CN112280992A - Recovery method of acid leaching lead mud - Google Patents
Recovery method of acid leaching lead mud Download PDFInfo
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- CN112280992A CN112280992A CN202011173370.7A CN202011173370A CN112280992A CN 112280992 A CN112280992 A CN 112280992A CN 202011173370 A CN202011173370 A CN 202011173370A CN 112280992 A CN112280992 A CN 112280992A
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- lead
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- slime
- acid leaching
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- 239000002253 acid Substances 0.000 title claims abstract description 92
- 238000000034 method Methods 0.000 title claims abstract description 72
- 238000002386 leaching Methods 0.000 title claims abstract description 69
- 238000011084 recovery Methods 0.000 title claims abstract description 28
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 118
- 238000006243 chemical reaction Methods 0.000 claims abstract description 107
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 77
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 77
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 75
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 59
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 45
- 230000023556 desulfurization Effects 0.000 claims abstract description 45
- 239000011505 plaster Substances 0.000 claims abstract description 39
- 239000012452 mother liquor Substances 0.000 claims abstract description 33
- 230000008929 regeneration Effects 0.000 claims abstract description 33
- 238000011069 regeneration method Methods 0.000 claims abstract description 33
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 29
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 29
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 29
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 22
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 22
- 229910000464 lead oxide Inorganic materials 0.000 claims abstract description 20
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000003860 storage Methods 0.000 claims abstract description 13
- 239000000243 solution Substances 0.000 claims description 84
- 239000000706 filtrate Substances 0.000 claims description 68
- 238000005406 washing Methods 0.000 claims description 49
- 238000000926 separation method Methods 0.000 claims description 35
- 229920002401 polyacrylamide Polymers 0.000 claims description 34
- 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 32
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 32
- 238000001514 detection method Methods 0.000 claims description 31
- 238000002156 mixing Methods 0.000 claims description 31
- 238000003756 stirring Methods 0.000 claims description 31
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 claims description 27
- 238000003825 pressing Methods 0.000 claims description 25
- 238000001914 filtration Methods 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 150000002500 ions Chemical class 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 21
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 14
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 13
- 229910017604 nitric acid Inorganic materials 0.000 claims description 13
- 238000000746 purification Methods 0.000 claims description 13
- 229910052602 gypsum Inorganic materials 0.000 claims description 12
- 239000010440 gypsum Substances 0.000 claims description 12
- 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
- 238000010008 shearing Methods 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 5
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 5
- 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 5
- 239000010413 mother solution Substances 0.000 claims description 2
- 239000006227 byproduct Substances 0.000 abstract description 7
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 17
- 239000012535 impurity Substances 0.000 description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 230000035484 reaction time Effects 0.000 description 12
- 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
- 238000004064 recycling Methods 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
- 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
- 238000007865 diluting Methods 0.000 description 2
- 230000003311 flocculating effect Effects 0.000 description 2
- 238000005189 flocculation Methods 0.000 description 2
- 230000016615 flocculation Effects 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
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 2
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 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
- 229920000642 polymer Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 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 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 229910052924 anglesite 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
- 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
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- -1 illustratively Polymers 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 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
Images
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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for recovering acid leaching lead slime, belongs to the technical field of lead-acid storage batteries, and solves the problems that the acid leaching lead slime has high desulfurization cost and byproducts cannot be treated in the prior art. According to the recovery method, mother liquor ammonium chloride is used as a desulfurizer to carry out desulfurization reaction on lead slime to be treated, ammonium sulfate solution obtained by desulfurization is subjected to regeneration reaction with calcium hydroxide, ammonia water obtained by regeneration is reacted 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 plaster combining process of a battery, and the regenerated ammonium chloride is used as mother liquor ammonium chloride, so that recovery of the acid leaching lead slime is completed. The recovery method can be used for recovering the acid leaching lead mud.
Description
Technical Field
The invention belongs to the technical field of lead-acid storage batteries, and particularly relates to a recovery method of acid leaching lead mud.
Background
The production of lead-acid storage batteries generally comprises the steps of plate casting, ball milling, plate coating, acid spraying, surface drying, curing, sheet separating, assembly, acidification formation, cleaning and packaging and the like. A large amount of acid leaching lead mud is generated in the processes of plate coating and/or acid leaching.
