CN102352443A - Method for producing zinc sulfate heptahydrate, crude tin and crude lead by using tin smelting dust - Google Patents

Method for producing zinc sulfate heptahydrate, crude tin and crude lead by using tin smelting dust Download PDF

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CN102352443A
CN102352443A CN2011103351701A CN201110335170A CN102352443A CN 102352443 A CN102352443 A CN 102352443A CN 2011103351701 A CN2011103351701 A CN 2011103351701A CN 201110335170 A CN201110335170 A CN 201110335170A CN 102352443 A CN102352443 A CN 102352443A
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zinc
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王文忠
杨洪飚
林耀新
杨茂才
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NANCANG METAL MATERIALS CO Ltd TAICANG CITY
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Abstract

The invention discloses a method for producing zinc sulfate heptahydrate, crude tin and crude lead by using tin smelting dust. The method comprises the following steps of: (1) pretreating the raw material; (2) leaching with a dilute sulphuric acid to separate out zinc; (3) purifying the crude zinc sulfate solution, preparing zinc sulfate heptahydrate; (4) performing electric furnace smelting on the tin-rich residue to prepare a tin-lead alloy; (5) adopting the conventional liquation process (the temperature is 500-600 DEG C) and the agglutination method (the temperature is 230-240 DEG C) to refine the tin-lead alloy and increase the Sn-Pb grade of the alloy to 94%-96%, and sending the refining residue back to the electric furnace to perform smelting and dosing treatment; and (6) performing high temperature vacuum distillation to produce crude tin and crude lead. By adopting the method, the tin smelting dust can be effectively utilized, the resource can be saved and metals such as tin, lead, zinc and copper can be recovered together.

Description

Produce the method for Zinc Sulphate Heptahydrate and thick tin and lead bullion with tin melting flue dust
One. technical field:
The present invention relates to a kind of method of producing Zinc Sulphate Heptahydrate and thick tin and lead bullion, belong to non-ferrous metal metallurgy and wet-pyrogenic process process integration technical field with tin melting flue dust.
Two. background technology:
Known, before the 1980's, the tin melting flue dust of domestic tin smeltery, the overwhelming majority returns reverberatory furnace to do the processing of melting again.Because tin melting flue dust zinc content more (Zn3%～26% does not wait), and the reverberatory smelting temperature is not high, furnace temperature inhomogeneous again (burner 1300oC～1350oC, stove tail 1000oC～1150oC), so the direct yield of melting again of tin is not high, generally all is lower than 60%; The thick tin that obtains nearly all is second tin, and the tin grade is less than 80%, and zinc also is difficult to enrichment.
A tree name Zhao Tian from, Wang alive " chief editor's of non-ferrous extractive metallurgy handbook editorial board versions in 1999 " and report in non-ferrous extractive metallurgy handbook (the tin antimony mercury) volume: after the 1980's, the domestic electro-smelting research that has begun tin melting flue dust.In September nineteen eighty-three, smeltery, Liuzhou at first adopts electric furnace smelting process to handle tin melting flue dust.Because the electrosmelting temperature is high, exhaust gas volumn little with dust rate at the bottom of, effect is better.This factory send the flue dust tin grade 32.81%～49.87% of electrosmelting, and is leaded 1.18%～7.05%, zinc 3.70%～16.67%.Product is thick tin, rich slag and flue dust.Thick tin divides two kinds: first tin tin grade 91.34%～93.70%, and leaded 2.0%～2.4%, second tin tin grade 77.20%～89.72%, leaded 0.6%～1.43%, second tin productive rate is 23.88%.Rich slag productive rate 26.89%, stanniferous 3.72%～8.17%.2 flue dust productive rates 20.30%, stanniferous 25.24%～29.05%, lead 0.60%～1.43%, zinc 33.33%～37.38%.The direct yield of melting again＞78% of tin; In the secondary smoke, zinc recovery 90.59%.
At the beginning of the 1970's ends to the 1980's, part tin smeltery begins the sharp deleading bismuth of high-temperature vacuum distillation technical finesse scolding tin that the academician of application project institute wears professor's research Yongnian, produces refined tin.It is short that vacuum distillation method has flow process, and metal recovery rate high (can reach 99%) consumes lowly, pollutes gently, and equipment is simple, and floor space such as lacks at advantage.
Zhou Lianjiang. happy will is auspicious in that " the inorganic chemicals industry handbook is write group chief editor's, " in inorganic chemicals industry handbook (second edition) volume two, introduces the technological process with the Production By Sulfuric Acid Process Zinc Sulphate Heptahydrate in 1996; The material that contains zinc and zinc oxide is after ball mill is pulverized, and the sulphuric acid soln with 18%～25% dissolves in the above temperature of 80oC, and reaction end pH is controlled at 5.1.Zinc solution concentration is 38 oBe, with zinc dust precipitation copper removal cadmium, and potassium permanganate oxidation, zinc oxide neutralization precipitation method is removed ferromanganese, passes through evaporation concentration, crystallisation by cooling again, centrifuge dehydration, operation process such as dry packing promptly make the Zinc Sulphate Heptahydrate finished product.
Three. summary of the invention
The purpose of this invention is to provide a kind of method of producing Zinc Sulphate Heptahydrate and thick tin and lead bullion with tin melting flue dust.Tin melting flue dust leaches separation of Zinc with dilution heat of sulfuric acid earlier at normal temperatures; Thick solution of zinc sulfate zinc replacement copper removal, the deironing of neutralizing hydrolysis method, antimony, aluminium, evaporation concentration, crystallisation by cooling and centrifugation mother liquor art breading are produced Zinc Sulphate Heptahydrate; Hardhead behind the leaching zinc obtains tinsel with electrosmelting, liquate and condensation refining, again through high-temperature vacuum distillation separation of lead and tin, and thick tin of output and lead bullion.Reach and effectively utilize tin melting flue dust, save resource, comprehensively reclaim the purpose of metals such as tin, lead, zinc, copper.
