CN106048229B - A kind of method of lead-containing compounds low-temperature reduction melting - Google Patents
A kind of method of lead-containing compounds low-temperature reduction melting Download PDFInfo
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- CN106048229B CN106048229B CN201610501980.2A CN201610501980A CN106048229B CN 106048229 B CN106048229 B CN 106048229B CN 201610501980 A CN201610501980 A CN 201610501980A CN 106048229 B CN106048229 B CN 106048229B
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- 238000000034 method Methods 0.000 title claims abstract description 59
- 238000002844 melting Methods 0.000 title claims abstract description 45
- 230000008018 melting Effects 0.000 title claims abstract description 45
- 150000001875 compounds Chemical class 0.000 title claims abstract description 34
- 230000009467 reduction Effects 0.000 title claims abstract description 27
- 229920002472 Starch Polymers 0.000 claims abstract description 18
- 235000019698 starch Nutrition 0.000 claims abstract description 18
- 239000008107 starch Substances 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 14
- 238000000498 ball milling Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 5
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 claims description 18
- 239000010935 stainless steel Substances 0.000 claims description 9
- 229910001220 stainless steel Inorganic materials 0.000 claims description 9
- 229910000464 lead oxide Inorganic materials 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- RYZCLUQMCYZBJQ-UHFFFAOYSA-H lead(2+);dicarbonate;dihydroxide Chemical compound [OH-].[OH-].[Pb+2].[Pb+2].[Pb+2].[O-]C([O-])=O.[O-]C([O-])=O RYZCLUQMCYZBJQ-UHFFFAOYSA-H 0.000 claims description 4
- 229910021514 lead(II) hydroxide Inorganic materials 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000007499 fusion processing Methods 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- 244000017020 Ipomoea batatas Species 0.000 claims description 2
- 235000002678 Ipomoea batatas Nutrition 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims description 2
- 235000007164 Oryza sativa Nutrition 0.000 claims description 2
- 241000209140 Triticum Species 0.000 claims description 2
- 235000021307 Triticum Nutrition 0.000 claims description 2
- 240000008042 Zea mays Species 0.000 claims description 2
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 2
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 2
- 239000003034 coal gas Substances 0.000 claims description 2
- 235000005822 corn Nutrition 0.000 claims description 2
- 239000003345 natural gas Substances 0.000 claims description 2
- 229920001592 potato starch Polymers 0.000 claims description 2
- 235000009566 rice Nutrition 0.000 claims description 2
- 238000007670 refining Methods 0.000 abstract description 13
- 239000003638 chemical reducing agent Substances 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 230000005540 biological transmission Effects 0.000 abstract description 2
- 238000003723 Smelting Methods 0.000 description 29
- 230000008569 process Effects 0.000 description 27
- 239000002253 acid Substances 0.000 description 16
- 239000006071 cream Substances 0.000 description 16
- 229910052949 galena Inorganic materials 0.000 description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 8
- 238000004070 electrodeposition Methods 0.000 description 8
- 239000012141 concentrate Substances 0.000 description 7
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 6
- 239000000956 alloy Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 6
- 238000002386 leaching Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000003500 flue dust Substances 0.000 description 4
- YADSGOSSYOOKMP-UHFFFAOYSA-N lead dioxide Inorganic materials O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 4
- XCAUINMIESBTBL-UHFFFAOYSA-N lead(ii) sulfide Chemical compound [Pb]=S XCAUINMIESBTBL-UHFFFAOYSA-N 0.000 description 4
- 239000011505 plaster Substances 0.000 description 4
- 239000002893 slag Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 229910052924 anglesite Inorganic materials 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229940056932 lead sulfide Drugs 0.000 description 3
- 229910052981 lead sulfide Inorganic materials 0.000 description 3
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 3
