CN117025951A - Method for recovering lead from sulfur-containing lead plaster - Google Patents
Method for recovering lead from sulfur-containing lead plaster Download PDFInfo
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- CN117025951A CN117025951A CN202310525085.4A CN202310525085A CN117025951A CN 117025951 A CN117025951 A CN 117025951A CN 202310525085 A CN202310525085 A CN 202310525085A CN 117025951 A CN117025951 A CN 117025951A
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- Prior art keywords
- lead
- pbso
- filtrate
- sulfur
- chiral
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- 238000000034 method Methods 0.000 title claims abstract description 84
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 239000011593 sulfur Substances 0.000 title claims abstract description 45
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 45
- 239000011505 plaster Substances 0.000 title abstract description 21
- 239000000706 filtrate Substances 0.000 claims abstract description 61
- 238000002386 leaching Methods 0.000 claims abstract description 59
- 239000002699 waste material Substances 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims abstract description 21
- 150000003839 salts Chemical class 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 238000004064 recycling Methods 0.000 claims abstract description 14
- -1 organic acid salt Chemical class 0.000 claims abstract description 12
- 238000001556 precipitation Methods 0.000 claims abstract description 10
- 230000032683 aging Effects 0.000 claims abstract description 8
- 239000012716 precipitator Substances 0.000 claims abstract description 5
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 claims description 67
- 239000007788 liquid Substances 0.000 claims description 44
- 229910000464 lead oxide Inorganic materials 0.000 claims description 36
- 239000002244 precipitate Substances 0.000 claims description 18
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 239000001569 carbon dioxide Substances 0.000 claims description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 6
- 230000003009 desulfurizing effect Effects 0.000 claims description 6
- HNDVDQJCIGZPNO-UHFFFAOYSA-N histidine Natural products OC(=O)C(N)CC1=CN=CN1 HNDVDQJCIGZPNO-UHFFFAOYSA-N 0.000 claims description 6
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 5
- 230000001172 regenerating effect Effects 0.000 claims description 5
- 239000001632 sodium acetate Substances 0.000 claims description 5
- 235000017281 sodium acetate Nutrition 0.000 claims description 5
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 239000001099 ammonium carbonate Substances 0.000 claims description 4
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 4
- 238000010668 complexation reaction Methods 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 claims description 4
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 3
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- JXKPEJDQGNYQSM-UHFFFAOYSA-M sodium propionate Chemical compound [Na+].CCC([O-])=O JXKPEJDQGNYQSM-UHFFFAOYSA-M 0.000 claims description 3
- 239000004324 sodium propionate Substances 0.000 claims description 3
- 229960003212 sodium propionate Drugs 0.000 claims description 3
- 235000010334 sodium propionate Nutrition 0.000 claims description 3
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 claims description 3
- 229910001866 strontium hydroxide Inorganic materials 0.000 claims description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- 239000004343 Calcium peroxide Substances 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- ZJRXSAYFZMGQFP-UHFFFAOYSA-N barium peroxide Chemical compound [Ba+2].[O-][O-] ZJRXSAYFZMGQFP-UHFFFAOYSA-N 0.000 claims description 2
- UCVMQZHZWWEPRC-UHFFFAOYSA-L barium(2+);hydrogen carbonate Chemical compound [Ba+2].OC([O-])=O.OC([O-])=O UCVMQZHZWWEPRC-UHFFFAOYSA-L 0.000 claims description 2
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 claims description 2
- NKWPZUCBCARRDP-UHFFFAOYSA-L calcium bicarbonate Chemical compound [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 claims description 2
- 229910000020 calcium bicarbonate Inorganic materials 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000292 calcium oxide Substances 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 2
- LHJQIRIGXXHNLA-UHFFFAOYSA-N calcium peroxide Chemical compound [Ca+2].[O-][O-] LHJQIRIGXXHNLA-UHFFFAOYSA-N 0.000 claims description 2
- 235000019402 calcium peroxide Nutrition 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 150000007942 carboxylates Chemical class 0.000 claims description 2
- 229940116318 copper carbonate Drugs 0.000 claims description 2
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- 125000000487 histidyl group Chemical group [H]N([H])C(C(=O)O*)C([H])([H])C1=C([H])N([H])C([H])=N1 0.000 claims description 2
- QWDJLDTYWNBUKE-UHFFFAOYSA-L magnesium bicarbonate Chemical compound [Mg+2].OC([O-])=O.OC([O-])=O QWDJLDTYWNBUKE-UHFFFAOYSA-L 0.000 claims description 2
- 239000002370 magnesium bicarbonate Substances 0.000 claims description 2
- 229910000022 magnesium bicarbonate Inorganic materials 0.000 claims description 2
- 235000014824 magnesium bicarbonate Nutrition 0.000 claims description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 2
- 239000001095 magnesium carbonate Substances 0.000 claims description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 2
- 235000014380 magnesium carbonate Nutrition 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- UHCGLDSRFKGERO-UHFFFAOYSA-N strontium peroxide Chemical compound [Sr+2].[O-][O-] UHCGLDSRFKGERO-UHFFFAOYSA-N 0.000 claims description 2
- 238000011084 recovery Methods 0.000 abstract description 38
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 35
- MFEVGQHCNVXMER-UHFFFAOYSA-L 1,3,2$l^{2}-dioxaplumbetan-4-one Chemical compound [Pb+2].[O-]C([O-])=O MFEVGQHCNVXMER-UHFFFAOYSA-L 0.000 description 19
- 229910000003 Lead carbonate Inorganic materials 0.000 description 18
- 239000000047 product Substances 0.000 description 18
- 239000002253 acid Substances 0.000 description 17
- 238000000926 separation method Methods 0.000 description 16
- 238000006477 desulfuration reaction Methods 0.000 description 15
- 230000023556 desulfurization Effects 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- 230000000694 effects Effects 0.000 description 7
- 238000003860 storage Methods 0.000 description 6
- 238000004448 titration Methods 0.000 description 6
- 239000012535 impurity Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 3
- 238000004070 electrodeposition Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 2
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- UBXAKNTVXQMEAG-UHFFFAOYSA-L strontium sulfate Chemical compound [Sr+2].[O-]S([O-])(=O)=O UBXAKNTVXQMEAG-UHFFFAOYSA-L 0.000 description 2
- 230000019635 sulfation Effects 0.000 description 2
- 238000005670 sulfation reaction Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 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
