CN105543498B - It is a kind of to be used to handle high impurity copper concentrate and shallow smelting process of the oxidation without reduction anode refining - Google Patents

It is a kind of to be used to handle high impurity copper concentrate and shallow smelting process of the oxidation without reduction anode refining Download PDF

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Publication number
CN105543498B
CN105543498B CN201510998775.7A CN201510998775A CN105543498B CN 105543498 B CN105543498 B CN 105543498B CN 201510998775 A CN201510998775 A CN 201510998775A CN 105543498 B CN105543498 B CN 105543498B
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oxygen
copper
refining furnace
refining
gas
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CN105543498A (en
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周松林
葛哲令
王志普
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Yanggu Xiangguang Copper Co Ltd
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Yanggu Xiangguang Copper Co Ltd
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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
    • C22B15/00—Obtaining copper
    • C22B15/0026—Pyrometallurgy
    • C22B15/006—Pyrometallurgy working up of molten copper, e.g. refining

Abstract

It is used to handle high impurity copper concentrate and shallow smelting process of the oxidation without reduction anode refining the invention discloses a kind of, the melting process carried out including priority, the process that blows and anode refining process, pass through extraneous oxygen-containing gas of being re-blow under the vacuum state during anode refining in refining furnace, carry out the oxidation operation of desulfurization deferrization removing impurities matter, improve the oxygen-containing gas ratio for being really used for oxidation sweetening in oxygen-containing gas, reduce the oxygen-containing gas ratio for making idle work, reduce the actual use amount of oxygen-containing gas during anode refining, reduce oxygen-containing gas waste, reduce the production cost of anode refining, realize anode refining of the shallow oxidation without reduction of blister copper.

Description

It is a kind of to be used to handle high impurity copper concentrate and shallow smelting of the oxidation without reduction anode refining Method
Technical field
The present invention relates to non-ferrous metal metallurgy technical field, it is used to handling high impurity copper concentrate and shallow more particularly, to one kind Aoxidize the smelting process without reduction anode refining.
Background technology
In Copper making industry, its primary routing is：Melting → blowing → anode refining → electrorefining.Blow process Output blister copper liquation, blister copper liquation is then sent into anode furnace and carries out anode refining, obtains anode copper and a small amount of clinker.Blister copper Liquation anode furnace carry out anode refining substantially process be：The blister copper liquation of converting furnace output flows into anode furnace along chute, reaches To after setting batch, stop blister copper and flow into, anode furnace is turned into oxygen supply oxidation position, side wall tracheae is begun through and is melted to blister copper Liquid blows oxygen-containing gas, such as air or oxygen-enriched air, by executeaaafunction, the sulfur content in sample examination liquation, if contained Sulfur content is not up to standard, continues to aoxidize, until sample examination is qualified, this process is oxidation operation process；Then followed by deslagging；So Afterwards, begin through above-mentioned side wall tracheae and reducibility gas, typically natural gas are blowed into liquation, by executeaaafunction, take Oxygen content in sample chemical examination liquation, if oxygen content is not up to standard, continues to reduce, until sample examination is qualified, this process is reduction Operation process, finally give anode copper melt；Then, cast, obtain anode copper coin.
In Copper making industry, it is well known that above-mentioned oxidation operation and reduction operation is two mutually contradictory operations Process, first oxygen blast desulfurization, when desulfurization is up to standard, according to metallurgical equilibrium principle, oxygen content automatically, inevitably raise with Redress the theoretical needs that should be balanced, as a result oxygen content inevitably excess, then blows natural gas deoxidation, oxygen content is dropped again Get off, process is similar to " first low cost is destroyed, then high cost is remedied ", it is seen that only have sub-fraction in oxygen-containing gas and be used to aoxidize Desulfurization, what remaining most of oxygen-containing gas was made is all idle work, does not play any beneficial effect；It is not only any without playing Beneficial effect, also create significant negative effect：Need to go to remove with the higher natural gas of cost so that whole anode refining Process needs to waste the oxygen-containing gas such as substantial amounts of air or oxygen-enriched air, causes the cost of anode refining very high.At present, Copper making Industry continued downturn and inefficiencies, existing anode refining technique are obviously not suitable for the development of industry.
Therefore, the oxygen-containing gas ratio for being really used for oxidation sweetening in oxygen-containing gas how is improved, idle work is made in reduction Oxygen-containing gas ratio, the actual use amount of oxygen-containing gas during anode refining is reduced, reduce oxygen-containing gas and waste, reduce anode The production cost of refining is the technical problem of those skilled in the art's urgent need to resolve.
The content of the invention
Based on described above, it is used to handle high impurity copper concentrate it is an object of the invention to provide one kind and shallow oxidation is without also The smelting process of former anode refining, this method can improve the oxygen-containing gas ratio for being really used for oxidation sweetening in oxygen-containing gas, The oxygen-containing gas ratio for making idle work is reduced, reduces the actual use amount of oxygen-containing gas during anode refining, is reduced oxygenous Body wastes, and reduces the production cost of anode refining.
To solve above-mentioned technical problem, the present invention adopts the following technical scheme that：
It is a kind of to be used to handle high impurity copper concentrate and shallow smelting process of the oxidation without reduction anode refining, including successively carry out Melting process, blowing process and anode refining process, the anode refining process specifically include following steps：
1) the blister copper liquation of melting is added in the Sheng copper container for containing blister copper liquation；Then refining will be arranged on Feed tube and drain pipe on furnace hearth wall are immersed in the upper liquid level certain depth below of copper melt in the Sheng copper container, Ran Houkai Open the cavity vacuum state in the refining furnace with the vavuum pump that the refining furnace connects, now the vacuum in refining furnace The copper melt contained in copper container is along the feed tube and institute in the presence of atm difference between residual voltage and external atmosphere pressure The cavity passage stated in drain pipe rises in the cavity of the inflow refining furnace；
The profile of the refining furnace is vertical type columnar, and inner hollow forms cavity, the refining furnace include steel shell with And build refractory lining in the steel shell inner surface by laying bricks or stones, be provided with the top of the refining furnace for and the vacuum The gas outlet of pump connection；
The feed tube and fire resisting of the drain pipe including steel-made inner shell, the inner surface for being arranged on the steel-made inner shell Material liner and be arranged on the steel-made inner shell outer surface refractory material outer lining, the feed tube and the drain pipe Length is identical；
The feed tube and the drain pipe be fixedly installed on the bottom wall of the refining furnace and with the bottom of the refining furnace Wall is tightly connected, and the cavity in the refining furnace is interconnected with the cavity passage in the feed tube, in the refining furnace Cavity is interconnected with the cavity passage in the drain pipe, it is all with the device that the refining furnace is connected with the refining furnace The position of connection carries out encapsulation process to prevent the vacuum state destroyed in the refining furnace；
2) driving gas with pressure is blown in the copper melt into the feed tube, then in atm difference and driving gas Drive under the copper melt contained in copper container constantly risen by the feed tube and flow into the refining furnace, it is then described Copper melt in refining furnace is constantly back in the Sheng copper container by the drain pipe by refining furnace outflow again, Described contain forms circulating for copper melt between copper container, feed tube, refining furnace and drain pipe；
Meanwhile in the refining furnace, the copper melt into the refining furnace blows oxygen-containing gas, in the oxygen-containing gas Oxygen element the element sulphur in copper melt is oxidized to the gaseous oxygen compound of sulphur, the oxygen element in the oxygen-containing gas is by copper melt In ferro element be oxidized to the oxide of iron, realize the oxidation operation process of desulfurization deferrization；
Meanwhile a part for whole contents of the impurity element included by the copper melt in the refining furnace is with simple substance shape State is directly volatilized, and the remainder of whole contents is oxidized to volatilize with oxide form after oxide by the oxygen-containing gas, While realizing the oxidation operation process of desulfurization deferrization, the refining process of imurity-removal element simultaneously, the impurity element are realized Including one or more or whole in lead, zinc, arsenic, antimony, bismuth and tin element；
Meanwhile control the vacuum residual voltage in the refining furnace horizontal so that the sulfur content in proper copper melt reaches target sun During requirement of the pole copper to sulfur content, the oxygen content for realizing reaction balance with the sulfur content also reaches target anode copper to oxygen content It is required that；
3) after the step 2) carries out a period of time, the component and content of the copper melt after sample examination anode refining, if Result of laboratory test reaches requirement of the target anode copper to sulfur content and iron content, then abolishes the vacuum shape in the refining furnace first State, the feed tube being arranged on the refining furnace hearth wall and drain pipe are then departed from into the copper melt contained in copper container, oxygen Change the end of job；If result of laboratory test miss the mark anode copper continues anode essence to the requirement of any one in both sulphur or iron Refining, until result of laboratory test reaches requirement of the target anode copper to sulfur content and iron content；Anode refining terminate to obtain sulphur, iron with And the content of oxygen reaches the anode copper melt of target call, containing SO2Flue gas and clinker.
Preferably, in the step 2), the oxygen-containing gas is blowed in a manner of submerging and blowing to the refining furnace Copper melt upper liquid level below, the gas outlet for spraying the oxygen-containing gas is located at the upper liquid level of the copper melt in the refining furnace Below.
Preferably, in the step 2), the oxygen-containing gas is blowed to described in a manner of top-blown gas oxygen rifle In copper melt in refining furnace, the gas outlet of the oxygen rifle is located at more than the upper liquid level of the copper melt in the refining furnace and and copper The upper liquid level of liquation is separated by a certain distance；
The oxygen rifle is the multilayer internal and external casing structure for the hollow pipe for including multiple inside and outside suits, and the oxygen rifle is included by sky It is that cavity between the tube wall of the hollow pipe of cavity in heart pipe or two neighboring inside and outside suit is formed and for conveying described contain The oxygen-containing gas passage of carrier of oxygen, the oxygen-containing gas passage connect with the compressed air source unit of the oxygen-containing gas；
The oxygen rifle also include formed by the cavity between the tube wall of the hollow pipe of two neighboring inside and outside suit and be used for The cooling circulating water passage of cooling protection is carried out to the oxygen rifle, the cooling circulating water passage connects with apparatus for supplying cool water It is logical；
The oxygen rifle also includes being used to improve the oxygen-containing gas spouting velocity and controls the oxygen-containing gas injection direction Shower nozzle, the shower nozzle is arranged on the bottom of the oxygen rifle, and the gas outlet of the oxygen rifle is arranged on the shower nozzle；
The oxygen rifle is arranged on the roof of the refining furnace and can slided up and down along the roof of the refining furnace.
Preferably, in the step 2), slag former is added in the copper melt into the refining furnace, slag former is made with oxidation Slag making reaction occurs for the oxide obtained after industry, obtains refining slag, and refining slag floats, on the copper melt in the Sheng copper container Refining slag blanket is formed at liquid level.
Preferably, in the step 2), the compressed gas for being blended with slag former powder are blown in a manner of submerging and blowing Below the upper liquid level of copper melt in the refining furnace, the gas outlet for spraying the compressed gas is located in the refining furnace Below the upper liquid level of copper melt.
Preferably, in the step 2), it is blended with oxygen rifle in a manner of top spray gas described in slag former powder Compressed gas are sprayed into the copper melt in the refining furnace, and the gas outlet of the oxygen rifle is located at the copper melt in the refining furnace Upper liquid level more than and be separated by a certain distance with the upper liquid level of copper melt；
The oxygen rifle is the multilayer internal and external casing structure for the hollow pipe for including multiple inside and outside suits, and the oxygen rifle is included by sky It is that cavity between the tube wall of the hollow pipe of cavity in heart pipe or two neighboring inside and outside suit is formed and be mixed with for conveying The compressed gas passage of the compressed gas of the slag former powder, the compressed gas passage connect with gas powder feedway It is logical；
The oxygen rifle also include formed by the cavity between the tube wall of the hollow pipe of two neighboring inside and outside suit and be used for The cooling circulating water passage of cooling protection is carried out to the oxygen rifle, the cooling circulating water passage connects with apparatus for supplying cool water It is logical；
The oxygen rifle is arranged on the roof of the refining furnace and can slided up and down along the roof of the refining furnace.