The present invention accomplishes by following technical scheme
Raw material is a tin melting flue dust, comprises electric furnace tin melting flue dust (being called for short electric furnace tin flue dust), reverberatory furnace tin melting flue dust (being called for short reverberatory furnace tin flue dust) and electric furnace secondary tin melting flue dust (being called for short secondary tin flue dust).Raw material main chemical mass percent is listed in table 1.
Table 1 tin melting flue dust main chemical mass percent (quality %)
Figure 863578DEST_PATH_IMAGE001
1. raw materials pretreatment:
Tin melting flue dust is a kind of light grey powder, and its granularity is more than 99%≤0.074mm, accounts for below 5% of material quantity through being dried to water content, inhales and the screen cloth of 8～10mm sieves with magnet, with iron block, the slag of removing mechanical entrapment, foreign material such as batten and stone.
2. dilution heat of sulfuric acid leaches separation of Zinc:
Tin melting flue dust is under normal temperature and agitation condition, at mechanical agitating tank (φ 2.5M * H2.5M, volume 12 m of inner lining polypropylene plastics 3Power of motor 7.5KW; Mixing speed 110r/min) in; Use dilution heat of sulfuric acid; Through 3 sections adverse current leachings-washing processs processing separation of Zinc, make the oxide dissolution of metals such as zinc and copper in the material, antimony, iron, aluminium change solution over to, obtain thick solution of zinc sulfate; And tin and lead are enriched in the leached mud, obtain hardhead.3 sections adverse current leaching-washing process technical qualification are listed in table 2.The concentration of thick solution of zinc sulfate is 28～32 oBe, pH value 2.0～2.5 send the zinc powder amount to change except that the copper process processing; Hardhead productive rate 55%～65%, tin, plumbous grade are brought up to respectively: Sn30.94%～42.14%, Pb3.81%～21.12%, zinc content drops to 1.0%～2.5%, zinc leaching rate 91%～97%.
3 sections adverse current leaching-washing processs of table 2 tin melting flue dust technical qualification
Figure 122259DEST_PATH_IMAGE002
3. thick solution of zinc sulfate purifies and produces Zinc Sulphate Heptahydrate:
(1) zinc dust precipitation copper removal:
The structure and the specification of zinc dust precipitation copper-stripping reaction groove are identical with the leaching steel basin; Having installed caliber in the groove additional is the snakelike heating unit of stainless steel of φ 32mm, uses the steam indirect heating; Groove covers and is provided with venting hole and exhaust line and is communicated with waste gas spray absorption unit, and acid mist and waste gas that replacement(metathesis)reaction produces discharge after spray absorbs processing.
Thick solution of zinc sulfate cupric 1.0g/L～2.0g/L is 55 oC～65 oUnder C temperature and the agitation condition, with the reduction zinc powder displacement copper removal of Zn quality grade>=98%.Every groove is handled thick solution of zinc sulfate 10 m 3～12 m 3, reaction initial pH value 2.0～2.5, the zinc powder consumption is every groove solution 32～48kg, adds several times, reaction times 40～60min, terminal point pH is controlled at 4.0～4.2.After reaction process finishes,, separate copper ashes with 40 ㎡ polypropylene chamber-type press filter press filtrations.Behind the copper removal in the liquid copper content reduce to 0.041g/L～0.089g/L, doing meter copper ashes quantum of output is 70～200kg/ groove, copper grade 8.98%～14.10%, water content 45%～55%.Copper removal rate 94%～96%.The suitable otherwise processed of copper ashes reclaims copper.
(2) the neutralizing hydrolysis method removal of impurity:
The neutralizing hydrolysis conversion unit is identical with displacement copper removal groove.With every groove 10 m 3～12 m 3Liquid is 55 behind the copper removal oC～75 oUnder C temperature and the agitation condition, with the industrial oxide powder and zinc of ZnO quality grade>=97%, in the free acid that discharges with Hydrolysis Reactions of Metal-ions reactions such as iron, antimony, aluminium, impurity such as iron, antimony, aluminium are removed from zinc solution with the form of precipitation of hydroxide.The oxide powder and zinc add-on is 10～16kg/ groove, reaction times 1.5～2.0h, reaction end pH value 5.2～5.4.After hydrolysis reaction finishes, with in the pressure filter press filtration separation and slag.The content that purifies impurity element in the liquid of back is Fe 0.001g/L～0.0001g/L, Sb 0.01g/L～0.02g/L, Al 1.68g/L～2.42g/L.In do meter quantum of output 160～220kg/ groove with slag, handle with returning the electrosmelting batching after the water washing.
(3) condensing crystal is produced Zinc Sulphate Heptahydrate:
After the clarification of zinc sulfate scavenging solution, at 10 m of inner lining polypropylene plastics 3Vacuum-evaporation concentrates, be concentrated into concentration 50～52 in the crystallisation by cooling groove oDuring Be, change crystallisation by cooling over to, reduce to 24～28 until the temperature of xln slip oC uses LWL350 type stainless steel high-speed screw whizzer fractional crystallization mother liquor then, obtains Zinc Sulphate Heptahydrate (ZnSO 47H 2O) finished product.About 9 m of every groove 3But concentrated zinc solution output Zinc Sulphate Heptahydrate 3.8～4.6t.Product master content is in Zn, and >=22.06%, quality meets industrial sulphuric acid zinc II class acceptable end product specification of quality.Crystalline mother solution returns purification system, round-robin after the removal of impurity, and production process is discharge technology waste water not.Zinc metal recovery rate 90.68%～95.18%.
