reaction, wherein the reaction temperature is 80 ℃, the reaction time is 3 hours, and filter pressing separation is carried out to obtain desulfurization lead slime and ammonium sulfate solution;
step D: sequentially adding 0.01% of polymeric ferric sulfate and 0.5% of polyacrylamide into the ammonium sulfate solution, stirring for 5min at normal temperature, and filtering and separating to obtain a purified solid and a purified filtrate;
step E: detecting the lead ion content of the purified filtrate, wherein the lead ion content of the purified filtrate is more than 20ppm, repeating the step D for twice, and purifying the ammonium sulfate solution to finish the purification of the purified filtrate;
step F: according to the molar ratio of the calcium hydroxide to the ammonium sulfate of 1.03: mixing and stirring the purified ammonium sulfate solution and calcium hydroxide for a regeneration reaction, wherein the reaction temperature is 35 ℃, and the reaction time is 3 hours of solid-liquid separation to obtain high-purity gypsum and ammonia water;
Step E: mixing and stirring the regenerated ammonia water and the lead plaster obtained by desulfurization for reaction, wherein the reaction temperature is 59 ℃, the reaction time of the reaction is 2 hours, and the solid-liquid separation is carried out to obtain lead oxide lead plaster and regenerated ammonium chloride, wherein the lead oxide lead plaster is used for a paste mixing procedure of a battery, and the regenerated ammonium chloride is used as mother liquor ammonium chloride, so that the recovery of lead mud after acid leaching is completed.
Example IV
The embodiment provides a method for recycling lead acid leaching mud, which comprises the following steps:
step A: carrying out filter pressing separation on lead mud subjected to acid leaching by adopting a filter press to obtain lead mud to be treated and filtrate, wherein the obtained filtrate is used for an acid leaching process of a lead-acid storage battery, and the obtained filter pressing lead mud is conveyed to a reaction kettle;
And (B) step (B): taking 2g of lead mud to be treated as a detection sample, placing the detection sample into a conical flask, adding 15ml of diluted nitric acid, heating to boil, naturally filtering to obtain primary filtrate and primary filter residue, washing the primary filter residue with pure water for one time until no lead ions exist, transferring the primary filter residue and filter paper into the conical flask, adding 75ml of 20% ammonium acetate solution, heating to boil for 6min, cooling, filtering to obtain secondary filtrate and secondary filter residue, washing the secondary filter residue with pure water for the second time until no lead ions exist, combining the primary washing liquid, the secondary washing liquid, the primary filtrate and the secondary filtrate, adding 10.5ml of 20% hexamethylenetetramine and 2-5 drops of xylenol orange, titrating with 0.1mol/l EDTA, calculating the quality of lead sulfate in the detection sample, and calculating the quality of lead sulfate in the lead mud according to the mass ratio of the detection sample to the lead mud to be detected;
Step C: the mass ratio is 3: mixing, shearing and stirring mother liquor ammonium chloride and lead slime to be treated for desulfurization reaction, wherein the reaction temperature is 70 ℃, the reaction time is 2 hours, and the lead slime to be treated and the ammonium sulfate solution are obtained through filter pressing and separation;
Step D: sequentially adding 0.1% of polymeric ferric sulfate and 0.4% of polyacrylamide into the ammonium sulfate solution, stirring for 30min at normal temperature, and filtering and separating to obtain a purified solid and a purified filtrate;
Step E: detecting the lead ion content of the purified filtrate, wherein the lead ion content of the purified filtrate is less than 20ppm, and the purification of the ammonium sulfate solution is completed;
Step F: the molar ratio of the calcium hydroxide to the ammonium sulfate is 1.1: mixing and stirring the purified ammonium sulfate solution and calcium hydroxide for a regeneration reaction at a reaction temperature of 40 ℃ for 5h, and carrying out solid-liquid separation to obtain high-purity gypsum and ammonia water;
Step E: mixing and stirring the regenerated ammonia water and the lead plaster obtained by desulfurization for reaction, wherein the reaction temperature is 20 ℃, the reaction time of the reaction is 1h, and the solid-liquid separation is carried out to obtain lead oxide lead plaster and regenerated ammonium chloride, wherein the lead oxide lead plaster is used for a paste mixing procedure of a battery, and the regenerated ammonium chloride is used as mother liquor ammonium chloride, so that the recovery of lead mud after acid leaching is completed.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions easily contemplated by those skilled in the art within the technical scope of the present invention should be included in the scope of the present invention.
