CN106756090B - The method of the continuous decopper(ing) of lead bullion - Google Patents
The method of the continuous decopper(ing) of lead bullion Download PDFInfo
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- CN106756090B CN106756090B CN201611193351.4A CN201611193351A CN106756090B CN 106756090 B CN106756090 B CN 106756090B CN 201611193351 A CN201611193351 A CN 201611193351A CN 106756090 B CN106756090 B CN 106756090B
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- 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
- C22B13/06—Refining
Abstract
The present invention provides a kind of methods of the continuous decopper(ing) of lead bullion.This method includes lead bullion liquid being passed through in decopper(ing) furnace to form molten bath, and the temperature for controlling molten bath gradually decreases from top to bottom, and the temperature at the top in molten bath is 1200~1300 DEG C, and the temperature of the bottom in molten bath is 400~450 DEG C；And vulcanizing agent is added into molten bath and carries out decopper(ing)；This method further includes adding cold burden into molten bath from the top of decopper(ing) furnace, and cold burden is lead of the copper content within the scope of 0.03~0.06wt%.By adding lead of the copper content within the scope of 0.03~0.06wt% as cold burden from the top of decopper(ing) furnace to molten bath, so that in lead bullion liquid copper content " being diluted " and reduce, so that being located at the concentration of copper in the lead bullion liquid on the equilibrium concentration liquid level that copper is precipitated originally reduces, and the copper in the furnace knot being adhered on inner wall is redissolved in lead bullion liquid, so that furnace knot returns molten prepurging, and then inhibit the generation of furnace knot.
Description
Technical field
The present invention relates to lead field of smelting, in particular to a kind of method of the continuous decopper(ing) of lead bullion.
Background technique
In lead smelting process, the refining of lead bullion generallys use electrolytic refining process.In electrorefining processes, as the Cu in lead
When higher than 0.06%, part Cu-Pb initially forms eutectic, this hard and fine and close, anodic passivity that anode plate can be made to become, and hinders lead
Normal dissolution, cause tank voltage to increase, thus cause copper dissolution and cathode be precipitated, make lead bullion cupric increase.To avoid
The problem generally requires anode plate cupric not higher than 0.06%, therefore must contain lead bullion before electrorefining processes in production
Copper reduces as far as possible.But existing smeltery is more difficult to accomplish this point, and some smelteries are still in the anode plate using cupric 0.08%.
Lead bullion (containing flux in 0.06~0.08wt%) copper removal operation used domestic at present is almost still in market pot
It carries out liquate and adds sulphur copper removal, the copper in lead bullion is made to be transferred to dross.Specifically, it is to pour into lead bullion in market pot, makes it certainly
It is so cooling；As temperature reduces, the copper dissolution degree in lead bullion is reduced, and metallic copper can be precipitated and float to surface；Manually pull one out
Behind part, then vulcanizing agent is added into market pot and carries out deep copper removal, principle is dissolved in vulcanizing agent and flux and lead bullion
Copper reacts to form matte and slag, floats to behind surface and manually pulls out again.Vulcanizing agent is added and carries out deep copper removal needs one
Determine temperature, it is therefore necessary to be heated, the lead bullion of natural cooling be heated up again to complete depth and remove in molten lead pot bottom
Copper.
There are several respects notable defects for this method:
1) market pot limited volume does not adapt to the requirement that present lead smelts enlargement development.This is because market pot needs
Manually to fish out slag, fishing matte, manual operation is limited in scope, and market pot diameter can not be made greatly, therefore volume also just by
Limit.On the other hand, present lead smelting generallys use bath smelting --- and Direct Reduction Technology, the process ability is big, single system
Enlarged development trend is obvious.Therefore, market pot copper removal smelts subsequent step as lead, has been not suitable with very much front process hair
The needs of exhibition.
2) market pot copper removal needs first to cool down, and heats up again after adding vulcanizing agent, and whole process is that have the case where fluctuation in temperature
Lower operation, it is difficult to control temperature in proper level.In fact, existing market pot copper removal and unrealized automatic control, only
By experiential operating.
3) market pot is a kind of open-top receptacle, and lead is a kind of more volatile and toxic metal, and market pot copper removal needs
Manual operation.Therefore the operating environment very severe of the production link, working condition are very poor.