4. hardhead electrosmelting tinsel:
(1) 3 kinds of tin melting smoke raw materials is leached 3 kinds of hardheads that obtain after the separation of Zinc, move in the material formula dryer, in 320 at 12m * 1.2m * 1.6m oC～360 oThe C temperature is dried to water content respectively and accounts for 12%～16% of hardhead weight, by the ratio mixing of dried mass ratio 1:1:1, obtains the hardhead compound then.
(2) the hardhead compound is a flux with the Wingdale, and coal is made reductive agent, melting in the 800KVA ore-smelting furnace.Ore-smelting furnace size of burner hearth φ 2.5m * 2.27m, hearth area 3.46 ㎡.Primary side voltage 10KV, secondary side voltage 95～110V (three-phase), secondary side current 4100～5770A; Negative pressure: 0～50Pa in the stove; Furnace roof jacket water internal circulating load 20m 3/ h, water temperature 70 oC～85 oC.
(3) ratio of components: hardhead compound: returning charge: Wingdale: the ratio of going back raw coal is 100:5～6:4～5:9～10 (mass ratioes).
(4) feeding manner is a batch feed, and every separated 2h advances a collection of furnace charge, and every batch of furnace charge average quality is for doing meter furnace charge 2t.
(5) melting method and index: ore-smelting furnace adopts submerged arc melting, intermittent type Job Operations.Under the normal working of a furnace, during slagging, burner hearth bottom keeps an amount of liquid slag and is used for the starting the arc, add first new furnace charge after, furnace temperature is minimum reduces to about 550 oC; Between smelting period, the highest smelting temperature 1400 oC～1500 oC; Melting one stove need add 11～12 batches in furnace charge, adds up to 22～24t.Go into the stove furnace charge when last batch of and melt fully, when the slag making reaction finishes, can emit tinsel and slag.Melting cycle 22～24h/ stove.Main economic and technical indices: tinsel productive rate 40%～42%, metal content: Sn60%～66%, Pb20%～24%; Slag productive rate 22%～27%, slag contain Sn1.0%～1.5%, Pb0.8%～1.2%; Slag can use the blast furnace fuming method to reclaim tin and lead.Dust rate 18%～22%, the Returning smelting electric furnace is done the batching processing after dust collecting system and the recovery of flue gas spray absorption unit.Hardhead melting once metal direct yield: Sn74%～77%, Pb76%～78%, total yield: Sn98%～99%, Pb98%～99%.Ton material electric energy consumption 860～1060KWh.
(6) tinsel adopts conventional liquation process and the refining of condensation method.In 500 oC～600 oThe liquation refining of C temperature is in 230 oC～240 oC temperature condensation refining is increased to 94%～96% with the grade of Sn+Pb in the alloy, and refining slag is returned the electrosmelting operation do returning charge and handle.
5. thick tin of high-temperature vacuum distillation production and lead bullion:
(1) tinsel after the refining is selected internal heat type multistage continuous still battery vacuum oven separation of lead and tin for use, produces thick tin and lead bullion.Vacuum oven day output: 8～10t/d; Rated output: 130KVA.
(2) distillation vacuum oven technical qualification: stove internal heat generation device capacity: 90～92KVA; Operating voltage 18～20V in the stove, working current: 3000A; Operating pressure: 4.0～2.6Pa in the stove; Furnace temperature: 350 oC～400 oC; Evaporating pan top temperature 1400 oC～1700 oC.Stove consumption of cooling-water: 2.0～2.5 m 3/ h.
(3) operation process and index: adopt the system of working continuously to distill.Tinsel is packed into behind the electric food warmer, begin power supply and make a pot interior alloy melting, add thermosiphon extremely about 400 oDuring the C temperature, Kei moves vacuum system, and send to vacuum oven; Reach fervid when being warming up to evaporating pan; When residual voltage is reduced to 15Pa in the stove, begin to add alloy in electric food warmer by the speed of 330～340kg tinsel per hour, alloy melt promptly is inhaled in the vacuum oven; Flow in the evaporating pan and distill; When melt is begun by the first step, the one-levels to the end at different levels of flowing through, and flow out to stove when outer by the last step evaporating pan; Promptly obtain thick tin product, the temperature 1000 of thick tin melt oC～1050 oC; The plumbous steam that still-process produces then is condensed into liquid lead, continuously flows out by putting lead pipe, becomes the lead bullion product.Distilling furnace 24h adds tinsel 8t altogether, the thick tin 5.6～5.9t of output, and tin grade 95%～97% contains Pb4%～2%; The about 2t of output lead bullion, plumbous grade>=96% contains Sn≤0.6%.Tin distillation direct yield >=98%, plumbous volatility >=90%.Handling tinsel power consumption index per ton is 380～420kwh.
The present invention compares the advantage and the positively effect of existence with technique known
1. the present invention uses tin melting flue dust to be raw material, and employing is wet-pyrogenic process associating metallurgical technology treatment technology, through wet method leaching, purification, concentrated, crystallization operation process separation of Zinc, output Zinc Sulphate Heptahydrate; Through pyrometallurgical smelting, refining and high-temperature vacuum distillation separation of lead and tin, obtain thick tin and lead bullion product, reasonable flowsheet structure, stronger to principle adaptability, metal recovery rate is high, can comprehensively reclaim metals such as tin, lead, zinc, copper, is easy to industrializing implementation.