Claims (4)
1. The recovery method of the lead acid leaching mud is characterized by comprising the following steps of:
step S1: carrying out filter pressing separation on lead mud to be treated to obtain lead mud to be treated and filtrate;
step S2: mixing, shearing and stirring mother liquor ammonium chloride and lead slime to be treated for desulfurization reaction, and carrying out filter pressing separation to obtain desulfurized lead slime and ammonium sulfate solution, wherein the mass ratio of the ammonium chloride in the mother liquor ammonium chloride to the lead sulfate in the lead slime to be treated is 2-3:1, the reaction temperature of the desulfurization reaction is 20-80 ℃, the reaction time of the desulfurization reaction is 1-3 h, and the reaction is as follows:
PbSO4+2NH4Cl→PbCl2+(NH4)2SO4；
step S3: mixing and stirring the ammonium sulfate solution and calcium hydroxide for a regeneration reaction, and carrying out solid-liquid separation to obtain gypsum and ammonia water;
Step S4: mixing and stirring the regenerated ammonia water and the desulfurized lead slime obtained by desulfurization for reaction, and carrying out solid-liquid separation to obtain lead oxide lead plaster and regenerated ammonium chloride, thereby completing the recovery of lead pickling slime;
The lead oxide lead plaster is used for a plaster combining procedure of a battery, and the regenerated ammonium chloride is used as mother liquor ammonium chloride;
After the step S1 and before the step S2, the method further comprises the following steps:
detecting the content of lead sulfate in lead slime to be treated, which is obtained by filter pressing separation; the detection comprises the following steps:
taking part of lead mud to be treated as a detection sample, adding diluted nitric acid into the detection sample, heating to boil, filtering to obtain primary filtrate and primary filter residue, washing the primary filter residue with water for one time until no lead ions are generated, combining the primary filter residue with filter paper, adding ammonium acetate solution, heating to boil, cooling, filtering to obtain secondary filtrate and secondary filter residue, washing the secondary filter residue with water until no lead ions are generated, combining the primary washing liquid, the secondary washing liquid, the primary filtrate and the secondary filtrate, adding hexamethylenetetramine and 2-5 drops of xylenol orange, titrating with EDTA, calculating the quality of lead sulfate in the detection sample, and calculating the quality of lead sulfate in the lead drenching acid lead mud according to the mass ratio of the detection sample to the lead mud to be treated;
in the step S3, the method further comprises the following steps before mixing and stirring the ammonium sulfate solution and the calcium hydroxide:
step a: sequentially adding polymeric ferric sulfate and polyacrylamide into the ammonium sulfate solution obtained in the step S2, stirring, filtering and separating to obtain a purified solid and a purified filtrate, wherein the polymeric ferric sulfate is added for multiple times, and the addition amount of each time is gradually reduced;
step b: detecting the lead ion content of the purified filtrate;
if the lead ion content of the purified filtrate is less than or equal to the threshold value, judging that the purification of the ammonium sulfate solution obtained in the step S2 is completed, and taking the purified ammonium sulfate solution as the ammonium sulfate solution in the step S3;
And if the lead ion content of the purified filtrate is greater than the threshold value, repeating the step a until the lead ion content of the purified filtrate is less than or equal to the threshold value.
2. The method for recovering lead acid leaching mud according to claim 1, wherein in the step S1, the obtained filtrate is used in an acid leaching process of a lead acid battery.
3. The method for recycling lead acid leaching mud according to claim 1, wherein the polymeric ferric sulfate accounts for 0.01-0.1% of the ammonium sulfate solution by mass, and the polyacrylamide accounts for 0.1-0.5% of the ammonium sulfate solution by mass.
