CN101633983B - Method for enhancing recovery rate of zinc fusion casting - Google Patents
Method for enhancing recovery rate of zinc fusion casting Download PDFInfo
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- CN101633983B CN101633983B CN2009100948662A CN200910094866A CN101633983B CN 101633983 B CN101633983 B CN 101633983B CN 2009100948662 A CN2009100948662 A CN 2009100948662A CN 200910094866 A CN200910094866 A CN 200910094866A CN 101633983 B CN101633983 B CN 101633983B
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Abstract
The invention relates to a method for enhancing the recovery rate of zinc fusion casting. The method comprises the following steps: a mixture of ammonium chloride and colophony is added as a slagging agent in the melting process of zinc, the specific weight of the colophony in the weight of the mixture is 1-80%; zinc metal and zinc oxide in scum are separated and recovered by the methods of sorting, sieving and reselecting; a zinc ball is adopted as a mineral milling medium in the milling process of the recovered scum for dry milling, the scum is sorted into a big zinc block by manual sorting, the zinc scum is milled by a ball mill, and thicker zinc powder and zinc granules are sieved and graded at an outlet of the ball mill; the thinner zinc powder and zinc oxide are blown away by wind, dust collection and grading are carried out by a cyclone collector and a bag collector, and products with different grades are obtained. The invention can obviously lower the yield of the scum in zincfusion casting; compared with an NH4Cl slagging agent which is independently added, the yield of the scum can be lowered by 3-5%, and the recovery rate of the zinc fusion casting is enhanced. In addition, the invention is beneficial to lowering the content of zinc-oxygen powder chlorine ions recovered in slag, conforms to the requirement of a work section for extracting indium and reduces the expenditure of dechlorination.
Description
Technical field the present invention relates to a kind of method that improves recovery rate of zinc fusion casting.
Background technology is smelted in the production process at zinc, and the resulting zinc metal sheet of solution of zinc sulfate electrolysis will be put in the casting furnace and melt, and casts zinc ingot metal again.When founding, zinc is easy to oxidized, and generates zinc oxide by following reaction:
Zn+H
2O＝ZnO+H
2
Zn+1/2O
2＝ZnO
Zn+C
2O＝ZnO+CO
Formed thus zinc oxide wraps up some zinc granules, just becomes scum silica frost.In order to reduce the amount of scum silica frost, in industrial practice, add ammonium chloride usually, the ammonium chloride that adds at high temperature decomposes the hydrogenchloride of generation and the zinc chloride that the zinc oxide reaction generates eutectic, impel the zinc granule polymerization that is wrapped like this, sink in the zinc melt, reduce scum silica frost output.Its reaction is as follows:
NH
4Cl＝NH
3↑+HCl
ZnO+2HCl＝ZnCl
2+H
2O
Therefore, scum silica frost is the mixture of a kind of zinc oxide, zinc chloride and metallic zinc.
In order to improve the founding rate of recovery, have two kinds of methods to adopt: the one, reduce the scum silica frost productive rate, the 2nd, from scum silica frost, reclaim zinc.
According to " zinc metallurgy " the 468th～475 page of introduction of metallurgical industry in November, 1978 press publication, the scum silica frost output capacity during the fusing cathode zinc will be seen the tightness degree of cathode deposit, and this tightness degree depends mainly on the purity and the technical qualification of electrolytic solution.The gained scum silica frost has 3.6～4.7% under situation preferably, also wants many sometimes.This scum silica frost generally contains zinc about 85%.The method of usually conduct scum silica frost has wet method and dry method.Wet method is that the metallic zinc granule of separating perhaps melts ingot casting separately, perhaps melts ingot casting with cathode zinc with scum silica frost cooling back ball milling separating metal zinc granule and zinc oxide, and the mud behind the ball milling separates the solid-liquid body with heavy heat-clearing method, reclaims zinc oxide.Dry method is that scum silica frost is sent into dry ball, and this ball mill is porose shell, and cylindrical screen is arranged around the shell.Ball mill slightly becomes inclination device with sea line.Have after material is packed into wherein and high-endly move to low side, the bulk of scum silica frost is destroyed in ball mill, and metallic zinc is separated with zinc oxide.The big grain of such metallic zinc is discharged by the bottom axle journal of ball mill, and tiny metallic zinc granule and zinc oxide fall into following screen cloth together, and this screen cloth separates metallic zinc granule and zinc oxide again.