In view of the foregoing, experimental exploration and industrial application have been carried out to continuous decopper(ing) technique both at home and abroad.It include: 1) lead liquid
The outer continuous decopper(ing) furnace of cooled of furnace and 2) the continuous decopper(ing) furnace of cooled in lead liquid furnace.The continuous decopper(ing) furnace of external-cooling type is general using anti-
The furnace type of furnace is penetrated, the general setting circulation lead well being connected with reverberatory furnace, low temperature lead pan puts lead pan.Lead liquid is by being arranged in outside furnace
Water cooling element cools down lead liquid.There are Australian Port Pirie lead factory, Ke Mingke in enterprise using the continuous decopper(ing) furnace of external-cooling type
The smeltery Te Leier, company and Jiangxi Copper Qian Xin metal Co., Ltd, concrete condition are summarized as follows:
About 200,000 t/a of Australian Port Pirie lead factory production scale.The continuous decopper(ing) furnace of the factory uses the rectangular reflection furnace type of furnace,
Specific capacity is 50t/ (m2D), decopper(ing) lead cupric is 0.06~0.1wt%.Third gear partition wall is set in furnace, stove is divided into four
Different temperature regions.Its collocation form is as shown in Figure 1, include feed chute 1；Put lead pan 2；Put sulphur, cinder notch 3；Recycle lead pump
Well 4；Low temperature lead pan 5；Recycle chute 6；Water-cooled plate 7；Water-cooled flue 8；Burner 9；Wherein, A is charging zone；The finished product area B；C is to follow
Ring lead returns to area, and D is circulation lead outlet area.In production process, hot lead is added to continuous decopper(ing) furnace charging from by feed chute 1
In area A, the molten bath Re Qian area is overflowed to by partition wall, the molten bath Re Qian area is followed successively by finished product area B close to charging zone A, circulation lead returns
Area C and circulation lead outlet area D.Partition wall between the molten bath the A and Re Qian area of charging zone is highest in three partition walls, it ensure that
The hot lead molten bath area Nei Ge will not excessively be fluctuated because of the agitation of charging zone.Lead is recycled in lead in hot lead pond to return to area C and follow
The division wall height of ring lead outlet area D is higher than finished product area B and recycles the division wall that lead returns to area C.Recycle the lead in lead outlet area D
It is conveyed by lead pump into circulation lead pump well 4, circulation lead and is cooled down in circulation chute 6 by water-cooled plate 7, after cooling
Lead bullion is flowed into low temperature lead pan, is added to circulation lead and returns to area C, finished product returns to lead and overflows to finished product lead area B by partition wall.
The Ke Mingke company smeltery Te Leier production scale is 100,000 t/a, is carried out using continuous decopper(ing) furnace cooling outside furnace thick
The continuous decopper(ing) of lead, hearth area 13.8m2, lead bullion internal circulating load is 300t/h, day handles lead bullion 300t.By natural in production
Gas burner carries out concurrent heating, and molten bath maintains the matte layer of one layer of 250~300mm thickness in furnace, and the purpose is to slag is isolated with lead bullion.It is logical
Lead bullion after crossing continuous copper removal is delivered to continuously plus sulphur is except dross process (CSD), after continuously sulphur being added to remove dross process, lead bullion
In copper be reduced to 0.005% or less.
Jiangxi Copper Qian Xin metal Co., Ltd has introduced continuous decopper(ing) technique within 2012, the system lead bullion internal circulating load
350t/h~450t/h, daily handling ability 300t.Hearth area is 13m2, identical as the type of cooling of Port Pirie early stage, this is de-
Copper furnace is also the cooling outside furnace, only difference is that the continuous decopper(ing) furnace cooling element of Port Pirie designs in circulation chute, and river
The water cooling element design of western Tong Yeqianxin metal Co., Ltd cools down lead in cooling pan, in addition, Jiangxi Copper lead zinc
It is circulation lead return area between the continuous decopper(ing) furnace finished product area of metal Co., Ltd and feed zone, and early stage Port Pirie and Te Leier
The finished product area of factory is all close to charging zone.Circular flow is calculated according to inlet amount and lead bullion temperature difference.