- XMFOQHDPRMAJNU-UHFFFAOYSA-N lead(II,IV) oxide Inorganic materials O1[Pb]O[Pb]11O[Pb]O1 XMFOQHDPRMAJNU-UHFFFAOYSA-N 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 229910000679 solder Inorganic materials 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- KEQXNNJHMWSZHK-UHFFFAOYSA-L 1,3,2,4$l^{2}-dioxathiaplumbetane 2,2-dioxide Chemical compound [Pb+2].[O-]S([O-])(=O)=O KEQXNNJHMWSZHK-UHFFFAOYSA-L 0.000 description 2
- 229910003638 H2SiF6 Inorganic materials 0.000 description 2
- 229910004039 HBF4 Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 235000019504 cigarettes Nutrition 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 150000002611 lead compounds Chemical class 0.000 description 2
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 1
- 229910000897 Babbitt (metal) Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910000003 Lead carbonate Inorganic materials 0.000 description 1
- 229910017704 MH-Ni Inorganic materials 0.000 description 1
- 229910017739 MH—Ni Inorganic materials 0.000 description 1
- 229910001245 Sb alloy Inorganic materials 0.000 description 1
- 241001417490 Sillaginidae Species 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910052767 actinium Inorganic materials 0.000 description 1
- QQINRWTZWGJFDB-UHFFFAOYSA-N actinium atom Chemical compound [Ac] QQINRWTZWGJFDB-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 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
- 239000002140 antimony alloy Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical group 0.000 description 1
- 239000011365 complex material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- -1 have lead oxide Chemical class 0.000 description 1
- 229960002050 hydrofluoric acid Drugs 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JQJCSZOEVBFDKO-UHFFFAOYSA-N lead zinc Chemical compound [Zn].[Pb] JQJCSZOEVBFDKO-UHFFFAOYSA-N 0.000 description 1
- SMBGWMJTOOLQHN-UHFFFAOYSA-N lead;sulfuric acid Chemical compound [Pb].OS(O)(=O)=O SMBGWMJTOOLQHN-UHFFFAOYSA-N 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000009856 non-ferrous metallurgy Methods 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000009853 pyrometallurgy Methods 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229940100486 rice starch Drugs 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 150000004763 sulfides Chemical group 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- ZEFWRWWINDLIIV-UHFFFAOYSA-N tetrafluorosilane;dihydrofluoride Chemical compound F.F.F[Si](F)(F)F ZEFWRWWINDLIIV-UHFFFAOYSA-N 0.000 description 1
- DNYWZCXLKNTFFI-UHFFFAOYSA-N uranium Chemical compound [U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U] DNYWZCXLKNTFFI-UHFFFAOYSA-N 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000009858 zinc metallurgy 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
- 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
- C22B7/001—Dry 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
- C22B13/00—Obtaining lead
- C22B13/02—Obtaining lead by dry processes
- C22B13/025—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
- C22B5/00—General methods of reducing to metals
- C22B5/02—Dry methods smelting of sulfides or formation of mattes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- 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
A kind of method of lead-containing compounds low-temperature reduction melting, lead-containing compounds are added to ball milling mixing in ball mill simultaneously with starch, mixed material continuous conveying is heated to requiring that temperature carries out melting into the melting pot of indirectly heat, the lead bullion of output power transmission solution refining treatment again.The essence of the technical program is to realize the purpose of lead-containing compounds low-temperature reduction melting output lead bullion as reducing agent using starch under the conditions of indirectly heat.The direct yield of lead reaches more than 96.0%, and reduction melting temperature is reduced into 800~850 DEG C as reducing agent using starch, greatly reduces the energy consumption of lead-containing compounds low-temperature reduction melting.
Description
Technical field
The present invention relates to the fire of pyrometallurgical processes in nonferrous metallurgy field, the particularly melting of lead-containing compounds low-temperature reduction
Method metallurgical method.