- 239000003929 acidic solution Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005363 electrowinning Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000003090 exacerbative effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 239000001999 grid alloy Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 150000002611 lead compounds Chemical group 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000009853 pyrometallurgy Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000010079 rubber tapping Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 229910052815 sulfur oxide Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 238000005303 weighing Methods 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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/008—Wet processes by an alkaline or ammoniacal leaching
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to the field of recycling of waste lead paste, and discloses a method for recycling lead from sulfur-containing lead paste. The method comprises the following steps: (1) Contacting sulfur-containing lead paste, chiral aminocarboxylic acid molecules and organic acid salt at pH 7-8.2 to obtain non-PbSO 4 Composition and PbSO 4 The components are leached simultaneously to obtain lead-containing filtrate and leaching residues; wherein the non-PbSO in the pre-contact material 4 Component and PbSO 4 The molar ratio of the components is 0.5-10:1, a step of; (2) And (3) carrying out an aging reaction on the lead-containing filtrate and a precipitator to obtain lead salt precipitation and regenerated filtrate. The method provided by the invention can realize direct and efficient leaching of the full-component lead in the sulfur-containing lead plaster by a one-step method, and has high lead recovery rate.
Description
Technical Field
The invention relates to the field of recycling of waste lead paste, in particular to a method for recycling lead from sulfur-containing lead paste.
Background
A typical waste lead acid battery consists essentially of four parts: including waste electrolyte, grid alloy, waste lead paste and polymeric materials. Among them, waste diachylon is the most complex active substance and is also the most difficult part to handle. The main components of the composition are PbSO respectively 4 (45～60wt％)、PbO 2 (35～40wt％)、PbO(10-15 wt%) and small amount of metallic lead (3-5 wt%) and in which PbSO 4 Is the most difficult component to handle, its decomposition temperature is up to 1000 ℃ or higher, and toxic sulfur oxides and lead-containing fumes are produced. In addition, the waste lead paste contains a small amount of impurities (about 1 wt%) such as iron, antimony, calcium, copper, magnesium, etc., and the presence of these impurities during the recovery process affects the electrochemical properties of the secondary lead compound, resulting in a decrease in the recycling performance. Therefore, it is necessary to develop an efficient, simple, and environmentally friendly recovery method of sulfur-containing lead paste.
At present, the recovery of waste lead plaster mainly comprises two methods of pyrometallurgy and wet recovery. The former preferably obtains the metal by high temperature operation, while the latter more emphasizes recovery of the metal from solution by use of special solvents under mild conditions. Wet recovery is also divided into electrodeposition recovery of metallic lead and direct recovery of lead oxide. In the process of recovering the metallic lead by electrodeposition, most leaching agents are fluoboric acid, fluosilicic acid, perchloric acid and other agents, so that the reaction equipment is corroded, and toxic gas is generated. And the raw material required by battery enterprises is mainly lead oxide, and the recovered product lead also needs to be subjected to a ball milling process to obtain the lead oxide required by the preparation of the lead-acid storage battery. Thus, in combination, the wet lead electrowinning process does not take into account the energy consumption of the electrodeposition process and the energy consumption of the refined lead to prepare lead oxide again, thereby causing a great deal of energy loss and additional carbon dioxide emission problems.
In the aspect of direct recovery of lead oxide, as the lead sulfate component is indissolvable in a general acidic solution, in the aspect of disposal of waste lead plaster containing lead sulfate and complex lead oxide components, the existing wet leaching process needs to perform pre-desulfurization (pre-desulfurization process) on the lead sulfate component to convert the lead sulfate component into lead oxide or lead carbonate which is easy to leach out, and then leaching the lead sulfate component. For example, CN104141045B reports that the waste lead paste is firstly subjected to pre-desulfurization and roasting treatment to obtain crude lead oxide, then is subjected to chiral molecule circulation leaching to obtain a lead complex, is carbonized to obtain lead carbonate precipitate, and is thermally decomposed to obtain lead oxide, so that the conversion of crude lead oxide into high-purity lead oxide is realized, and the basic flow is shown in fig. 1. CN107460339B reports that waste lead plaster is firstLead oxide is obtained through pre-desulfurization, complexation, dissociation and solid-liquid separation. A further idea is to uniformly convert the lead oxide and lead sulfate mixture into lead sulfate, and then to convert it. For example, CN107779603A reports the conversion of waste diachylon to PbSO by vulcanization 4 And then, the conjugate solution is adopted to realize the effective leaching of the lead sulfate, the lead sulfate solid is changed into a complex lead solution, and then, the lead oxide product is obtained through carbonization, roasting and other processes, so that the problems of incomplete desulfurization reaction and the like of the lead sulfate solid in the past are solved, and the leaching rate of lead sulfate of over 99.8 percent is realized. However, this process can produce more lead sulfate than the original lead paste during sulfation and promote the production of a large amount of low value sulfate (e.g., sodium sulfate or ammonium sulfate) byproducts, exacerbating the desulfurization costs of the subsequent desulfurization process. And the sulfation process consumes a large amount of sulfuric acid, and has high cost and strong corrosiveness. In addition, part of the lead oxide is coated in the lead sulfate particles, which also results in a decrease in lead recovery rate. CN106916952a reports that the composite leaching agent is adopted to realize the effective leaching of the lead sulfate-containing waste, lead sulfate solid is changed into complex lead solution, then the lead oxide product is obtained through carbonization, roasting and other processes, and finally the lead removal mother liquor is desulfurized to realize the recycling, but the method is difficult to realize the recovery of all component lead in the lead sulfate-containing waste lead paste with complex components such as lead sulfate, lead oxide and the like.