2. technology of the present invention leaches tin melting flue dust separation of Zinc with dilute sulphuric acid earlier; Make zinc no longer with tin flue dust Returning smelting electric furnace; Not only help the recovery of zinc; Also help alleviating the load of electric furnace and dust collecting system; And fusion process not have rich slag and hardhead be iron tin tin alloy output; Can improve smelting efficient, save the energy, reduce consuming.
3. Zinc Sulphate Heptahydrate production technology of the present invention is not used poisonous and hazardous chemical reagent, and operation process does not discharge industrial gaseous waste, waste residue and processing wastewater, helps factory's protection of ecotope on every side.
Four. description of drawings:
Fig. 1 is a process flow sheet of the present invention.
Five. embodiment
Embodiment 1: raw material electric furnace tin flue dust main chemical mass percent (quality %): Sn 19.78, and Pb 12.30, and Zn 26.32, and Cu 0.35, and As 1.69, and Sb 0.62, and S 1.25, and FeO 1.41, and CaO 1.12, and SiO2 1.40, and Al2O3 1.68.
(1) with raw material dehydration to 5 quality %, screen out mechanical entrapment >=foreign material such as the iron block of 8～10mm, slag.
(2) under normal temperature and the agitation condition, carry out 1 section leaching of electric furnace tin flue dust with No. 1 12m3 steel basin; Pump into 2 about 10m3 of leach liquor that handle last batch materials in No. 1 reservoir earlier; Start stirrer; Every groove drops into electric furnace stannum smoke raw material 3.5t; The industrial sulphuric acid that adds the 1.25t quality; Add leach liquor to cumulative volume 12 m3 2 times; Gu: liquid=1:3.4 (t:m3), agitation leach 2.5h, endpoint pH 2.5.Leach slip and carry with 65-Z * B-40 type vacuum primingpump, through 110 ㎡ polypropylene pressure filter press filtrations, obtaining concentration is thick solution of zinc sulfate and 1 leached mud of 30 oBe.Thick solution of zinc sulfate quality composition (quality g/L): Zn 84～86, and Sn 1.04～1.86, and Pb 0.14～0.18, and Cu 1.6～1.95, and Fe 0.10～0.16, and Sb 0.12～0.23, and Al 2.1～4.2, send zinc dust precipitation to remove copper process and handle; 1 time leached mud changes 2 leachings over to.
(3) under normal temperature and the agitation condition, 1 leached mud is carried out 2 sections leachings with No. 2 steel basins.Leached mud washing lotion and workshop trench (hole) water with handling last batch materials in No. 2 reservoirs are sized mixing; Every groove adds the industrial sulphuric acid of 1.25t quality; Gu: liquid=1:4.8 (t:m3); Behind the agitation leach 3h; With 80 ㎡ pressure filter press filtrations; Obtain pH≤0.5, concentration is that 2 leach liquors of 14oBe pump into reservoir No. 1, makes the next batch raw material and leaches the adjusting slurry use for 1 time; 2 leached muds after the press filtration send 3 sections washery slags.
(4) under normal temperature and the agitation condition, 2 leached muds are carried out 3 sections washery slags with No. 3 steel basins.Size mixing with tap water, Gu: liquid=1:3 (t:m3), behind the agitator treating 1.5h,, obtain pH value 3.0 with 80 ㎡ pressure filter press filtrations, concentration is that the leached mud washing lotion of 7 oBe pumps into reservoir No. 2, makes the adjusting slurry of 2 sections leachings of next batch raw material; Leached mud behind the washing and filter pressing is hardhead, and the dried meter quality of each batch hardhead is 2.1～2.25t, and main chemical mass percent (quality %): Sn 31.25, and Pb 19.48; Zn 2.23, and Cu 0.08, and Fe 1.2, and Sb 0.53; As 1.30, and CaO 0.23, and SiO2 0.58.In hardhead, zinc leaching rate 92.91%, the tin rate of recovery 99.00%, lead recovery 98.95%.Hardhead is sent to the electrosmelting operation and concentrates melting.
(5) thick solution of zinc sulfate is in interior No. 5 steel basins establishing heating unit, under 55 oC～65 oC temperature and agitation condition, with the zinc dust precipitation copper removal of Zn quality grade >=98%.Every groove (inferior) is handled 10～12m3 solution, and zinc powder consumption 40～48kg/ groove adds reaction times 40～60min, endpoint pH 4.0～4.2 several times.Obtain removing copper solutions and copper ashes after the press filtration of displacement slurries.Copper content is reduced to 0.041g/L～0.089 g/ in the solution, and copper removal rate 95%～95.7 % send the removal of impurities operation to handle.Every groove (inferior) output is done meter quality copper ashes 160～200kg, copper grade 9.3%～12.2 %, and suitable otherwise processed reclaims copper.
(6) behind the copper removal liquid in interior No. 6 steel basins establishing heating unit, under 60 oC～75 oC temperature and agitation condition, with the industrial oxide powder and zinc neutralizing hydrolysis removal of impurity of ZnO quality grade >=97%.Every groove (inferior) is handled 10～12 m3 solution, oxide powder and zinc consumption 10～16kg/ groove, reaction times 1.5～2.0h, endpoint pH 5.2～5.4.Obtain after the press filtration of removal of impurities slurries the zinc sulfate scavenging solution with in and slag.Scavenging solution concentration 30～32oBe, the content of impurity element (quality g/L): Fe 0.001, and Sb 0.012, and Al 1.68, are sent to the condensing crystal operation and produce the Zinc Sulphate Heptahydrate product.In do meter quantum of output 170～220kg/ groove (inferior) with slag, slag contains Sn 0.06%, Sb 0.023%, uses with returning the electrosmelting batching after the water washing.