The 223rd page of introduction of " heavy metal metallurgy " volume two according to another Chinese industrial press publication in 1961; some factory be with scum silica frost pack into the heating rotating cylinder in carry out good mixing; the oxide film that is wrapped in above the metallic zinc is destroyed; make zinc granule merge into liquid zinc; flow into the bogey from cylinder, termly zinc casting is become zinc ingot metal then.Scum silica frost after handling through rotating cylinder, through vibratory screening apparatus, the macrobead scum silica frost is delivered to crusher in crushing on the sieve, and the scum silica frost after the fragmentation has through sifting out isolates the metallic zinc fritter, and the closed cycle several times are up to scum silica frost again till the fragmentation.The method of above-mentioned processing scum silica frost, its purpose are the zinc that be to reclaim in the scum silica frost, key step be grind, screening.Equipment is simple, and is easy to operate, is effectively to handling the bigger scum silica frost of bulk or particle, can directly reclaim metallic zinc.But, weak point be exactly for particle thinner, particularly less than the zinc in the scum silica frost of 0.833mm (20 order), use above-mentioned treatment process, the rate of recovery of zinc is low, generally can not really directly reclaim metallic zinc, but as producing zinc oxide or producing the raw material of other zinc products, value of the product is lower.In order effectively to reclaim the zinc in the fine fraction scum silica frost, the metallargist has done further research to this.
According to " Hydrometallurgy " 1981.6 (3+4) 261～267, the zinc dross of Hindustan zinc industry company limited smeltery's cathode furnace output, be divided into three parts through grinding, first part be rich zinciferous＞0.25mm (＞50 order) part, directly send back to cathode furnace again founding become zinc ingot metal; Third part is rich in zinc oxide＜0.074mm (＜-200 order), returns Production Flow Chart through stoving oven; Second section, promptly that part of 0.25～0.074mm of intermediary (50 orders～20 orders) is the mixture of metallic zinc and zinc oxide.Through identifying that zinc content is 85～90%, wherein metallic zinc is 55～65%, and zinc chloride is 0.3～0.4%, and all the other are zinc oxide.The metal particle that metallic zinc, zinc oxide is arranged in the mixture in this section and wrapped up by one deck zinc-oxide film, this mixture should not enter the cathode furnace founding, also should not enter the stoving oven roasting, need handle the zinc and the zinc oxide that could reclaim wherein.The method of handling be will become through the second section mixture screen analysis of grinding 0.25mm ,-0.25mm+0.18mm and-three kinds of screen analysis things of 0.18mm+0.074mm (50 orders ,-50 orders+70 orders ,-70 orders+200 orders), leached 30 minutes with 5% sulphuric acid soln respectively, discharge oxide-free and contain＞the metallic zinc particulate of 99%Zn, solution after the leaching contains Zn25～28g/l, chloride 0.25g/l.The solution of zinc sulfate of chloride returns Production Flow Chart after treatment.To leach through 5% sulfuric acid 0.25mm ,-0.25mm+0.18mm and-three kinds of screen analysis things of 0.18mm+0.074mm (50 orders ,-50 orders+70 orders ,-70 orders+200 orders) melt ingot casting respectively, find that the thin more founding rate of recovery of particle is low more.The founding rate of recovery average out to 85% of zinc, the total yield of zinc is 45.15%.In order to improve the founding rate of recovery, send the cathode furnace founding to become zinc ingot metal the metallic zinc particulate of 0.25mm and-0.25mm+0.18mm (50 orders ,-50 orders+70 orders), the founding rate of recovery is respectively 90.6% and 88.5%, the metal recovery rate of-0.18mm+0.074mm (70 orders+200 orders) only 76%, therefore, the metal zinc of-0.18mm+0.074mm (70 orders+200 orders) be used to replace heavy cadmium be only suitable.The advantage of this method is that flow process is simple, is particularly suitable for handling the fine fraction zinc dross, the zinc recovery height; Its shortcoming is; part zinc is metallic zinc granule or metal zinc, and founding is zinc ingot metal or is used to precipitate cadmium, and a part of zinc enters solution and forms the low vitriol oil zinc solution that contains Cl 0.25g/l, Zn 25～25g/l; if directly return Production Flow Chart, bring difficulty to production technique.