Preferably, in the step 3), when result of laboratory test reaches requirement of the target anode copper to sulphur and iron, abolishing Before vacuum state in the refining furnace, the copper melt in the Sheng copper container is subjected to pure circular treatment certain time, so Abolish the vacuum state in the refining furnace again afterwards.
Preferably, in the step 3), when result of laboratory test reaches requirement of the target anode copper to sulphur and iron, abolishing Before vacuum state in the refining furnace, by being arranged at the bottom-blowing device of the Sheng copper container bottom to the Sheng copper container Middle copper melt carries out bottom blown gas processing, then abolishes the vacuum state in the refining furnace again, the bottom-blowing device injection Gas is nitrogen or argon gas.
Preferably, during anode refining, when the cavity in the refining furnace is in vacuum state, by oxygen rifle with The mode of top-blown gas is blown fuel gas and oxygen-containing gas into the refining furnace, by the fuel gas and described oxygenous Body lights burning, using the combustion reaction liberated heat of the fuel gas and the oxygen-containing gas in the refining furnace Copper melt carries out supplementary heating processing, using the combustion reaction liberated heat of the fuel gas and the oxygen-containing gas to spray The dross thing formed after the copper melt cooling splashed on the refining furnace inwall is purged processing；
The gas outlet of the oxygen rifle be located at more than the upper liquid level of the copper melt in the refining furnace and with the upper liquid of copper melt Face is separated by a certain distance；
The oxygen rifle is the multilayer internal and external casing structure for the hollow pipe for including multiple inside and outside suits, and the oxygen rifle is included by sky It is that cavity between the tube wall of the hollow pipe of cavity in heart pipe or two neighboring inside and outside suit is formed and for convey it is described can The fuel gas passage of combustion gas body, the fuel gas passage connect with the compressed air source unit of the fuel gas；
The oxygen rifle is also included between the tube wall of the hollow pipe by the cavity in hollow pipe or two neighboring inside and outside suit It is that cavity is formed and for conveying the oxygen-containing gas passage of the oxygen-containing gas, the oxygen-containing gas passage and the oxygen-containing gas Compressed air source unit connection；
The oxygen rifle also include formed by the cavity between the tube wall of the hollow pipe of two neighboring inside and outside suit and be used for The cooling circulating water passage of cooling protection is carried out to the oxygen rifle, the cooling circulating water passage connects with apparatus for supplying cool water It is logical；
The oxygen rifle is arranged on the roof of the refining furnace and can slided up and down along the roof of the refining furnace.
Preferably, when the cavity in the refining furnace is in atmospheric pressure state, oxygen rifle in a manner of top-blown gas Fuel gas and oxygen-containing gas are blown into the refining furnace, the fuel gas and the oxygen-containing gas are lighted into burning, profit With copper of the combustion reaction liberated heat of the fuel gas and the oxygen-containing gas to splash on the refining furnace inwall The dross thing formed after liquation cooling carries out melting removing processing, and the burning using the fuel gas and the oxygen-containing gas is anti- Liberated heat is answered to carry out baker processing to the refining furnace；
The oxygen rifle is the multilayer internal and external casing structure for the hollow pipe for including multiple inside and outside suits, and the oxygen rifle is included by sky It is that cavity between the tube wall of the hollow pipe of cavity in heart pipe or two neighboring inside and outside suit is formed and for convey it is described can The fuel gas passage of combustion gas body, the fuel gas passage connect with the compressed air source unit of the fuel gas；
The oxygen rifle is also included between the tube wall of the hollow pipe by the cavity in hollow pipe or two neighboring inside and outside suit It is that cavity is formed and for conveying the oxygen-containing gas passage of the oxygen-containing gas, the oxygen-containing gas passage and the oxygen-containing gas Compressed air source unit connection；
The oxygen rifle also include formed by the cavity between the tube wall of the hollow pipe of two neighboring inside and outside suit and be used for The cooling circulating water passage of cooling protection is carried out to the oxygen rifle, the cooling circulating water passage connects with apparatus for supplying cool water It is logical；
The oxygen rifle is arranged on the roof of the refining furnace and can slided up and down along the roof of the refining furnace.
Compared with prior art, it is used to handle high impurity copper concentrate the invention provides one kind and shallow oxidation is without reduction anode The smelting process of refining, the smelting process have technique effect beneficial below：
1. in the present invention, the initial oxygen content and later stage that are carried in copper melt re-blow what oxygen-containing gas was supplemented by the external world Oxygen content almost all it is used for oxidation sweetening and oxidation deferrization, the oxygen-containing gas that the external world re-blows will not do a large amount of as original Idle work, what the oxygen-containing gas amount of the extraneous supplement that oxidation operation is consumed only accounted for that former anode refining oxidation operation consumed contains The 10%~30% of the oxygen scale of construction, reduce 70% compared to the oxygen-containing gas amount that is consumed of former anode refining oxidation operation~ 90%, therefore the present invention is a kind of shallow oxidizing anode refining, is improved in oxygen-containing gas really for the oxygenous of oxidation sweetening Body ratio, reduce the oxygen-containing gas ratio for making idle work, reduce the actual use amount of oxygen-containing gas during anode refining, Reduce oxygen-containing gas waste, reduce the production cost of anode refining.
2. the present invention in oxygen-containing gas is improved really be used for oxidation sweetening oxygen-containing gas ratio, reduce make it is useless While the oxygen-containing gas ratio of work(, the present invention also achieves unexpected technique effect：The liquation obtained after oxidation operation Middle oxygen content can meet normal requirement of the target anode copper to oxygen content, need not subsequently carry out reduction operation, realize really Without reduction anode refining.
3. the present invention in oxygen-containing gas is improved really be used for oxidation sweetening oxygen-containing gas ratio, reduce make it is useless While the oxygen-containing gas ratio of work(, the present invention also achieves another unexpected technique effect：In the present invention, not In the case of carrying out reduction operation, it is whole can to reach former anode refining for oxygen content in the anode copper melt that anode refining terminal obtains The 1/100~1/10 of point oxygen content, 1 to 2 orders of magnitude are reduced than former anode refining terminal oxygen content.The less sun of oxygen content Pole copper melt can be more beneficial for producing surface quality and the more preferable positive plate of internal soundness, can be more beneficial for follow-up electrorefining Carry out, the sedimentation earth of positive pole can be significantly reduced and float the quantum of output of the earth of positive pole, cathode plate surface particle is reduced, improve electrolysis The current efficiency of refining, improve the internal soundness and surface quality of the cathode plate of electrorefining output.
4. the present invention in oxygen-containing gas is improved really be used for oxidation sweetening oxygen-containing gas ratio, reduce make it is useless While the oxygen-containing gas ratio of work(, the present invention also achieves another unexpected technique effect：The present invention can incite somebody to action The reduction of operation process time is aoxidized within 1 hour, most of heat can reduce within 40 minutes, along with the present invention It can realize without reduction anode refining, therefore the present invention can be by anode refining process time (not including feed time and casting Time) reduce within 1 hour, most of heat can reduce within 40 minutes, and Yuanyang pole refining process (does not include Feed time and casting time) required time generally 2 hours, so, present invention significantly reduces anode refining process Required time, reduction amplitude are about 50%~66.67%, considerably improve production efficiency and rhythm of production.
5. the present invention in oxygen-containing gas is improved really be used for oxidation sweetening oxygen-containing gas ratio, reduce make it is useless While the oxygen-containing gas ratio of work(, the present invention also achieves another unexpected technique effect：The present invention compared to Simple vacuum distillation refining, considerably improve arsenic, the removing speed of three kinds of elements of antimony and tin and removing degree, arsenic and antimony Less than 0.01% can be removed to, the removal efficiency of arsenic can be improved to more than 95%, and the removal efficiency of antimony can be improved to more than 75%, tin Less than 0.0050% can be removed to, the removal efficiency of tin is improved to more than 90%, is realized while is removed lead, zinc, arsenic, antimony, bismuth With the refining process of six kinds of impurity elements of tin so that anode refining method provided by the invention can both refine normal level range Blister copper, the blister copper of high impurity content can also be handled.
6. in the present invention, the recycle stream of liquation is formed between the Sheng copper container, feed tube, refining furnace and drain pipe It is dynamic, flow the such big cycle volume of liquation and improve extremely advantageous dynamics bar for the non-metallic inclusion in removing copper melt Part, improves the collision probability and agglomeration of non-metallic inclusion in copper melt, the non-metallic inclusion after agglomeration Easily float, be mixed into the slag blanket of copper melt upper surface by the buoyancy of itself, it is non-in copper melt so as to considerably improve The removing speed and removing degree of metallic inclusion, improve the cleanliness factor of the anode copper melt obtained after anode refining terminates.
7. slag former is added in copper melt by present invention selection in refining furnace, slag former is fallen into copper melt can be fast Slag making reaction fastly occurs with the oxide in copper melt, there is the reaction rate of higher deferrization removing impurities matter and reacted full journey Degree.
8. the present invention improves heat utilization ratio and heat transfer efficiency by improving mode of heating, it ensure that and carry out oxidation work Requirement of the copper melt of industry to temperature, improve the carry out speed and performance level of oxidation operation；And the mode of heating carries simultaneously Temperature in high refining furnace upper space, it is therefore prevented that the copper melt cooled and solidified of splash forms dross thing, finishes so as to reduce The generation of effluent；So that dross thing melted by heat becomes liquid again, the inwall along refining furnace flows downward, and is back to again In the copper melt circulated, anode refining process is completed, so as to reduce the quantity of the dross thing generated, so as to weaken A series of negative influences caused by above-mentioned dross thing.
Brief description of the drawings
Fig. 1 is provided in an embodiment of the present invention for handling high impurity copper concentrate and shallow smelting of the oxidation without reduction anode refining The operation principle schematic diagram of smelting method.
In figure：1 refining furnace, 2 feed tubes, 201 driving flues, 3 drain pipes, 4 oxygen rifles, 5 Rotary Anode Furnaces.
Embodiment
To make the purpose, technical scheme and advantage of the embodiment of the present invention clearer, below in conjunction with the embodiment of the present invention In accompanying drawing, the technical scheme in the embodiment of the present invention is clearly and completely described, it is clear that described embodiment is The part of the embodiment of the present invention, rather than whole embodiments.Based on the embodiment in the present invention, ordinary skill people The every other embodiment that member is obtained on the premise of creative work is not made, belongs to the scope of protection of the invention.
In the description of the invention, it is to be understood that term " " center ", " axial direction ", " radial direction ", " longitudinal direction ", " transverse direction ", " length ", " width ", " on ", " under ", "front", "rear", "left", "right", " top ", " bottom ", " interior ", " outer ", " clockwise ", " inverse The orientation or position relationship of the instruction such as hour hands ", " level ", " vertical " are based on the orientation or position shown in accompanying drawing or in practical application Relation is put, it is of the invention necessary with simplified description, rather than the device or element of instruction or hint meaning to be for only for ease of description With specific orientation, with specific azimuth configuration and operation, therefore be not considered as limiting the invention.
As shown in figure 1, Fig. 1 be it is provided in an embodiment of the present invention be used for handle high impurity copper concentrate and it is shallow oxidation without also Yuanyang The operation principle schematic diagram of the smelting process of pole refining.
According to metallurgy of copper theory, the main purpose of blister copper anode refining is oxidation sweetening and oxidation deferrization.Target is by sulphur Less than 0.0050% is removed to, iron is removed to less than 0.0100%；After reducing operation, by oxygen removal to less than 0.2000%.
According to metallurgy of copper, can obtain：
The key reaction formula of oxidation sweetening is：[S]+2 [O]=SO2(gaseous state) (1)；
Oxidation deferrization key reaction formula be：[Fe]+[O]=(FeO) (2).
Wherein, the equilibrium constant of formula (1) is：
In above formula, [%S] is the weight percent content of element sulphur in copper melt；
[%O] is the weight percent content of oxygen element in copper melt；
For SO in gas in copper melt liquid level above free space2The partial pressure of gas.
According to metallurgical thermodynamics, equilibrium constant K is only relevant with temperature, and equilibrium constant K is a constant at a certain temperature, Formula (3) can then be obtained：Wherein, k is constant coefficient.Thus it is clear that when temperature andAfter certain, copper The product of sulfur content and oxygen content in liquation is a definite value.Such as：Anode refining is carried out at normal atmospheric pressure, works as oxidation During operation terminal, and ought now SO in gas in copper melt liquid level space above2The percent by volume of gas is 10%, then now 'sFor the 10% of a standard atmospheric pressure, i.e. 10.1KPa, if sulfur content is down into 0.003%, correspondingly oxygen contains Amount can automatically, be inevitably increased to 0.65%.For formula (2), because its reactant and product are all condensed states, all Gaseous state, therefore, its extent of reaction or reaction balance do not influenceed by ambient pressure, its do not have be similar to formula (1) this The product of the balanced reaction equation or the equilibrium constant relevant with air pressure of sample, its iron content and oxygen content is not a definite value, when When iron content is down into desired value, corresponding oxygen content can reduce because take part in reaction, and oxidation deferrization process will not be to oxygen The oxygen content for being turned into industry terminal causes significantly to negatively affect.
First, according to metallurgical principles, a metallurgical reaction occurs and first has to meet metallurgical thermodynamics principle：There is foot Enough reaction raw materials.According to formula (1), the relative atomic mass of element sulphur is 32, and the relative atomic mass of oxygen element is 16, then for The oxidation reaction of formula (1) is realized, it is necessary to the matter of the element sulphur of 32 mass parts and the oxygen element of 32 mass parts, element sulphur and oxygen element It is 1 ﹕ 1 to measure ratio.It can be seen that quality needed for the theory of oxygen element is equal with the quality of element sulphur during oxidation sweetening, i.e., in anode In refining process, if contemplated sulphur oxidation removal only according to the oxygen element carried in blister copper, the initial oxygen content carried in blister copper It is at least equal with the initial sulfur content in blister copper.
According to formula (2), the relative atomic mass of ferro element is 56, and the relative atomic mass of oxygen element is 16, then is realization The oxidation reaction of formula (2) is, it is necessary to the mass ratio of the element sulphur of 56 mass parts and the oxygen element of 16 mass parts, ferro element and oxygen element For 7 ﹕ 2, the quality of ferro element is 3.5 times of oxygen element quality, and the percentage of the quality and ferro element quality of oxygen element is 28.57%.It can be seen that the percentage of quality needed for the theory of oxygen element and ferro element quality is 28.57% during oxidation deferrization, I.e. during anode refining, if contemplated iron oxidation removal only according to the oxygen element carried in blister copper, carried in blister copper just Beginning oxygen content, removing meet oxidation sweetening to the requirement of oxygen element outside, remaining part at least with the initial iron in blister copper The percentage of element quality is 28.57%.
And according to metallurgy of copper and practical production experience, the oxygen content in the blister copper liquation that blowing end point obtains will not remain It is how much remaining：When using suspension converting process, such as flash to blow, the oxygen content in the blister copper liquation that blowing end point obtains is most absolutely In the case of number below 0.0050%, and sulfur content is 0.25%~0.45%, and iron content belongs to oxygen 0.50%~0.80% It is very low, and sulphur is very high, and the pattern that iron is very high；When use molten bath converting process, such as P-S is bessemerized, Ausmelt furnace blows Refining etc., the oxygen content in the blister copper liquation that blowing end point obtains between 0.05%~0.1%, and sulfur content 0.1%~ 0.5%, iron content also belongs to the high pattern of oxygen low-sulfur 0.010%~0.10%.
Therefore, for using suspension converting process, such as flash to blow, during output blister copper liquation, by its output It is very low that blister copper liquation belongs to oxygen, and sulphur is very high, and the pattern that iron is very high, and the initial oxygen content carried in blister copper is far smaller than blister copper In the initial sulfur content that carries, i.e., the initial oxygen content carried in blister copper is far smaller than theory of the oxidation sweetening process to oxygen element Requirement, the initial oxygen content are much for above-mentioned initial sulfur content is reduced into requirement of the target anode copper to sulfur content It is inadequate, so, for suspension converting process, it is contemplated that only according to the oxygen element carried in blister copper by sulphur oxidation removal be not meet The metallurgical thermodynamics principle stated, be it is impossible,
Further, according to metallurgy of copper general knowledge, the inherent structure design of suspension converting furnace (such as flash converting furnace) and The design of its suspension converting process just determines that the blister copper liquation of its output must be that oxygen is very low, and sulphur is very high, and the mould that iron is very high Formula, howsoever optimize the terminal point control of suspension converting process, be impossible to the blister copper liquation of its output changing over oxygen high-sulfur Low pattern.Therefore, for the terminal point control of suspension converting process, howsoever optimization suspension converting process, it is contemplated that by thick Sulphur and iron oxidation removal are realized autoxidation or non-oxidation anode refining by the initial oxygen element carried in copper, and being all impossible real Existing.
Further, according to metallurgy of copper general knowledge, oxygen of the blister copper liquation in suck is rolled up in stirring roll procedure Amount is seldom, and whole Entrainment Velocity is also very slow.If blister copper liquation achieves that certainly by the oxygen in volume suck Refining process obtains anode copper, and that can place greatly a stove blister copper liquation in atmospheric environment, allows their own oxygen uptake to complete refining Process, without artificial refining operation, silently await and can be obtained by the desired anode copper of target.Obviously, this is simply a kind of false Think vision, this is if it is impossible.The journey it is therefore contemplated that stirring by improving the blister copper liquation in anode furnace is rolled Degree, the oxygen that allows in blister copper liquation volume suck supplement the deficiency of oxygen element during anode refining, complete anode refining mistake Journey, and it is impossible.
Furthermore it is slightly above oxidation sweetening for oxygen content and aoxidizes the blister copper of the theoretical requirement of deferrization, although it meets Above-mentioned metallurgical thermodynamics condition, still, this oxygen content for by sulphur and iron be removed to target anode copper to sulfur content and The requirement of iron content or far from being enough, reason is：According to formula (1), want sulfur content being removed to less than 0.0050%, then As far as possible formula (1) must be promoted to carry out to the right；And according to the principles of chemistry, in order to allow a chemical reaction to carry out to the right as far as possible, Aequum when then the amount positioned at the reactant in left side have to be larger than its chemical reaction equilibrium；Obviously, sulphur is the target being removed Element, its content can not be too big, it is impossible to aequum during more than its reaction balance, are then only left oxygen content, then oxygen content is necessary It is larger, it is necessary to aequum during more than its reaction balance；For example：Such as：Anode refining is carried out at normal atmospheric pressure, when When aoxidizing operation terminal, and ought now SO in gas in copper melt liquid level space above2The percent by volume of gas is 10%, then NowFor the 10% of a standard atmospheric pressure, i.e. 10.1KPa, if sulfur content is down into 0.003%, when formula (1) is anti- After should balancing, correspondingly the aequum of oxygen content is 0.65%, according to above-mentioned theory, in order to which sulfur content is down into 0.003%, slightly Initial oxygen content in copper have to be larger than 0.65%, or in the case of oxygen of re-blowing in the external world in aoxidizing operation process, by blister copper In oxygen content rise above 0.65%, the oxygen content is the actual oxygen demand of oxidation sweetening.Obviously, current suspension is blown The oxygen content that sweetening process and the blister copper liquation of molten bath converting process institute output carry can not all meet the reality of above-mentioned oxidation sweetening Border oxygen demand, unlikely meet above-mentioned oxidation sweetening and aoxidize the actual oxygen demand of deferrization.
To sum up, either suspend converting process, or molten bath converting process, in order to during anode refining by sulphur and iron Oxidation removal, output sulfur content and iron content reach the anode copper of target call, it is necessary to are supplemented during anode refining external Oxygen element, it is necessary to external world's injection oxygen-containing gas, it is necessary to carry out oxidation operation.
Furthermore according to metallurgical principles, a metallurgical reaction, two above-mentioned metallurgical thermodynamics conditions are only met, Or it is inadequate, also need to meet metallurgy kinetics principle, i.e., with preferable metallurgy kinetics condition.For anode refining, compared with Good metallurgy kinetics condition is exactly that liquation is carried out sufficiently to stir or flow.
According to above-mentioned analytical conclusions, it is used to handle high impurity copper concentrate the invention provides one kind and shallow oxidation is without also Yuanyang The smelting process of pole refining, including melting process, blowing process and the anode refining process successively carried out, the anode refining Process specifically includes following steps：
1) the blister copper liquation of melting is added in the Sheng copper container for containing blister copper liquation；Then refining will be arranged on Feed tube 2 and drain pipe 3 on the bottom wall of stove 1 are immersed in the upper liquid level certain depth below of copper melt in the Sheng copper container, so Open the cavity vacuum state in the refining furnace 1 afterwards with the vavuum pump that the refining furnace 1 connects, now in refining furnace The copper melt contained in copper container is along the feed liquor in the presence of atm difference in 1 between vacuum residual voltage and external atmosphere pressure Cavity passage in pipe 2 and the drain pipe 3, which rises, to be flowed into the cavity of the refining furnace 1；
The profile of the refining furnace 1 is vertical type columnar, and inner hollow forms cavity, and the refining furnace 1 includes steel shell And build refractory lining in the steel shell inner surface by laying bricks or stones, the top of the refining furnace 1 be provided with for it is described The gas outlet of vavuum pump connection；
The feed tube 2 and the drain pipe 3 include steel-made inner shell, be arranged on the steel-made inner shell inner surface it is resistance to Fiery material liner and the refractory material outer lining for the outer surface for being arranged on the steel-made inner shell, the feed tube 2 with it is described go out liquid The length of pipe 3 is identical；
The feed tube 2 and the drain pipe 3 be fixedly installed on the bottom wall of the refining furnace 1 and with the refining furnace 1 Bottom wall be tightly connected, the cavity in the refining furnace 1 is interconnected with the cavity passage in the feed tube 2, the refining Cavity in stove 1 is interconnected with the cavity passage in the drain pipe 3, it is all with the device that the refining furnace 1 is connected with The position that the refining furnace 1 connects carries out encapsulation process to prevent the vacuum state destroyed in the refining furnace 1；
2) driving gas with pressure is blown in the copper melt into the feed tube 2, then in atm difference and driving gas The copper melt contained in copper container is constantly risen by the feed tube 2 under the drive of body flows into the refining furnace 1, then Copper melt in the refining furnace 1 is constantly back to the Sheng copper by the drain pipe 3 by the refining furnace 1 outflow again to be held In device, circulating for copper melt is formed between the Sheng copper container, feed tube 2, refining furnace 1 and drain pipe 3；
Meanwhile in the refining furnace 1, the copper melt into the refining furnace 1 blows oxygen-containing gas, the oxygen-containing gas In oxygen element the element sulphur in copper melt is oxidized to the gaseous oxygen compound of sulphur, the oxygen element in the oxygen-containing gas melts copper Ferro element in liquid is oxidized to the oxide of iron, realizes the oxidation operation process of desulfurization deferrization；
Meanwhile a part for whole contents of the impurity element included by the copper melt in the refining furnace 1 is with simple substance Form is directly volatilized, and the remainder of whole contents is oxidized to volatilize with oxide form after oxide by the oxygen-containing gas, While the oxidation operation process of desulfurization deferrization is realized, the refining process of imurity-removal element simultaneously, the impurity member are realized Element includes one or more or whole in lead, zinc, arsenic, antimony, bismuth and tin element；
Meanwhile the vacuum residual voltage level in the refining furnace 1 is controlled so that the sulfur content in proper copper melt reaches target During requirement of the anode copper to sulfur content, the oxygen content for realizing reaction balance with the sulfur content also reaches target anode copper to oxygen content Requirement；
3) after the step 2) carries out a period of time, the component and content of the copper melt after sample examination anode refining, if Result of laboratory test reaches requirement of the target anode copper to sulfur content and iron content, then abolishes the vacuum in the refining furnace 1 first State, the feed tube 2 being arranged on the bottom wall of refining furnace 1 and drain pipe 3 are then departed from into the copper in the Sheng copper container and melted Liquid, aoxidize the end of job；If result of laboratory test miss the mark anode copper continues sun to the requirement of any one in both sulphur or iron Pole refines, until result of laboratory test reaches requirement of the target anode copper to sulfur content and iron content；Anode refining terminate to obtain sulphur, The content of iron and oxygen reaches the anode copper melt of target call, containing SO2Flue gas and clinker.
In the present invention, before anode refining terminates, in above-mentioned Sheng copper container, and in refining furnace 1, feed tube 2 and drain pipe 3 in the copper melt that circulates be blister copper liquation because anode refining does not terminate, it is meant that sample examination Above-mentioned copper melt is not reaching to requirement of the target anode copper to sulfur content and iron content.
In the present invention, above-mentioned oxygen-containing gas is preferably air or oxygen-enriched air, the volume hundred of oxygen in the oxygen-enriched air Divide than being 25%~95%.
In the present invention, with sulfur content in the copper melt of sample examination and iron content reach target anode copper to sulfur content and The requirement of iron content for mark refer to, as oxidation operation terminal time, as lead impurity element, zinc, arsenic, antimony, bismuth and/or Whether tin element reaches ideal value, and the present invention does not make hard requirement, can be rear because not removing clean above-mentioned impurity element Further removed in continuous electrorefining processes.
In the present invention, above-mentioned driving gas is nitrogen or argon gas, preferably nitrogen.
In the present invention, above-mentioned vacuum residual voltage refers to the pressure of the internal cavity of refining furnace 1 remaining gas under vacuum conditions, As the meaning of noun vacuum.
In the present invention, the above-mentioned Sheng copper container for being used to contain blister copper liquation is preferably Rotary Anode Furnace 5, actual production In, adaptability structural modification need to be made to Rotary Anode Furnace 5, to adapt to coordinate the use of refining furnace 1, be included in swinging anode The opening for entering or going out for refining furnace 1 is opened up on the furnace wall of stove 5.
In the present invention, by being arranged in copper melt of the driving flue 201 into the feed tube 2 on feed tube 2 It is blown driving gas with pressure.
In the present invention, high impurity copper concentrate means that the content of impurity element in copper concentrate is higher, and the impurity element includes One or more or whole in lead, zinc, arsenic, antimony, bismuth and tin element, the content of impurity element contains more than Copper making industry to it The general claimed range of amount.In the present invention, in actual production, above-mentioned high impurity copper concentrate not necessarily includes whole above-mentioned six Kind impurity element, the one or more of above-mentioned six kinds of impurity elements may be included, it is also possible to include above-mentioned six kinds of elements of whole. In actual production, though above-mentioned high impurity copper concentrate includes a certain kind of six kinds of above-mentioned impurity elements, but the impurity element Content and may be no more than industry universal standard, but the content of certain contained other impurity element exceedes industry universal mark It is accurate.In actual production, as long as impurity element contained in above-mentioned copper concentrate is one of above-mentioned six kinds of impurity elements and impurity member Cellulose content exceedes industry universal standard, and the copper concentrate is just high impurity copper concentrate.
The smelting blister copper with output after blowing of high impurity copper concentrate is typically exactly high impurity crude copper.The present invention is accessible The preferable higher limit of the percentage by weight of above-mentioned six kinds of impurity elements that may be present is in high impurity crude copper：Lead≤1.4%, Zinc≤0.05%, arsenic≤1.0%, antimony≤0.1%, bismuth≤0.5%, tin≤0.1%.
It is used to handle high impurity copper concentrate and shallow smelting process of the oxidation without reduction anode refining the invention provides a kind of, It should be evident that the smelting process is not that can only handle high impurity copper concentrate, it is only the smelting side to handle high impurity copper concentrate Ratio in numerous functions of method it is more prominent a bit；Since the smelting process can handle high impurity copper concentrate, it is clear that it also can The normal copper concentrate of enough processing element contents.Using the normal copper concentrate of smelting process processing element content provided by the invention Within the scope of the present invention.As long as copper concentrate, the guarantor in the present invention are handled using smelting process provided by the invention In the range of shield.
The principle of above-mentioned anode refining method provided by the invention is：
(1) is according to metallurgical thermodynamics, the key reaction formula of oxidation sweetening：[S]+2 [O]=SO2(gaseous state) (1)；
The equilibrium constant of formula (1) is：
In above formula, [%S] is the weight percent content of element sulphur in copper melt；
[%O] is the weight percent content of oxygen element in copper melt；
For SO in gas in copper melt liquid level above free space2The partial pressure of gas.
According to metallurgical thermodynamics, equilibrium constant K is only relevant with temperature, and equilibrium constant K is a constant at a certain temperature, Formula (3) can then be obtained：Wherein, k is constant coefficient.Thus it is clear that when temperature andAfter certain, copper The product of sulfur content and oxygen content in liquation is a definite value.Just because of this, when sulfur content is reduced to very little by oxidation sweetening Desired value when, oxygen content automatic trim, inevitably become very big, as a result more than normal range (NR).Such as：In normal atmosphere Pressure carries out anode refining, when aoxidizing operation terminal, and ought now SO in gas in copper melt liquid level space above2Gas Percent by volume is 10%, then nowFor the 10% of a standard atmospheric pressure, i.e. 10.1KPa, if sulfur content dropped To 0.003%, then correspondingly oxygen content is increased to 0.65%.
According to above-mentioned, at a certain temperature, the product of sulfur content and oxygen content in copper melt withPartial pressure is Linear relationship, if willPartial pressure reduces, then the product of the sulfur content in copper melt and oxygen content also reduces, Now if the desired value for continuing to keep aoxidizing operation final sulfur content is constant, then the oxygen content with the sulfur content trim can then subtract It is small.Based on the theory, if willPartial pressure reduces, when sulfur content is reduced to the desired value of very little by oxidation sweetening, Although oxygen content can also automatic trim, but not became as originally very big, but one withPartial pressure reduces journey Spend the less value to match.Such as：Anode refining is carried out at normal atmospheric pressure, when aoxidizing operation terminal, and ought be now SO in gas in copper melt liquid level space above2The percent by volume of gas is 10%, then nowIt is big for a standard The 10% of air pressure, i.e. 10.1KPa, if sulfur content is down into 0.003%, correspondingly oxygen content is increased to 0.65%.As generalDifferential pressure drop is to the 1/10 of above-mentioned 10.1KPa, i.e. 1.01KPa, then when sulfur content is down to 0.003%, correspondingly equilibrium oxygen contains Measure as 0.065%；As generalDifferential pressure drop is to the 1/100 of above-mentioned 10.1KPa, i.e. 101Pa, then when sulfur content is down to 0.003%, it is then 0.0065% correspondingly to balance oxygen content；As generalDifferential pressure drop is to the 1/1000 of above-mentioned 10.1KPa, i.e., 10.1Pa, then when sulfur content is down to 0.003%, it is then 0.00065% correspondingly to balance oxygen content.Above-mentioned correspondingly equilibrium oxygen Content 0.065%, 0.0065% or 0.00065% is only theoretical value, in actual production, due to the influence of other factorses, accordingly The actual value of ground balance oxygen content is hardly possible to be reduced to above-mentioned respective horizontal, but bigger than above-mentioned theoretical value.
(2) for according to above-mentioned, the product of oxidation sweetening is SO2Gas, the present invention is using vavuum pump constantly by SO2Gas is taken out Walk so that formula (1) reaction does not reach poised state all the time, carries out to the right all the time, improves desulfurization degree and rate of sulphur expulsion.
(3) principle that copper melts circulate：Soaked when by the feed tube 2 being arranged on the bottom surface of refining furnace 1 and drain pipe 3 Enter the upper liquid level certain depth below to the Sheng copper container inner melt, be then turned on the vavuum pump connected with the refining furnace 1 It is now big between vacuum residual voltage and external atmosphere pressure in refining furnace 1 by the cavity vacuum state in the refining furnace 1 Cavity passage upper up-flow of the liquation contained in copper container along the feed tube 2 and the drain pipe 3 in the presence of draught head In the cavity for entering the refining furnace 1；Blister copper liquation now does not circulate；To circulate blister copper liquation, to described Driving gas with pressure is blown in liquation in feed tube 2, driving gas enters after the liquation in feed tube 2 due to expanded by heating Decline with pressure, cause isothermal expansion, in feed tube 2 moment produce substantial amounts of nuclei of bubbles and expand rapidly, the gas of expansion Blister copper liquation is driven to rise, the liquation contained in copper container is constantly by described under the drive of atm difference and driving gas Feed tube 2, which rises, to be flowed into the refining furnace 1, then the liquation in the refining furnace 1 again by the drain pipe 3 constantly by The outflow of refining furnace 1 is back in the Sheng copper container, in Sheng copper container, feed tube 2, refining furnace 1 and the drain pipe 3 Between form liquation and circulate.
According to above-mentioned principle (1), in of the invention, due to inciting somebody to actionPartial pressure reduces, when sulfur content drops in oxidation sweetening During low desired value for very little, although oxygen content can also automatic trim, but not became very big as originally, but one withPartial pressure reduces the less value that matches of degree, so so that the initial oxygen content that is carried in copper melt and after The oxygen content almost all that phase is supplemented by extraneous oxygen-containing gas of re-blowing it is used for oxidation sweetening and oxidation deferrization, oxidation operation end There is not much left for point oxygen content, and the oxygen-containing gas that the external world re-blows will not do substantial amounts of idle work as original, be aoxidized in the present invention The oxygen-containing gas amount for the extraneous supplement that operation is consumed only accounts for the oxygen-containing gas amount that former anode refining oxidation operation is consumed 10%~30%, the oxygen-containing gas amount consumed compared to the oxidation operation of former anode refining reduces 70%~90%, so this Invention is a kind of shallow oxidizing anode refining, improves the oxygen-containing gas ratio for being really used for oxidation sweetening in oxygen-containing gas, reduces Make the oxygen-containing gas ratio of idle work, reduce the actual use amount of oxygen-containing gas during anode refining, reduce oxygen-containing Gas wastes, and reduces the production cost of anode refining.
The present invention is really used for the oxygen-containing gas ratio of oxidation sweetening in oxygen-containing gas is improved, and reduces and makees idle work Oxygen-containing gas ratio while, also achieve unexpected technique effect：Oxygen content in the liquation obtained after oxidation operation Normal requirement of the target anode copper to oxygen content can be met, reduction operation need not be subsequently carried out, realize really without reduction Anode refining, principle are：According to above-mentioned principle (1), in of the invention, if willPartial pressure reduces, when oxidation sweetening will When sulfur content is reduced to the desired value of very little, although oxygen content can also automatic trim, but not became as originally very big, and Be one withPartial pressure reduces the less value that degree matches；Further, if controlled in the refining furnace 1 Vacuum residual voltage it is horizontal, willPartial pressure is reduced to some reasonable interval so that when the sulfur content in copper melt reaches mesh When marking requirement of the anode copper to sulfur content, although oxygen content can also automatic trim, but not more than target anode copper to oxygen content Normal requirement scope since oxygen content has met target anode copper to oxygen content in obtained copper melt after oxidation operation Normal requirement, then subsequently without carrying out reduction operation again.
The present invention is really used for the oxygen-containing gas ratio of oxidation sweetening in oxygen-containing gas is improved, and reduces and makees idle work Oxygen-containing gas ratio while, also achieve another unexpected technique effect：In the present invention, without reduction In the case of operation, oxygen content can reach former anode refining terminal oxygen content in the anode copper melt that anode refining terminal obtains 1/100~1/10, reduce 1 to 2 orders of magnitude than former anode refining terminal oxygen content.It should be evident that 1 to 2 quantity The reduction degree of level is very significant technological progress for metallurgy industry, i.e., the present invention achieves having for highly significant Beneficial technique effect.It should be evident that the less anode copper melt of oxygen content is advantageous to output surface quality and internal soundness is more preferable Positive plate, the progress of follow-up electrorefining can be more beneficial for, can significantly reduce sedimentation the earth of positive pole and float the earth of positive pole production Output, cathode plate surface particle is reduced, improve the current efficiency of electrorefining, improve the cathode plate of electrorefining output Internal soundness and surface quality.