(7) with after the clarification of zinc sulfate scavenging solution; Pump in 10 m3 evaporation concentration, the crystallisation by cooling groove; Using steam indirect heating evaporation concentration to concentration is 50～52oBe (containing Zn 158～160 g/L); Then under agitation condition; Use water coolant instead and be cooled to 24 oC～26 oC temperature indirectly; Zinc is separated out with the form of ZnS047H2O xln, leave main frame fractional crystallization mother liquor at a high speed through LwL～350 types again, obtain the Zinc Sulphate Heptahydrate product.The about 9 m3 zinc sulfate concentrated solution crystallization output Zinc Sulphate Heptahydrate finished products of every groove 3.8～4.2t, product master content be in Zn, and >=22.06%, quality meets the requirement of II class acceptable end product Zinc Sulphate Heptahydrate quality product; Crystalline mother solution quantum of output 3.6～3.8 m3/ grooves, concentration 42～44oBe, after returning purification system and handling, round-robin.From electric furnace tin flue dust to the Zinc Sulphate Heptahydrate finished product, zinc recovery 91.62%.
Embodiment 2: raw material reverberatory furnace tin flue dust main chemical mass percent (quality %): Sn 28.28, and Pb 10.59, and Zn 12.45, and Cu 0.18, and As 0.96, and Sb 0.01, and S 1.96, slag making element 16～22.
(1) with below raw material drying to the water content 5 quality %, screen out mechanical entrapment >=the block foreign material of 8mm.
(2) under normal temperature and the agitation condition, do 1 section leaching of reverberatory furnace tin flue dust with No. 1 steel basin.Size mixing with 2 leach liquors, every groove (inferior) drops into reverberatory furnace stannum smoke raw material 4.8t, adds the 0.86t industrial sulphuric acid, Gu: liquid=1:2.5 (t:m3), press filtration behind the agitation leach 2h obtains concentration 29 oBe, the thick solution of zinc sulfate of pH value 2.0 and 1 leached mud.Zinc solution quality composition (quality g/L): Zn 82～85, and Sn 2.12～2.94, and Pb 0.12～0.16, and Cu 1.04～1.26, and Fe 0.11～0.13, and Sb 0.02～0.04, and Al 3.41～5.63, send to purify and remove the copper process processing; 1 time leached mud send 2 sections leachings.
(3) under normal temperature and the agitation condition, with 2 sections leachings of 1 leached mud of No. 2 steel basin works.Wash heat liquid and ground, workshop effluent with No. 3 reservoirs are sized mixing; Every groove (inferior) adds the 0.86t industrial sulphuric acid; Gu: liquid=1:3.2 (t:m3); Press filtration behind the agitation leach 3h; Obtain pH value＜0.5; 2 leach liquors of concentration 12 oBe, it is subsequent use to pump into No. 2 reservoirs, and 2 times leached mud send the steel basin washery slag No. 3.
(4) under normal temperature and the agitation condition, with 3 sections washery slags of 2 leached muds of No. 3 steel basin works.Size mixing with tap water, Gu: liquid=1:2.5 (t:m3), press filtration behind the agitator treating 1h obtains pH value 2.5, and it is subsequent use that concentration is that the leached mud washing lotion of 6 oBe is delivered to No. 2 reservoirs.It is the 3.41t/ groove that hardhead after the washing is done the meter quality, and main chemical mass percent (quality %): Sn 39.25, and Pb 14.58, and Zn 1.05, and Cu 0.06, and Fe 1.26, and Sb 0.01, and As 0.66.In slag, zinc leaching rate is 91.86%, the tin rate of recovery 98.6%, lead recovery 97.8%.Hardhead is sent to the electrosmelting operation and concentrates melting.
(5) thick solution of zinc sulfate under 55 oC～65 oC temperature and agitation condition, is used the zinc dust precipitation copper removal in No. 5 steel basins.Each treatment soln 10～12 m3 add the zinc powder/groove of 32～38kg quality, press filtration behind the replacement(metathesis)reaction 40min several times.Liquid pH4.0～4.2 behind the copper removal, cupric 0.04g/L～0.06 g/L, copper removal rate 94%～96%, output are done meter quality copper ashes 70～95kg/ groove, copper grade 13.2%～14.1%, the copper ashes otherwise processed reclaims copper.
(6) behind the copper removal liquid in No. 6 steel basins, under 60 oC～70 oC temperature and agitation condition, with in the oxide powder and zinc and the removal of impurity.Each 11 m3 solution of handling add oxide powder and zinc 14kg several times, press filtration behind the reaction 2h.Scavenging solution pH value >=5.2, concentration 32 oBe, the quality grams per liter content (quality g/L) of impurity element: Fe 0.0065, and Sb 0.016, and Al 1.97, is sent to the condensing crystal operation and produces Zinc Sulphate Heptahydrate; Output is done among meter quality 150～180kg and slag/groove, handles with returning the electrosmelting batching after the water washing.
(7) the zinc sulfate scavenging solution after will clarifying is sent into 10 m3 evaporation concentration, crystallisation by cooling groove to be concentrated into concentration is 50～52 oBe; Restir cools off, crystallizes to 25 oC temperature; Through whizzer fractional crystallization mother liquor, obtain meeting the Zinc Sulphate Heptahydrate product of II class acceptable end product specification of quality.The about 9m3 concentrated solution of every groove output 4.0～4.5tZnSO47H2O salable product, zinc recovery 90.68%.After crystalline mother solution returns zinc displacement and removes copper process and purify, round-robin.