In summary, the pre-desulfurization process has the problems of low lead recovery rate, low product purity, complex process flow and the like. Therefore, there is a need to develop a method for recovering lead from sulfur-containing lead paste to improve lead recovery and product purity, and to have a simple process.
Disclosure of Invention
The invention aims to solve the problems of complex process flow, low lead recovery rate, low product purity and the like in the prior art, and provides a method for recovering lead from sulfur-containing lead plaster. The method provided by the invention can realize direct and efficient leaching of the full-component lead in the sulfur-containing lead plaster by a one-step method, and has high lead recovery rate.
In order to achieve the above object, the present invention provides, in one aspect, a method for recovering lead from a sulfur-containing lead paste, the method comprising the steps of:
(1) Contacting sulfur-containing lead paste, chiral aminocarboxylic acid molecules and organic acid salt at pH 7-8.2 to obtain non-PbSO 4 Composition and PbSO 4 The components are leached simultaneously to obtain lead-containing filtrate and leaching residues; wherein the non-PbSO in the pre-contact material 4 Component and PbSO 4 The molar ratio of the components is 0.5-10:1, a step of;
(2) And (3) carrying out an aging reaction on the lead-containing filtrate and a precipitator to obtain lead salt precipitation and regenerated filtrate.
Preferably, the pH of the contacting of step (1) is from 7.3 to 7.8.
Preferably, the non-PbSO in the pre-contact material 4 Component and PbSO 4 The molar ratio of the components is 3-10:1.
preferably, the temperature of the contacting in step (1) is in the range 50 to 180 ℃, preferably 80 to 160 ℃.
Through the technical scheme, the beneficial effects of the invention include:
in the method provided by the invention, sulfur-containing lead sulfate and chiral aminocarboxylic molecules and organic acid salt are contacted under specific pH, and the non-PbSO in the material before contact is regulated and controlled 4 Composition and PbSO 4 The leaching rate of lead sulfate can be greatly improved, and PbSO can be realized 4 Component and non-PbSO 4 The direct leaching of the components solves the problems of difficult treatment of lead sulfate, high desulfurization cost and low lead recovery rate in the traditional recovery process. The method has simple process, is easy to realize large-scale production, and has better development prospect.
The method provided by the invention omits a pre-desulfurization step, can effectively reduce lead loss, and fully realizes effective utilization of resources; the method provided by the invention can realize the recycling of the chiral aminocarboxylic molecules in the recovery process, reduce the consumption of chemical raw materials and the production of waste liquid to the greatest extent, and realize the closed-loop direct leaching and lead recovery process of the sulfur-containing lead plaster.
In the method provided by the invention, the rotating liquid film reactor is preferably adopted, so that the reaction time is greatly shortened, and the reaction efficiency is improved.
Drawings
FIG. 1 is a flow chart of a prior art process for recovering lead oxide from sulfur-containing lead paste;
FIG. 2 is a flow chart of the process of the present invention for recovering lead oxide from sulfur-containing lead paste;
FIG. 3 is a schematic diagram of a rotating liquid film reactor;
FIG. 4 is a schematic diagram of the operation of a rotating liquid film reactor;
FIG. 5 is an SEM (panel a) and XRD (panel b) of the original sulfur-containing lead paste of example 1;
fig. 6 is SEM images (panel a) and XRD (panel c) of lead carbonate recovered from sulfur-containing lead paste and SEM images (panel b) and XRD (panel d) of lead oxide product of example 1.
Description of the reference numerals
In the case of the view of figure 3,
1. a hopper; 2. A stator; 3. A rotor; 4. A pneumatic motor;
5. a circulation pipe; 6. A discharge pipe; 7. A body; a. Operating the device;
B. a power plant.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
In one aspect, the present invention provides a method for recovering lead from a sulfur-containing lead paste, the method comprising the steps of:
(1) Contacting sulfur-containing lead paste, chiral aminocarboxylic acid molecules and organic acid salt at pH 7-8.2 to obtain non-PbSO 4 Composition and PbSO 4 The components are leached simultaneously to obtain lead-containing filtrate and leaching residues; wherein the non-PbSO in the pre-contact material 4 Component and PbSO 4 Of componentsThe molar ratio is 0.5-10:1, a step of;
(2) And (3) carrying out an aging reaction on the lead-containing filtrate and a precipitator to obtain lead salt precipitation and regenerated filtrate.