The present invention is really used for the oxygen-containing gas ratio of oxidation sweetening in oxygen-containing gas is improved, and reduces and makees idle work Oxygen-containing gas ratio while, also achieve another unexpected technique effect：In the present invention, taken off in oxidation sweetening During iron, because formula (1) is carried out in vacuum state so that the reaction product SO of formula (1)2Gas is constantly pumped, formula (1) reaction does not reach poised state all the time, carries out to the right all the time so that oxidation sweetening has good metallurgical thermodynamics bar Part, and copper melt big cycle volume circulate so that oxidation sweetening deferrization has good metallurgy kinetics condition, can will The reduction of operation process time is aoxidized within 1 hour, most of heat can reduce within 40 minutes, along with the present invention It can realize without reduction anode refining, therefore the present invention can be by anode refining process time (not including feed time and casting Time) reduce within 1 hour, most of heat can reduce within 40 minutes, and Yuanyang pole refining process (does not include Feed time and casting time) required time generally 2 hours, so, present invention significantly reduces anode refining process Required time, reduction amplitude are about 50%~66.67%, considerably improve production efficiency and rhythm of production.
The present invention is really used for the oxygen-containing gas ratio of oxidation sweetening in oxygen-containing gas is improved, and reduces and makees idle work Oxygen-containing gas ratio while, also achieve another unexpected technique effect：In blister copper generally also containing lead, The impurity elements such as zinc, arsenic, antimony, bismuth and/or tin element, anode refining is except desulfurization and deferrization, it is also necessary to by above-mentioned impurity member Element removes as far as possible.In recent years because Copper making ability is acutely expanded, the supply of high-quality copper concentrate becomes more and more nervous, copper concentrate Gradually become " high impurity ".The impurity element such as high impurity, the lead being primarily referred to as in copper concentrate, zinc, arsenic, antimony, bismuth and/or tin contains Amount is higher.The smelting blister copper with output after blowing of high impurity copper concentrate is typically exactly high impurity crude copper.For above-mentioned impurity member Element, disclose melted using the simple above-mentioned blister copper of vacuum distillation technique (not extraneous oxygen-containing gas of re-blowing) refining in the prior art Liquid removing impurities.When refining above-mentioned blister copper liquation using simple vacuum distillation technique (not extraneous oxygen-containing gas of re-blowing), as long as temperature, Vacuum and refining time are suitable, and the lead, zinc and bismuth element in above-mentioned impurity element can become gaseous state volatilization, obtain Removing well, the content of three can relatively easily be down to less than 0.0050%, and the removal efficiency of lead and bismuth is 95% More than, the removal efficiency of zinc is more than 85%；And the arsenic, antimony and tin element in above-mentioned impurity element are difficult then to become gaseous state to wave Hair, removal effect is very poor, and removal efficiency is in 10%~30%, reason：The affinity of arsenic and antimony and copper is relatively strong, is easily formed Stable arsenic-copper compound and antimony-copper compound, stable arsenic-copper compound and antimony-copper compound volatilize under vacuum conditions Property it is very weak, removed so as to limit the volatilization of arsenic and two kinds of elements of antimony, the boiling point of simple substance tin is 2270 DEG C, is connect very much with the boiling point of copper Closely, simple vacuum distillation refining is difficult to separate tin from copper to evaporate.And the present invention is in above-mentioned simple vacuum distillation On the basis of technique, improved, the liquation under the vacuum state in refining furnace 1 into the refining furnace 1 blows oxygen-containing Gas, a part for whole contents of lead, zinc and bismuth element in above-mentioned impurity element is directly volatilized with elemental form, with list Pure vacuum distillation technique is the same, and the remainder of whole contents is oxidized to after oxide with oxide shape by above-mentioned oxygen-containing gas State is volatilized, and the volatility of the oxide is also preferable, does not interfere with the removing speed and removing degree of lead, zinc and bismuth element；On State a part for whole contents of the arsenic in impurity element, antimony and tin element still can directly be volatilized with elemental form, with list Pure vacuum distillation technique is the same, and the remainder of whole contents is oxidized to after oxide with oxide shape by above-mentioned oxygen-containing gas State is volatilized, and arsenic is oxidized to arsenic oxide, arsenic is freed from arsenic-copper compound by oxygen-containing gas, so as to break away from original arsenic- Antimony is oxidized to sb oxide by the serious negative influence that copper compound volatilizees to arsenic element, oxygen-containing gas, by antimony from antimony-copper chemical combination Freed in thing, so as to break away from the serious negative influence that original antimony-copper compound volatilizees to antimony element, oxygen-containing gas is by tin oxygen Tin oxide is melted into, the boiling point of tin oxide is 1430 DEG C, and 1250 DEG C of the temperature of the boiling point and copper melt during anode refining connects very much Closely so that tin oxide can volatilize ratio more thoroughly, the volatility of arsenic oxide, sb oxide and tin oxide is all relatively good, It can be removed to antimony so as to considerably improve arsenic, the removing speed of three kinds of elements of antimony and tin and removing degree, arsenic Less than 0.01%, the removal efficiency of arsenic can be improved to more than 95%, and the removal efficiency of antimony can be improved to more than 75%, and tin can be removed to Less than 0.0050%, the removal efficiency of tin is improved to more than 90%.Therefore, the present invention is realizing shallow oxidation without the same of reduction operation When, achieve another unexpected technique effect：Realize while imurity-removal Element Lead, zinc, arsenic, antimony, bismuth and tin The refining process of six kinds of impurity elements so that anode refining method provided by the invention can both refine the thick of normal level range Copper, the blister copper of high impurity content can also be handled.
In the present invention, the circulation of liquation is formed between the Sheng copper container, feed tube 2, refining furnace 1 and drain pipe 3 Flowing, flow the such big cycle volume of liquation and improve extremely advantageous dynamics for the non-metallic inclusion in removing copper melt Condition, improves the collision probability and agglomeration of non-metallic inclusion in copper melt, the nonmetal inclusion after agglomeration Thing is easier to float by the buoyancy of itself, is mixed into the slag blanket of copper melt upper surface, so as to considerably improve in copper melt Nonmetallic removing speed and removing degree, improve the cleanliness factor of the anode copper melt obtained after anode refining terminates.
The specific of oxygen-containing gas is blowed for the copper melt into the refining furnace 1 and blows mode, at one of the present invention In embodiment, there is provided one kind blows mode：In the step 2), by the oxygen-containing gas blowed in a manner of submerging and blowing to Below the upper liquid level of copper melt in the refining furnace 1, the gas outlet for spraying the oxygen-containing gas is located in the refining furnace 1 Below the upper liquid level of copper melt.
In one embodiment of the invention, additionally provide another and blow mode：In the step 2), pass through oxygen rifle 4 are blowed the oxygen-containing gas into the copper melt in the refining furnace 1 in a manner of top-blown gas, the outlet of the oxygen rifle 4 It is separated by a certain distance more than the upper liquid level of copper melt of the mouth in the refining furnace 1 and with the upper liquid level of copper melt；
The oxygen rifle 4 is the multilayer internal and external casing structure for the hollow pipe for including multiple inside and outside suits, the oxygen rifle 4 include by It is that cavity between the tube wall of the hollow pipe of cavity or two neighboring inside and outside suit in hollow pipe is formed and described for conveying The oxygen-containing gas passage of oxygen-containing gas, the oxygen-containing gas passage connect with the compressed air source unit of the oxygen-containing gas；
The oxygen rifle 4 also include formed by the cavity between the tube wall of the hollow pipe of two neighboring inside and outside suit and be used for The cooling circulating water passage of cooling protection is carried out to the oxygen rifle 4, the cooling circulating water passage connects with apparatus for supplying cool water It is logical；
The oxygen rifle 4 also includes being used to improve the oxygen-containing gas spouting velocity and controls the oxygen-containing gas injection direction Shower nozzle, the shower nozzle is arranged on the bottom of the oxygen rifle 4, and the gas outlet of the oxygen rifle 4 is arranged on the shower nozzle；
The oxygen rifle 4 is arranged on the roof of the refining furnace 1 and can slided up and down along the roof of the refining furnace 1.
Preferably, in actual production, mode can be blowed using two kinds of above-mentioned oxygen-containing gas simultaneously.
In order to improve the removing speed and removing degree of oxidation deferrization removing impurities matter, in one embodiment of the invention, institute State in step 2), slag former, slag former and the oxide obtained after oxidation operation are added in the copper melt into the refining furnace 1 Generation slag making is reacted, and obtains refining slag, and refining slag floats, and refining slag is formed at liquid level on the copper melt in the Sheng copper container Layer.Because the slag former of addition can be sent out with the oxide of iron and the oxide of above-mentioned impurity element obtained after oxidation operation Slag reaction is coined, therefore the product content of oxidation reaction can be significantly reduced, breaks the former poised state of oxidation reaction, is promoted Oxidation reaction is set to carry out to the right, for example, for above-mentioned formula (2), slag former can be with the oxidation of the iron obtained after oxidation operation Slag making reaction occurs for thing, generates slag phase, such as silicic acid scum, significantly decreases the oxide content of iron in copper melt, break The former poised state of formula (2), promotes formula (2) constantly to carry out to the right, so as to improve the removing speed of oxidation deferrization and Removing degree.The present invention further, selects slag former being added in copper melt in refining furnace 1, due to above-mentioned oxygenous Body is to be blown into refining furnace 1 in copper melt, and the oxidation reaction in copper melt is mainly carried out in refining furnace 1, above-mentioned The oxide for coordinating slag making with slag former also mainly generates in refining furnace 1, that is, the oxide for participating in slag making is raw in refining furnace 1 Into then slag former is added in refining furnace 1, and two kinds of materials for participating in slag making are respectively positioned in refining furnace 1, and slag former falls into copper and melted Slag making reaction can rapidly occur in liquid with the oxide in copper melt, there is higher reaction rate and reacted full journey Degree, unlike the addition place of other slag formers and feed postition, such as slag former are added to outside refining furnace 1 and contained in copper container In copper melt, also need to wait for oxide and slowly spread in the huge copper melt of the scale of construction with slag former, final diffusion collides one Slag making reaction can just be occurred by rising, and slag making reaction speed is relatively low and slag making reaction is not very thorough.
Preferably, slag former is quartz particles or powder.
Specific addition manner for adding slag former in from the copper melt to the refining furnace 1, at one of the present invention In embodiment, there is provided a kind of addition manner：In the step 2), the compressed gas for being blended with slag former powder are blown with submerging The mode sent is blown to the upper liquid level of the copper melt in the refining furnace 1, and the gas outlet for spraying the compressed gas is located at Below the upper liquid level of copper melt in the refining furnace 1.
In one embodiment of the invention, another addition manner is additionally provided：In the step 2), pass through oxygen rifle 4 compressed gas that slag former powder is blended with a manner of top spray gas are sprayed to the copper melt in the refining furnace 1 In, the gas outlet of the oxygen rifle 4 be located at more than the upper liquid level of the copper melt in the refining furnace 1 and with the upper liquid level phase of copper melt Away from certain distance；
The oxygen rifle 4 is the multilayer internal and external casing structure for the hollow pipe for including multiple inside and outside suits, the oxygen rifle 4 include by It is that cavity between the tube wall of the hollow pipe of cavity in hollow pipe or two neighboring inside and outside suit is formed and for conveying mixing There is the compressed gas passage of the compressed gas of the slag former powder, the compressed gas passage connects with gas powder feedway It is logical；
The oxygen rifle 4 also include formed by the cavity between the tube wall of the hollow pipe of two neighboring inside and outside suit and be used for The cooling circulating water passage of cooling protection is carried out to the oxygen rifle 4, the cooling circulating water passage connects with apparatus for supplying cool water It is logical；
The oxygen rifle 4 is arranged on the roof of the refining furnace 1 and can slided up and down along the roof of the refining furnace 1.
Preferably, in actual production, the addition manner of two kinds of above-mentioned slag formers can be used simultaneously.