Background technology
Lead is one of the IVth A races element, atomic number 82, atomic weight 207.21, density 11.34g/cm in the periodic table of elements
3,327.43 DEG C of fusing point, 1525 DEG C of boiling point.The physical property of lead is that hardness is small, density is big, fusing point is low, malleability is good, ductility is poor, right
Conductibility electrically and thermally is poor, high temperature is readily volatilized, fluidity of molten is big.The chemical property torpescence of lead, the table in humid air
Face generates PbO2Film, lose metallic luster and be changed into dark gray.The formation of oxide is raised when lead heats in atmosphere with temperature
Sequentially it is：PbO→Pb2O3→Pb3O4→PbO2, the high oxide of lead will be decomposed into when temperature is higher than 600 DEG C PbO and
O2, therefore PbO is oxide uniquely stable under high temperature.Lead is soluble in nitric acid（HNO3）, boron fluoric acid（HBF4）, silicofluoric acid
（H2SiF6）And acetic acid（CH3COOH）Deng, but when being acted under normal temperature with sulfuric acid and hydrochloric acid, due to Surface Creation PbSO4And PbCl2And
Suppress reaction no longer to carry out.The chemical valence of lead is mainly 0 ,+2 ,+4 valencys, and the sulfide of lead has vulcanized lead（PbS）, oxide is aerobic
Change lead（PbO）, brown lead oxide（PbO2）And lead orthoplumbate（Pb3O4）, important lead compound has ceruse（PbCO3）, hydrogen-oxygen
Change lead（Pb(OH)2）, lead sulfate（PbSO4）And lead chloride（PbCl2）.
It is primarily used to manufacture alloy based on the special physicochemical properties of lead.Corrosion resistant alloy is used for accumulator grid, electricity
Cable sheath, chemical industry equipment liner plate and pipeline etc., solder alloy are used for electronics industry, high-temperature solder, and battery alloy is used to produce electricity
Pond, bearing metal, mould alloy etc.；Lead is the product after radioactive element uranium, actinium and thorium division, can absorb radioactivity and penetrate
Line, it is widely used in the protective materials of X-ray machine and atomic energy apparatus.The compound of lead is mainly used in pigment, porcelain, glass and rubber
The industrial departments such as glue and medical department.Wherein lead-acid accumulator is most important consumer field, and it accounts for global total lead consumption
More than 80.0%.Although lead-acid accumulator weight energy ratio is less than MH-Ni batteries and Li-ion batteries, due to its is cost-effective,
Technology maturation and the advantages that having a safety feature, it is widely used in the every field of national economy, lead-acid accumulator usage amount accounts for entirely
More than the 70.0% of the ball secondary cell market share.China has become lead-acid accumulator manufacturing nation maximum in the world, country of consumption
And exported country, a large amount of uses of lead-acid accumulator will certainly produce a considerable amount of lead-acid accumulators so that waste and old lead acid stores
Battery has changed into most important lead regenerated resources（Lead-acid accumulator recovery technology present situation [J] such as Dai Shaozhen worlds are coloured
Metal, 2015,9,15-17.）.According to State Statistics Bureau and association of China Non-Ferrous Metals Industry data, China's essence in 2014
Refining lead yield reaches 421.8 ten thousand tons, and wherein reviver yield is 160.0 ten thousand tons, accounts for the 37.9% of annual lead yield, and have into one
Walk increased trend.
The smelting resource of lead mainly includes galena, lead oxide ore and secondary resource, because lead oxide ore amount is much smaller than
Galena, so the primary raw material of lead smelting industry is sulphide ore, main galena is galena（PbS）.Vulcanized lead
Raw ore leaded generally 0.4~9% by the leaded lead concentrate between 50~75% of beneficiation enrichment output, it is necessary to could enter smelting
Refining system.Other lead secondary resource is also that important lead smelts resource, is mainly closed including used and scrapped battery, lead mud, lead pipe, printing
Gold and plumber's solder etc..
