CN106756090A - 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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- CN106756090A CN106756090A CN201611193351.4A CN201611193351A CN106756090A CN 106756090 A CN106756090 A CN 106756090A CN 201611193351 A CN201611193351 A CN 201611193351A CN 106756090 A CN106756090 A CN 106756090A
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Abstract
The invention provides a kind of method of the continuous decopper(ing) of lead bullion.The method includes being passed through lead bullion liquid and forming molten bath in decopper(ing) stove, and controls the temperature in molten bath gradually to reduce 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 carry out decopper(ing) to vulcanizing agent is added in molten bath；The method also includes adding cold burden into molten bath from the top of decopper(ing) stove, and cold burden is lead of the copper content in the range of 0.03~0.06wt%.It is used as cold burden by adding lead of the copper content in the range of 0.03~0.06wt% from the top of decopper(ing) stove to molten bath, so that in lead bullion liquid copper content " being diluted " and reduce, so that the concentration of copper is reduced in the lead bullion liquid being located at originally on the equilibrium concentration liquid level that copper is separated out, and the copper sticked in the stove knot on inwall is redissolved in lead bullion liquid, so that stove knot returns molten prepurging, and then suppress the generation of stove 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 technology
In lead smelting process, the refining of lead bullion generally uses electrolytic refining process.In electrorefining processes, as the Cu in lead
During higher than 0.06%, part Cu-Pb initially forms eutectic, and this can make hard and fine and close, the anodic passivity that positive plate becomes, and hinders lead
Normal dissolving, cause tank voltage to raise, thus cause copper dissolving and negative electrode separate out, make lead bullion cupric raise.To avoid
The problem, typically requires that positive plate cupric must contain lead bullion before electrorefining processes in being not higher than 0.06%, therefore production
Copper is tried one's best reduction.But existing smeltery is more difficult to accomplish this point, some smelteries are still in the positive plate using cupric 0.08%.
Lead bullion (containing flux in 0.06~0.08wt%) copper removal operation for using domestic at present is still almost in market pot
Carry out liquate and add sulphur copper removal, the copper in lead bullion is transferred to scum silica frost.Specifically, it is to pour into market pot lead bullion, makes it certainly
So cooling；With temperature reduction, the copper dissolution degree reduction in lead bullion, metallic copper can be separated out and float to surface；Manually pull one out
Behind part, then deep copper removal is carried out to addition vulcanizing agent in market pot, its principle is vulcanizing agent and flux and dissolving in lead bullion
Copper reacts to form matte and slag, is manually pulled out again after floating to surface.Adding vulcanizing agent to carry out deep copper removal needs one
Constant temperature degree, it is therefore necessary to heated in molten lead pot bottom, the lead bullion of natural cooling is heated up again and is removed with completing depth
Copper.
There is several respects notable defect in this method：
1) market pot limited volume, it is impossible to adapt to the requirement that present lead smelts maximization development.Because market pot is needed
Manually to drag for slag, drag for matte, artificial opereating specification is limited, market pot diameter can not possibly be made thin big, therefore volume is also just received
Limit.On the other hand, present lead is smelted and generally uses bath smelting --- Direct Reduction Technology, and the PROCESS FOR TREATMENT ability is big, single system
Maximization development trend is obvious.Therefore, market pot copper removal smelts subsequent step as lead, has been not suitable with very much FEOL hair
The need for exhibition.
2) market pot copper removal needs first to lower the temperature, plus is heated up again after vulcanizing agent, and whole process is the situation for having fluctuation in temperature
Lower operation, it is difficult to by temperature control in proper level.In fact, existing market pot copper removal and it is unrealized automatically control, simply
By experiential operating.
3) market pot is a kind of open-top receptacle, and lead is a kind of more volatile and poisonous metal, and market pot copper removal needs
Artificial operation.Therefore the operating environment very severe of the production link, working condition extreme difference.
In view of the foregoing, experimental exploration and commercial Application have been carried out to continuous decopper(ing) technique both at home and abroad.Including：1) lead liquid
The outer continuous decopper(ing) stove of cooled of stove and 2) the continuous decopper(ing) stove of cooled in lead liquid stove.The continuous decopper(ing) stove of external-cooling type is general using anti-
The stove 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 on outside stove
Water cooling element is cooled down to lead liquid.There are Australian Port Pirie lead factory, Ke Mingke in enterprise using the continuous decopper(ing) stove of external-cooling type
Te Leier smelteries of company and Jiangxi Copper Qian Xin metals Co., Ltd, concrete condition are summarized as follows：
The Australian t/a of Port Pirie lead factory production scale about 200,000.The continuous decopper(ing) stove of the factory uses the rectangular reflection stove type of furnace,
Specific capacity is 50t/ (m2D), decopper(ing) lead cupric is 0.06~0.1wt%.Third gear partition wall is set in stove, stove is divided into four
Different temperature provinces.Its collocation form is as shown in figure 1, including feed chute 1；Put lead pan 2；Put sulphur, cinder notch 3；Circulation lead pump
Well 4；Low temperature lead pan 5；Circulation chute 6；Cooled plate 7；Water-cooled flue 8；Burner 9；Wherein, A is charging zone；B finished products area；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) stove charging from by feed chute 1
In area A, Re Qian molten baths area is overflowed to by partition wall, Re Qian molten baths area is followed successively by finished product area B, circulation lead and returns near charging zone A
Area C and circulation lead outlet area D.Partition wall between A and Re Qian the molten bath area of charging zone is highest in three road partition walls, it ensure that
Hot lead molten bath Nei Ge areas will not too fluctuate because of the agitation of charging zone.Lead is circulated in lead in hot lead pond to return to area C and follow
The division wall of ring lead outlet area D highly returns to the division wall of area C higher than finished product area B with circulation lead.Lead in circulation lead outlet area D
Circulation lead pump well 4, circulation lead is pumped into by lead to be lowered the temperature by cooled plate 7 in circulation chute 6, by after cooling
Lead bullion is flowed into low temperature lead pan, is added to circulation lead and returns to area C, and finished product returns to lead and overflows to finished product lead area B by partition wall.
Ke Mingke companies Te Leier smelteries production scale is 100,000 t/a, is carried out slightly using continuous decopper(ing) stove is cooled down outside stove
The continuous decopper(ing) of lead, hearth area is 13.8m2, lead bullion internal circulating load is 300t/h, day treatment lead bullion 300t.By natural in production
Gas burner carries out concurrent heating, and molten bath maintains the thick matte layers of one layer of 250~300mm in stove, the purpose is to slag is isolated with lead bullion.It is logical
The lead bullion crossed after continuous copper removal is delivered to continuously plus sulphur is except scum silica frost flow (CSD), after continuously adding sulphur except scum silica frost flow, lead bullion
In copper be reduced to less than 0.005%.
Jiangxi Copper Qian Xin metals 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, the type of cooling with Port Pirie early stage is identical, and this takes off
Copper stove is also to be cooled down outside stove, only difference is that the continuous decopper(ing) stove cooling element design of Port Pirie in chute is circulated, and river
The water cooling element design of western Tong Yeqianxin metals Co., Ltd is cooled down in cooling pan to lead, in addition, Jiangxi Copper lead zinc
It is circulation lead return area between the continuous decopper(ing) stove 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 the continuous decopper(ing) stove cooled down in lead liquid stove.Neat nurse Kent
Maximum lead smelting enterprise of the Qian Changshi former Soviet Unions, produces about 200,000 tons of lead bullion per year, is cooled down using the furnace bottom air with suspension furnace roof
Continuous decopper(ing) stove.The furnace bed area is 28.85m2, decopper(ing) lead put into fireless cooker by way of siphon, fireless cooker
Volume 310t, pulls scum silica frost out in fireless cooker again.Quartz and soda are added in decopper(ing) stove by crane.The stove is used
Used as vulcanizing agent, vulcanizing agent is added in stove lead concentrate 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 is also needed to plus sulphur copper removal operation.
The continuous decopper(ing) stove of Shenyang Smeltery Factory put into production in the second half year in 1974, and the stove day treatment lead bullion 200t, interruption adds
Material, feed about 20t every time.Its structure is as shown in Fig. 2 including burner 1 '；Lead bullion import 2 '；Operation door 3 '；Slag, sulphur discharge port
4’；Barricade 5 '；Put lead bath 6 '；Put lead scraper-trough conveyer 7 '；Thermometer hole 8 '.Bottom temperature is controlled in 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 stove.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 is put from finished product area C ' afterbody siphons
Go out.The setting of barricade separates smelting zone B ' and finished product area C ' in stove, it is to avoid smelting zone B ' tops matte enters into finished product area C '.
The decopper(ing) stove is exactly in simple terms the combination of reverberatory furnace and market pot, is stopped production in 1980.
In summary, market pot discontinuous running decopper(ing) technique, the process is cycleoperation, and it is strong that scum silica frost such as skims at the process work
Degree is big, and lead steam volatilization can not be controlled effectively, and effect on environment is very big.And be the characteristics of outer, internal cooled type continuous decopper(ing) stove
Specific capacity is high, but it is rear reluctant to there are problems that stove knot is formed.According to the production of Jiangxi Copper Qian Xin metals Co., Ltd
Practice, continuous decopper(ing) stove stove knot is generally divided into molten bath stove knot in surface stove knot and stove, and surface stove knot is general to be produced in circulation pot,
This part stove knot can be removed by way of manually dragging for slag, and molten bath area stove knot is general in furnace bottom, because furnace bottom is chronically at
Low-temperature space, occurs that stove knot is more intractable, and the treatment currently for this class stove knot can only integrally heat up by molten bath, typically needs
3~5 days are taken, lead bullion cannot be processed during this, have impact on the continuity of production.
Therefore, it is badly in need of being improved existing continuous decopper(ing) stove, is produced to suppress stove knot while continuous decopper(ing),
Improve the stability and continuity of production.
The content of the invention
Method it is a primary object of the present invention to provide a kind of continuous decopper(ing) of lead bullion, to solve lead bullion of the prior art
The stove knot that continuous decopper(ing) stove is easily produced, and cause the problem of production stability difference.
To achieve these goals, 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 is passed through molten bath is formed in decopper(ing) stove, and control the temperature in molten bath gradually to reduce 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 to adding vulcanizing agent in molten bath
Carry out decopper(ing)；The method also includes：Cold burden is added into molten bath from the top of decopper(ing) stove, cold burden is copper content 0.03~
Lead in the range of 0.06wt%.
Further, cold burden is selected from the decopper(ing) lead of remaining anode anode scrap or secondary recovery after lead electrolysis.
Further, decopper(ing) stove is rotary furnace.
Further, the method also includes：The step of decopper(ing) stove is carried out into gyration, the angle of gyration is θ,
And -30 ° of ＜ θ≤30 °.
Further, the method is also included to being passed through nitrogen in molten bath or the step of inert gas carries out Gas Stirring.
Further, the step of temperature in above-mentioned control molten bath is gradually reduced from top to bottom includes：Top layer to molten bath is entered
The step of row heating.
Further, the step of top layer to molten bath is heated is heated by the way of fuel combustion.
Further, the step of temperature in above-mentioned control molten bath is gradually reduced from top to bottom is carried out including the bottom to molten bath
The step of cooling.
Further, the step of above-mentioned bottom to molten bath lowers the temperature sets cooling pipe using the furnace bottom in decopper(ing) stove
Mode the bottom in molten bath is lowered the temperature.
Further, above-mentioned vulcanizing agent is lead concentrate, the sulphur scum silica frost of 20~30wt% of 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 copper and sulphur the affinity many characteristic big compared with lead, the control top-down temperature in molten bath gradually drops
It is low so that copper is separated out and floated in the relatively low lead bullion liquid of the temperature of decopper(ing) furnace bottom, because the copper of liquate has certain viscosity, because
And the formation stove knot on inwall is easily adhered in floating-upward process.And copper content is added from the top of decopper(ing) stove to molten bath 0.03
On the one hand lead in the range of~0.06wt% be less than the copper content in lead bullion liquid as cold burden due to the copper content of lead in cold burden,
So that in lead bullion liquid copper content " being diluted " and reduce so that originally positioned at copper separate out equilibrium concentration liquid level on lead bullion liquid in
The concentration reduction of copper, and the copper sticked in the stove knot on inwall is redissolved in lead bullion liquid so that stove knot is returned molten and reached
The effect of prepurging.On the other hand, the temperature of cold burden is low, makes liquid in stove with the corresponding rapid decrease of addition of cold burden, and then cause
Lead bullion liquid is rapidly achieved the saturated concentration of copper dissolution, so cause copper and its compound more than equilibrium concentration to upper strata temperature compared with
Partial dislocation that is high and not up to balancing, then vulcanizes generation Cu by the vulcanizing agent of PbS in lead bullion or addition2S, so as to promote
Copper in furnace bottom lead bullion liquid is constantly diffused up, so as to realize the depth decopper(ing) to lead bullion.
Brief description of the drawings
The Figure of description for constituting the part of the application is used for providing a further understanding of the present invention, of the invention to show
Meaning property and its illustrates, for explaining the present invention, not constitute inappropriate limitation of the present invention embodiment.In the accompanying drawings：
Fig. 1 shows the structural representation of the continuous decopper(ing) stove of the lead bullion of a kind of outer cooled of prior art；And
Fig. 2 shows the structural representation of the continuous decopper(ing) stove of the lead bullion of a kind of interior cooled of prior art.
Fig. 3 shows the knot of the continuous decopper(ing) device of helicoid lead bullion in a kind of preferred embodiment of the 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 of the invention
View.
Wherein, above-mentioned accompanying drawing is marked including the following drawings：
1st, feed chute；2nd, lead pan is put；3rd, sulphur, cinder notch are put；4th, lead pump well is circulated；5th, low temperature lead pan；6th, chute is circulated；7、
Cooled plate；8th, water-cooled flue；9th, burner；
1 ', burner；2 ', lead bullion import；3 ', door is operated；4 ', slag, sulphur discharge port；5 ', barricade；6 ', lead bath is put；7 ', put
Lead scraper-trough conveyer；8 ', thermometer hole；
10th, continuous decopper(ing) furnace body；20th, support roller device；30th, drive device；
11st, furnace wall；12nd, furnace chamber；
111st, cold burden adds mouth；112nd, burner opening；113rd, decopper(ing) lead outlet；114th, partition wall；115th, Gas Stirring enters
Mouthful；116th, outlet flue；117th, lead bullion liquid entrance.
Specific embodiment
It should be noted that in the case where not conflicting, the feature in embodiment and embodiment in the application can phase
Mutually combination.The present invention is described in detail below in conjunction with embodiment.
As background section is previously mentioned, the continuous decopper(ing) stove of lead bullion of the prior art exists and easily produce stove knot and lead
The defect of production stability difference is caused, in order to improve this situation, in a kind of typical implementation method of the application, there is provided a kind of
The method of the continuous decopper(ing) of lead bullion, the method includes：Lead bullion liquid is passed through molten bath is formed in decopper(ing) stove, and control the temperature in molten bath from
Gradually reduce from top to bottom, the temperature at the top in molten bath is 1200~1300 DEG C, the temperature of the bottom in molten bath is 400~450 DEG C；
And decopper(ing) is carried out to vulcanizing agent is added in lead bullion liquid, decopper(ing) lead is obtained after cooling；The method also includes：From the top of decopper(ing) stove
Portion is lead of the copper content in the range of 0.03~0.06wt% to cold burden, cold burden is added in molten bath.
The continuous method for decoppering of above-mentioned lead bullion of the invention is reduced with the reduction of temperature based on copper solubility in lead
And the copper many characteristic big compared with sulphur and lead with the affinity of sulphur.The decopper(ing) stove of prior art is respectively provided with the temperature in control molten bath certainly
The function of gradually being reduced under above, control the temperature in molten bath gradually reduces from from top to bottom so that the temperature of molten bath bottom is relatively low
Lead bullion liquid in copper separate out and by floating, because the copper of liquate has certain viscosity, thus be easily adhered in floating-upward process
Stove knot is formed on decopper(ing) stove inwall.And lead of the copper content in the range of 0.03~0.06wt% is added from decopper(ing) furnace roof portion to molten bath
As cold burden, on the one hand because the copper content of lead in cold burden is less than the copper content in lead bullion liquid so that copper content " quilt in lead bullion liquid
Dilute " and reduce so that the concentration reduction of copper in the lead bullion liquid on equilibrium concentration liquid level for being separated out positioned at copper originally, and then make to glue
Copper in the stove knot being attached on inwall is redissolved in lead bullion liquid, to realize that stove knot returns effect that is molten and reaching prepurging.It is another
Aspect, the temperature of cold burden is low, makes liquid in stove with the corresponding rapid decrease of addition of cold burden, and then causes that lead bullion liquid is rapidly achieved copper
The saturated concentration of dissolving, and then cause higher to upper strata temperature more than the copper and its compound of equilibrium concentration and be not up to what is balanced
Partial dislocation, then vulcanizes generation Cu by the vulcanizing agent of PbS in lead bullion or addition2S, so as to promote the bottom lead bullion liquid in molten bath
In copper constantly diffuse up, so as to realize the depth decopper(ing) to 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 stove knot processed so that decopper(ing) stove keeps relatively low stove knot rate, reduces the production procedure that individually cleaning stove connects, and improves
Lead smelts the stability of production.In the above method, lead to copper content in the range of 0.03~0.06wt%
Specifically originate and be not particularly limited, above-mentioned cold burden includes but are not limited to remaining anode anode scrap or secondary recovery after lead electrolysis
Decopper(ing) lead.The decopper(ing) lead of secondary recovery can be that the underproof chloride plate of casting, or copper content exist herein
The decopper(ing) lead that other techniques in the range of 0.03~0.06wt% are reclaimed, such as the present processes obtain decopper(ing) lead.It is preferred that making
With lead be electrolysed after remaining anode anode scrap as cold burden, can twice laid, can suppress again stove knot generation, moreover it is possible to realize in stove
The quick regulation of temperature.
The above method adds above-mentioned cold burden in including the lead bullion liquid to body of heater and is capable of achieving to suppress the effect of stove knot, in order to
The removing to stove knot is more effectively realized during continuous decopper(ing), it is above-mentioned de- in a kind of preferred embodiment of the application
Copper stove is rotary furnace.Because rotary furnace is easy to implement gyration, and works as the relatively low region of decopper(ing) stove middle and lower part temperature and form stove
During knot, gyration can be carried out in the range of certain angle, by stove knot position go to chaotropic face closer to high-temperature region, so as to suppress
Stove knot is produced.
Additionally, rotary furnace has proved to be metallurgical furnace structure type the most stable, the big of decopper(ing) furnace volume is easy to implement
Type, maximization can meet the t/a lead bullion treating capacities of single series the biggest in the world 400,000.In another preferred embodiment of the invention,
The above method also includes the step of decopper(ing) stove is carried out into back rotation, and the angle of gyration is θ, -30 ° of ＜ θ≤30 °.At the angle
Gyration is carried out in the range of degree is conducive to the stove that will be sticked on inwall to carry down to temperature region higher so that stove knot returns molten
In lead bullion liquid.As shown in figure 4, rotary furnace can from M points be positioned around central shaft turn left -30 ° arrival M1 positions
Or turn right 30 ° and reach the position of M2, the angular range of (or rotating clockwise) of turning left herein is designated as bearing, and
The angular range of (or rotating counterclockwise) of turning right is designated as just.
In an advantageous embodiment, the method for the continuous decopper(ing) of above-mentioned lead bullion also includes to being passed through nitrogen in the middle part of decopper(ing) stove
Or inert gas is the step of carry out Gas Stirring.Decopper(ing) stove central region is stirred using gas can reduce slag it is leaded and
Cupric, stabilization discard slag with copper, improves copper recovery.
In the above-mentioned methods, the step of temperature in molten bath is gradually reduced from top to bottom in control decopper(ing) stove is except above-mentioned from de-
To being added outside cold burden in molten bath, the step of also heated including the top layer to molten bath, (top layer in molten bath is at the top of copper stove
The liquid level in molten bath).The step of heating, is able to maintain that the high temperature on molten bath top layer, makes whole molten bath maintain temperature from top to bottom gradually to drop
Low variation tendency.Thus, any mode of heating is applied to the present invention.In a preferred embodiment, the top layer to molten bath is entered
The step of row heating, is heated by the way of fuel combustion.Such as can be by being arranged on the burning of body of heater one or both sides
Device, carries out burning and is heated using pure oxygen as fuel.