In the prior art, the acid leaching lead slime is treated by the following two methods. In one method, acid leaching lead slime is directly converted into a lead ingot according to a certain proportion and then used for a plate casting and/or ball milling process, and the waste of the acid leaching lead slime is caused because the proportion of the acid leaching lead slime for converting the lead ingot is not high, so that the production cost of the battery is increased; meanwhile, lead is harmful to the environment and human health, and if the lead is improperly disposed, environmental pollution or harm to human health are possibly caused in the transfer process of the acid-leaching lead slime. According to the other method, sodium hydroxide is used for carrying out sulfur removal on the leached lead mud, so that lead sulfate is converted into lead oxide and then recycled, the method solves the problem of environmental protection in the leached lead mud exchange and transportation process, the value of the lead mud is effectively improved, however, the cost of desulfurization is still high due to the high price of the sodium hydroxide, and a byproduct sodium sulfate obtained by desulfurization is low in value and cannot be treated.
Disclosure of Invention
In view of the above analysis, the present invention aims to provide a method for recovering lead acid leaching mud, which solves the problems of high desulfurization cost and incapability of treating by-products of lead acid leaching mud in the prior art.
The purpose of the invention is mainly realized by the following technical scheme:
the invention provides a recovery method of lead mud leached by acid, which adopts mother liquor ammonium chloride as a desulfurizer to carry out desulfurization reaction on lead mud to be treated, ammonium sulfate solution obtained by desulfurization and calcium hydroxide carry out regeneration reaction, ammonia water obtained by regeneration and lead plaster obtained by desulfurization react to obtain lead oxide lead plaster and regenerated ammonium chloride, the lead oxide lead plaster is used for a plaster combining process of a battery, and the regenerated ammonium chloride is used as mother liquor ammonium chloride, thereby completing the recovery of the lead mud leached by acid.
Further, the recovery method of the acid leaching lead slime comprises the following steps:
step S1: carrying out filter pressing separation on the acid leaching lead slime by using a filter press to obtain lead slime to be treated and filtrate, and conveying the obtained filter pressing lead slime to a reaction kettle;
step S2: mixing, shearing and stirring mother liquor ammonium chloride and lead slime to be treated to perform desulfurization reaction, and performing filter pressing and separation to obtain desulfurized lead slime and an ammonium sulfate solution;
step S3: mixing and stirring an 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: and mixing and stirring the regenerated ammonia water and the desulfurized lead plaster for reaction, and carrying out solid-liquid separation to obtain lead oxide lead plaster and regenerated ammonium chloride, thereby completing the recovery of the acid leaching lead slime.
Further, after the step S1 and before the step S2, the method further includes the following steps:
and detecting the content of lead sulfate in the lead mud to be treated obtained by filter pressing separation.
Further, the detection comprises the following steps:
taking part of lead slime to be treated (2 +/-0.2 g) as a detection sample, putting the detection sample into an erlenmeyer flask, adding diluted nitric acid (the mass ratio of the diluted nitric acid to the lead slime to be treated is 1: 7-8, 15 +/-0.5 ml) and heating to boil, filtering (for example, natural filtering) to obtain a primary filtrate and a primary filter residue, carrying out primary washing on the primary filter residue with water (for example, pure water) to lead-free ions, transferring the primary filter residue and the filter paper into the erlenmeyer flask, adding 80-100 ml (for example, 100ml) of 20% ammonium acetate solution and heating to boil for 3-6 min (for example, 5min), cooling and filtering to obtain a secondary filtrate and a secondary filter residue, carrying out secondary washing on the secondary filter residue with water (for example, pure water) to lead-free ions, mixing the washing solution of the primary washing, the washing solution of the secondary washing, the primary filtrate and the secondary filtrate, adding 9-10.5 ml (for example, 10ml) of 20% hexamethinetetrammonium and 2-, titrating by using 0.1mol/l EDTA, calculating the mass of lead sulfate in the detection sample, and calculating the mass of lead sulfate in the lead mud leached by acid according to the mass ratio of the detection sample to the lead mud to be detected.
Further, the diluted nitric acid is obtained by diluting concentrated nitric acid and water (for example, pure water) in a volume ratio of 1: 3.5 to 4.5 (e.g., 1: 4).
Further, the two times of washing until lead-free ions are judged by the following method: and (4) detecting the washing liquid by using 20% dilute sulfuric acid, and if no white precipitate is separated out in the washing liquid, indicating that the washing liquid is washed to be free of lead ions.
Further, in the step S1, the obtained filtrate is used in an acid leaching process of the lead-acid storage battery.
Further, in the step S2, the mass ratio of ammonium chloride in the mother liquor ammonium chloride to lead sulfate in the lead slime to be treated is 2-3: 1, wherein the mass fraction of the mother liquor ammonium chloride is 5-20%.