There are neat nurse Kent lead factory and Shenyang Smeltery Factory in enterprise using continuous decopper(ing) furnace cooling in lead liquid furnace.Neat nurse Kent
Lead factory is maximum lead smelting enterprise, the former Soviet Union, produces about 200,000 tons of lead bullion per year, cooling using the furnace bottom air with suspension furnace roof
Continuous decopper(ing) furnace.The furnace bed area is 28.85m2, decopper(ing) lead is put into fireless cooker by way of siphon, fireless cooker
Volume 310t pulls dross out in fireless cooker again.Quartz and soda are added in decopper(ing) furnace by crane.The furnace uses
Lead concentrate is as vulcanizing agent, and vulcanizing agent is added in furnace together after being added in the pot of melt lead bullion, and the lead bullion cupric of output exists
Between 0.06%~0.20%, therefore the decopper(ing) lead of output also needs plus the operation of sulphur copper removal.
The continuous decopper(ing) furnace of Shenyang Smeltery Factory put into production in the second half year in 1974, handled lead bullion 200t the furnace day, and interruption adds
Material, feed about 20t every time.Its structure is as shown in Fig. 2, include burner 1 '；Lead bullion import 2 '；Operate door 3 '；Slag, sulphur discharge port
4'；Barricade 5 '；Put lead bath 6 '；Put lead scraper-trough conveyer 7 '；Thermometer hole 8 '.Bottom temperature control is at 400 DEG C~450 DEG C, top molten bath temperature
1050 DEG C~1150 DEG C of degree.It is divided into charging zone A ', smelting zone B ', finished product area C ' in furnace.Three region areas are respectively 4.2m2,
12.5m2, 5.3m2.Charging zone pool depth 1.2m, smelting zone pool depth 1.9m, decopper(ing) lead are put from the finished product area tail portion C ' siphon
Out.The setting of barricade separates smelting zone B ' and finished product area C ' in furnace, and the smelting zone top B ' matte is avoided to enter finished product area C '.
The decopper(ing) furnace is exactly the combination of reverberatory furnace and market pot in simple terms, is stopped production in 1980.
In summary, market pot discontinuous running decopper(ing) technique, the process are cycleoperation, and it is strong that dross such as skims at the processes labour
Degree is big, and lead steam volatilization not can be effectively controlled, and effect on environment is very big.And the characteristics of outer, internal cooled type continuous decopper(ing) furnace, is
Specific capacity is high, but there is furnace knot and form rear reluctant problem.According to the production of Jiangxi Copper Qian Xin metal Co., Ltd
Practice, continuous decopper(ing) furnace furnace knot are generally divided into molten bath furnace knot in surface furnace knot and furnace, and surface furnace knot generally generates in circulation pot,
This part furnace knot can be removed by way of manually fishing out slag, and molten bath area furnace knot is generally in furnace bottom, since furnace bottom is chronically at
Low-temperature space, occurs that furnace knot is more intractable, can only generally be needed by integrally heating up to molten bath for the processing of this kind of furnace knots at present
3~5 days are taken, lead bullion can not be handled during this, affect the continuity of production.
Therefore, it is badly in need of improving existing continuous decopper(ing) furnace, to inhibit furnace knot to generate while continuous decopper(ing),
Improve the stability and continuity of production.
Summary of the invention
The main purpose of the present invention is to provide a kind of methods of the continuous decopper(ing) of lead bullion, to solve lead bullion in the prior art
The furnace knot that continuous decopper(ing) furnace easily generates, and lead to the problem of production stability difference.
To achieve the goals above, according to an aspect of the invention, there is provided a kind of method of the continuous decopper(ing) of lead bullion, is somebody's turn to do
Method includes: lead bullion liquid to be passed through in decopper(ing) furnace to form molten bath, and the temperature for controlling molten bath gradually decreases from top to bottom, molten bath
The temperature at top is 1200~1300 DEG C, and the temperature of the bottom in molten bath is 400~450 DEG C；And vulcanizing agent is added into molten bath
Carry out decopper(ing)；This method further include: cold burden is added into molten bath from the top of decopper(ing) furnace, cold burden is copper content 0.03~
Lead within the scope of 0.06wt%.