The smelting process of lead includes pyrometallurgical smelting of lead and wet method refining lead, but commercial Application is entirely pyrometallurgical smelting of lead method.Fire
Method refining lead mainly includes direct smelting method, bake with agglomeration-three kinds of shaft smelting and direct lead smelting process（Peng Rong autumn lead zinc
Metallurgy [M] Beijing:Science Press, 2003.）.Direct smelting method includes two kinds of precipitation melting and smelting,
It is to make reducing agent with iron to precipitate melting, makes vulcanized lead that precipitation reaction occur in certain temperature and obtains metallic lead；Smelting is then
Part PbS in concentrate of lead sulfide ore is oxidized to PbO, is then allowed to react generation metallic lead with unoxidized PbS.Both refinings
There is the shortcomings of metal recovery rate is low, yield is small, working condition is poor in lead method, few producers use.Due to sintering
Roasting-blast furnace smelting process is once widely used in industrial production, i.e. concentrate of lead sulfide ore to the strong adaptability of raw material
By output agglomerate of baking with agglomeration, lead bullion is obtained subsequently into shaft smelting, by pyro-refining and electrorefining output
Electric lead.For simplification of flowsheet, improve production environment, raising heat utilization efficiency, metallargist explores concentrate of lead sulfide ore always
The method for directly refining lead, this method is the O that PbS is highly dispersed in melt or gas2Oxidation produces metallic lead and PbO, after
Person is with FeO and other component slag making fusing, final output lead bullion, high lead slag and containing SO2Flue gas.Successively it is applied to the side of industry
Method has：Oxygen bottom blowing smelting bath smelting process（QSL, SKS etc.）With base husband's C1-esteraseremmer-N smelting process of flash smelting etc..
Research method on wet method refining lead is a lot, mainly there is chloride leaching, amine aqueous solution leaching, ammonium sulfate dissolving and alkali
Property leach etc., but use wet method lead-smelting method currently without factory, reason is each method all without the operability of pyrometallurgical smelting of lead
By force, there is a small amount of application during the leaded complex materials of only a small number of factory processes.
Usual lead-containing compounds mainly have lead oxide, brown lead oxide, lead sulfate, ceruse and lead hydroxide etc., wherein containing
Lead compound main source has two aspects：Lead-acid accumulator disassemble after lead plaster and pyrometallurgical smelting of lead process cigarette ash.
The recycling process of lead-acid accumulator is separately recovered again after typically first disassembling（Height is pretty to wait waste and old lead acids to store
Battery crushing separation system research and discussion [J] batteries, 2013,50 (1), 3-7）, disassembling product has four kinds, when
Waste electrolyte, composition are sulfuric acid solution, generally send wastewater treatment；Second, grid, main component is lead-antimony alloy, is generally melted again
Cast alloy；Third, plastics, generally return to plastics producer and re-use；Fourth, scrap lead cream, main component is lead sulfate and lead oxygen
Compound, it is generally used for refining leady raw materialses, the weight of these four products accounts for 10-20%, 20-30%, 10- of battery gross weight respectively
15% and 35-50%.The composition of scrap lead cream is because cell production companies are different and scrap degree difference, each component content ripple
It is dynamic, respectively PbSO4(40-60%)、PbO2(25-35%), PbO (5-10%) and Pb (1-5%) and a small amount of Sb (0.5%).Due to useless
Contain substantial amounts of lead sulfate and a variety of oxides of lead in lead plaster, intractability is big, becomes lead-acid accumulator recovery
The bottleneck utilized.The processing of scrap lead cream is divided into thermal process and wet processing, and both techniques are generally all using cathode lead as target
Product, cut both ways, wherein thermal process is applied widely.