The prior art CN104141045B (fig. 1) discloses that waste lead paste is firstly subjected to pre-desulfurization and roasting treatment to obtain crude lead oxide, then chiral molecule circulation leaching is carried out to obtain a lead complex, further carbonization is carried out to obtain lead carbonate precipitate, and lead carbonate is thermally decomposed to obtain lead oxide, so that the conversion of the crude lead oxide into high-purity lead oxide is realized. The inventor finds that part of lead can be taken away by the desulfurization mother liquor in the pre-desulfurization process in the research process, so that lead pollution and loss are caused, the lead recovery rate is reduced, the process flow is complex, and the cost is increased. The inventor further found in the research process that the lead sulfate-containing sulfur-containing lead paste is contacted with chiral aminocarboxylic acid molecules and organic acid salt, and the pH value of the solution is regulated to be 7-8.2 and the non-PbSO in the material before the contact is controlled 4 Composition and PbSO 4 The molar ratio of the lead sulfate is in the range of 0.5-10, the leaching rate of the lead sulfate can be greatly improved, and the non-PbSO is realized by a one-step method 4 Composition and PbSO 4 The common leaching of the components solves the problems of low leaching rate of lead sulfate, high pre-desulfurization cost and the like of the traditional waste lead plaster. And then the lead-containing filtrate and the precipitant are subjected to an aging reaction, and finally the lead carbonate product with the purity of 99.99 percent can be obtained. The method omits a pre-desulfurization treatment step, shortens the wet lead recovery process, can effectively reduce lead loss, improves lead recovery rate, and fully realizes effective utilization of resources.
According to the invention, the pH of the contact of step (1) is preferably between 7.3 and 7.8, for example between 7.3, 7.4, 7.5, 7.6, 7.7, 7.8, and any value in the range constituted by any two of these values. With this preferred embodiment, it is more advantageous to use a non-PbSO 4 Composition and PbSO 4 The components are leached simultaneously, and the leaching rate of lead sulfate is improved more favorably.
The invention leaches at higher temperature, breaks through the limitation of the prior reaction temperature, and can realize non-PbSO 4 Composition and PbSO 4 The components are leached out quickly, and the leaching rate is improved. Preferably, the step (1) of joiningThe contact temperature is 50-180deg.C, preferably 80-160deg.C, such as 50deg.C, 60deg.C, 70deg.C, 80deg.C, 90deg.C, 100deg.C, 110deg.C, 120deg.C, 130deg.C, 140deg.C, 150deg.C, 160deg.C, 170deg.C, 180deg.C, and any value in the range of any two of these values.
According to the invention, preferably the non-PbSO in the pre-contact material 4 Component and PbSO 4 The molar ratio of the components is 3-10:1, for example 3: 1. 3.5: 1. 4: 1. 4.5: 1.5: 1. 5.5: 1. 6: 1. 6.5: 1. 7: 1. 7.5: 1. 8: 1. 8.5: 1. 9: 1. 9.5: 1. 10:1, and any value in the range formed by any two of these values. The preferred embodiment is more advantageous for non-PbSO 4 Component and PbSO 4 The components are leached simultaneously.
non-PbSO in sulfur-containing lead paste 4 Component and PbSO 4 When the molar ratio of the components meets the conditions, no additional addition of non-PbSO is needed 4 Component (preferably with addition of PbO component) or PbSO 4 A component (C); non-PbSO in sulfur-containing lead paste 4 Component and PbSO 4 When the molar ratio of the components does not meet the above conditions, non-PbSO may be additionally added 4 Component (preferably with addition of PbO component) or PbSO 4 A component to satisfy the above conditions.
According to the present invention, preferably, in step (1), the non-PbSO 4 The composition includes PbO.
The PbO component in the pre-contact material is derived from the original PbO of the sulfur-containing lead plaster and the PbO which is optionally additionally added.
Preferably, the non-PbSO 4 The composition also comprises Pb and PbO 2 。
Pb and PbO during the contacting in the step (1) of the present invention 2 And reacting to generate PbO.
PbSO in the material before contact 4 The components are derived from the original PbSO of the sulfur-containing lead plaster 4 Optionally additionally added PbSO 4 。
To further realize non-PbSO 4 Component and PbSO 4 The simultaneous leaching of the components improves the leaching rate, preferablyThe chiral aminocarboxylic acid molecule is preferably used in a molar ratio to the organic acid salt of from 1 to 10:1, preferably from 1 to 6:1, for example 1:1,2:1,3:1,4:1,5:1,6:1,7:1,8:1,9:1, 10:1, and any value in the range of any two of these values.
According to the invention, preferably, the molar ratio of the amount of chiral aminocarboxylic acid molecules in step (1) to the theoretical amount required for lead complexation in the waste diachylon is between 1 and 8:1, preferably 2.5-5:1, for example 1: 1. 1.5: 1. 2: 1. 2.5: 1. 3: 1. 3.5: 1. 4: 1. 4.5: 1.5: 1. 5.5: 1. 6: 1. 6.5: 1. 7: 1. 7.5: 1. 8:1, and any value in the range formed by any two of these values.
According to the invention, the chiral aminocarboxylic acid molecule is preferably provided in the form of a solution having a concentration of from 20 to 180g/L, preferably from 80 to 160g/L.
Preferably, the solvent in the chiral aminocarboxylic acid molecule solution is an organic solvent and/or water, preferably water.
The chiral aminocarboxylic acid molecule has a wide selection range for the types of the chiral aminocarboxylic acid molecules, and can be various common chiral aminocarboxylic acid molecules. In order to optimise the complexation effect, preferably the chiral aminocarboxylic molecule is histidine.
The organic acid salt and the chiral aminocarboxylic acid molecule cooperate to be more beneficial to non-PbSO 4 Composition and PbSO 4 The components are leached simultaneously. Preferably, the organic acid salt is a C1-C5 carboxylate, preferably sodium acetate and/or sodium propionate.
In the invention, the main component of the leaching residue is insoluble impurities in the sulfur-containing lead plaster. Preferably, the leaching residue comprises at least one of Cu, ca, mg, bi, sb, sn and Fe.