In order to overcome the shortcoming that above-mentioned zinc dross treatment process exists, the method that Chinese patent 91105757.9 adopts is as follows:
After the zinc dross that contains zinc 75～85% of output cools off during by founding negative electrode zinc metal sheet, in ore mill, add earlier entry and add zinc dross again and carry out wet grinding, in process of lapping, wipe the zinc-oxide film on zinc granule surface, discharge metallic zinc, after discharging ball mill, classified machine and vibratory screening apparatus are isolated＞metallic zinc granule of 0.05mm, send the direct founding of smelting furnace to become zinc ingot metal, and output secondary scum silica frost, this part zinc accounts for 36% of scum silica frost weight, the founding rate of recovery＞87%.Sieve the trickle material of following＜0.5mm, send shaking table to sort, the zinc of output metal zinc accounts for 80% of scum silica frost weight respectively, after metal zinc drying, the packing, can be used as finished product uses, for example be used for zinc dust precipitation precipitation purifying zinc sulfate solution or send the smelting furnace fusing to cast zinc ingot metal, and output secondary scum silica frost.The mine tailing of shaking table output be contain Zn70% ± quality oxide zinc, sell as finished product drying, packing back.The intermediates of shaking table output are the zinc granules that has zinc oxide by film wrapped.These intermediates return ore mill, carry out again levigate, wipe the surface zinc-oxide film, discharge metallic zinc, send grading machine, vibratory screening apparatus, ball mill to carry out classification, sieve, sort, output metal zinc and oxide powder and zinc and the metallic zinc granule that is wrapped in by zinc-oxide film, i.e. secondary intermediates respectively.These secondary intermediates return ore mill again, fine grinding again, classification again, sieve, sort and form a closed cycle, further reclaim metallic zinc and zinc oxide.The secondary scum silica frost of output in sending the smelting furnace fusion-casting process returns ore mill and continue to handle, through levigate, classification, sieve, sort, output metal zinc and oxide powder and zinc and the metallic zinc granule that is wrapped in by zinc-oxide film, i.e. secondary intermediates respectively.These secondary intermediates return ore mill again, fine grinding again, classification again, sieve, sort and form a closed cycle, further reclaim metallic zinc and zinc oxide.
Above-mentioned prior art belongs to the category of physical concentration in essence to the processing mode of zinc dross; be metallic zinc and zinc oxide to be separated according to difference in specific gravity or size; resulting spelter, zinc granule or zinc powder still will return the casting furnace circulation, whenever return once just to produce once new scum silica frost.Can not fundamentally solve the low problem of recovery rate of zinc fusion casting.And utilize beneficiation method handle to reclaim that zinc will consume a large amount of power and consumptive material, the production cost height in the scum silica frost.Sometimes will lose more than gain.
And the method that reduces the scum silica frost productive rate in the prior art when founding still rests on original level, and the way of promptly above-mentioned interpolation ammonium chloride, this way can not satisfy current people to improving the pursuit of recovery rate of zinc fusion casting.
Summary of the invention purpose of the present invention is exactly the method that proposes a kind of new raising recovery rate of zinc fusion casting at above-mentioned prior art problems, this method can obviously be improved the separation performance between zinc dross and the zinc molten mass, reduce zinc content in scum silica frost productive rate and the slag, overcome the deficiencies in the prior art with this.