Embodiment 3: raw material secondary (electric furnace) tin flue dust main chemical mass percent (quality %): Sn 25.24, and Pb 2.42, and Zn 34.74, and Cu 0.30; As 2.41, and Sb 0.18, and S 0.75, and FeO 1.08; CaO 0.34, and SiO2 2.51, and Al2O3 1.48.
(1) with raw material dehydration to 5 quality %, screen out >=the block entrainment of 8mm.
(2) under normal temperature and agitation condition, in No. 1 steel basin, carry out 1 section leaching of secondary tin flue dust.Size mixing with 2 leach liquors, drop into secondary stannum smoke raw material 2.8t/ groove, add industrial sulphuric acid 1.05t/ groove, Gu: liquid=1:4.3 (t:m3), press filtration behind the agitation leach 2.5h obtains concentration 32 oBe, the thick solution of zinc sulfate of pH value 2.5 and 1 leached mud.Zinc solution quality composition (quality g/L): Zn 86～90, and Sn 0.96～1.68, and Pb 0.11～0.13, and Cu 1.32～1.64, and Fe 0.13～0.15, and Sb 0.08～0.12, send except that the copper process processing.1 time leached mud goes to 2 sections leachings.
(3) under normal temperature and agitation condition, carry out 2 sections leachings of 1 leached mud in No. 2 steel basins.With leached mud washing lotion and workshop trench (hole) water slurrying in No. 2 reservoirs; Add industrial sulphuric acid 1.05t/ groove; Gu: liquid=1:6 (t:m3); Press filtration behind the agitation leach 3.5h; Obtain pH value≤0.5; 2 leach liquors of concentration 14 oBe, pump to 1 storage tank liquid is subsequent use, and 2 times leached mud send 3 sections washery slags.
(4) under normal temperature and agitation condition, with 3 sections washery slags of 2 leached muds of No. 3 steel basin works.Use tap water slurrying, Gu: liquid=1:3 (t:m3), press filtration behind the washing 1h.Obtain pH3.0, concentration is the leached mud washing lotion and the hardhead of doing meter quality 2.06t/ groove of 8 oBe.Wash heat liquid pump to 2 reservoir is subsequent use, and hardhead main chemical mass percent (quality %): Sn 33.97, and Pb 3.04, and Zn 1.47, and Cu 0.12, and Fe 1.04, and Sb 0.12, and As 1.84.In hardhead, zinc leaching rate is 96.88%, the tin rate of recovery 99%, lead recovery 92.41%.Hardhead is sent to the electrosmelting operation and concentrates melting.
(5) under 55 oC～65 oC temperature and agitation condition, thick solution of zinc sulfate pumps into steel basin No. 5, uses the zinc dust precipitation copper removal.Every groove is handled 11 m3 solution, adds the zinc powder of 40kg quality several times, press filtration behind the replacement(metathesis)reaction 60min.Liquid pH value 4.0～4.2 contains Cu 0.06 g/L～0.09g/L behind the copper removal, copper removal rate 94%～95 %, and output is done meter quality copper ashes 140～160kg/ groove, copper grade 8.9%～11.6%, the copper ashes otherwise processed reclaims copper.
(6) under 65 oC～75 oC temperature and agitation condition, liquid is in No. 6 steel basins, with in the oxide powder and zinc and the removal of impurity behind the copper removal.Every groove is handled 11 m3 solution, adds oxide powder and zinc 12.6kg/ groove several times, press filtration behind the reaction 2h.Scavenging solution pH value 5.2～5.4, the quality grams per liter content (quality g/L) of impurity element: Fe 0.0001, and Sb 0.019, and Al 2.42, is sent to the condensing crystal operation and produces the Zinc Sulphate Heptahydrate product.Output is done among meter quality 160～180kg and slag/groove, handles with returning electrosmelting operation batching after the water washing.
(7) the zinc sulfate scavenging solution after the clarification is in 10 m3 evaporation concentration, crystallisation by cooling groove; Be concentrated into 50～52oBe, crystallisation by cooling then is when stirring is cooled to 24 oC～25 oC temperature; With supercentrifuge fractional crystallization mother liquor, obtain the Zinc Sulphate Heptahydrate product.After the about 9 m3 concentrated solution crystallizations of every groove, output 4.2～4.6tZnS047H2O, quality meets II class acceptable end product Zinc Sulphate Heptahydrate product requirement, zinc recovery 95.18%; Crystalline mother solution concentration 46 oBe return to purify and remove copper process processing back round-robin.
(8) hardhead electrosmelting tinsel
1. the hardhead with 3 kinds of application example treating processes outputs dewaters to 12～16 quality % respectively at 320 oC～360 oC temperature dryings, by mass ratio 1:1:1 3 kinds of hardheads is mixed then and obtains the hardhead compound.Main chemical mass percent (quality %) is: Sn 34.82, and Pb 12.37, and Zn 1.58, and Cu 0.087, and Fe 1.17, and Sb 0.22, and As 1.27.
2. the hardhead compound is a flux with the Wingdale, and coal is made reductive agent, melting in the 800KVA ore-smelting furnace.
3. ratio of components: hardhead compound: returning charge: Wingdale: the ratio of going back raw coal is 100:5.5:4.5:9.5 (mass ratio).
4. feeding manner is a batch feed, and every separated 2h advances a collection of furnace charge, and every batch of furnace charge average quality is for doing meter furnace charge 2t.