Thermal process is that scrap lead cream obtains lead bullion by reduction melting, then electrorefining output cathode lead, is had individually molten
Refining and the class of mixed smelting two.（Regeneration techniques present situation and progress [J] China YouSes are metallurgical before the lead-acid accumulators such as Li Weifeng,
2011, (6): 53-57.）, directly individually smelting process refer to scrap lead cream directly reverberatory furnace, blast furnace, rotary furnace, bottom convertor and
Reduction melting in the smelting furnaces such as side-blown converter, discharged after melting flue gas is scrubbed, there is the advantages of flow is short and obtain and extensively should
With, but the shortcomings of melting high energy consumption, high-temperature lead dust harzard and gas pollution control difficulty are big be present, generally believe that this is due to
In scrap lead cream caused by the presence of lead sulfate.Mixed smelting method is by melting after scrap lead cream and lead concentrate collocation, utilizes lead essence
The chemical reaction heat of ore deposit, make both synchronous melting output lead bullion.This method is applied widely in primary lead smeltery, surface
On solve requirement of the scrap lead cream fusion process to temperature and treating tail gas, but by impurity content low high-grade lead plaster and lead
Concentrate mixed smelting, the lead bullion of output is of poor quality, adds the difficulty of purification.The shortcomings that in order to overcome thermal process to handle, grind
Study carefully the wet processing process of staff development scrap lead cream, i.e. scrap lead cream passes through electrodeposition output negative electrode after Solid phase electrolysis or wet dissolution
Lead, mainly include Solid phase electrolysis technique, leaching-electrodeposition process and conversion-class of leaching-electrodeposition process three（The such as Yang Jiakuan scrap lead acid
Progress [J] modern chemical industries of battery lead plaster recovery technology, 2009,29 (3): 32-37.）.Solid phase electrolysis technique is
Scrap lead cream is coated on minus plate and in alkaline system diaphragm electrolysis output cathode lead.Leaching-electrodeposition process is by scrap lead cream
Simultaneously electrodeposition output cathode lead is leached, the direct leaching process of scrap lead cream is usually using acetic acid, the hydroxide that complex can be formed with lead
The reagents such as sodium, ammonium salt, chloride and alkaline organic.Conversion-leaching-electrodeposition process is passed through again after scrap lead cream converts desulfurization
Simultaneously electrodeposition output cathode lead is leached, the technique focuses on the extraction efficiency of lead and solution regeneration etc. in scrap lead cream, so leaching
With electrodeposition generally in HBF4Or H2SiF6System is carried out, but different process is slightly different to conversion sweetening process.
In existing lead bath smelting system, lead concentrate oxidizing semlting, high lead dross reduction melting and reducing slag fuming three
Canonical process can output leaded flue dust, wherein lead is mainly to aoxidize Lead speciation presence, wherein oxidizing semlting and reduction melting
Flue dust returns to respective blending process processing, and fuming furnace flue dust then needs to send zinc hydrometallurgy factory because wherein Zn content is high
After sulfuric acid leaching zinc, the sulfuric acid lead skim of output returns again to lead smelting system dispensing.By the lead oxide in original fuming furnace cigarette ash
Lead sulfate is converted into, not only increases the difficulty of subsequent recovery processing, and brings the risk of environmental pollution.
The content of the invention
In order to overcome the shortcomings of traditional lead-containing compounds method for smelting reduction of Ni, the present invention is provided one kind and reduced using starch
Agent low-temperature reduction melting lead-containing compounds and output lead bullion, and energy consumption is low and the small pyrometallurgic methods of environmental pollution.
It is to reach above-mentioned purpose the technical solution adopted by the present invention：Lead-containing compounds are added to ball mill simultaneously with starch
Middle ball milling mixing, in the melting pot of mixed material continuous conveying to indirectly heat, it is heated to requiring that temperature carries out melting, output
Lead bullion power transmission solution refining treatment again.The essence of the technical program is that starch is used under the conditions of indirectly heat as reducing agent, real
The purpose of existing lead-containing compounds low-temperature reduction melting output lead bullion.
Specific technical process and parameter are as follows：
1st, ball mill mixing
Lead-containing compounds are sufficiently mixed in ball mill with starch.By lead-containing compounds and starch according to weight than 100:
6.0~15.0 are added in stainless steel ball grinding machine, control ratio of grinding media to material（Stainless steel ball weight kg and lead-containing compounds weight kg ratios
Value）For 0.5~2: 1 stainless steel ball for adding a diameter of 5mm, start ball mill, keep velocity of rotation 60~150r/min ball millings
30~120min, ball milling terminate rear mixed material and send low-temperature reduction fusion process to use.
2nd, low-temperature reduction melting
Mixed material passes through low-temperature reduction melting output lead bullion.Said mixture material is added continuously in melting pot, led to
Crossing the external heating mode of burning coal or natural gas makes melting pot temperature maintain 800~850 DEG C, starts and stirs and maintain rotating speed
In 60~150r/min, the lead bullion of melting output continuously discharges melting pot, the further electrorefining purification of lead bullion.Low-temperature reduction melts
Refining process main chemical reactions are as follows：
（1）
（2）
（3）
（4）
Described lead-containing compounds are the one or more in lead monoxide, brown lead oxide, ceruse and lead hydroxide.