Further, cold burden is selected from remaining anode anode scrap or the decopper(ing) lead of secondary recovery after lead electrolysis.
Further, decopper(ing) furnace is rotary furnace.
Further, this method further include: the step of decopper(ing) furnace is carried out rotary motion, the angle of rotary motion are θ,
And -30 ° of θ≤30 ° <.
Further, this method further includes the steps that nitrogen or inert gas are passed through into molten bath carries out Gas Stirring.
Further, the step of temperature in above-mentioned control molten bath gradually decreases from top to bottom include: to the surface layer in molten bath into
The step of row heating.
Further, the step of heating to the surface layer in molten bath is heated by the way of fuel combustion.
Further, the step of temperature in above-mentioned control molten bath gradually decreases from top to bottom includes carrying out to the bottom in molten bath
The step of cooling.
Further, cooling pipe is arranged using the furnace bottom in decopper(ing) furnace in the step of above-mentioned bottom to molten bath cools down
Mode cool down to the bottom in molten bath.
Further, above-mentioned vulcanizing agent is the sulphur dross of 20~30wt% of lead concentrate, troilite or sulfur content；Or vulcanization
Agent is sulphur simple substance.
Apply the technical scheme of the present invention, the continuous method for decoppering of lead bullion of the invention be based on copper in lead solubility with temperature
The reduction of degree and reduce and more characteristics that the affinity of copper and sulphur is big compared with lead, the control top-down temperature in molten bath gradually drop
It is low, so that copper is precipitated and floats in the lower lead bullion liquid of the temperature of decopper(ing) furnace bottom, since the copper of liquate has certain viscosity, because
And formation furnace knot on inner wall is easily adhered in floating-upward process.And copper content is added 0.03 from the top of decopper(ing) furnace to molten bath
Lead within the scope of~0.06wt% is as cold burden, on the one hand since the copper content of lead in cold burden is lower than the copper content in lead bullion liquid,
So that in lead bullion liquid copper content " being diluted " and reduce so that originally be located at copper be precipitated equilibrium concentration liquid level on lead bullion liquid in
The concentration of copper reduces, and the copper in the furnace knot being adhered on inner wall is redissolved in lead bullion liquid, so that furnace knot returns molten and reaches
The effect of prepurging.On the other hand, the temperature of cold burden is low, makes liquid in furnace with the corresponding rapid decrease of addition of cold burden, so that
Lead bullion liquid is rapidly achieved the saturated concentration of copper dissolution so that be more than equilibrium concentration copper and its compound to upper layer temperature compared with
Partial dislocation that is high and not up to balancing, is then vulcanized by the vulcanizing agent of PbS in lead bullion or addition and generates Cu2S, to promote
Copper in furnace bottom lead bullion liquid constantly diffuses up, to realize the depth decopper(ing) to lead bullion.
Detailed description of the invention
The accompanying drawings constituting a part of this application is used to provide further understanding of the present invention, and of the invention shows
Examples and descriptions thereof are used to explain the present invention for meaning property, does not constitute improper limitations of the present invention.In the accompanying drawings:
Fig. 1 shows a kind of structural schematic diagram of the continuous decopper(ing) furnace of lead bullion of outer cooled of the prior art；And
Fig. 2 shows a kind of structural schematic diagrams of the continuous decopper(ing) furnace of lead bullion of interior cooled of the prior art.
Fig. 3 shows the knot of the continuous decopper(ing) device of helicoid lead bullion in a kind of preferred embodiment according to the present invention
Structure schematic diagram；And
Fig. 4 shows the side of the continuous decopper(ing) device of helicoid lead bullion in a kind of preferred embodiment according to the present invention
View.
Wherein, the above drawings include the following reference numerals:
1, feed chute；2, lead pan is put；3, sulphur, cinder notch are put；4, lead pump well is recycled；5, low temperature lead pan；6, chute is recycled；7,
Water-cooled plate；8, water-cooled flue；9, burner；
1 ', burner；2 ', lead bullion import；3 ', door is operated；4 ', slag, sulphur discharge port；5 ', barricade；6 ', lead bath is put；7 ', it puts
Lead scraper-trough conveyer；8 ', thermometer hole；
10, continuous decopper(ing) furnace body；20, support roller device；30, driving device；
11, furnace wall；12, furnace chamber；
111, mouth is added in cold burden；112, burner opening；113, decopper(ing) lead outlet；114, partition wall；115, Gas Stirring enters
Mouthful；116, outlet flue；117, lead bullion liquid entrance.
Specific embodiment
It should be noted that in the absence of conflict, the features in the embodiments and the embodiments of the present application can phase
Mutually combination.Below in conjunction with embodiment, the present invention will be described in detail.
As background technology part is previously mentioned, the continuous decopper(ing) furnace of lead bullion in the prior art, which exists, to be easy to produce furnace knot and leads
The defect of production stability difference is caused in a kind of typical embodiment of the application, to provide one kind to improve this situation
The method of the continuous decopper(ing) of lead bullion forms molten bath this method comprises: lead bullion liquid is passed through in decopper(ing) furnace, and control the temperature in molten bath from
It gradually decreases from top to bottom, the temperature at the top in molten bath is 1200~1300 DEG C, and the temperature of the bottom in molten bath is 400~450 DEG C；
And add vulcanizing agent into lead bullion liquid and carry out decopper(ing), decopper(ing) lead is obtained after cooling；This method further include: from the top of decopper(ing) furnace
Portion adds cold burden into molten bath, and cold burden is lead of the copper content within the scope of 0.03~0.06wt%.
The continuous method for decoppering of above-mentioned lead bullion of the invention is that solubility is reduced with the reduction of temperature in lead based on copper
And more characteristics that the affinity of copper and sulphur is big compared with sulphur and lead.The decopper(ing) furnace of the prior art all has the temperature in control molten bath certainly
The function of gradually decreasing under above, controls the temperature in molten bath from gradually decreasing from top to bottom, so that the temperature of molten bath bottom is lower
Lead bullion liquid in copper be precipitated and by floating, easily adhered to since the copper of liquate has certain viscosity, thus in floating-upward process
Furnace knot is formed on decopper(ing) furnace inner wall.And lead of the copper content within the scope of 0.03~0.06wt% is added from decopper(ing) furnace roof portion to molten bath
As cold burden, on the one hand since the copper content of lead in cold burden is lower than the copper content in lead bullion liquid, so that copper content " quilt in lead bullion liquid
Dilute " and reduce, so that being located at the concentration of copper in the lead bullion liquid on the equilibrium concentration liquid level that copper is precipitated originally reduces, and then make to glue
The copper in furnace knot being attached on inner wall is redissolved in lead bullion liquid, to realize that furnace knot returns molten and achievees the effect that prepurging.It is another
The temperature of aspect, cold burden is low, makes liquid in furnace with the corresponding rapid decrease of addition of cold burden, so that lead bullion liquid is rapidly achieved copper
The saturated concentration of dissolution so that be more than equilibrium concentration copper and its compound it is to upper layer temperature higher and not up to balance
Partial dislocation is then vulcanized by the vulcanizing agent of PbS in lead bullion or addition and generates Cu2S, to promote the bottom lead bullion liquid in molten bath
In copper constantly diffuse up, to realize to the depth decopper(ing) of lead bullion.
The continuous method for decoppering of above-mentioned lead bullion of the invention, can not only realize the continuous decopper(ing) to lead bullion, and can also press down
The generation of furnace knot processed reduces the production procedure that individually cleaning furnace connects, improves so that decopper(ing) furnace keeps relatively low furnace knot rate
Lead smelts the stability of production.In the above method, to lead of the copper content within the scope of 0.03~0.06wt%
Specific source is simultaneously not particularly limited, and above-mentioned cold burden includes but are not limited to remaining anode anode scrap after lead electrolysis or secondary recovery
Decopper(ing) lead.The decopper(ing) lead of secondary recovery can be the underproof chloride plate of casting herein, is also possible to copper content and exists
The decopper(ing) lead of other techniques recycling within the scope of 0.03~0.06wt%, such as the present processes obtain decopper(ing) lead.It is preferred that making
Remaining anode anode scrap is as cold burden after using lead to be electrolysed, and waste utilization and furnace knot can be inhibited to generate, moreover it is possible to realize in furnace
The quick adjusting of temperature.
The above method is including adding above-mentioned cold burden in lead bullion liquid to furnace body and can be realized to inhibit the effect of furnace knot, in order to
The removing to furnace knot is more effectively realized during continuous decopper(ing), it is in a preferred embodiment of the present application, above-mentioned de-
Copper furnace is rotary furnace.Since rotary furnace is easy to implement rotary motion, and when temperature lower region in decopper(ing) furnace middle and lower part forms furnace
When knot, rotary motion can be carried out within the scope of certain angle, furnace knot position is gone into the closer high-temperature region in chaotropic face, to inhibit
Furnace knot generates.
In addition, rotary furnace has proved to be metallurgical furnace structure type the most stable, it is easy to implement the big of decopper(ing) furnace volume
Type, enlargement can meet 400,000 t/a lead bullion treating capacity of single series the biggest in the world.In another preferred embodiment of the present invention,
The above method further includes the steps that, by decopper(ing) furnace progress back rotation, the angle of rotary motion is θ, -30 ° of θ≤30 ° <.At the angle
Degree range in carry out rotary motion be conducive to the furnace being adhered on inner wall be carried down to the higher region of temperature so that furnace knot return it is molten
In lead bullion liquid.As shown in figure 4, rotary furnace can from M point be positioned around central axis turn left -30 ° arrival M1 positions
Perhaps turn right 30 ° reach the position of M2 herein by turn left (or rotating clockwise) angular range be denoted as it is negative, and
The angular range of (or rotating counterclockwise) of turning right is denoted as just.
In an advantageous embodiment, the method for the continuous decopper(ing) of above-mentioned lead bullion further includes being passed through nitrogen in the middle part of decopper(ing) furnace
Or inert gas carries out the step of Gas Stirring.Decopper(ing) furnace central region is stirred using gas can reduce clinker it is leaded and
Cupric stablizes discard slag with copper, improves copper recovery.
In the above-mentioned methods, the step of temperature in molten bath gradually decreases from top to bottom in control decopper(ing) furnace is in addition to above-mentioned from de-
The top of copper furnace adds outside cold burden into molten bath, further includes the steps that heating the surface layer in molten bath that (surface layer in molten bath is
The liquid level in molten bath).The step of heating, is able to maintain that the high temperature on molten bath surface layer, and making entire molten bath maintenance, temperature gradually drops from top to bottom
Low variation tendency.Thus, any heating method is suitable for the present invention.In a preferred embodiment, to the surface layer in molten bath into
The step of row heating, is heated by the way of fuel combustion.Such as it can be by the way that the burnings of furnace body one or both sides be arranged in
Device carries out burning as fuel using pure oxygen and is heated.
In the above-mentioned methods, it controls in the step of the temperature in molten bath gradually decreases from top to bottom, the temperature of molten bath bottom can
Cooled down with natural cooling, can also be cooled down by way of forced cooling according to needs of production.It is existing to molten bath
The mode that the temperature of bottom cools down is suitable for the present invention.In an advantageous embodiment, the temperature in above-mentioned control molten bath
The step of gradually decreasing from top to bottom includes the steps that cooling down to the bottom in molten bath.It is highly preferred that the bottom in molten bath into
The step of row cooling, cools down to the bottom in molten bath using in such a way that cooling pipe is arranged in the bottom of decopper(ing) furnace.
Vulcanizing agent used in the above-mentioned continuous method for decoppering of lead bullion uses existing vulcanizing agent.In the present invention, sulphur
Agent includes but are not limited to the sulphur dross that lead concentrate, troilite or sulfur content are 20~30wt%；Or vulcanizing agent is sulphur list
Matter.Sulphur dross herein can derive from the sulphur dross of sulfur content within the above range in prior art, for example, can be logical
It crosses and adds sulfur-bearing dross obtained in the technique of vulcanizing agent progress decopper(ing) into lead pan.