Further, in the 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 step S3, before mixing and stirring the ammonium sulfate solution and the calcium hydroxide, the method further includes the following steps:
step a: sequentially adding polymeric ferric sulfate and polyacrylamide into the ammonium sulfate solution obtained in the step S2, stirring at normal temperature for 5-30 min, and filtering and separating to obtain purified solid and purified filtrate;
step b: detecting the content of lead ions in the purified filtrate;
if the lead ion content of the purified filtrate is less than or equal to a threshold value (for example, 20ppm), judging that the purification of the ammonium sulfate solution obtained in the step S2 is completed, and using 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 the threshold value (e.g., 20ppm), then step a is repeated until the lead ion content of the purge filtrate is less than or equal to the threshold value.
Further, the polymeric ferric sulfate accounts for 0.01-0.1% of the mass of the ammonium sulfate solution, and the polyacrylamide accounts for 0.1-0.5% of the mass of the ammonium sulfate solution.
Further, the polymeric ferric sulfate is added in multiple 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 multiple 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 step S3, the molar ratio of calcium hydroxide to ammonium sulfate is 1 to 1.1: 1.
further, in the 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 step S4, the reaction temperature is 20 to 60 ℃ (e.g., 20 ℃, 31 ℃, 44 ℃, 56 ℃ and 60 ℃) and the reaction time 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 can realize at least one of the following beneficial effects:
a) according to the recovery method of the acid leaching lead mud, mother liquor ammonium chloride is used as a desulfurizer, and the desulfurization reaction of lead sulfate in the acid leaching lead 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 plaster obtained by desulfurization are sequentially carried out. In the recycling process, the consumable is basically only calcium hydroxide, and the price of the calcium hydroxide is far lower than that of sodium hydroxide, so that the desulfurization cost of the acid leaching lead mud can be greatly reduced, and the recycling cost of the lead-acid storage battery is greatly reduced.
b) According to the method for recovering the acid leaching lead mud, no by-product is generated basically in the process of recovering and utilizing the acid leaching lead mud, the by-product is not required to be treated, and therefore the whole process of recovering and utilizing can be effectively simplified.
c) According to the recovery method of the acid leaching lead 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, and the quality of generated gypsum is influenced by the existence of 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 amount of macromolecular complexes and hydrophobic hydroxide polymers and has a good adsorption effect, so that the impurities in the ammonium sulfate solution can be adsorbed, and meanwhile, the polymeric ferric sulfate has a large floc surface area, a high surface energy, a compact structure, a certain strength and a large adsorption amount of the impurities; then, adopt polyacrylamide to carry out further purification to the ammonium sulfate solution after polyferric sulfate purifies, polyacrylamide has good flocculation nature, can reduce the frictional resistance between the liquid for polyferric sulfate's wadding can further grow up, thereby the follow-up separation of being convenient for.
d) In the recovery method of the acid leaching lead mud, at the initial stage of adding polymeric ferric sulfate, the ferric sulfate solution obtained in the step S2 contains more impurities, and the part of polymeric ferric sulfate added first can adsorb most of the impurities and is basically close to the state of adsorption saturation; the subsequent added polymeric ferric sulfate can further adsorb impurities among floccules formed by the previously added polymeric ferric sulfate, thereby playing a role in improving the purification degree.
e) According to the recovery method of the acid leaching lead mud, the polyacrylamide added for the first time can be wrapped outside the flocculating group of the polyferric sulfate to increase the volume of the flocculating group of the polyferric sulfate, and the polyacrylamide added for the second time can be wrapped outside the polyacrylamide added for the first time to further increase the polyferric sulfate, and so on, so that the subsequent separation is further promoted, and the influence of the addition of the polyferric 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 will be realized and attained by the structure particularly pointed out in the written description and drawings.
Drawings
The drawings are only for purposes of illustrating the particular invention and are not to be construed as limiting the invention, wherein like reference numerals are used to designate like parts throughout the figures.
Fig. 1 is a flow chart of the method for recovering the acid leaching lead slime provided by the invention.
Detailed Description
The preferred invention will now be described in detail with reference to the accompanying drawings, which form a part hereof, and which together with the description serve to explain the principles of the invention.
The invention provides a recovery method of lead slime of stranguria acid, which comprises the steps of taking mother liquor ammonium chloride as a desulfurizer to carry out desulfurization reaction on lead slime to be treated, carrying out regeneration reaction on ammonium sulfate solution obtained by desulfurization and calcium hydroxide, reacting ammonia water obtained by regeneration and lead plaster (lead chloride) obtained by desulfurization to obtain lead oxide lead plaster and regenerated ammonium chloride, wherein the lead oxide lead plaster is used for a plaster combining process of a battery, and the regenerated ammonium chloride is taken as the mother liquor ammonium chloride, so that the recovery of the lead slime of stranguria acid is completed.
Note that both the mother liquor ammonium chloride and the regenerated ammonium chloride are ammonium chloride, and the "mother liquor" and "regenerated" are only for distinguishing ammonium chloride in different steps.
Compared with the prior art, the recovery method of the acid leaching lead mud adopts the mother liquor ammonium chloride as a desulfurizer, and sequentially carries out the desulfurization reaction of lead sulfate in the acid leaching lead 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 plaster obtained by desulfurization, so that the lead sulfate can be converted into lead plaster oxide for the paste mixing process of the battery, the mother liquor ammonium chloride is reacted and recycled 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 acid leaching lead mud and the ammonium chloride. In the recycling process, the consumable is basically only calcium hydroxide, and the price of the calcium hydroxide is far lower than that of sodium hydroxide, so that the desulfurization cost of the acid leaching lead mud can be greatly reduced, and the recycling cost of the lead-acid storage battery is greatly reduced.
Meanwhile, in the recycling process of the acid leaching lead mud, byproducts are basically not generated, and the byproducts are not required to be treated, so that the whole recycling process can be effectively simplified.
Specifically, the recovery method of the acid leaching lead slime comprises the following steps:
step S1: carrying out filter pressing separation on the acid leaching lead slime by using a filter press to obtain lead slime to be treated and filtrate, and conveying the obtained filter pressing lead slime to a reaction kettle;
step S2: mixing, shearing and stirring mother liquor ammonium chloride and lead slime to be treated to perform desulfurization reaction, and performing filter pressing and separation to obtain desulfurized lead slime and an ammonium sulfate solution;
the reaction takes place as follows:
PbSO4+2NH4Cl→PbCl2+(NH4)2SO4
step S3: mixing and stirring an 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: and mixing and stirring the regenerated ammonia water and the desulfurized lead plaster for reaction, and carrying out solid-liquid separation to obtain lead oxide lead plaster and regenerated ammonium chloride, thereby completing the recovery of the acid leaching lead slime.
In order to determine the lead sulfate content in the filter-pressing lead slime so as to accurately add corresponding sodium chloride, the method further comprises the following steps after the step S1 and before the step S2:
and detecting the content of lead sulfate in the lead mud to be treated obtained by filter pressing separation.
Specifically, the detection includes the following steps:
taking part of lead slime to be treated (2 +/-0.2 g) as a detection sample, putting the detection sample into an erlenmeyer flask, adding diluted nitric acid (the mass ratio of the diluted nitric acid to the lead slime to be treated is 1: 7-8, 15 +/-0.5 ml) and heating to boil, filtering (for example, natural filtering) to obtain a primary filtrate and a primary filter residue, carrying out primary washing on the primary filter residue with water (for example, pure water) to lead-free ions, transferring the primary filter residue and the filter paper into the erlenmeyer flask, adding 80-100 ml (for example, 100ml) of 20% ammonium acetate solution and heating to boil for 3-6 min (for example, 5min), cooling and filtering to obtain a secondary filtrate and a secondary filter residue, carrying out secondary washing on the secondary filter residue with water (for example, pure water) to lead-free ions, mixing the washing solution of the primary washing, the washing solution of the secondary washing, the primary filtrate and the secondary filtrate, adding 9-10.5 ml (for example, 10ml) of 20% hexamethinetetrammonium and 2-, titrating by using 0.1mol/l EDTA, calculating the mass of lead sulfate in the detection sample, and calculating the mass of lead sulfate in the lead mud leached by acid according to the mass ratio of the detection sample to the lead mud to be detected.
The diluted nitric acid is obtained by diluting concentrated nitric acid and water (for example, pure water) at a volume ratio of 1: 3.5 to 4.5 (e.g., 1: 4).
Also, the above two washes to lead-free ions are judged by the following method: and (4) detecting the washing liquid by using 20% dilute sulfuric acid, and if no white precipitate is separated out in the washing liquid, indicating that the washing liquid is washed to be free of lead ions.
Considering that the main component of the filtrate generated in the filter-pressing separation process is dilute sulfuric acid, and dilute sulfuric acid needs to be adopted for acid leaching in the acid leaching process of the lead-acid storage battery, in order to realize the recycling of the obtained filtrate and improve the overall value of the recovery method of the acid leaching lead mud, in the step S1, the obtained filtrate is used for 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, in the step S2, the mass ratio of ammonium chloride in the mother liquor ammonium chloride to lead sulfate in the lead slime to be treated is 2-3: 1, wherein the mass fraction of the mother liquor ammonium chloride is 5-20%.
In order to control the reaction rate of the desulfurization reaction and ensure the desulfurization effect of the lead slime to be treated, in the 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 vigorous 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 within 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 the impurities in the mother liquor, in the step S3, before mixing and stirring the ammonium sulfate solution and the calcium hydroxide, the method 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 at normal temperature for 5-30 min, and filtering and separating to obtain purified solid and purified filtrate;
step b: detecting the content of lead ions in the purified filtrate;
if the lead ion content of the purified filtrate is less than or equal to a threshold value (for example, 20ppm), judging that the purification of the ammonium sulfate solution obtained in the step S2 is completed, and using 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 the threshold value (e.g., 20ppm), then step a is repeated until the lead ion content of the purge filtrate is less than or equal to the threshold value.
The ammonium sulfate solution obtained in the step S2 is purified by the above method, because impurities, such as metal impurities (antimony, barium, and residual lead and iron dissolved in the mother solution), may exist in the ammonium sulfate solution obtained in the step S2, and the existence of the impurities may affect the quality of gypsum produced, firstly, the ammonium sulfate solution obtained in the step S2 is purified by polyferric sulfate, and in the ammonium sulfate solution obtained in the step S2, the polyferric sulfate provides a large amount of macromolecular complexes and hydrophobic hydroxide polymers, and has a good adsorption effect, so that the impurities in the ammonium sulfate solution can be adsorbed, and meanwhile, the polyferric sulfate has a large floc surface area, a high surface energy, a compact structure, a certain strength, and a large adsorption amount of the impurities; then, adopt polyacrylamide to carry out further purification to the ammonium sulfate solution after polyferric sulfate purifies, polyacrylamide has good flocculation nature, can reduce the frictional resistance between the liquid for polyferric sulfate's wadding can further grow up, thereby the follow-up separation of being convenient for.
In order to ensure the purification effect of the polyferric sulfate and the polyacrylamide on the ammonium sulfate solution, the mass percentage of the polyferric sulfate in the ammonium sulfate solution is 0.01-0.1%, and the mass percentage of the polyacrylamide in the ammonium sulfate solution is 0.1-0.5%.
For the adding mode of the polymeric ferric sulfate, illustratively, the polymeric ferric sulfate is added in a plurality of times, and the adding amount of each time is gradually reduced, for example, the polymeric ferric sulfate is added in three times, the first adding amount is 50% of the total amount of the polymeric ferric sulfate, the second adding amount is 30% of the total amount of the polymeric ferric sulfate, and the third adding amount is 20% of the total amount of the polymeric ferric sulfate. This is because, in the initial stage of the addition of the polymeric ferric sulfate, the iron sulfate solution obtained in step S2 contains many impurities, and the portion of the polymeric ferric sulfate added first can adsorb most of the impurities and is substantially close to the state of adsorption saturation; the subsequent added polymeric ferric sulfate can further adsorb impurities among floccules formed by the previously added polymeric ferric sulfate, thereby playing a role in improving the purification degree.
Similarly, for the manner of adding polyacrylamide, illustratively, polyacrylamide is added in multiple portions, and the addition amount of each portion is gradually decreased, for example, polyacrylamide is added in three portions, the first portion is 50% of the total amount of polyacrylamide, the second portion is 30% of the total amount of polyacrylamide, and the third portion is 20% of the total amount of polyacrylamide. The polyacrylamide added for the first time can be wrapped outside the polyferric sulfate floc to increase the volume of the polyferric sulfate floc, and the polyacrylamide added for the second time can be wrapped outside the polyacrylamide added for the first time to further increase the polyferric sulfate, and so on, thereby further promoting the subsequent separation and reducing the influence of the addition of the polyferric sulfate and the polyacrylamide on the ammonium sulfate solution.
In order to ensure the regeneration effect of the ammonium sulfate solution in the step S3, in the step S3, the molar ratio of calcium hydroxide to ammonium sulfate is 1 to 1.1: 1. that is, the calcium hydroxide is added in excess relative to the ammonium sulfate, which enables substantially all of the ammonium sulfate in the ammonium sulfate solution to be converted to gypsum and aqueous ammonia.
In order to control the reaction rate of the regeneration reaction and ensure the regeneration effect of the ammonium sulfate solution, in the 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 violent 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 on the basis of ensuring the sufficient reaction of the regeneration reaction.
Similarly, in order to control the reaction rate of the reaction in step S4 and ensure the sufficiency of the regenerated ammonia water and the desulfurized lead paste, 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) in step S4. This is because limiting the reaction temperature of the reaction in step S4 to the above range can suitably increase the reaction rate of the reaction and ensure vigorous progress of the reaction, thereby improving the reaction safety of the reaction; the reaction time in the reaction in step S4 is limited to the above range, and the reaction efficiency can be suitably improved and the reaction time can be reduced while ensuring a sufficient reaction.
Example one
The embodiment provides a method for recovering leached acid lead mud, which comprises the following steps:
step A: carrying out filter pressing separation on the acid leaching lead slime by using a filter press to obtain lead slime to be treated and filtrate, using the obtained filtrate for the acid leaching process of the lead-acid storage battery, and conveying the obtained filter pressing lead slime to a reaction kettle;
and B: taking 2g of lead slime to be treated as a detection sample, putting 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 the first time till lead-free ions, transferring the primary filter residue and filter paper into the conical flask together, adding 100ml of 20% ammonium acetate solution, heating to boil for 5min, cooling and filtering to obtain secondary filtrate and secondary filter residue, washing the secondary filter residue with pure water for the second time till lead-free ions, mixing the washing solution of the primary washing, the washing solution of the secondary washing, the primary filtrate and the secondary filtrate, adding 10ml of 20% hexamethylenetetramine and 2-5 drops of xylenol orange, titrating with 0.1mol/l of EDTA, calculating the quality of lead sulfate in the detection sample, calculating the mass of lead sulfate in the acid leaching lead slime according to the mass ratio of the detection sample to the lead slime to be detected;
and C: according to the mass ratio of 2: 1, mixing, shearing and stirring mother liquor ammonium chloride and lead slime to be treated to perform desulfurization reaction at the temperature of 20 ℃ for 1.5h, and performing filter pressing separation to obtain desulfurized lead slime and an 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 purified solid and 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 finished;
step F: according to the molar ratio of calcium hydroxide to ammonium sulfate of 1: 1, mixing and stirring the purified ammonium sulfate solution and calcium hydroxide for regeneration reaction at the reaction temperature of 25 ℃ for 2h, and carrying out solid-liquid separation to obtain high-purity gypsum and ammonia water;
step E: and mixing and stirring the regenerated ammonia water and the desulfurized lead plaster for reaction at the reaction temperature of 30 ℃ for 3h, and carrying out solid-liquid separation to obtain lead oxide lead plaster and regenerated ammonium chloride, wherein the lead oxide lead plaster is used for a plaster combining process of a battery, and the regenerated ammonium chloride is used as mother liquor ammonium chloride, so that the recovery of the acid leaching lead mud is completed.
Example two
The embodiment provides a method for recovering leached acid lead mud, which comprises the following steps:
step A: carrying out filter pressing separation on the acid leaching lead slime by using a filter press to obtain lead slime to be treated and filtrate, using the obtained filtrate for the acid leaching process of the lead-acid storage battery, and conveying the obtained filter pressing lead slime to a reaction kettle;
and B: taking 2g of lead slime to be treated as a detection sample, putting 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 the first time till lead-free ions, transferring the primary filter residue and filter paper into the conical flask together, adding 95ml of 20% ammonium acetate solution, heating to boil for 3min, cooling and filtering to obtain secondary filtrate and secondary filter residue, washing the secondary filter residue with pure water for the second time till lead-free ions, mixing the washing solution of the primary washing, the washing solution of the secondary washing, the primary filtrate and the secondary filtrate, adding 9ml of 20% hexamethylenetetramine and 2-5 drops of xylenol orange, titrating with 0.1mol/l of EDTA, and calculating the quality of lead sulfate in the detection sample, calculating the mass of lead sulfate in the acid leaching lead slime according to the mass ratio of the detection sample to the lead slime to be detected;
and C: according to the mass ratio of 2.5: 1, mixing, shearing and stirring mother liquor ammonium chloride and lead slime to be treated to perform desulfurization reaction at the temperature of 45 ℃ for 2.5 hours, and performing filter pressing separation to obtain desulfurized lead slime and an 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 purified solid and 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 finished;
step F: according to the molar ratio of calcium hydroxide to ammonium sulfate of 1: 1, mixing and stirring the purified ammonium sulfate solution and calcium hydroxide for regeneration reaction at the reaction temperature of 20 ℃ for 5 hours for solid-liquid separation to obtain high-purity gypsum and ammonia water;
step E: and mixing and stirring the regenerated ammonia water and the desulfurized lead plaster for reaction at the reaction temperature of 60 ℃ for 1h, carrying out solid-liquid separation to obtain lead oxide lead plaster and regenerated ammonium chloride, wherein the lead oxide lead plaster is used for a plaster combining process of a battery, and the regenerated ammonium chloride is used as mother liquor ammonium chloride, so that the recovery of the acid leaching lead mud is completed.
EXAMPLE III
The embodiment provides a method for recovering leached acid lead mud, which comprises the following steps:
step A: carrying out filter pressing separation on the acid leaching lead slime by using a filter press to obtain lead slime to be treated and filtrate, using the obtained filtrate for the acid leaching process of the lead-acid storage battery, and conveying the obtained filter pressing lead slime to a reaction kettle;
and B: taking 2g of lead slime to be treated as a detection sample, putting 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 the first time till lead-free ions, transferring the primary filter residue and filter paper into the conical flask together, adding 97ml of 20% ammonium acetate solution, heating to boil for 3min, cooling and filtering to obtain secondary filtrate and secondary filter residue, washing the secondary filter residue with pure water for the second time till lead-free ions, mixing the washing solution of the primary washing, the washing solution of the secondary washing, the primary filtrate and the secondary filtrate, adding 10ml of 20% hexamethylenetetramine and 2-5 drops of xylenol orange, titrating with 0.1mol/l of EDTA, calculating the quality of lead sulfate in the detection sample, calculating the mass of lead sulfate in the acid leaching lead slime according to the mass ratio of the detection sample to the lead slime to be detected;
and C: according to the mass ratio of 2: 1, mixing, shearing and stirring mother liquor ammonium chloride and lead slime to be treated to perform desulfurization reaction at the reaction temperature of 80 ℃ for 3 hours, and performing filter pressing separation to obtain desulfurized lead slime and an 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 purified solid and purified filtrate;
step E: d, 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, and purifying the filtrate twice until the lead ion content is less than 20ppm, so that the ammonium sulfate solution is purified;
step F: according to the molar ratio of calcium hydroxide to ammonium sulfate of 1.03: 1, mixing and stirring the purified ammonium sulfate solution and calcium hydroxide for regeneration reaction at the reaction temperature of 35 ℃ for 3h, and carrying out solid-liquid separation to obtain high-purity gypsum and ammonia water;
step E: and mixing and stirring the regenerated ammonia water and the desulfurized lead plaster for reaction at the reaction temperature of 59 ℃ for 2h, and carrying out solid-liquid separation to obtain lead oxide lead plaster and regenerated ammonium chloride, wherein the lead oxide lead plaster is used for a plaster combining process of a battery, and the regenerated ammonium chloride is used as mother liquor ammonium chloride, so that the recovery of the acid leaching lead mud is completed.
Example four
The embodiment provides a method for recovering leached acid lead mud, which comprises the following steps:
step A: carrying out filter pressing separation on the acid leaching lead slime by using a filter press to obtain lead slime to be treated and filtrate, using the obtained filtrate for the acid leaching process of the lead-acid storage battery, and conveying the obtained filter pressing lead slime to a reaction kettle;
and B: taking 2g of lead slime to be treated as a detection sample, putting 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 the first time till lead-free ions, transferring the primary filter residue and the filter paper into the conical flask together, adding 75ml of 20% ammonium acetate solution, heating to boil for 6min, cooling and filtering to obtain secondary filtrate and secondary filter residue, washing the secondary filter residue with pure water for the second time till lead-free ions, combining the washing solution of the primary washing, the washing solution of the secondary washing, 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 of EDTA, calculating the quality of lead sulfate in the detection sample, calculating the mass of lead sulfate in the acid leaching lead slime according to the mass ratio of the detection sample to the lead slime to be detected;
and C: according to the mass ratio of 3:1, mixing, shearing and stirring mother liquor ammonium chloride and lead slime to be treated to perform desulfurization reaction at the temperature of 70 ℃ for 2 hours, and performing filter pressing separation to obtain desulfurized lead slime and an ammonium sulfate solution;
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 purified solid and 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 finished;
step F: according to the molar ratio of calcium hydroxide to ammonium sulfate of 1.1: 1, mixing and stirring the purified ammonium sulfate solution and calcium hydroxide for regeneration reaction at 40 ℃ for 5h to obtain high-purity gypsum and ammonia water;
step E: and mixing and stirring the regenerated ammonia water and the desulfurized lead plaster for reaction at the reaction temperature of 20 ℃ for 1h, and carrying out solid-liquid separation to obtain lead oxide lead plaster and regenerated ammonium chloride, wherein the lead oxide lead plaster is used for a plaster combining process of a battery, and the regenerated ammonium chloride is used as mother liquor ammonium chloride, so that the recovery of the acid leaching lead mud is completed.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.