The method of this raising recovery rate of zinc fusion casting that the present invention proposes is characterized in that adding ammonium chloride and rosiny mixture as slag former or be flux in the zinc melting process, the proportion of rosin in mixture weight is 1-80%.
Scum silica frost adopts letter sorting, screening and reselecting method Separation and Recovery zinc metal and zinc oxide wherein, adopts the zinc ball as grinding media in the attrition process that reclaims scum silica frost.Used zinc spherical diameter is 10mm～200mm.Scum silica frost grinds and adopts the ball mill dry grinding.The proportion of rosin in mixture is that 20-50% is advisable.
The scum silica frost letter sorting is selected big spelter for people's work point, and zinc dross is joined in the ball mill, and in the ball mill outlet, thicker zinc powder and zinc granule are through sieve classification; Thinner zinc powder and zinc oxide are taken away by wind, and is dust collection classified through cyclone, bagroom, obtains the product of different stage.
The material that ball milling comes out is through screening and air classification, and the screening of ball milling outlet is by sieve or secondary screen are formed together.Purpose is to obtain the size fractionated intermediates by the different screenings of purposes by the coarse-grained material that air-flow is taken away.Collect through cyclone and bagroom by the fine that air-flow is taken away.
The beneficial effect that the present invention carries is:
The first, obviously reduced the productive rate of scum silica frost in the zinc founding, with independent interpolation NH
4The Cl slag former is compared, and the scum silica frost productive rate can reduce 3-5 percentage point, thereby has improved the rate of recovery of zinc founding greatly.
The second, add rosin and participate in slag making and make that the content of chlorion reduces in the slag, the zinc white chloride ion content that helps reclaiming in the slag meets the requirement of carrying indium workshop section, reduces the spending of dechlorination.
Description of drawings Fig. 1 is a process flow diagram of the present invention.
Fig. 2 is production unit annexation figure of the present invention.
Embodiment further specifies beneficial effect of the present invention below in conjunction with accompanying drawing.
Zinc dross mainly is zinc granule, oxide powder and zinc and the ZnCl that zinc granule or spelter, zinc-oxide film are wrapped in
2, MnO
2, NH
4The Cl mixture, general zinc dross contains zinc 75～85%.
As depicted in figs. 1 and 2, put in the casting furnace, add by NH by the zinc metal sheet of solution of zinc sulfate electrolysis production
4The slag former slag making that Cl and rosin mixture are formed is skimmed then.By the zinc dross of main frequency furnace (zinc casting furnace) output after stacking naturally cooling, at first artificial separation is chosen big block zinc and is returned casting furnace, and powdery and granular scum silica frost are added in the ball mill 2 by charging opening 1, zinc-oxide film on the zinc granule is wiped, also wiped NH simultaneously
4Cl, ZnCl
2The mode of device zinc ball, employing dry grinding in the ball mill.Ball milling outlet is a trommel screen 3, screen overflow is＞and the broken zinc of 5mm (4 order), discharge by relief outlet 6; The rotating screen screen underflow is the following zinc granule of 5mm (4 order), discharges rotating screen by relief outlet 5; The rotating screen screen underflow is again through 0.38mm (40 order) stationary screen 4 screening, and screen overflow is-5mm (4 order)～+ zinc granule of 0.38mm (40 order), screen underflow is+zinc granule of 60 orders (0.25mm)～-40 orders (0.38mm).Zinc granule less than 0.25mm (60 order) is siphoned away through pipeline 7 by wind in the ball mill outlet, enter cyclone 8, the discharging of cyclone 9 is sieved into two kinds of products through revolving the sieve that shakes, a kind of be-60～+ 80 orders (0.25mm～+ 0.18mm) zinc powder and greater than 80 orders (0.18mm) oxide powder and zinc; What taken down by bagroom 10 mainly is particulate zinc oxide, and it is higher to contain Cl.Tail gas after gathering dust is through dust collecting fan 11 emptyings.