In another preferred embodiment of the application, a kind of rotary furnace suitable for the continuous decopper(ing) of lead bullion is additionally provided,
As shown in figure 3, the rotary furnace includes: continuous decopper(ing) furnace body 10, support roller device 20 and driving device 30, wherein continuous de-
10 outer layer of copper furnace body is steel shell, and inside is formed with fire resisting brick masonry, and shape is cylindrical shape, and continuous decopper(ing) furnace body 10 includes
The furnace chamber 12 that furnace wall 11 and furnace wall 11 surround is provided with cold burden on the roof of furnace wall 11 and mouth 111 and exhanst gas outlet is added
116, be provided on side wall burner opening 112, be arranged below burner opening 112 decopper(ing) lead outlet 113, with burner opening 112
Lead bullion liquid entrance 117 is set on opposite side furnace wall, furthermore can also be arranged one or more in furnace chamber 12 according to production needs
A partition wall 114 is being provided with multiple Gas Stirring entrances 115 below continuous 10 axis of decopper(ing) furnace body.
In another preferred embodiment, as shown in figure 4, above-mentioned rotary furnace is supported by two groups of support roller devices 20, pass through driving
Device 30 realizes the revolution of furnace body, and driving device 30 can both be combined using motor for speed reducer, can also use telescopic hydraulic cylinder
Furnace body is driven to realize the rotary motion within the scope of certain angle.
Due to furnace chamber 12 be temperature in molten bath by 1200 DEG C~1300 DEG C of top be gradually decrease to 400 DEG C of bottom~
450 DEG C, in the temperature lower than copper dissolution degree hereinafter, copper, which is easy to be precipitated, forms furnace knot, and since above-mentioned rotary furnace is able to carry out back
Transhipment is dynamic, can rotate the furnace wall 11 for having furnace knot to relatively high temperature, re-dissolve furnace knot.The process is equivalent to
The process of prepurging reduces so that continuous decopper(ing) furnace body 10 keeps relatively low furnace knot rate and individually clears up furnace knot
Production procedure improves the stability of decopper(ing).Moreover, cold burden is provided at the top of furnace wall is added mouth 111, so that
The cold burden for adding lead of the copper content within the scope of 0.03~0.06wt% into furnace body from furnace roof, due to the copper content of lead in cold burden
Lower than the copper content in lead bullion liquid so that in lead bullion liquid copper content " being diluted " and reduce so that be located at originally copper be precipitated it is flat
The concentration of copper reduces in the lead bullion liquid to weigh on concentration liquid level, and the copper in the furnace knot being adhered on inner wall is redissolved in lead bullion liquid
In, so that furnace knot returns molten and achievees the effect that furnace knot is inhibited to generate.
It can be seen from the above description that the above embodiments of the present invention realized the following chievements: due to furnace knot
Mainly high-grade matte solidifies and bonds since fusing point is high, and anode scrap or cold conditions lead are cast by decopper(ing) lead, are contained
Amount of copper is 0.03%~0.06%, is added in furnace chamber when these low copper raw materials, will substantially reduce the copper content of molten bullion.It returns
Rotatable continuous decopper(ing) furnace makes high-grade matte furnace knot return and melt into molten bath with its rotary movement, to solve furnace knot
Problem.