4. The method for recovering lead acid leaching mud according to claim 1, wherein in the step S3, the molar ratio of calcium hydroxide to ammonium sulfate is 1-1.1: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011173370.7A CN112280992B (en) | 2020-10-28 | 2020-10-28 | Recovery method of lead acid leaching mud |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011173370.7A CN112280992B (en) | 2020-10-28 | 2020-10-28 | Recovery method of lead acid leaching mud |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112280992A CN112280992A (en) | 2021-01-29 |
| CN112280992B true CN112280992B (en) | 2024-07-23 |
Family
ID=74373677
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011173370.7A Active CN112280992B (en) | 2020-10-28 | 2020-10-28 | Recovery method of lead acid leaching mud |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112280992B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113880973A (en) * | 2021-08-20 | 2022-01-04 | 湖南江冶机电科技股份有限公司 | Preparation method of polyacrylamide for lead plaster sedimentation in lead-acid storage battery |
| CN115350588B (en) * | 2022-08-16 | 2024-04-12 | 沈阳三聚凯特催化剂有限公司 | Method for recycling deactivated iron-based desulfurizing agent |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019171282A1 (en) * | 2018-03-08 | 2019-09-12 | Engitec Technologies S.P.A. | Process for recovering lead from a lead pastel and use thereof in a process for recovering lead-acid accumulator components |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1191650B (en) * | 1986-01-09 | 1988-03-23 | Tecneco Spa | HYDROMETALLURGIC PROCESS FOR A TOTAL RECOVERY OF THE COMPONENTS OF EXHAUSTED LEAD ACID BATTERIES |
| ITMI20072257A1 (en) * | 2007-11-30 | 2009-06-01 | Engitec Technologies S P A | PROCESS FOR PRODUCING METALLIC LEAD FROM DESOLFORATED PASTEL |
| CN101994007B (en) * | 2009-08-28 | 2012-08-15 | 沈阳有色金属研究院 | Method for removing sulfur from waste lead-acid storage battery gypsum mud by using magnesium chloride |
| CN102689921B (en) * | 2011-03-24 | 2017-08-08 | 杨春晓 | The preparation method for the Pb nm-class oxide powders for reclaiming and manufacturing for lead-acid accumulator |
| CN102306855A (en) * | 2011-08-22 | 2012-01-04 | 铜梁县诚信电极板厂 | Method for recycling lead plaster from waste lead storage battery |
| CN106916952B (en) * | 2017-01-04 | 2019-01-04 | 北京化工大学 | A kind of round-robin method of sulfur acid scrap lead sulfur removal technology and its desulphurization mother solution |
| CN111172395A (en) * | 2019-10-23 | 2020-05-19 | 超威电源集团有限公司 | Method for preparing lead oxide from waste lead paste |
-
2020
- 2020-10-28 CN CN202011173370.7A patent/CN112280992B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019171282A1 (en) * | 2018-03-08 | 2019-09-12 | Engitec Technologies S.P.A. | Process for recovering lead from a lead pastel and use thereof in a process for recovering lead-acid accumulator components |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112280992A (en) | 2021-01-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103773972B (en) | A kind of processing method of raw material containing lead | |
| US8685349B2 (en) | Extraction of uranium from wet-process phosphoric acid | |
| CN101274806B (en) | A New Method of Recycling Wastewater Containing CN- and NH3 or NH4+ | |
| CN106048217B (en) | The comprehensive reutilization method of oxide powder and zinc | |
| CN110734169B (en) | Method for removing chlorine from acid solution | |
| CN105219969B (en) | Utilize vanadium wastewater and the method for tailings in vanadium extraction extraction manganese metal | |
| CN112280992B (en) | Recovery method of lead acid leaching mud | |
| CN104692579A (en) | Advanced recycling method for wastewater generated in making acid by using smelting flue gas | |
| CN112267023B (en) | Two-stage defluorination method for fluorine-containing material | |
| CN111547892A (en) | Treatment method of ammonia nitrogen wastewater in manganese chemical industry | |
| CN105567976A (en) | Method for treating vanadium extracting industrial acid wastewater and comprehensively recycling valuable metal | |
| CN102633295A (en) | Oxidation pretreatment method of soot containing zinc | |
| CN109607849B (en) | Method for treating low-ammonia nitrogen uranium-containing wastewater in nitrate radical system | |
| CN104862487B (en) | A kind of resource high-efficiency method for transformation of non-ferrous metal zinc metallurgy flying dust | |
| CN114558440A (en) | Process for efficiently extracting zinc by high-chlorine zinc ash ammonia-ammonium sulfate method and flue gas desulfurization and carbon fixation by coupled slurry method | |
| CN107099672B (en) | The recovery method of the fume from steel making containing zinc | |
| CN102925899A (en) | Method for refining copper chloride etching waste liquor | |
| CN113088702B (en) | Method for recovering valuable elements from acid leaching solution of roasting slag of gold-containing sulfur concentrate | |
| CN105347546A (en) | Treatment method and system of waste water produced by acid preparation from pyrite | |
| CN113816534A (en) | A process for deep impurity removal and resource recovery of gold smelting wastewater | |
| CN109231258B (en) | Method for comprehensively treating copper slag tailings and smelting flue gas | |
| CN103007588B (en) | The method of the ammonium sulfate liquor purification that a kind of sintering flue gas ammonia method desulfurizing technique produces | |
| CN216934550U (en) | Regenerated lead smelting soot desulfurization and dechlorination device | |
| CN203392950U (en) | System for treating acidic wastewater in acid preparing process by metallurgical off-gas | |
| CN102492956A (en) | Electrolytic manganese dioxide and preparation method thereof |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |