CN105779786A - Shallow-oxidation reduction-free anode refining system for processing high-impurity crude copper - Google Patents

Shallow-oxidation reduction-free anode refining system for processing high-impurity crude copper Download PDF

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CN105779786A
CN105779786A CN201610141854.0A CN201610141854A CN105779786A CN 105779786 A CN105779786 A CN 105779786A CN 201610141854 A CN201610141854 A CN 201610141854A CN 105779786 A CN105779786 A CN 105779786A
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oxygen
containing gas
copper
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refining furnace
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杨伟燕
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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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Abstract

The invention discloses a shallow-oxidation reduction-free anode refining system for processing high-impurity crude copper. The shallow-oxidation reduction-free anode refining system for processing high-impurity crude copper comprises a copper container for containing a crude copper solution, a refining furnace, a liquid inflow pipe, a liquid outflow pipe, a vacuum pump, a drive gas pipe, a top-blowing nozzle, a condenser for cooling smoke generated in the anode refining process and a lifting device for lifting the refining furnace. Oxygen-containing gas in the outside is supplemented and blown in the refining furnace under the vacuum state, the oxidation work of desulfurization, deferrization and impurity removal is carried out, the proportion of the oxygen-containing gas, truly used for oxidative desulfurization, in the oxygen-containing gas is increased, the proportion of the oxygen-containing gas doing the idle work is reduced, the actual usage amount of the oxygen-containing gas in the positive pole refining process is reduced, waste of the oxygen-containing gas is reduced, the production cost on anode refining is reduced, and shallow-oxidation reduction-free anode refining of the crude copper is achieved.

Description

A kind of shallow oxidation anode refining system without reduction for processing high impurity crude copper
Technical field
The present invention relates to non-ferrous metal metallurgy technical field, especially relate to a kind of shallow oxidation anode refining system without reduction for processing high impurity crude copper.
Background technology
In Copper making industry, its primary routing is: melting → blowing → anode refining → electrorefining.Blowing operation output blister copper liquation, then sends blister copper liquation into anode furnace and carries out anode refining, obtain anode copper and a small amount of slag.The substantially process that blister copper liquation carries out anode refining at anode furnace is: the blister copper liquation of converting furnace output flows into anode furnace along chute, after reaching setting batch, stop blister copper and flow into, anode furnace is turned to oxygen supply oxidation position, begin through side wall trachea and blow oxygen-containing gas to blister copper liquation, such as air or oxygen-enriched air, the sulfur content in executeaaafunction, sample examination liquation, if sulfur content is not up to standard, continuing oxidation, until sample examination is qualified, this process is oxidation operation process；It is then followed by deslagging；Then, begin through above-mentioned side wall trachea and blow reducibility gas in liquation, usually natural gas, oxygen content in executeaaafunction, sample examination liquation, if oxygen content is not up to standard, continue reduction, until sample examination is qualified, this process is reduction operation process, finally gives anode copper liquation；Then, casting, obtain anode copper coin.
In Copper making industry, it is known that, above-mentioned oxidation operation and reduction operation are two mutually contradictory operation process, first oxygen blast desulfurization, by the time desulfurization is up to standard, according to metallurgical equilibrium principle, oxygen content is automatically, inevitably raise with the theoretical demand of trim molecular balance, result oxygen content inevitably excess, then natural gas deoxidation is blown again, oxygen content is lowered, process is similar to " first low cost destruction, high cost is remedied again ", visible oxygen-containing gas only has sub-fraction for oxidation sweetening, what remaining major part oxygen-containing gas was made is all idle work, do not play any beneficial effect；Not only do not play any beneficial effect, also create significant negative effect: need to go elimination with more costly natural gas 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 costly of anode refining.At present, Copper making industry continued downturn and inefficiencies, existing anode refining technique is obviously not suitable for the development of industry.
Therefore, how to improve the real oxygen-containing gas ratio for oxidation sweetening in oxygen-containing gas, reduce the oxygen-containing gas ratio making idle work, reduce the actually used amount of oxygen-containing gas in anode refining process, reducing oxygen-containing gas waste, the production cost reducing anode refining is that those skilled in the art need badly and solve the technical problem that.
Summary of the invention
Based on described above, it is an object of the invention to provide a kind of shallow oxidation anode refining system without reduction for processing high impurity crude copper, this anode refining system can improve the real oxygen-containing gas ratio for oxidation sweetening in oxygen-containing gas, reduce the oxygen-containing gas ratio making idle work, reduce the actually used amount of oxygen-containing gas in anode refining process, reduce oxygen-containing gas waste, reduce the production cost of anode refining.
For solving above-mentioned technical problem, the present invention adopts the following technical scheme that
A kind of shallow oxidation anode refining system without reduction for processing high impurity crude copper, including for containing containing copper container, refining furnace, feed tube, drain pipe, vacuum pump, driving gas tube, top blast nozzle, carrying out the condenser that cools down and for lifting the lowering or hoisting gear of described refining furnace for the flue gas produced in antianode refining process of blister copper liquation；
The profile of described refining furnace is vertical type columnar, inner hollow forms cavity, described refining furnace includes steel shell and builds the refractory lining at described steel shell inner surface by laying bricks or stones, the top of described refining furnace is provided with the gas outlet for being connected with described vacuum pump, the gas outlet of described refining furnace connects with the air inlet of described condenser, and the gas outlet of described condenser connects with described vacuum pump；
Described feed tube and described drain pipe all include steel-made inner shell, be arranged on the refractory lining of the inner surface of described steel-made inner shell and be arranged on the refractory material outer lining of outer surface of described steel-made inner shell；
Described feed tube and described drain pipe are fixedly installed on the diapire of described refining furnace and are tightly connected with the diapire of described refining furnace, cavity in described refining furnace is interconnected with the cavity passage in described feed tube, cavity in described refining furnace is interconnected with the cavity passage in described drain pipe, and the device that all and described refining furnace is connected all carries out encapsulation process to prevent from destroying the vacuum state in described refining furnace at the position being connected with described refining furnace；
Described driving gas tube is arranged on described feed tube with driving gas with pressure of jetting in the copper melt in described feed tube；
Described top blast nozzle be arranged on the roof of described refining furnace and can along the roof of described refining furnace slide up and down for by described top blast nozzle to blow oxygen-containing gas in the copper melt in described refining furnace in the way of top-blown gas；
Described top blast nozzle is the multilamellar internal and external casing structure of the hollow pipe including multiple inside and outside suit, described top blast nozzle include by inside and outside the cavity in hollow pipe or adjacent two suit hollow pipe tube wall between cavity formed and for carrying the first oxygen-containing gas passage of described oxygen-containing gas, described first oxygen-containing gas passage connects with the compressed air source unit of described oxygen-containing gas；
That described top blast nozzle also includes being formed by cavity between the tube wall of the hollow pipe of suit inside and outside adjacent two and for described top blast nozzle carries out the cool cycles aquaporin of cooling protection, described cool cycles aquaporin connects with apparatus for supplying cool water；
The gas outlet of described top blast nozzle is positioned at more than the upper liquid level of the copper melt of described refining furnace and with the upper liquid level of copper melt in a distance.
Preferably, described top blast nozzle also include by inside and outside the cavity in hollow pipe or adjacent two suit hollow pipe tube wall between cavity formed and for carrying the compressed gas passage of the compressed gas being mixed with slag former powder, described compressed gas passage connects with gas powder feedway.
Preferably, described top blast nozzle also includes that the cavity between the tube wall by the hollow pipe being set with inside and outside the cavity in hollow pipe or adjacent two is formed and for transporting combustible gases fuel gas passage, and described fuel gas passage connects with the compressed air source unit of described fuel gas.
Preferably, described top blast nozzle also include the cavity in hollow pipe or inside and outside adjacent two cavity between the tube wall of the hollow pipe of suit formed and the second oxygen-containing gas passage of oxygen-containing gas for gas fuel burning described with carrying, described second oxygen-containing gas passage connects with the compressed air source unit of described oxygen-containing gas.
Preferably, described fuel gas passage and described second oxygen-containing gas passage are integral type structure, and the integral structure of described fuel gas passage and described second oxygen-containing gas passage is split-type structural with described first oxygen-containing gas passage, the integral structure of described fuel gas passage and described second oxygen-containing gas passage can slide up and down relative to described first oxygen-containing gas passage in the vertical direction.
Preferably, the side lower of described refining furnace is provided with side-blown nozzle and blows oxygen-containing gas in the way of blowing by submergence below the upper liquid level of the copper melt in described refining furnace, and the gas outlet of described side-blown nozzle is positioned at below the upper liquid level of the copper melt of described refining furnace；
Described side-blown nozzle is the multilamellar internal and external casing structure of the hollow pipe including multiple inside and outside suit, described side-blown nozzle include by inside and outside the cavity in hollow pipe or adjacent two suit hollow pipe tube wall between cavity formed and for carrying the oxygen-containing gas passage of described oxygen-containing gas, described oxygen-containing gas passage connects with the compressed air source unit of described oxygen-containing gas；
That described side-blown nozzle also includes being formed by cavity between the tube wall of the hollow pipe of suit inside and outside adjacent two and for described side-blown nozzle carries out the cool cycles aquaporin of cooling protection, described cool cycles aquaporin connects with apparatus for supplying cool water.
Preferably, described side-blown nozzle also include by inside and outside the cavity in hollow pipe or adjacent two suit hollow pipe tube wall between cavity formed and for carrying the compressed gas passage of the compressed gas being mixed with slag former powder, described compressed gas passage connects with gas powder feedway.
Preferably, described Sheng copper container is Rotary Anode Furnace, and described Rotary Anode Furnace includes opening that is that offer on its furnace wall and that lower into for described refining furnace or rise away.
Compared with prior art, the invention provides a kind of shallow oxidation anode refining system without reduction for processing high impurity crude copper, this anode refining system has following useful technique effect:
null1. use anode refining system provided by the invention，The initial oxygen content carried in copper melt and later stage are re-blow oxygen content that oxygen-containing gas supplemented almost fully for oxidation sweetening and oxidation deferrization by the external world，The oxygen-containing gas re-blow in the external world will not do substantial amounts of idle work as original，The oxygen-containing gas amount that the external world that oxidation operation consumes supplements only accounts for the 10%～30% of the oxygen-containing gas amount that the oxidation operation of former anode refining consumes，The oxygen-containing gas amount consumed compared to the oxidation operation of former anode refining decreases 70%～90%，Therefore the present invention is a kind of shallow oxidizing anode rectification systems，Improve the real oxygen-containing gas ratio for oxidation sweetening in oxygen-containing gas，Decrease the oxygen-containing gas ratio making idle work，Decrease the actually used amount of oxygen-containing gas in anode refining process，Decrease oxygen-containing gas waste，Reduce the production cost of anode refining.
2. use anode refining system provided by the invention real oxygen-containing gas ratio for oxidation sweetening in improve oxygen-containing gas, while decreasing the oxygen-containing gas ratio making idle work, the present invention also achieves unforeseeable technique effect: in the liquation obtained after oxidation operation, oxygen content can meet the target anode copper normal requirement to oxygen content, follow-up without carrying out reduction operation, it is achieved that real nothing reduction anode refining.
3. use anode refining system provided by the invention real oxygen-containing gas ratio for oxidation sweetening in improve oxygen-containing gas, while decreasing the oxygen-containing gas ratio making idle work, the present invention also achieves the unforeseeable technique effect of another one: in the present invention, when not carrying out reduction operation, in the anode copper liquation that anode refining terminal obtains, oxygen content can reach the 1/100～1/10 of former anode refining terminal oxygen content, reduces 1 to 2 orders of magnitude than former anode refining terminal oxygen content.The less anode copper liquation of oxygen content can be more beneficial for producing surface quality and the better positive plate of internal soundness, the carrying out of follow-up electrorefining can be more beneficial for, the quantum of output of the sedimentation earth of positive pole and the floating earth of positive pole can be significantly reduced, reduce cathode plate surface particle, improve the current efficiency of electrorefining, improve internal soundness and the surface quality of the cathode plate of electrorefining output.
null4. use anode refining system provided by the invention real oxygen-containing gas ratio for oxidation sweetening in improve oxygen-containing gas，While decreasing the oxygen-containing gas ratio making idle work，The present invention also achieves the unforeseeable technique effect of another one: the oxidation operation process time can be reduced within 1 hour by the present invention，Major part heat can reduce within 40 minutes，Add the present invention can realize without reduction anode refining，Therefore anode refining process time (not including feed time and casting time) can be reduced within 1 hour by the present invention，Major part heat can reduce within 40 minutes，And pole, Yuanyang refining process (not including feed time and casting time) required time is generally 2 hours，So，Present invention significantly reduces the time needed for anode refining process，Reduction amplitude is about 50%～66.67%，Considerably improve production efficiency and rhythm of production.
null5. use anode refining system provided by the invention real oxygen-containing gas ratio for oxidation sweetening in improve oxygen-containing gas，While decreasing the oxygen-containing gas ratio making idle work，The present invention also achieves the unforeseeable technique effect of another one: the present invention is compared to simple vacuum distilling refine，Considerably improve arsenic、The elimination speed of antimony and three kinds of elements of stannum and elimination degree，Arsenic and antimony can be removed to less than 0.01%，The removal efficiency of arsenic can be increased to more than 95%，The removal efficiency of antimony can be increased to more than 75%，Stannum can be removed to less than 0.0050%，The removal efficiency of stannum is increased to more than 90%，Achieve and remove lead simultaneously、Zinc、Arsenic、Antimony、The refining process of bismuth and six kinds of impurity elements of stannum，Make the anode refining method provided by the invention both can the blister copper of refine normal level range，The blister copper of high impurity content can also be processed.
6. in the present invention, at described Sheng copper container, feed tube, circulating of liquation is formed between refining furnace and drain pipe, the such big cycle volume ground flowing of liquation is that the non-metallic inclusion in elimination copper melt improves extremely advantageous dynamic conditions, improve collision probability and the agglomeration of non-metallic inclusion in copper melt, non-metallic inclusion after agglomeration is easier to rely on the buoyancy of self to float, it is mixed in the slag blanket of copper melt upper surface, thus considerably improving elimination speed and the elimination degree of non-metallic inclusion in copper melt, improve the cleanliness factor of the anode copper liquation obtained after anode refining terminates.
7. the present invention selects to join in copper melt slag former in refining furnace, and slag former falls in copper melt and can react with the oxide generation slag making in copper melt rapidly, has reaction rate and the complete degree of reaction of higher deferrization removing impurities matter.
8. the present invention improves heat utilization ratio and heat transfer efficiency by improving mode of heating, it is ensured that carrying out the copper melt the aoxidizing operation requirement to temperature, what improve oxidation operation carries out speed and performance level；And this mode of heating improves the temperature in refining furnace upper space simultaneously, it is therefore prevented that the copper melt cooled and solidified of splash forms dross thing, thus decreasing the generation of dross thing；Dross thing melted by heat is made again to become liquid, inwall along refining furnace flows downward, and is again back in the copper melt circulated, and completes anode refining process, thus decreasing the quantity of the dross thing generated, thus reducing a series of negative influences that above-mentioned dross thing brings.
Accompanying drawing explanation
Fig. 1 is the shallow oxidation structural representation without the anode refining system of reduction of the high impurity crude copper that the embodiment of the present invention provides.