Preferably, the leaching residue further comprises unreacted residual Pb or PbO 2 。
Preferably, the material obtained by the contact in the step (1) is subjected to solid-liquid separation to obtain lead-containing filtrate and leaching residues.
The solid-liquid separation is not particularly limited, and can be performed according to conventional technical means in the art, and the invention is not described herein.
The sulfur-containing lead paste is not particularly limited, and can be various sulfur-containing lead pastes commonly known in the art. Preferably, the sulfur-containing lead plaster is from waste lead acid storage batteries, lead mud for acid leaching generated in the preparation process of lead acid batteries or lead mud for plaster generated in the preparation process of lead acid batteries.
Preferably, the waste lead acid storage battery is crushed, screened and dried to obtain the sulfur-containing lead plaster.
Further preferably, the treatment process of the self-detaching waste lead acid storage battery comprises the following steps:
s1, washing the self-detaching waste lead acid storage battery until the washing liquid is neutral;
s2, crushing and screening the washed self-detaching waste lead acid storage battery, and then drying to obtain the sulfur-containing lead plaster.
The crushing and sieving are not particularly limited, and can be carried out according to the conventional technical means in the field, so as to obtain the sulfur-containing lead paste with the particle size of 50-200 meshes.
The specific conditions for the drying are not particularly limited and may be carried out by referring to a method conventional in the art. Preferably, the drying conditions include: the temperature is 80-180 ℃ and the time is 5-12h.
Preferably, lead mud subjected to acid leaching generated in the preparation process of the lead-acid battery or lead mud subjected to paste generated in the preparation process of the lead-acid battery is dried to obtain sulfur-containing lead paste.
The specific conditions for the drying are not particularly limited and may be carried out by referring to a method conventional in the art.
According to the present invention, preferably, the reaction conditions of step (2) include: the temperature is 10-90 ℃, preferably 40-65 ℃; the time is 1-120min, preferably 1-10min.
The invention has a wide selection range of the types of the precipitants, and can be a routine choice in the field. Preferably, the precipitant is at least one selected from carbon dioxide, ammonium carbonate, sodium carbonate, potassium carbonate, magnesium carbonate, copper carbonate, calcium carbonate, barium carbonate, ammonium bicarbonate, sodium bicarbonate, potassium bicarbonate, magnesium bicarbonate, calcium bicarbonate, barium bicarbonate, and urea.
Preferably, the amount of the precipitant is 0.5 to 2mol with respect to 1mol of soluble lead ions in the lead-containing filtrate.
Preferably, the materials obtained in the step (2) are subjected to solid-liquid separation to obtain lead salt precipitation and regeneration filtrate.
The solid-liquid separation is not particularly limited, and can be performed according to conventional technical means in the art, and the invention is not described herein.
The complexing auxiliary agent and the chiral aminocarboxylic acid molecule can realize conjugation effect, and the synergistic effect is favorable for rapid leaching of the lead sulfate component. According to the method, a complexing auxiliary agent can be added according to the requirement.
In the method, lead salt precipitate can be recovered as a product, and lead oxide obtained by lead salt precipitation treatment can also be recovered.
The method for obtaining lead oxide by the lead salt precipitation treatment is not particularly limited, and may be carried out by referring to a method conventional in the art. Preferably, the method further comprises: roasting the lead salt precipitate to obtain lead oxide.
Preferably, the roasting conditions include: the temperature is 350-700 ℃, preferably 400-550 ℃; the time is 5-180min, preferably 10-40min. The calcination is typically carried out in an air atmosphere, which may include a flowing atmosphere or a stationary atmosphere.
According to the invention, preferably, the method further comprises: and carrying out desulphation treatment on the regenerated filtrate to obtain sulfate precipitation and residual filtrate. With the adoption of the preferred embodiment, sulfate ions in the filtrate can be removed, and the recovery and the use of the residual filtrate are realized.
The conditions for the desulphation treatment are not particularly limited and may be carried out by referring to a method conventional in the art.
The invention has wider selection range of the types of the desulfurizing agents used for the desulphurizing acid radical treatment, and can be a routine choice in the field. Preferably, the desulfurizing agent used in the desulphation treatment is at least one selected from the group consisting of barium hydroxide, calcium hydroxide, strontium hydroxide, barium oxide, calcium oxide, strontium oxide, barium peroxide, calcium peroxide and strontium peroxide.
The desulfurizing agent of the invention can be directly used or can be used in the form of solution.
When the desulfurizing agent is used in the form of a solution, the concentration and the amount of the desulfurizing agent are not particularly limited, and may be appropriately selected according to the specific circumstances, as long as sulfate ions in the regenerated filtrate can be completely removed.
Preferably, the material obtained by desulphation treatment is subjected to solid-liquid separation to obtain sulfate precipitation and residual filtrate.
The solid-liquid separation is not particularly limited, and can be performed according to conventional technical means in the art, and the invention is not described herein.
According to the invention, the remaining filtrate obtained is preferably returned to step (1) for recycling to provide at least part of the chiral aminocarboxylic acid molecules. By adopting the preferred embodiment, the chiral aminocarboxylic acid molecule can be recycled in the recovery process, the consumption of chemical raw materials and the production of waste liquid are reduced to the greatest extent, and the closed-loop direct leaching and lead recovery process of the sulfur-containing lead plaster is realized.
The lead recovery of the present invention may be carried out in any reaction apparatus common in the art, and in order to further enhance the effect of lead recovery, it is preferable that the lead recovery is carried out in a rotating liquid film reactor.
The rotary liquid film reactor disclosed by the invention is a reactor with strengthening effect on solid-liquid reaction, has a narrow reaction space and high shearing speed, and can effectively disperse, homogenize and crush materials by relatively rotating a rotor and a stator at high speed, so that the effects of superfine crushing and emulsification of the materials are achieved, and the reaction energy consumption is greatly reduced while the higher leaching rate is ensured.
According to the present invention, preferably, the contacting of step (1), the reacting of step (2) and the regenerating filtrate desulphation treatment are performed in a rotating liquid film reactor, as shown in fig. 3, comprising: operating the equipment A and the power equipment B;
the operation equipment A comprises a stator 2 and a rotor 3, and is used for carrying out the contact in the step (1), the reaction in the step (2) and the desulphation treatment of the regenerated filtrate;
the power equipment B is used for providing power for the reactor.
According to the invention, the operating device a preferably also comprises a tapping pipe 6 for the outflow of the lead salt precipitate.
According to the invention, preferably, the discharge pipe 6 is provided with a circulating pipe 5 for recycling the residual filtrate. By adopting the preferred embodiment, the residual filtrate is provided with at least part of the chiral aminocarboxylic molecules, so that the chiral aminocarboxylic molecules can be recycled in the recovery process, the consumption of chemical raw materials and the production of waste liquid are reduced to the greatest extent, and the closed-loop direct leaching and lead recovery process of the sulfur-containing lead plaster is realized.
According to the present invention, preferably, the operating device a is fixedly installed above the body 7.
According to the invention, preferably, the power plant B comprises a pneumatic motor 4 for powering the reactor.
According to the invention, the rotating liquid film reactor preferably further comprises a hopper 1, said hopper 1 being fixedly mounted above the operating device a in the direction of flow for feeding.
According to the present invention, it is preferable that the nozzle of the circulation pipe 5 is disposed above the hopper 1.
The contacting in the step (1), the reacting in the step (2) and the regenerated filtrate desulphating treatment are carried out in a rotary liquid film reactor, and the time of each step can be greatly shortened.
Preferably, the contact time in step (1) is 10s-5min.
Preferably, the rotating liquid film reactor is pre-heated prior to use.
The method of the preheating treatment is not particularly limited, and may be carried out by a technique commonly used in the art.
It should be noted that the rotating liquid film reactor of the present invention generates heat during operation, so that the system temperature can be maintained without the need of heating the rotating liquid film reactor continuously during lead recovery.
According to a preferred embodiment of the present invention, as shown in fig. 3 and 4, the rotating liquid film reactor is preheated, and then sulfur-containing lead paste, chiral aminocarboxylic molecules and organic acid salt are respectively introduced into an operation device a fixedly installed above a machine body 7 from a hopper 1 of the rotating liquid film reactor, and the materials are fully contacted by relatively high-speed rotation of a rotor 3 and a stator 2 in the operation device a, and simultaneously the contact is accelerated, so that lead-containing filtrate and leaching residues are obtained, and the leaching residues are discharged through a discharge pipe 6. And (3) feeding the precipitant into an operation device A from a hopper 1 of the rotating liquid film reactor to react with the lead-containing filtrate to obtain lead salt precipitate and regenerated filtrate, wherein the lead salt precipitate is discharged through a discharge pipe 6. The precipitator enters the operation equipment A from the hopper 1 of the rotating liquid film reactor to react with regenerated filtrate to obtain sulfate precipitate and residual filtrate, the residual filtrate enters the operation equipment A from the hopper 1 of the rotating liquid film reactor through the circulating pipe 5 to be recycled, and the sulfate precipitate is discharged through the discharging pipe 6. The pneumatic motor 4 of the power plant B provides power for the rotating liquid membrane reactor during the whole process.
The present invention will be described in detail by examples.
In the following examples, the PbO leaching rate, pbSO 4 The leaching rate parameter was measured by chemical titration analysis (EDTA-2 Na titration).
Test example 1
For explaining the effect of the ratio of lead oxide to lead sulfate on the lead leaching effect
(1) Weighing a certain mass of lead oxide and lead sulfate in a 250mL three-neck flask according to the mol ratio of the lead oxide to the lead sulfate of 1:1, controlling the reaction temperature to be 100 ℃, then adding 100g/L histidine solution, starting stirring for 30min, and setting the stirring speed to be 600rpm;
(2) After the reaction, the reaction mixture was filtered, and the filtrate was collected for titration analysis, and the reaction results are shown in Table 1.
Test examples 2 to 6
According to the method of test example 1, except that PbO/PbSO was changed 4 Molar ratio. The reaction results are shown in Table 1.
TABLE 1
Note that: total lead leaching rate
Wherein m (g) is the mass sum of the weighed lead oxide and lead sulfate; omega 1 (%) is the total lead content therein; c (mol L) -1 ) The concentration of disodium ethylenediamine tetraacetate used for titration in the leaching solution; v (L) is the volume of disodium ethylenediamine tetraacetate used for titration in the leachate.
As can be seen from the results of Table 1, in test examples 1 to 5, by controlling the ratio of lead oxide to lead sulfate, the combined leaching of lead sulfate and lead oxide components was achieved, and the synergistic effect of the leaching process was achieved, as compared with test example 6.
Example 1
The process flow is shown in fig. 2.
As an experimental sample, 100g of waste lead paste of an automotive lead-acid battery was taken, in which 28.7wt% (mass fraction) of PbO (0.129 mol), 14.45wt% of PbSO 4 (0.048mol)，26.8wt％Pb(0.129mol)，14.45wt％PbO 2 (0.105 mol) with the balance being water.
(1) The waste sulfur-containing lead plaster, 2.5L of histidine water solution and 0.32mol of sodium acetate are placed in a rotary liquid film reactor which is preheated in advance. Starting, and reacting for 5min at 100 ℃. PbO leaching rate and PbSO 4 The leaching rate and specific reaction conditions of the step (1) are shown in table 3.
(2) After the reaction is finished, lead-containing filtrate and leaching residue are obtained through solid-liquid separation, and a proper amount of CO is introduced into the lead-containing filtrate at 60 DEG C 2 (1 mol for 1mol of soluble lead ions in the lead-containing filtrate, 1mol of carbon dioxide), aging for 2min, and performing solid-liquid separation to obtain lead salt precipitate (PbCO) 3 ) And regenerating the filtrate. The purity of the obtained lead carbonate product is 99.99 percent by the ICP method.
(3) And (2) reacting the regenerated filtrate with calcium hydroxide at 80 ℃ for 3min, standing for 5min at 80 ℃ and then carrying out solid-liquid separation to obtain residual filtrate and sulfate precipitate (calcium sulfate), and returning the residual filtrate to the step (1) for recycling.
(4) Precipitating the lead salt obtained in step (2) (PbCO 3 ) Roasting at 400 ℃ for 40min to obtain the PbO product, wherein the recovery rate of Pb is 99.08%.
An SEM (figure 5 a) and an XRD (figure 5 b) of the original sulfur-containing lead paste are given as examples, and as can be seen from the figure (5 a), the morphology of the sulfur-containing lead paste is irregular, no obvious characteristic exists, and the particle size distribution is uneven; it can be seen from FIG. 5b that the sulfur-containing lead paste is composed mainly of PbO 2 Pb, pbO and PbSO 4 Composition is prepared.
An SEM image (fig. 6 a) and an XRD image (fig. 6 c) of the recovered lead carbonate and an SEM image (fig. 6 b) and an XRD image (fig. 6 d) of the lead oxide product are exemplarily given, and it can be seen from fig. 6a that the morphology of the lead carbonate exhibits a regular long conical shape; from FIG. 6c, it can be seen that the intensity of the diffraction peak of lead carbonate is high, indicating that the crystallinity is good. It can be seen from fig. 6b that the lead oxide morphology retains part of the lead carbonate structure, in a stacked form, and fig. 6d demonstrates that the lead carbonate product obtained after the roasting treatment is lead oxide.
The impurity content of the resulting lead salt precipitate is exemplified as shown in table 2. Further proved that the purity of the lead carbonate is high.
TABLE 2
Example 2
The process flow is shown in fig. 2.
(1) Taking the same waste sulfur-containing lead plaster 1 public as in example 1Jin (wherein PbO: 1.284 mol, pbSO) 4 ：0.487mol，Pb：1.293mol，PbO 2 :1.049 mol) and 25L of histidine aqueous solution, 4.84mol of sodium acetate were placed in a rotating liquid film reactor preheated beforehand. Starting, when the reaction was carried out at 120℃for 5min. PbO leaching rate and PbSO 4 The leaching rate and specific reaction conditions of the step (1) are shown in table 3.
(2) After the reaction is finished, lead-containing filtrate and leaching residue are obtained through solid-liquid separation, and CO is introduced into the lead-containing filtrate at 60 DEG C 2 (1 mol for 1mol of soluble lead ions in the lead-containing filtrate, 1mol of carbon dioxide), aging for 2min, and performing solid-liquid separation to obtain lead salt precipitate (PbCO) 3 ) And regenerating the filtrate. The purity of the obtained lead carbonate product is 99.99 percent by the ICP method.
(3) And (2) reacting the regenerated filtrate with 0.05mol/L barium hydroxide solution at 80 ℃ for 3min, standing for 5min at 80 ℃ and then carrying out solid-liquid separation to obtain residual filtrate and sulfate precipitate (barium sulfate), and returning the residual filtrate to the step (1) for recycling.
(4) Precipitating the lead salt obtained in step (2) (PbCO 3 ) Roasting at 400 ℃ for 40min to obtain the PbO product. The recovery rate of Pb was 99.21%.
Example 3
The process flow is shown in fig. 2.
Taking 1 kg of waste sulfur-containing lead paste obtained from waste super-power batteries as an experimental sample, and performing EDTA titration analysis on the lead paste, wherein the lead paste contains 14.34wt% of PbO (0.6425 mol), 15.61wt% of Pb (0.7534 mol) and 31.1wt% of PbSO 4 (1.0255mol)、33.67wt％PbO 2 (1.4076 mol) the balance being water.
(1) The above waste sulfur-containing lead paste was placed in a preheated rotary liquid film reactor together with 25L of histidine aqueous solution, 7.53mol of sodium propionate, and 90gPbO (0.4032 mol) was added thereto. Starting, and reacting for 5min at 80 ℃. PbO leaching rate and PbSO 4 The leaching rate and specific reaction conditions of the step (1) are shown in table 3.
(2) After the reaction is finished, lead-containing filtrate and leaching residue are obtained through solid-liquid separation, and lead-containing filtration is carried out at 60 DEG CCO is introduced into the liquid 2 (1 mol for 1mol of soluble lead ions in the lead-containing filtrate, 1mol of carbon dioxide), aging for 2min, and performing solid-liquid separation to obtain lead salt precipitate (PbCO) 3 ) And regenerating the filtrate. The purity of the obtained lead carbonate product is 99.99% as determined by ICP method, and the specific impurity types and contents in the lead carbonate product are shown in Table 2.
(3) Reacting the regenerated filtrate with 0.05mol/L strontium hydroxide solution at 80 ℃ for 3min, standing for 5min at 80 ℃ and then carrying out solid-liquid separation to obtain residual filtrate and sulfate precipitate (strontium sulfate), and returning the residual filtrate to the step (1) for recycling.
(4) Precipitating the lead salt obtained in step (2) (PbCO 3 ) Roasting at 400 ℃ for 40min to obtain the PbO product. The recovery rate of Pb was 98.28%.
Example 4
The procedure of example 1 was followed, except that the contact temperature in step (1) was 60 ℃. The leaching rate of PbO is 91.14 percent, and the leaching rate of lead sulfate is 68.78 percent.
The purity of the obtained lead carbonate was 99.97%. The recovery rate of Pb was 62.06%.
Comparative example 1
The procedure of example 1 was followed, except that the pH in step (1) was 6.2. The leaching rate of PbO is 98.5 percent, and the leaching rate of lead sulfate is 40.1 percent.
The purity of the obtained lead carbonate was 99.97%. The recovery rate of Pb was 39.97%.
Comparative example 2
The procedure of example 1 was followed, except that sodium acetate was not added, the leaching rate of PbO was 95.4%, and the leaching rate of lead sulfate was 48.5%.
The purity of the obtained lead carbonate was 99.95%. The recovery rate of Pb was 45.8%.
TABLE 3 Table 3
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (10)
1. A method of recovering lead from sulfur-containing lead paste, the method comprising the steps of:
(1) Contacting sulfur-containing lead paste, chiral aminocarboxylic acid molecules and organic acid salt at pH 7-8.2 to obtain non-PbSO 4 Composition and PbSO 4 The components are leached simultaneously to obtain lead-containing filtrate and leaching residues; wherein the non-PbSO in the pre-contact material 4 Component and PbSO 4 The molar ratio of the components is 0.5-10:1, a step of;
(2) And (3) carrying out an aging reaction on the lead-containing filtrate and a precipitator to obtain lead salt precipitation and regenerated filtrate.
2. The method of claim 1, wherein,
the pH of the contacting of step (1) is 7.3-7.8;
preferably, the non-PbSO in the pre-contact material 4 Component and PbSO 4 The molar ratio of the components is 3-10:1.
3. the method of claim 1, wherein,
the temperature of the contact in the step (1) is 50-180 ℃, preferably 80-160 ℃;
preferably, the molar ratio of chiral aminocarboxylic acid molecule to organic acid salt is 1-10:1, preferably 1-6:1;
preferably, the molar ratio of the chiral aminocarboxylic acid molecule amount in the step (1) to the theoretical amount required for lead complexation in the waste lead paste is 1-8:1, preferably 2.5-5:1, a step of;
preferably, the chiral aminocarboxylic acid molecule is provided in the form of a solution having a concentration of from 20 to 180g/L, preferably from 80 to 160g/L;
preferably, the chiral aminocarboxylic acid molecule is histidine;
preferably, the organic acid salt is a C1-C5 carboxylate, preferably sodium acetate and/or sodium propionate.
4. The method of claim 1, wherein in step (1), the non-PbSO 4 The composition includes PbO.
5. The method according to any one of claims 1 to 4, wherein,
the reaction conditions of step (2) include: the temperature is 10-90 ℃, preferably 40-65 ℃; the time is 1-120min, preferably 1-10min;
preferably, the precipitant is at least one selected from carbon dioxide, ammonium carbonate, sodium carbonate, potassium carbonate, magnesium carbonate, copper carbonate, calcium carbonate, barium carbonate, ammonium bicarbonate, sodium bicarbonate, potassium bicarbonate, magnesium bicarbonate, calcium bicarbonate, barium bicarbonate, and urea.
6. The method according to any one of claims 1 to 5, wherein,
the method further comprises the steps of: roasting the lead salt precipitate to obtain lead oxide;
preferably, the roasting conditions include: the temperature is 350-700 ℃, preferably 400-550 ℃; the time is 5-180min, preferably 10-40min.
7. The method according to any one of claims 1 to 5, wherein,
the method further comprises the steps of: carrying out desulphation treatment on the regenerated filtrate to obtain sulfate precipitation and residual filtrate;
preferably, the desulfurizing agent used in the desulphation treatment is at least one selected from the group consisting of barium hydroxide, calcium hydroxide, strontium hydroxide, barium oxide, calcium oxide, strontium oxide, barium peroxide, calcium peroxide and strontium peroxide;
preferably, the remaining filtrate obtained is returned to step (1) for recycling to provide at least part of the chiral aminocarboxylic acid molecules.
8. The method of claim 7, wherein,
the contacting of step (1), the reacting of step (2), and the regenerating filtrate desulphation treatment are performed in a rotating liquid film reactor comprising: an operating device (A) and a power device (B);
the operating device (A) comprises a stator (2) and a rotor (3) for the contacting of step (1), the reaction of step (2) and the desulphation treatment of the regenerated filtrate;
the power plant (B) is used for powering the reactor.
9. The method of claim 8, wherein,
the operating device (A) also comprises a discharge pipe (6) for outflow of lead salt precipitate;
preferably, the discharging pipe (6) is provided with a circulating pipe (5) for recycling the residual filtrate;
preferably, the operating device (a) is fixedly mounted above the fuselage (7);
preferably, the power plant (B) comprises a pneumatic motor (4) for powering the reactor.
10. The method of claim 9, wherein,
the rotary liquid film reactor also comprises a hopper (1), wherein the hopper (1) is fixedly arranged above the operation equipment (A) along the material flow direction and is used for feeding;
preferably, the orifice of the circulating pipe (5) is arranged above the hopper (1).
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117737791A (en) * | 2024-02-21 | 2024-03-22 | 东北大学 | Method for preparing elemental lead from lead sulfate-containing waste |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117737791A (en) * | 2024-02-21 | 2024-03-22 | 东北大学 | Method for preparing elemental lead from lead sulfate-containing waste |
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