Described starch is the one or more in wheat, corn, rice, sweet potato and potato starch crops.
The present invention is applied to processing lead-containing compounds, and its main component is by weight percentage（%）：Pb30.0~
90.0% and H2O1.0~5.0%.It also is adapted for handling leaded flue dust and waste lead acid battery lead cream desulfurization conversion slag,
It is of the invention compared with traditional lead-containing compounds processing method, have the advantage that：1st, the present invention is in indirectly heat side
Using starch as reducing agent under formula, make lead-containing compounds low-temperature reduction melting output lead bullion, vertical yield reach 96.0% with
On；2nd, reduction melting temperature is reduced to 800~850 DEG C by the present invention using starch as reducing agent, is greatly reduced containing leaded
The energy consumption of compound low-temperature reduction melting；3rd, the present invention have that technical process is simple to operate, technical indicator is stable, labor intensity is small and
The advantages such as production cost is low.
Brief description of the drawings
Fig. 1：Present invention process schematic flow sheet.
Embodiment
Embodiment 1：
Lead-containing compounds main component is by weight percentage（%）：Pb75.0% and H2O3.0%, used starch are
Wheaten starch.2000g lead-containing compounds and 180g wheaten starches are added in ball mill, control ratio of grinding media to material（Stainless steel ball weight
Measure kg and lead-containing compounds weight kg ratios）For 1.0: 1 stainless steel balls for adding a diameter of 5mm, start ball mill, keep rotating
Speed 90r/min ball milling 60min, ball milling terminate rear mixed material and are added in melting pot, using the external heating mode of burning coal
Melting pot temperature is set to maintain 810 DEG C, starting stirring makes rotating speed maintain 120r/min, output lead bullion weight 1452g, vertical receipts
Rate reaches 96.8%.
Embodiment 2：
Lead-containing compounds main component is by weight percentage（%）：Pb75.0% and H2O3.0%, used starch are
Wheaten starch.2000g lead-containing compounds and 160g rice starch are added in ball mill, control ratio of grinding media to material（Stainless steel ball weight
Measure kg and lead-containing compounds weight kg ratios）For 1.0: 1 stainless steel balls for adding a diameter of 5mm, start ball mill, keep rotating
Speed 90r/min ball milling 60min, ball milling terminate rear mixed material and are added in melting pot, using the external heating mode of burning coal
Melting pot temperature is set to maintain 815 DEG C, starting stirring makes rotating speed maintain 120r/min, output lead bullion weight 1460g, vertical receipts
Rate reaches 97.3%.
Claims (4)
- A kind of 1. method of lead-containing compounds low-temperature reduction melting, it is characterised in that comprise the following steps：（1）Ball mill mixingLead-containing compounds and starch are added in ball mill according to weight than 100: 6.0~15.0, control stainless steel ball weight Kg and lead-containing compounds weight kg ratio of grinding media to material is 0.5~2: 1, adds a diameter of 5mm of stainless steel ball, starts ball mill and protects Velocity of rotation 60~150r/min, 30~120min of ball milling are held, ball milling terminates rear mixed material and send low-temperature reduction fusion process to make With；（2）Low-temperature reduction meltingSaid mixture material is added continuously in melting pot, melting pot temperature is made by the external heating mode of burn coal or natural gas Degree maintains 800~850 DEG C, starts and stirs and rotating speed is maintained 60~150r/min, the lead bullion of melting output is continuously discharged Melting pot, the further electrorefining purification of lead bullion.
- 2. the method for lead-containing compounds low-temperature reduction melting as claimed in claim 1, it is characterised in that described leaded chemical combination Thing is the one or more in lead monoxide, brown lead oxide, ceruse and lead hydroxide.
- 3. the method for lead-containing compounds low-temperature reduction melting as claimed in claim 1, it is characterised in that described starch is small One or more in wheat, corn, rice, sweet potato and potato starch crops.
- 4. the method for lead-containing compounds low-temperature reduction melting as claimed in claim 1, it is characterised in that：The lead-containing compounds Main component be by weight percentage：Pb30.0~90.0% and H2O1.0~5.0%.
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