In one embodiment of the invention, in the step 3), when result of laboratory test reach target anode copper to sulphur and During the requirement of iron, before the vacuum state in the refining furnace 1 is abolished, the copper melt in the Sheng copper container is subjected to pure follow Ring handles certain time, then abolishes the vacuum state in the refining furnace 1 again.Pure circular treatment is exactly only to allow copper in short Liquation circulates between Sheng copper container, feed tube 2, refining furnace 1 and drain pipe 3, without making other processing to copper melt. Due to a variety of and a certain amount of non-metallic inclusion, mainly oxide, sulfide and silicon can be produced during anode refining Hydrochlorate etc., these non-metallic inclusions are remained in copper melt, can have a strong impact on surface quality and the inside of product anode copper coin Quality, therefore it is necessary to remove as far as possible.Present invention selection is carried out the copper melt in the Sheng copper container pure within above-mentioned opportunity Circular treatment certain time, flow the such big cycle volume of copper melt and improve pole for the non-metallic inclusion in removing copper melt For favourable dynamic conditions, the collision probability and agglomeration of non-metallic inclusion in copper melt, agglomeration are improved Non-metallic inclusion afterwards is easier to float by the buoyancy of itself, is mixed into the slag blanket of copper melt upper surface, so as to significantly The removing speed and removing degree of non-metallic inclusion in copper melt after oxidation operation are improved, further increasing anode essence The cleanliness factor for the anode copper melt that refining obtains after terminating.
In one embodiment of the invention, in the step 3), when result of laboratory test reach target anode copper to sulphur and During the requirement of iron, before the vacuum state in the refining furnace 1 is abolished, by the bottom blowing for being arranged at the Sheng copper container bottom Device carries out bottom blown gas processing to copper melt in the Sheng copper container, then abolishes the vacuum state in the refining furnace 1 again, The gas of the bottom-blowing device injection is nitrogen or argon gas.Bottom blown gas is carried out to containing copper melt in copper container by bottom-blowing device Processing, the stirring rolling degree for containing copper melt in copper container can be significantly increased, for the nonmetal inclusion in removing copper melt Thing improves extremely advantageous dynamic conditions, improves the collision probability of non-metallic inclusion and aggregation length in copper melt Greatly, the non-metallic inclusion after agglomeration is easier to float by the buoyancy of itself, is mixed into the slag blanket of copper melt upper surface, So as to considerably improve the removing speed and removing degree of non-metallic inclusion in copper melt after oxidation operation, further carry The cleanliness factor for the anode copper melt that high anode refining obtains after terminating.
Preferably, in actual production, can be handled simultaneously using above-mentioned pure circular treatment and bottom blown gas, to maximize Ground reduces the content of non-metallic inclusion in copper melt, improves the cleanliness factor of the anode copper melt obtained after anode refining terminates.
Anode refining process needs certain time, and within the period, the temperature of copper melt can inevitable underground Drop, it is therefore desirable to which heat make-up heat is carried out to copper melt.It is thick with the anode refining of Rotary Anode Furnace 5 general in current industry Exemplified by process for copper, Rotary Anode Furnace 5 is a horizontal oval cylindrical barrel body, using the burning of burn combustible thing and oxygen-containing gas Device carries out heating and thermal insulation to the copper melt in Rotary Anode Furnace 5, and burner is arranged at Rotary Anode Furnace 5 with charging aperture One end on length direction, exhanst gas outlet are arranged on the other end on the length direction of Rotary Anode Furnace 5, and burner is so set Put, Railway Project be present：1. mode of heating so is similar to the pattern of " broad irrigation ", heat caused by burner is let alone certainly Stream, heat caused by burner are not applied fully in the place really needed, and heat waste phenomenon is serious, heat utilization ratio It is relatively low；2. heat caused by burner will heat in copper melt liquid level space above first, then the heat in upper space with The mode of radiant heat transfer pass to lower section copper melt, in this process heat transfer modes have and only radiant heat transfer pattern this Kind, and according to metallurgical thermodynamics principle, radiant heat transfer pattern is minimum one of several of heat transfer efficiency in numerous heat transfer modes, because This, current mode of heating has that heat utilization ratio is low and the less problem of heat transfer rate；It is 3. this for Rotary Anode Furnace 5 For the container of long cartridge type, it is irrational that one end only on the length direction in Rotary Anode Furnace 5, which sets burner, is shown So, close to preferable, more remote from the burner copper melt of the copper melt heating and thermal insulation effect of burner, heating and thermal insulation effect is poorer, For whole copper melts in Rotary Anode Furnace 5, heating and thermal insulation effect is extremely uneven.It should be evident that exist above-mentioned The current mode of heating of multiple problems, it is unfavorable for solving the above-mentioned technical problem referred in the present invention, is unfavorable for anode refining During the process such as desulfurization deferrization removing impurities matter progress.Therefore, in one embodiment of the invention, in anode refining process In, when the cavity in the refining furnace 1 is in vacuum state, oxygen rifle 4 in a manner of top-blown gas to the refining furnace 1 Interior injection fuel gas and oxygen-containing gas, light burning by the fuel gas and the oxygen-containing gas, utilize the combustible gas The combustion reaction liberated heat of body and the oxygen-containing gas carries out supplementary heating processing to the copper melt in the refining furnace 1, Using the combustion reaction liberated heat of the fuel gas and the oxygen-containing gas to splash on the inwall of refining furnace 1 The dross thing formed after copper melt cooling carries out melting removing processing；
The gas outlet of the oxygen rifle 4 is located at more than the upper liquid level of the copper melt in the refining furnace 1 and upper with copper melt Liquid level is separated by a certain distance；
The oxygen rifle 4 is the multilayer internal and external casing structure for the hollow pipe for including multiple inside and outside suits, the oxygen rifle 4 include by It is that cavity between the tube wall of the hollow pipe of cavity or two neighboring inside and outside suit in hollow pipe is formed and described for conveying The fuel gas passage of fuel gas, the fuel gas passage connect with the compressed air source unit of the fuel gas；
The oxygen rifle 4 is also included between the tube wall of the hollow pipe by the cavity in hollow pipe or two neighboring inside and outside suit It is that cavity is formed and for conveying the oxygen-containing gas passage of the oxygen-containing gas, the oxygen-containing gas passage and the oxygen-containing gas Compressed air source unit connection；
The oxygen rifle 4 also include formed by the cavity between the tube wall of the hollow pipe of two neighboring inside and outside suit and be used for The cooling circulating water passage of cooling protection is carried out to the oxygen rifle 4, the cooling circulating water passage connects with apparatus for supplying cool water It is logical；
The oxygen rifle 4 is arranged on the roof of the refining furnace 1 and can slided up and down along the roof of the refining furnace 1.
Preferably, fuel gas is natural gas or coal gas.
The present invention, when the cavity in refining furnace 1 is in vacuum state, oxygen rifle 4 in a manner of top-blown gas to institute Injection fuel gas and oxygen-containing gas in refining furnace 1 are stated, the fuel gas and the oxygen-containing gas are lighted into burning, utilize institute State fuel gas and the oxygen-containing gas combustion reaction liberated heat the copper melt in the refining furnace 1 is carried out supplement plus Heat treatment, so heating, because oxidation operation is all carried out and completed in refining furnace 1, and pass through the combustion heating of oxygen rifle 4 All carried out in refining furnace 1, heat supply side and heat need Fang Jun in refining furnace 1, therefore caused heat can be complete Portion and be directly transferred to carried out in refining furnace 1 aoxidize operation this part copper melt, caused heat amount compared to Significantly reduced before improvement, but this part copper melt for carrying out aoxidizing operation process in refining furnace 1 is enough, using a small amount of And sufficient heat is only accurately supplemented this part copper melt for aoxidize operation, caused heat is all used in needs Place, avoid the heating mode of original " broad irrigation ", it is not excessive, do not waste, improve heat utilization ratio, reduce flammable The consumption of thing and oxygen-containing gas；Unnecessary heat can be delivered to essence as the big cycle volume of copper melt flows out of refining furnace 1 Outside furnace 1, the copper melt at remaining position of Rotary Anode Furnace 5 is passed to, essence is being entered to the copper melt in Rotary Anode Furnace 5 Furnace 1 carries out carrying out preheating insulation before oxidation operation, and big cycle volume flowing heat transfer belongs to convection heat transfer' heat-transfer by convection in metallurgical thermodynamics, The heat transfer efficiency of convection heat transfer' heat-transfer by convection wants high more compared to radiant heat transfer, therefore the present invention is except this heat transfer efficiency of radiant heat transfer Relatively low heat transfer modes, also with the higher heat transfer modes of this heat transfer efficiency of convection heat transfer' heat-transfer by convection, so as to considerably improve this The heat transfer efficiency of invention mode of heating；Due to the present invention only directly to carried out in refining furnace 1 aoxidize operation this part copper Liquation carries out heating and thermal insulation, it should be apparent that, be not in the uneven phenomenon of above-mentioned heating.To sum up, heating of the invention Mode ensure that requirement of the copper melt for carrying out aoxidizing operation to temperature, improves the carry out speed of oxidation operation and completes journey Degree.
Doped with driving gas copper melt enter the vacuum environment in refining furnace 1 after, and in extraneous oxygen-containing gas of re-blowing In the case of, the copper melt in refining furnace 1 will not imperturbably be circulated, but violent splash, in this way, inevitably With regard on the inwall of the copper melt splash of some to refining furnace 1, due to the temperature of the upper space of refining furnace 1 and upper inside wall compared with It is low, the copper melt meeting cooled and solidified of liquid, in the course of time, just form one layer of hard dross thing in the inner wall surface of refining furnace 1. It should be evident that the cold conditions dross thing does not all have positive role, example to anode refining process and to the service life of refining furnace 1 Such as：Due to containing the elements such as higher sulphur, iron, oxygen, lead, zinc, arsenic, antimony, bismuth, after anode refining terminates, the knot in dross thing Effluent can cause the anode copper melt for having reached target component requirement to return sulphur, Hui Tie, return oxygen etc., cause in anode copper melt Sulphur, iron or oxygen element raise again；Dross thing can corrode the refractory lining of refining furnace 1；Dross thing can also reduce refining furnace 1 Dischargeable capacity.Therefore, in the present embodiment, during anode refining, when the cavity in the refining furnace 1 is in vacuum state When, fuel gas and oxygen-containing gas are blown in a manner of top-blown gas into the refining furnace 1 oxygen rifle 4, will be described flammable Gas and the oxygen-containing gas light burning, utilize the fuel gas and the combustion reaction liberated heat of the oxygen-containing gas Processing is purged to the dross thing formed after copper melt cooling of the splash on the inwall of refining furnace 1, improved in refining furnace 1 The temperature of upper space and upper inside wall prevents the copper melt cooled and solidified of splash from forming dross thing, so as to reduce dross thing Generation；The temperature for improving the internal upper part space of refining furnace 1 and upper inside wall causes dross thing melted by heat to become liquid again, along The inwall of refining furnace 1 flows downward, and is back to again in the copper melt circulated, anode refining process is completed, so as to reduce The quantity of the dross thing generated, so as to reducing a series of negative influences caused by above-mentioned dross thing.