5. adopt the submerged arc melting, the intermittent type Job Operations.Under the normal working of a furnace, during slagging, burner hearth bottom keeps an amount of liquid slag and is used for the starting the arc, add first new furnace charge after, furnace temperature is reduced to about 550oC, the highest smelting temperature 1400oC～1500oC, melting one stove adds 11～12 batches in furnace charge altogether, total 22～24t.Go into the stove furnace charge when last batch of and melt fully, slagging process is emitted tinsel and slag after finishing, and changes the melting of next stove then over to, melting cycle 22～24h/ stove.Tinsel productive rate 40%～42%, metal content: Sn63.2%～64.4%, Pb22.5%～23.6%; Slag productive rate 24%～26%, content Sn1.26%, Pb0.94%, slag mainly form mass percent (quality %): FeO4～6, CaO13～19, SiO225～35, Al2O37～10, MgO1.0～2.0.Slag can use the blast furnace fuming method to reclaim tin and lead; Dust rate 18%～22% returns the electrosmelting burden process and handles after dust collecting system and the recovery of flue gas spray absorption unit.Hardhead melting once metal direct yield: Sn74%～77%, Pb76%～78%, total yield: Sn98%～99%, Pb98～99%.
6. with the tinsel of tin grade 64.32% and plumbous grade 23.52% after 500oC～600oC temperature liquation refining and 230oC～240oC temperature condensation refining; Metal content in the alloy is increased to Sn69.58%; Pb25.46% (Sn+Pb95.04%) returns refining slag to the electrosmelting operation and does the returning charge processing.
(9) thick tin and lead bullion are produced in vacuum distilling
1. the tinsel of Sn+Pb grade 95.04% after the refining, using day output is the multistage continuous still battery vacuum oven of internal heat type fractionation by distillation lead and the tin of 8～10t, obtains thick tin and lead bullion.Vacuum oven rated output 130KVA; Cooling water circulation amount 2.0～2.5 m3/h.
2. the electric food warmer of tinsel being packed into, alloy in the power supply melting tank, the preheating siphon pipe is to about 400oC; Kei moves vacuum system; Send electricity, be warming up to evaporating pan and reach fervid to vacuum oven; When residual voltage is reduced to 15Pa in the stove; Begin to add alloy continuously to electric food warmer by the speed of 330～340kg tinsel per hour; The alloy of fusing promptly is inhaled in the vacuum oven by siphon pipe, flows to evaporating pan and distills.
3. in still-process, control operating voltage 18～20V in the stove, electric current 3000A; Operating pressure 4.0～2.6Pa in the stove; Vacuum oven evaporating pan top temperature 1400oC～1700oC, the thick tin melt temperature 1000oC～1050oC that obtains after plumbous vapour condensation is liquid lead, also flows out by putting lead pipe, is cast into thick tin slab and base bullion lead product respectively.
4. vacuum oven 24h handles the 8t tinsel; The thick tin 5.73t of output, tin grade 95.46%, leaded 2.3%, tin metal direct yield 98.45%; Output lead bullion 1.97t, plumbous grade 96.6%, stanniferous 0.58%, lead metal evaporation rate 93.42%.The indicator of power consumption of handling tinsel per ton is 380～420KWh.

Claims (1)

1. method of producing Zinc Sulphate Heptahydrate and thick tin and lead bullion with tin melting flue dust, it is characterized in that: it is accomplished according to the following steps,
(1), raw materials pretreatment: tin melting flue dust (comprising electric furnace tin flue dust, reverberatory furnace tin flue dust and electric furnace secondary tin flue dust) is below drying and dehydrating to the 5 quality %, screen out mechanical entrapment >=iron block of 8mm, slag, foreign material such as batten and stone;
(2), dilution heat of sulfuric acid leaches separation of Zinc: under normal temperature and the agitation condition; 3 kinds of tin melting smoke raw materials are used dilution heat of sulfuric acid respectively; Handle (technical qualification are as shown in the table) separation of Zinc through 3 sections adverse current leaching-washing processs, obtain thick solution of zinc sulfate and hardhead;
3 sections adverse current leaching-washing processs of tin melting flue dust technical qualification
Figure 338665DEST_PATH_IMAGE001
(3), thick solution of zinc sulfate purifies and produces Zinc Sulphate Heptahydrate:
1. zinc dust precipitation copper removal: thick solution of zinc sulfate concentration 28～32 oBe, pH value 2.0～2.5 contains Cu 1.0～2.0g/L; 55 oC～65 oUnder C temperature and the agitation condition, with the zinc dust precipitation copper removal of Zn quality grade>=98%; Every groove (inferior) is handled 10 m 3～12 m 3Solution, zinc powder consumption 32～48kg/ groove adds reaction times 40～60min, endpoint pH 4.0～4.2 several times; After the pressure filter press filtration, obtain removing copper solutions and copper ashes; Copper removal liquid contains Cu 0.04 g/L～0.09g/L, copper removal rate 94%～96%, copper ashes quantum of output (doing meter) 70～200kg/ groove, copper grade 8.95%～14.10%;