The continuous method for decoppering of above-mentioned lead bullion of the invention, by increase added into furnace body from furnace roof copper content 0.03~
The step of lead within the scope of 0.06wt% is as cold burden, on the one hand since the copper content of lead in cold burden is lower than the cupric in lead bullion liquid
Amount so that in lead bullion liquid copper content " being diluted " and reduces so that originally be located at copper precipitation equilibrium concentration liquid level on lead bullion
The concentration of copper reduces in liquid, and the copper in the furnace knot being adhered on inner wall is redissolved in lead bullion liquid so that furnace knot return it is molten and
Achieve the effect that prepurging.On the other hand, the temperature of cold burden is low, makes liquid in furnace with the corresponding rapid decrease of addition of cold burden, in turn
So that lead bullion liquid is rapidly achieved the saturated concentration of copper dissolution, so that the copper and its compound that are more than equilibrium concentration are to upper layer temperature
Partial dislocation that is higher and not up to balancing is spent, is then vulcanized by the vulcanizing agent of PbS in lead bullion or addition and generates Cu2S, thus
The copper in furnace bottom lead bullion liquid is promoted constantly to diffuse up, to realize the depth decopper(ing) to lead bullion.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (5)
1. a kind of method of the continuous decopper(ing) of lead bullion, which comprises
Lead bullion liquid is passed through in decopper(ing) furnace and forms molten bath, and the temperature for controlling the molten bath gradually decreases from top to bottom, it is described molten
The temperature at the top in pond is 1200~1300 DEG C, and the temperature of the bottom in the molten bath is 400~450 DEG C；And
Vulcanizing agent is added into the molten bath carries out decopper(ing)；
It is characterized in that, the method also includes:
Cold burden is added into the molten bath from the top of decopper(ing) furnace, the cold burden is copper content within the scope of 0.03~0.06wt%
Lead, since the copper content of lead in cold burden is lower than the copper content in lead bullion liquid so that in lead bullion liquid copper content " being diluted " and drop
It is low, so that being located at the concentration of copper in the lead bullion liquid on the equilibrium concentration liquid level that copper is precipitated originally reduces, and it is adhered on inner wall
Copper in furnace knot is redissolved in lead bullion liquid, so that furnace knot returns molten and achievees the effect that furnace knot is inhibited to generate；
The cold burden is remaining anode anode scrap or the decopper(ing) lead of secondary recovery after lead electrolysis,
The decopper(ing) furnace is rotary furnace, and the rotary furnace includes: continuous decopper(ing) furnace body (10), support roller device (20) and driving
Device (30), wherein continuous decopper(ing) furnace body (10) outer layer is steel shell, and inside is formed with fire resisting brick masonry, and shape is cylinder
Shape, continuous decopper(ing) furnace body (10) include the furnace chamber (12) that furnace wall (11) and furnace wall (11) surround, on the roof of furnace wall (11)
It is provided with cold burden and mouth (111) and exhanst gas outlet (116) is added, be provided with burner opening (112), burner opening on side wall
(112) lead bullion liquid entrance is set on lower section setting decopper(ing) lead outlet (113) and burner opening (112) opposite side furnace wall
(117), one or more partition walls (114) are set in furnace chamber (12), in the setting below continuous decopper(ing) furnace body (10) axis
There are multiple Gas Stirring entrances (115), the rotary furnace is supported by two groups of support roller devices (20), is realized by driving device (30)
The revolution of furnace body；
The method also includes: the step of decopper(ing) furnace is carried out rotary motion, the angle of the rotary motion are θ, and-
30 ° of θ≤30 ° <,
The method also includes being passed through nitrogen or inert gas progress Gas Stirring into the molten bath,
The vulcanizing agent is the sulphur dross of 20~30wt% of lead concentrate, troilite or sulfur content.
2. the method according to claim 1, wherein what the temperature for controlling the molten bath gradually decreased from top to bottom
Step includes: the step of heating to the surface layer in the molten bath.
3. according to the method described in claim 2, it is characterized in that, the step of heating to the surface layer in the molten bath is using combustion
The mode of material burning is heated.
4. the method according to claim 1, wherein what the temperature for controlling the molten bath gradually decreased from top to bottom
Step includes the steps that the bottom to the molten bath cools down.
5. according to the method described in claim 4, it is characterized in that, using the furnace bottom setting cooling pipe in the decopper(ing) furnace
Mode cools down to the bottom in the molten bath.
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| CN110184474B (en) * | 2019-05-16 | 2022-02-11 | 江西铜业股份有限公司 | Low-temperature casting process for lead anode plate |
| CN110184473A (en) * | 2019-05-31 | 2019-08-30 | 郴州融源环保科技股份有限公司 | A kind of new-type Decoppering in lead bullion detinning method |
| CN112899494B (en) * | 2021-01-27 | 2022-11-01 | 河南豫光金铅股份有限公司 | Method for continuous refining and decoppering of lead bullion and producing high-grade matte |
| CN113178636A (en) * | 2021-04-27 | 2021-07-27 | 宁夏瑞银铅资源再生有限公司 | Process method for producing low-tin lead-calcium alloy by using waste lead-acid storage battery waste lead grid |
| CN114686925B (en) * | 2022-04-07 | 2023-09-29 | 中国恩菲工程技术有限公司 | Lead bullion refining device and lead bullion refining method |
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