In the above-mentioned methods, in the step of temperature in control molten bath is gradually reduced from top to bottom, the temperature of molten bath bottom can
Lowered the temperature with natural cooling, it is also possible to lowered the temperature by way of forced cooling according to needs of production.It is existing to molten bath
The mode that the temperature of bottom is lowered the temperature is applied to the present invention.In an advantageous embodiment, the temperature in above-mentioned control molten bath
The step of the step of gradually reducing from top to bottom is lowered the temperature including the bottom to molten bath.It is highly preferred that entering to the bottom in molten bath
The step of row cooling, is lowered the temperature using the bottom to molten bath by the way of the bottom of decopper(ing) stove setting cooling pipe.
Vulcanizing agent used uses existing vulcanizing agent in the above-mentioned continuous method for decoppering of lead bullion.In the present invention, sulphur
Agent includes but are not limited to the sulphur scum silica frost that lead concentrate, troilite or sulfur content are 20~30wt%；Or vulcanizing agent is sulphur list
Matter.Sulphur scum silica frost herein can derive from the sulfur content sulphur scum silica frost within the above range in existing process, such as, can be logical
Cross to the sulfur-bearing scum silica frost obtained in the technique for vulcanizing agent is added in lead pan carrying out decopper(ing).
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 drive device 30, wherein, it is continuous de-
The outer layer of copper furnace body 10 is box hat, and inside is formed with laying fireproof bricks, and it is shaped as 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 and adds mouth 111 and exhanst gas outlet on the roof of furnace wall 11
116, burner opening 112, the lower section of burner opening 112 are provided with the wall of side decopper(ing) lead outlet 113 and burner opening 112 are set
Lead bullion liquid entrance 117 is set on relative side furnace wall, one or many can also be set according to production needs in furnace chamber 12 in addition
Individual partition wall 114, multiple Gas Stirring entrances 115 are being provided with below the continuous axis of decopper(ing) furnace body 10.
In another preferred embodiment, as shown in figure 4, above-mentioned rotary furnace is supported by two groups of support roller devices 20, by driving
Device 30 realizes the revolution of body of heater, and drive device 30 can both be combined using motor for speed reducer, it would however also be possible to employ telescopic hydraulic cylinder
Body of heater is driven to realize the gyration in the range 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, below less than the temperature of copper dissolution degree, copper is easily separated out and forms stove knot, and because above-mentioned rotary furnace can be returned
Transhipment is dynamic, and the furnace wall 11 that can will have stove knot is rotated to of a relatively high temperature, stove knot is dissolved again.The process equivalent to
The process of prepurging, so that continuous decopper(ing) furnace body 10 keeps relatively low stove knot rate, reduces and individually clears up stove knot
Production procedure, improves the stability of decopper(ing).And, cold burden is provided with the top of furnace wall and adds mouth 111 so that
The cold burden of lead of the copper content in the range of 0.03~0.06wt% is added in from furnace roof to body of heater, due to the copper content of lead in cold burden
Less than the copper content in lead bullion liquid so that copper content " being diluted " in lead bullion liquid and reduce so that originally positioned at copper separate out it is flat
The concentration reduction of copper in lead bullion liquid on weighing apparatus concentration liquid level, and the copper sticked in the stove knot on inwall is redissolved in lead bullion liquid
In so that stove knot returns molten and reaches and suppress the effect that stove knot is produced.
As can be seen from the above description, the above embodiments of the present invention realize following technique effect：Due to stove knot
Mainly high-grade matte solidifies bonding because fusing point is high and forms, and anode scrap or cold conditions lead are formed by the casting of 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.Return
Rotatable continuous decopper(ing) stove causes high-grade matte stove knot as its swinging is moved and returns and melt into molten bath, so as to solve stove knot
Problem.