Claims (10)
1. A recovery method of lead slime of acid leaching is characterized in that mother liquor ammonium chloride is used as a desulfurizer to carry out desulfurization reaction on lead slime to be treated, ammonium sulfate solution obtained by desulfurization carries out regeneration reaction with calcium hydroxide, and ammonia water obtained by regeneration reacts with lead plaster obtained by desulfurization to obtain lead oxide lead plaster and regenerated ammonium chloride, so that the recovery of the lead slime of acid leaching is completed.
2. The method for recovering the lead acid leaching mud as claimed in claim 1, wherein the lead oxide lead paste is used in a paste mixing process of a battery, and the regenerated ammonium chloride is used as a mother liquor ammonium chloride.
3. The method for recovering the lead drenching mud as claimed in claims 1 and 2, which is characterized by comprising the following steps:
step S1: carrying out filter pressing separation on the acid leaching lead mud 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 to perform desulfurization reaction, and performing filter pressing and separation to obtain desulfurized lead slime and an ammonium sulfate solution;
step S3: mixing and stirring an ammonium sulfate solution and calcium hydroxide for regeneration reaction, and carrying out solid-liquid separation to obtain gypsum and ammonia water;
step S4: and mixing and stirring the regenerated ammonia water and the desulfurized lead plaster for reaction, and carrying out solid-liquid separation to obtain lead oxide lead plaster and regenerated ammonium chloride, thereby completing the recovery of the acid leaching lead slime.
4. The method for recovering the lead acid leaching mud as claimed in claim 3, wherein after the step S1 and before the step S2, the method further comprises the following steps:
and detecting the content of lead sulfate in the lead mud to be treated obtained by filter pressing separation.
5. The method for recovering the lead drenching acid mud as claimed in claim 4, wherein the detection comprises the following steps:
taking part of lead slime to be treated as a detection sample, adding diluted nitric acid into the detection sample, heating to boil, filtering to obtain primary filter liquor and primary filter residue, washing the primary filter residue with water for the first time till lead ions are free, combining the primary filter residue with filter paper, adding an ammonium acetate solution, heating to boil, cooling and filtering to obtain secondary filter liquor and secondary filter residue, washing the secondary filter residue with water for the second time till lead ions are free, combining the washing liquor of the primary washing, the washing liquor of the secondary washing, the primary filter liquor and the secondary filter liquor, 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 slime according to the mass ratio of the detection sample to the lead slime to be detected.
6. The method for recovering the leached acid lead mud of claim 3, wherein in the step S1, the obtained filtrate is used for the acid leaching process of the lead-acid storage battery.
7. The method for recovering the lead sulfate leaching mud as claimed in claim 3, wherein in the step S2, the mass ratio of ammonium chloride in the mother solution ammonium chloride to lead sulfate in the lead sulfate leaching mud to be treated is 2-3: 1.
8. The method for recovering the lead acid leaching mud as claimed in claim 3, wherein the step S3 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, and filtering and separating to obtain purified solid and purified filtrate;
step b: detecting the content of lead ions in 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 finished, and taking the purified ammonium sulfate solution as the ammonium sulfate solution in the step S3;
and if the lead ion content of the purification filtrate is larger than the threshold value, repeating the step a until the lead ion content of the purification filtrate is smaller than or equal to the threshold value.
9. The method for recovering the lead acid leaching mud as claimed in claim 8, wherein the polymeric ferric sulfate accounts for 0.01-0.1% by mass of the ammonium sulfate solution, and the polyacrylamide accounts for 0.1-0.5% by mass of the ammonium sulfate solution.
10. The method for recovering the lead acid leaching mud as set forth in claim 3, wherein in the step S3, the molar ratio of calcium hydroxide to ammonium sulfate is 1-1.1: 1.
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| 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 |
| CN115350588A (en) * | 2022-08-16 | 2022-11-18 | 沈阳三聚凯特催化剂有限公司 | Method for recycling inactivated iron system desulfurizer |
| 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 |
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