At present, regardless of optimizing refinery practice during anode refining, after anode refining terminates, the inwall of refining furnace 1 Upper or a certain amount of dross thing of meeting remaining.At present, for the dross thing, it is typically employed in blowing out gap, mechanically Remove, such as cut using chisel, rooted out using spatula etc..Several drawbacks be present in mechanical removal mode：1. due to dross thing Or dross nitride layer hardness is very high, mechanical removal mode is difficult to remove totally；2. mechanical removal mode is easy to the inwall of refining furnace 1 Cause damage, cause subsequently repair furnace wall；3. mechanical removal mode, wastes time and energy so that between adjacent two heat The gap time is longer, so that the anode refining cycle is longer, has had a strong impact on rhythm of production and production efficiency.Therefore, in this hair In bright one embodiment, when the cavity in the refining furnace 1 is in atmospheric pressure state, by oxygen rifle 4 with top-blown gas Mode is blown fuel gas and oxygen-containing gas into the refining furnace 1, and the fuel gas and the oxygen-containing gas are lighted into combustion Burn, using the combustion reaction liberated heat of the fuel gas and the oxygen-containing gas to splash in the inwall of refining furnace 1 On copper melt cooling after the dross thing that is formed carry out melting removing processing, utilize the fuel gas and the oxygen-containing gas Combustion reaction liberated heat carries out baker processing to the refining furnace 1；
The oxygen rifle 4 is the multilayer internal and external casing structure for the hollow pipe for including multiple inside and outside suits, the oxygen rifle 4 include by It is that cavity between the tube wall of the hollow pipe of cavity or two neighboring inside and outside suit in hollow pipe is formed and described for conveying The fuel gas passage of fuel gas, the fuel gas passage connect with the compressed air source unit of the fuel gas；
The oxygen rifle 4 is also included between the tube wall of the hollow pipe by the cavity in hollow pipe or two neighboring inside and outside suit It is that cavity is formed and for conveying the oxygen-containing gas passage of the oxygen-containing gas, the oxygen-containing gas passage and the oxygen-containing gas Compressed air source unit connection；
The oxygen rifle 4 also include formed by the cavity between the tube wall of the hollow pipe of two neighboring inside and outside suit and be used for The cooling circulating water passage of cooling protection is carried out to the oxygen rifle 4, the cooling circulating water passage connects with apparatus for supplying cool water It is logical；
The oxygen rifle 4 is arranged on the roof of the refining furnace 1 and can slided up and down along the roof of the refining furnace 1.
The present invention is when the cavity in the refining furnace 1 is in atmospheric pressure state, oxygen rifle 4 in a manner of top-blown gas Fuel gas and oxygen-containing gas are blown into the refining furnace 1, the fuel gas and the oxygen-containing gas are lighted into burning, profit With copper of the combustion reaction liberated heat of the fuel gas and the oxygen-containing gas to splash on the inwall of refining furnace 1 The dross thing formed after liquation cooling carries out melting removing processing, and the temperature improved in the upper space of refining furnace 1 causes dross thing Melted by heat becomes liquid again, and the inwall along refining furnace 1 flows downward, final to flow out refining furnace 1；Due to the oxygen rifle 4 It is arranged on the roof of the refining furnace 1 and can be slided up and down along the roof of the refining furnace 1 so that completes to remove a certain position Dross thing after, oxygen rifle 4 can carry out melting removing processing with ascending motion or descending motion to other positions in refining furnace 1, The final fusing realized to dross thing on the whole inwall of refining furnace 1 is removed, so as to reduce above-mentioned mechanical removal mode institute band A series of negative influences come.
For a further understanding of the present invention, with reference to embodiment to provided by the invention a kind of for handling high impurity copper The smelting process of concentrate and shallow oxidation without reduction anode refining is described in detail, and protection scope of the present invention is not by following implementation The limitation of example.
Embodiment 1
High impurity copper concentrate is successively carried out to melting process, blowing process and anode refining process, specifically using flash Converting process output blister copper liquation, the blister copper liquation include following components in percentage by weight：0.35% sulphur, 0.76% Iron, 0.0010% oxygen, 0.69% lead, 0.020% zinc, 0.44% arsenic, 0.041% antimony, 0.15% bismuth, 0.02% tin.
The anode refining process specifically includes following steps：
1) the blister copper liquation of melting is added in the Sheng copper container for containing blister copper liquation；Then refining will be arranged on Feed tube 2 and drain pipe 3 on the bottom wall of stove 1 are immersed in the upper liquid level certain depth below for containing copper melt in copper container, Ran Houkai Open the cavity vacuum state in refining furnace 1 with the vavuum pump that refining furnace 1 connects, now the vacuum residual voltage in refining furnace 1 The copper melt in copper container is contained in the presence of atm difference between external atmosphere pressure along the sky in feed tube 2 and drain pipe 3 Chamber passage, which rises, to be flowed into the cavity of refining furnace 1；
2) driving gas with pressure is blown in the copper melt into feed tube 2, then in atm difference and driving gas Drive the lower copper melt contained in copper container constantly by feed tube 2 to be risen to flow into refining furnace 1, then the copper in refining furnace 1 melts Liquid is constantly back to by the outflow of refining furnace 1 by drain pipe 3 contains in copper container again, is containing copper container, feed tube 2, refining furnace 1 And circulating for copper melt is formed between drain pipe 3；Meanwhile in refining furnace 1, the copper melt into refining furnace 1 blows Element sulphur in copper melt is oxidized to the gaseous oxygen compound of sulphur by oxygen-containing gas, the oxygen element in oxygen-containing gas, in oxygen-containing gas Oxygen element the ferro element in copper melt is oxidized to the oxide of iron, realize the oxidation operation process of desulfurization deferrization；Meanwhile institute The part for stating whole contents of impurity element included in the copper melt in refining furnace is directly volatilized with elemental form, all The remainder of content is oxidized to volatilize with oxide form after oxide by the oxygen-containing gas, is realizing the oxygen of desulfurization deferrization Change operation process while, realize simultaneously imurity-removal element refining process, the impurity element include lead, zinc, arsenic, antimony, It is one or more or whole in bismuth and tin element；Meanwhile the vacuum residual voltage level in refining furnace 1 is controlled so that proper copper melt In sulfur content when reaching requirement of the target anode copper to sulfur content, the oxygen content for realizing reaction balance with the sulfur content also reaches Requirement of the target anode copper to oxygen content；Slag former is added in copper melt into refining furnace 1；By oxygen rifle 4 with top-blown gas Mode fuel gas and oxygen-containing gas are blown into refining furnace 1, fuel gas and oxygen-containing gas are lighted into burning, utilization is flammable The combustion reaction liberated heat of gas and oxygen-containing gas carries out supplementary heating processing to the copper melt in refining furnace 1, using can What the combustion reaction liberated heat of combustion gas body and oxygen-containing gas was formed after being cooled down to copper melt of the splash on the inwall of refining furnace 1 Dross thing is purged processing；
3) after step 2) carries out a period of time, the component and content of the copper melt after sample examination anode refining, if chemical examination As a result reach requirement of the target anode copper to sulfur content and iron content, then the copper melt contained in copper container is subjected to pure follow first Ring handles certain time, while contains the bottom-blowing device of copper container bottom to containing copper melt progress bottom blowing in copper container by being arranged at Gas treatment, the vacuum state in refining furnace 1 is then abolished again, then the feed tube 2 that be arranged on the bottom wall of refining furnace 1 and will go out Liquid pipe 3 departs from the copper melt contained in copper container, aoxidizes the end of job；If result of laboratory test miss the mark anode copper is to sulphur or iron two The requirement of any one in person, continue anode refining, until result of laboratory test reaches target anode copper to sulfur content and iron content Requirement；The content that anode refining terminates to obtain sulphur, iron and oxygen reaches the anode copper melt of target call, containing SO2Flue gas And clinker.
Gained anode copper melt includes following components in percentage by weight：0.0030% sulphur, 0.0035% iron, 0.02% oxygen, 0.0033% lead, 0.0019% zinc, 0.009% arsenic, 0.01% antimony, 0.0042% bismuth, 0.0019% tin；Removal efficiency is respectively accordingly：Sulphur：99.14%th, iron：99.54%th, lead：99.52%th, zinc：90.5%th, Arsenic：97.95%th, antimony：75.61%th, bismuth：97.2%th, tin：90.5%.
Embodiment 2
High impurity copper concentrate is successively carried out to melting process, blowing process and anode refining process, specifically using flash Converting process output blister copper liquation, flash converting process output blister copper liquation specifically is used, the blister copper liquation includes following weight The component of percentage：0.50% sulphur, 0.69% iron, 0.0010% oxygen, 0.58% lead, 0.016% zinc, 0.40% Arsenic, 0.038% antimony, 0.13% bismuth, 0.02% tin.
The anode refining process specifically includes following steps：
1) the blister copper liquation of melting is added in the Sheng copper container for containing blister copper liquation；Then refining will be arranged on Feed tube 2 and drain pipe 3 on the bottom wall of stove 1 are immersed in the upper liquid level certain depth below for containing copper melt in copper container, Ran Houkai Open the cavity vacuum state in refining furnace 1 with the vavuum pump that refining furnace 1 connects, now the vacuum residual voltage in refining furnace 1 The copper melt in copper container is contained in the presence of atm difference between external atmosphere pressure along the sky in feed tube 2 and drain pipe 3 Chamber passage, which rises, to be flowed into the cavity of refining furnace 1；
2) driving gas with pressure is blown in the copper melt into feed tube 2, then in atm difference and driving gas Drive the lower copper melt contained in copper container constantly by feed tube 2 to be risen to flow into refining furnace 1, then the copper in refining furnace 1 melts Liquid is constantly back to by the outflow of refining furnace 1 by drain pipe 3 contains in copper container again, is containing copper container, feed tube 2, refining furnace 1 And circulating for copper melt is formed between drain pipe 3；Meanwhile in refining furnace 1, the copper melt into refining furnace 1 blows Element sulphur in copper melt is oxidized to the gaseous oxygen compound of sulphur by oxygen-containing gas, the oxygen element in oxygen-containing gas, in oxygen-containing gas Oxygen element the ferro element in copper melt is oxidized to the oxide of iron, realize the oxidation operation process of desulfurization deferrization；Meanwhile institute The part for stating whole contents of impurity element included in the copper melt in refining furnace is directly volatilized with elemental form, all The remainder of content is oxidized to volatilize with oxide form after oxide by the oxygen-containing gas, is realizing the oxygen of desulfurization deferrization Change operation process while, realize simultaneously imurity-removal element refining process, the impurity element include lead, zinc, arsenic, antimony, It is one or more or whole in bismuth and tin element；Meanwhile the vacuum residual voltage level in refining furnace 1 is controlled so that proper copper melt In sulfur content when reaching requirement of the target anode copper to sulfur content, the oxygen content for realizing reaction balance with the sulfur content also reaches Requirement of the target anode copper to oxygen content；Slag former is added in copper melt into refining furnace 1；By oxygen rifle 4 with top-blown gas Mode fuel gas and oxygen-containing gas are blown into refining furnace 1, fuel gas and oxygen-containing gas are lighted into burning, utilization is flammable The combustion reaction liberated heat of gas and oxygen-containing gas carries out supplementary heating processing to the copper melt in refining furnace 1, using can What the combustion reaction liberated heat of combustion gas body and oxygen-containing gas was formed after being cooled down to copper melt of the splash on the inwall of refining furnace 1 Dross thing is purged processing；
3) after step 2) carries out a period of time, the component and content of the copper melt after sample examination anode refining, if chemical examination As a result reach requirement of the target anode copper to sulfur content and iron content, then the copper melt contained in copper container is subjected to pure follow first Ring handles certain time, while contains the bottom-blowing device of copper container bottom to containing copper melt progress bottom blowing in copper container by being arranged at Gas treatment, the vacuum state in refining furnace 1 is then abolished again, then the feed tube 2 that be arranged on the bottom wall of refining furnace 1 and will go out Liquid pipe 3 departs from the copper melt contained in copper container, aoxidizes the end of job；If result of laboratory test miss the mark anode copper is to sulphur or iron two The requirement of any one in person, continue anode refining, until result of laboratory test reaches target anode copper to sulfur content and iron content Requirement；The content that anode refining terminates to obtain sulphur, iron and oxygen reaches the anode copper melt of target call, containing SO2Flue gas And clinker.
Gained anode copper melt includes following components in percentage by weight：0.0030% sulphur, 0.0035% iron, 0.006% oxygen, 0.0028% lead, 0.0023% zinc, 0.008% arsenic, 0.009% antimony, 0.0039% bismuth, 0.0015% tin；Removal efficiency is respectively accordingly：Sulphur：99.4%th, iron：99.49%th, lead：99.52%th, zinc：85.63%th, Arsenic：98%th, antimony：76.32%th, bismuth：97%th, tin：92.5%.
The present invention is for thinking technical problems to be solved, there is provided multiple laddering technical schemes, it is multiple laddering Technical scheme is mutually combined superposition, cooperates, mutually promotes, and forms an overall plan, and the technique effect of acquirement is much better than The technique effect of any of the above technical schemes, synergistic effect are notable.
The method and apparatus of the not detailed description of the present invention are prior art, are repeated no more.Each implementation in this specification Example is described by the way of progressive, and what each embodiment stressed is the difference with other embodiments, each to implement Example between same or similar part mutually referring to.