2. the neutralizing hydrolysis method removal of impurity: with liquid behind the copper removal 55 oC～75 oUnder C temperature and the agitation condition, remove impurity such as Fe, Sb, Al with the oxide powder and zinc neutralizing hydrolysis of ZnO quality grade>=97%; Every groove (inferior) is handled 10～12 m 3Solution, oxide powder and zinc consumption 10～16kg/ groove, reaction times 1.5～2.0h, reaction end pH value 5.2～5.4; Obtain after the press filtration zinc sulfate purify back liquid and in and slag; Scavenging solution concentration 30～32 OBe, impurity content (g/L) Fe 0.001～0.0001, Sb 0.01～0.02, and Al 1.68～2.42; In with slag quantum of output (do meter) 160～220kg/ groove, handle with returning the electrosmelting batching after the water washing;
3. condensing crystal is produced Zinc Sulphate Heptahydrate: after the clarification of zinc sulfate scavenging solution, at 10 m 3Vacuum-evaporation concentrates, be concentrated into concentration 50～52 in the crystallisation by cooling groove oBe changes crystallisation by cooling to 24～26 then over to oThe C temperature through LWL350 type high-speed screw whizzer fractional crystallization mother liquor, obtains the Zinc Sulphate Heptahydrate finished product that quality meets II class acceptable end product again;
About 9 m of every groove 3But concentrated zinc solution output 3.8～4.6t ZnSO 47H 2O; Crystalline mother solution is returned zinc dust precipitation purify the back round-robin again except that copper process;
(4). hardhead electrosmelting tinsel:
1. the hardhead after 3 kinds of tin melting smoke raw material separation of Zinc is respectively at 320 oC～360 oThe dehydration of C temperature drying mixes 3 kinds of hardheads by mass ratio 1:1:1 then and obtains the hardhead compound to 12～16 quality %;
2. the hardhead compound is a flux with the Wingdale, and coal is made reductive agent, with the melting of 800KVA ore-smelting furnace;
3. ratio of components: hardhead compound: returning charge: Wingdale: the ratio of going back raw coal is 100:5～6:4～5:9～10 (mass ratioes);
4. feeding manner is a batch feed, and every separated 2h advances a collection of furnace charge, and every batch of furnace charge average quality is for doing meter furnace charge 2t;
5. melting method and index: adopt the submerged arc melting, the intermittent type Job Operations;
Under the normal working of a furnace, during slagging, burner hearth bottom keeps an amount of liquid slag and is used for the starting the arc, add first new furnace charge after, furnace temperature is minimum reduces to about 550 oC; Between smelting period, the highest furnace temperature 1400 oC～1500 oC; Melting one stove adds 11～12 batches in furnace charge; Melting cycle 22～24h; Main economic and technical indices: tinsel productive rate 40%～42%, metal content: Sn 60%～66%, Pb 20%～24%; Slag productive rate 22%～27%, slag contain Sn 1.0%～1.5%, and Pb 0.8%～1.2%; Dust rate 18%～22% returns the electric furnace batching after dust collecting system and the recovery of flue gas spray equipment;
Hardhead melting once metal direct yield: Sn 74%～77%, and Pb 76%～78%, total yield: Sn 98%～99%, and Pb 98%～99%; Melting furnace charge electric energy consumption per ton 860～1060KWh;
(5) tinsel adopts conventional liquation process (temperature 500 oC～600 oC) and condensation method (temperature 230 oC～240 oC) refining is increased to 94%～96% with Sn+Pb grade in the alloy;
Refining slag is returned the electrosmelting batching to be handled;
(6) thick tin of high-temperature vacuum distillation production and lead bullion:
1. the tinsel after the refining is selected internal heat type multistage continuous still battery vacuum oven separation of lead and tin for use;
Vacuum oven day output: 8～10t/d; Rated output: 130KVA;
2. vacuum distillation furnace technical qualification: stove internal heat generation device capacity: 90～92KVA; Operating voltage 18～20V, working current: 3000A; Operating pressure: 4.0～2.6Pa in the stove; Furnace temperature: 350 oC～400 oC; Evaporating pan top temperature 1400 oC～1700 oC;
Stove consumption of cooling-water: 2.0～2.5 m 3/ h;
3. operation process and index: adopt the system of working continuously to distill;
The tinsel add-on is 330～340kg per hour, and 24h adds the 8t tinsel altogether, the thick tin 5.6～5.9t of output, tin grade 95%～97%, leaded 4%～2%; The about 2t of output lead bullion, plumbous grade>=96%, stanniferous≤0.6%;
Tin distillation direct yield >=98%, plumbous volatility >=90%, handling tinsel power consumption index per ton is 380～420kwh,
Said electric furnace tin melting flue dust main chemical mass percent is Sn 19.78, and Pb 12.30, and Zn 26.32, and Cu 0.35, and As 1.69, and Sb 0.62, and S 1.25, and FeO 1.41, and CaO 1.12, SiO 21.40, Al 2O 31.68;
Reverberatory furnace tin melting flue dust main chemical mass percent is Sn 28.28, and Pb 10.59, and Zn 12.45, and Cu 0.18, and As 0.96, and Sb 0.01, and S 1.96, slag making element 18～22;
Electric furnace secondary tin melting flue dust main chemical mass percent Sn 25.24, Pb 2.42, and Zn 34.74, and Cu 0.30, and As 2.41, and Sb 0.18, and S 0.75, and FeO 1.08, and CaO 0.34, SiO 22.51, Al 2O 31.48.
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CN112095010A (en) * 2020-08-28 2020-12-18 昆明理工大学 Method for separating and recovering tin and zinc from tin-zinc-containing gold spraying powder
CN113564370A (en) * 2021-08-18 2021-10-29 云南锡业股份有限公司锡业分公司 Treatment system and method for complex tin smelting smoke dust
CN114317986A (en) * 2021-11-30 2022-04-12 西安建筑科技大学 Process for extracting lead from zinc-lead dust
CN114317986B (en) * 2021-11-30 2023-10-13 西安建筑科技大学 Process for extracting lead from zinc-lead dust

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