Example: in the casting furnace of founding cathode zinc, drop into negative electrode zinc metal sheet 90.5t, add by NH
4Cl and rosin are pressed 5: 1 weight ratio blended flux 8kg, claw scum silica frost.The scum silica frost of output after cooling, sort out＞the bulk zinc of 20mm after, add the ball mill ball milling, outlet screening place 720kg, at bagroom with revolve the sieve output oxide powder and zinc 1.61t that shakes.Zinc zincification oxygen weight is 2.33t, and the scum silica frost productive rate only is 2.59%.And only add NH
4The productive rate of scum silica frost was all at 6-8% when Cl made flux.This measure has obviously improved recovery rate of zinc fusion casting.Simultaneously, add rosin and participate in slag making also to have produced the another one positively effect be that the content of chlorine in the oxide powder and zinc that reclaims from scum silica frost has reduced, can directly enter and carry indium workshop section and extract indium metal.
The proportion of rosin in mixed flux is adjusted by 1%, 80%, 40% respectively, and when all the other conditions were constant, gained scum silica frost productive rate all had reduction in various degree, and along with the increase of rosin proportion, the content of chlorine also reduces thereupon in the zinc white that reclaims in the slag.The Comprehensive Experiment situation, suitable rosin proportion is 20-50%.
Claims (5)
1. a method that improves recovery rate of zinc fusion casting is characterized in that adding ammonium chloride and rosiny mixture as slag former in the zinc melting process, and the proportion of rosin in mixture weight is 1-80%; Scum silica frost adopts letter sorting, screening and reselecting method Separation and Recovery zinc metal and zinc oxide wherein, adopts the zinc ball as grinding media in the attrition process that reclaims scum silica frost; The scum silica frost letter sorting is selected big spelter for people's work point, and zinc dross is joined in the ball mill, and in the ball mill outlet, thicker zinc powder and zinc granule are through sieve classification; Thinner zinc powder and zinc oxide are taken away by wind, and is dust collection classified through cyclone, bagroom, obtains the product of different stage; The material that ball milling comes out is through screening and air classification, the screening of ball milling outlet by together or secondary screen form.
2. the method for raising recovery rate of zinc fusion casting according to claim 1 is characterized in that scum silica frost grinds the dry grinding of employing ball mill.
3. the method for raising zinc recovery according to claim 1 is characterized in that the proportion of rosin in mixture is that 20-50% is advisable.
4. the method for raising recovery rate of zinc fusion casting according to claim 1 is characterized in that used zinc spherical diameter is 10mm～200mm.
5. the method for raising recovery rate of zinc fusion casting according to claim 1, the fine that it is characterized in that being taken away by air-flow is through cyclone and bagroom collection.
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| CN102423803B (en) * | 2011-11-24 | 2013-06-05 | 云南云铜锌业股份有限公司 | Method for extracting metal zinc powder with different purposes from zinc dross |
| CN102443708A (en) * | 2011-12-08 | 2012-05-09 | 葫芦岛锌业股份有限公司 | Device and method for extracting zinc powder from zinc casting floating slag |
| CN103194619A (en) * | 2013-04-23 | 2013-07-10 | 吴鋆 | Fusion casting method of cathode zinc sheets |
| CN103212716A (en) * | 2013-04-23 | 2013-07-24 | 吴鋆 | Method of preparing metal zinc powder |
| CN103643055B (en) * | 2013-11-02 | 2015-03-04 | 株洲冶炼集团股份有限公司 | Total wet method zinc smelting concentrate production material preparation technology |
| CN104772271A (en) * | 2014-01-10 | 2015-07-15 | 汉中锌业特种材料有限公司 | Separation method of zinc ash in smelting zinc dross |
| CN109019668B (en) * | 2018-10-09 | 2021-09-28 | 湖南工业大学 | Method for preparing superfine active zinc oxide powder by hot ball milling oxidation |
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