The explanation of above example is only intended to help the method and its core concept for understanding the present invention.It should be pointed out that pair For those skilled in the art, under the premise without departing from the principles of the invention, the present invention can also be carried out Some improvement and modification, these are improved and modification is also fallen into the protection domain of the claims in the present invention.

Claims (10)

1. a kind of be used to handle high impurity copper concentrate and shallow smelting process of the oxidation without reduction anode refining, it is characterised in that bag Include the melting process successively carried out, blowing process and anode refining process, the anode refining process and specifically include following step Suddenly：
1) the blister copper liquation of melting is added in the Sheng copper container for containing blister copper liquation；Then refining furnace bottom will be arranged on Feed tube and drain pipe on wall be immersed in it is described Sheng copper container in copper melt upper liquid level certain depth below, be then turned on The vavuum pump of refining furnace connection is by the cavity vacuum state in the refining furnace, the now vacuum residual voltage in refining furnace In the presence of atm difference between external atmosphere pressure it is described contain copper container in copper melt along the feed tube and it is described go out Cavity passage in liquid pipe, which rises, to be flowed into the cavity of the refining furnace；
The profile of the refining furnace is vertical type columnar, and inner hollow forms cavity, and the refining furnace includes steel shell and block The refractory lining in the steel shell inner surface is built, is provided with the top of the refining furnace for connecting with the vavuum pump The gas outlet connect；
The feed tube and refractory material of the drain pipe including steel-made inner shell, the inner surface for being arranged on the steel-made inner shell Liner and be arranged on the steel-made inner shell outer surface refractory material outer lining, the length of the feed tube and the drain pipe It is identical；
The feed tube is fixedly installed on the bottom wall of the refining furnace and close with the bottom wall of the refining furnace with the drain pipe Envelope connects, and the cavity in the refining furnace is interconnected with the cavity passage in the feed tube, the cavity in the refining furnace It is interconnected with the cavity passage in the drain pipe, it is all to be connected with the device that the refining furnace is connected with the refining furnace Position carry out encapsulation process to prevent the vacuum state destroyed in the refining furnace；
2) driving gas with pressure is blown in the copper melt into the feed tube, then in atm difference and the band of driving gas The copper melt contained in copper container is constantly risen by the feed tube under dynamic flows into the refining furnace, the then refining Copper melt in stove is constantly back in the Sheng copper container by the drain pipe by refining furnace outflow again, described Contain and circulating for copper melt is formed between copper container, feed tube, refining furnace and drain pipe；
Meanwhile in the refining furnace, the copper melt into the refining furnace blows oxygen-containing gas, the oxygen in the oxygen-containing gas Element sulphur in copper melt is oxidized to the gaseous oxygen compound of sulphur by element, and the oxygen element in the oxygen-containing gas is by copper melt Ferro element is oxidized to the oxide of iron, realizes the oxidation operation process of desulfurization deferrization；
Meanwhile a part for whole contents of the impurity element included by the copper melt in the refining furnace is straight with elemental form Volatilization is connect, the remainder of whole contents is oxidized to be volatilized with oxide form after oxide, realized by the oxygen-containing gas While the oxidation operation process of desulfurization deferrization, the refining process of imurity-removal element simultaneously is realized, the impurity element includes It is one or more or whole in lead, zinc, arsenic, antimony, bismuth and tin element；
Meanwhile the vacuum residual voltage level in the refining furnace is controlled so that the sulfur content in proper copper melt reaches target anode copper During requirement to sulfur content, realize that the oxygen content of reaction balance also reaches target anode copper and oxygen content is wanted with the sulfur content Ask；
3) after the step 2) carries out a period of time, the component and content of the copper melt after sample examination anode refining, if chemical examination As a result reach requirement of the target anode copper to sulfur content and iron content, then abolish the vacuum state in the refining furnace first, Then the feed tube being arranged on the refining furnace hearth wall and drain pipe are departed from into the copper melt contained in copper container, oxidation is made Industry terminates；If result of laboratory test miss the mark anode copper continues anode refining, directly to the requirement of any one in both sulphur or iron Reach requirement of the target anode copper to sulfur content and iron content to result of laboratory test；Anode refining terminates to obtain sulphur, iron and oxygen Content reach the anode copper melt of target call, containing SO2Flue gas and clinker.
2. smelting process according to claim 1, it is characterised in that in the step 2), by the oxygen-containing gas to soak The mode not blowed is blowed to the upper liquid level of the copper melt in the refining furnace, sprays the gas outlet position of the oxygen-containing gas Below the upper liquid level of the copper melt in the refining furnace.
3. smelting process according to claim 1 or 2, it is characterised in that in the step 2), by oxygen rifle with top blast gas The mode of body blows the oxygen-containing gas into the copper melt in the refining furnace, and the gas outlet of the oxygen rifle is located at the essence It is separated by a certain distance more than the upper liquid level of the copper melt in furnace and with the upper liquid level of copper melt；
The oxygen rifle is the multilayer internal and external casing structure for the hollow pipe for including multiple inside and outside suits, and the oxygen rifle is included by hollow pipe It is that cavity between interior cavity or the tube wall of the hollow pipe of two neighboring inside and outside suit is formed and described oxygenous for conveying The oxygen-containing gas passage of body, the oxygen-containing gas passage connect with the compressed air source unit of the oxygen-containing gas；
The oxygen rifle also include is formed by the cavity between the tube wall of the hollow pipe of two neighboring inside and outside suit and be used for institute The cooling circulating water passage that oxygen rifle carries out cooling protection is stated, the cooling circulating water passage connects with apparatus for supplying cool water；
The oxygen rifle also includes being used to improve the oxygen-containing gas spouting velocity and controls the spray of the oxygen-containing gas injection direction Head, the shower nozzle are arranged on the bottom of the oxygen rifle, and the gas outlet of the oxygen rifle is arranged on the shower nozzle；
The oxygen rifle is arranged on the roof of the refining furnace and can slided up and down along the roof of the refining furnace.
4. smelting process according to claim 1, it is characterised in that in the step 2), the copper into the refining furnace Slag former is added in liquation, slag former occurs slag making reaction with the oxide obtained after oxidation operation, obtains refining slag, refining slag Float, refining slag blanket is formed at liquid level on the copper melt in the Sheng copper container.
5. smelting process according to claim 4, it is characterised in that in the step 2), be blended with slag former powder Compressed gas be blown in a manner of submerging and blowing to the upper liquid level of the copper melt in the refining furnace, spray it is described with pressure The gas outlet of gas is located at below the upper liquid level of the copper melt in the refining furnace.
6. the smelting process according to claim 4 or 5, it is characterised in that in the step 2), by oxygen rifle with top spray gas The compressed gas that the mode of body is blended with slag former powder are sprayed into the copper melt in the refining furnace, the oxygen rifle Gas outlet be located at more than the upper liquid level of the copper melt in the refining furnace and be separated by a certain distance with the upper liquid level of copper melt；
The oxygen rifle is the multilayer internal and external casing structure for the hollow pipe for including multiple inside and outside suits, and the oxygen rifle is included by hollow pipe It is that cavity between the tube wall of the hollow pipe of interior cavity or two neighboring inside and outside suit is formed and described in being mixed with for conveying The compressed gas passage of the compressed gas of slag former powder, the compressed gas passage connect with gas powder feedway；
The oxygen rifle also include is formed by the cavity between the tube wall of the hollow pipe of two neighboring inside and outside suit and be used for institute The cooling circulating water passage that oxygen rifle carries out cooling protection is stated, the cooling circulating water passage connects with apparatus for supplying cool water；
The oxygen rifle is arranged on the roof of the refining furnace and can slided up and down along the roof of the refining furnace.
7. smelting process according to claim 1, it is characterised in that in the step 3), when result of laboratory test reaches target During requirement of the anode copper to sulphur and iron, before the vacuum state in the refining furnace is abolished, by the Sheng copper container Copper melt carries out pure circular treatment certain time, then abolishes the vacuum state in the refining furnace again.
8. the smelting process according to claim 1 or 7, it is characterised in that in the step 3), when result of laboratory test reaches mesh When marking requirement of the anode copper to sulphur and iron, before the vacuum state in the refining furnace is abolished, by being arranged at the Sheng The bottom-blowing device of copper container bottom carries out bottom blown gas processing to copper melt in the Sheng copper container, then abolishes the refining again Vacuum state in stove, the gas of the bottom-blowing device injection is nitrogen or argon gas.
9. smelting process according to claim 1, it is characterised in that during anode refining, when in the refining furnace Cavity when being in vacuum state, fuel gas and oxygen-containing is blown into the refining furnace in a manner of top-blown gas oxygen rifle Gas, the fuel gas and the oxygen-containing gas are lighted into burning, utilize the combustion of the fuel gas and the oxygen-containing gas Burn reaction liberated heat and supplementary heating processing is carried out to the copper melt in the refining furnace, utilize the fuel gas and described The dross that the combustion reaction liberated heat of oxygen-containing gas is formed after being cooled down to copper melt of the splash on the refining furnace inwall Thing is purged processing；
The gas outlet of the oxygen rifle be located at more than the upper liquid level of the copper melt in the refining furnace and with the upper liquid level phase of copper melt Away from certain distance；
The oxygen rifle is the multilayer internal and external casing structure for the hollow pipe for including multiple inside and outside suits, and the oxygen rifle is included by hollow pipe It is that cavity between the tube wall of the hollow pipe of interior cavity or two neighboring inside and outside suit is formed and for conveying the combustible gas The fuel gas passage of body, the fuel gas passage connect with the compressed air source unit of the fuel gas；
The oxygen rifle also includes the cavity between the tube wall of the hollow pipe by the cavity in hollow pipe or two neighboring inside and outside suit Gas that is being formed and being used for the oxygen-containing gas passage for conveying the oxygen-containing gas, the oxygen-containing gas passage and the oxygen-containing gas Source device connects；
The oxygen rifle also include is formed by the cavity between the tube wall of the hollow pipe of two neighboring inside and outside suit and be used for institute The cooling circulating water passage that oxygen rifle carries out cooling protection is stated, the cooling circulating water passage connects with apparatus for supplying cool water；
The oxygen rifle is arranged on the roof of the refining furnace and can slided up and down along the roof of the refining furnace.
10. smelting process according to claim 1, it is characterised in that when the cavity in the refining furnace is in atmospheric pressure During state, fuel gas and oxygen-containing gas are blown in a manner of top-blown gas into the refining furnace oxygen rifle, can by described in Combustion gas body and the oxygen-containing gas light burning, the heat released using the combustion reaction of the fuel gas and the oxygen-containing gas Measure and the dross thing that is formed after copper melt cooling of the splash on the refining furnace inwall is carried out melting removing processing, using described The combustion reaction liberated heat of fuel gas and the oxygen-containing gas carries out baker processing to the refining furnace；
The oxygen rifle is the multilayer internal and external casing structure for the hollow pipe for including multiple inside and outside suits, and the oxygen rifle is included by hollow pipe It is that cavity between the tube wall of the hollow pipe of interior cavity or two neighboring inside and outside suit is formed and for conveying the combustible gas The fuel gas passage of body, the fuel gas passage connect with the compressed air source unit of the fuel gas；
The oxygen rifle also includes the cavity between the tube wall of the hollow pipe by the cavity in hollow pipe or two neighboring inside and outside suit Gas that is being formed and being used for the oxygen-containing gas passage for conveying the oxygen-containing gas, the oxygen-containing gas passage and the oxygen-containing gas Source device connects；
The oxygen rifle also include is formed by the cavity between the tube wall of the hollow pipe of two neighboring inside and outside suit and be used for institute The cooling circulating water passage that oxygen rifle carries out cooling protection is stated, the cooling circulating water passage connects with apparatus for supplying cool water；
The oxygen rifle is arranged on the roof of the refining furnace and can slided up and down along the roof of the refining furnace.
CN201510998775.7A 2015-12-26 2015-12-26 It is a kind of to be used to handle high impurity copper concentrate and shallow smelting process of the oxidation without reduction anode refining Active CN105543498B (en)

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