The continuous method for decoppering of above-mentioned lead bullion of the invention, by increase in from furnace roof to body of heater add copper content 0.03~
The step of lead in the range of 0.06wt% is as cold burden, on the one hand because the copper content of lead in cold burden is less than the cupric in lead bullion liquid
Amount so that copper content " being diluted " in lead bullion liquid and reduces so that originally positioned at copper precipitation equilibrium concentration liquid level on lead bullion
The concentration reduction of copper in liquid, and the copper sticked in the stove knot on inwall is redissolved in lead bullion liquid so that stove knot return it is molten and
Reach the effect of prepurging.On the other hand, the temperature of cold burden is low, makes liquid in stove with the corresponding rapid decrease of addition of cold burden, and then
So that lead bullion liquid is rapidly achieved the saturated concentration of copper dissolution, and then cause copper and its compound more than equilibrium concentration to upper strata temperature
Partial dislocation that is higher and not up to balancing is spent, generation Cu is then vulcanized by the vulcanizing agent of PbS in lead bullion or addition2S, so that
The copper in furnace bottom lead bullion liquid is promoted constantly to diffuse up, so as to realize the depth decopper(ing) to lead bullion.
The preferred embodiments of the present invention are the foregoing is only, is not intended to limit the invention, for the skill of this area
For art personnel, the present invention can have various modifications and variations.It is all within the spirit and principles in the present invention, made any repair
Change, equivalent, improvement etc., should be included within the scope of the present invention.
Claims (10)
1. a kind of method of the continuous decopper(ing) of lead bullion, methods described includes：
Lead bullion liquid is passed through molten bath is formed in decopper(ing) stove, and control the temperature in the molten bath gradually to reduce 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
Decopper(ing) is carried out to vulcanizing agent is added in the molten bath；
Characterized in that, methods described also includes：
Cold burden is added into the molten bath from the top of decopper(ing) stove, the cold burden is copper content in the range of 0.03~0.06wt%
Lead.
2. method according to claim 1, it is characterised in that the cold burden is remaining anode anode scrap or two after lead electrolysis
The decopper(ing) lead of secondary recovery.
3. method according to claim 1, it is characterised in that the decopper(ing) stove is rotary furnace.
4. method according to claim 3, it is characterised in that methods described also includes：The decopper(ing) stove is turned round
The step of motion, the angle of the gyration is θ, and -30 ° of ＜ θ≤30 °.
5. method according to claim 1, it is characterised in that methods described also include to be passed through in the molten bath nitrogen or
The step of inert gas carries out Gas Stirring.
6. method according to claim 1, it is characterised in that what the temperature in the control molten bath was gradually reduced from top to bottom
Step includes：The step of top layer to the molten bath is heated.
7. method according to claim 6, it is characterised in that the step of top layer to the molten bath is heated is using combustion
Expect that the mode of burning is heated.
8. method according to claim 1, it is characterised in that what the temperature in the control molten bath was gradually reduced from top to bottom
Step includes the step of lowering the temperature to the bottom in the molten bath.
9. method according to claim 8, it is characterised in that cooling pipe is set using the furnace bottom in the decopper(ing) stove
Mode is lowered the temperature to the bottom in the molten bath.
10. method according to claim 1, it is characterised in that the vulcanizing agent is lead concentrate, troilite or sulfur content 20
The sulphur scum silica frost of~30wt%；Or the vulcanizing agent is sulphur simple substance.
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| CN110184474A (en) * | 2019-05-16 | 2019-08-30 | 江西铜业股份有限公司 | A kind of chloride plate low temperature casting process |
| 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 |
| CN112899494A (en) * | 2021-01-27 | 2021-06-04 | 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 |
| CN114686925A (en) * | 2022-04-07 | 2022-07-01 | 中国恩菲工程技术有限公司 | Crude lead refining device and crude lead refining method |
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| CN110184474A (en) * | 2019-05-16 | 2019-08-30 | 江西铜业股份有限公司 | A kind of chloride plate low temperature casting process |
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| 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 |
| CN112899494A (en) * | 2021-01-27 | 2021-06-04 | 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 |
| CN114686925A (en) * | 2022-04-07 | 2022-07-01 | 中国恩菲工程技术有限公司 | Crude lead refining device and crude lead refining method |
| 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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