In figure: 1 refining furnace, 101 gas outlets, 2 feed tubes, 201 drive gas tube, 3 drain pipes, 4 top blast nozzles, 5 Rotary Anode Furnace, 6 side-blown nozzles.
Detailed description of the invention
For making the purpose of the embodiment of the present invention, technical scheme and advantage clearly, below in conjunction with the accompanying drawing in the embodiment of the present invention, technical scheme in the embodiment of the present invention is clearly and completely described, obviously, described embodiment is a part of embodiment of the present invention, rather than whole embodiments.Based on the embodiment in the present invention, the every other embodiment that those of ordinary skill in the art obtain under the premise not making creative work, broadly fall into the scope of protection of the invention.
In describing the invention, it will be appreciated that, term " " center ", " axially ", " radially ", " longitudinal direction ", " transverse direction ", " length ", " width ", " on ", D score, " front ", " afterwards ", " left side ", " right side ", " top ", " end ", " interior ", " outward ", " clockwise ", " counterclockwise ", " level ", orientation or the position relationship of the instruction such as " vertically " are based on the orientation shown in accompanying drawing or in practical application or position relationship, it is for only for ease of the description present invention and simplifies description, rather than the device of instruction or hint indication or element must have specific orientation, with specific azimuth configuration and operation, therefore it is not considered as limiting the invention.
As it is shown in figure 1, the shallow oxidation of the high impurity crude copper that Fig. 1 is the embodiment of the present invention to be provided is without the structural representation of the anode refining system of reduction.
According to metallurgy of copper theory, the main purpose of blister copper anode refining is oxidation sweetening and oxidation deferrization.Sulfur is removed to less than 0.0050% by target, and ferrum is removed to less than 0.0100%；After reduction operation, by oxygen removal to less than 0.2000%.
According to metallurgy of copper, can obtain:
The dominant response formula of oxidation sweetening is: [S]+2 [O]=SO2(gaseous state) (1)；
The dominant response formula of oxidation deferrization is: [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 the above free space of copper melt liquid level2The dividing potential drop 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, then can obtain formula (3):Wherein, k is constant coefficient.Visible, when temperature andAfter certain, sulfur content and the product of oxygen content in copper melt are a definite value.Such as: carry out anode refining at normal atmospheric pressure, 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 nowBe the 10% of a normal atmosphere, i.e. 10.1KPa, if sulfur content is down to 0.003%, then correspondingly oxygen content automatically, inevitably can be increased to 0.65%.For formula (2), owing to its reactant and product are all condensed states, it it not gaseous state, therefore, its extent of reaction or molecular balance be not all by the impact of ambient pressure, it does not have the such balancing response equation relevant with air pressure of the formula of being similar to (1) or equilibrium constant, the product of its iron content and oxygen content is not a definite value, when iron content is down to desired value, corresponding oxygen content can reduce because take part in reaction, and the oxygen content of oxidation operation terminal will not be caused obvious negative effect by oxidation deferrization process.
First, according to metallurgical principles, occur a metallurgical reaction to first have to meet metallurgical thermodynamics principle: namely to have 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 realizing the oxidation reaction of formula (1), needing the element sulphur of 32 mass parts and the oxygen element of 32 mass parts, the mass ratio of element sulphur and oxygen element is 11.Visible, in oxidation sweetening process, the theoretical required quality of oxygen element is equal with the quality of element sulphur, namely, in anode refining process, if imagined sulfur oxidation removal only according to the oxygen element carried in blister copper, the initial oxygen content carried in blister copper is at least equal with the initial sulfur content in blister copper.
According to formula (2), the relative atomic mass of ferrum element is 56, the relative atomic mass of oxygen element is 16, then for realizing the oxidation reaction of formula (2), need the element sulphur of 56 mass parts and the oxygen element of 16 mass parts, the mass ratio of ferrum element and oxygen element is 72, and the quality of ferrum element is 3.5 times of oxygen element quality, and the percentage ratio of the quality of oxygen element and ferrum element quality is 28.57%.Visible, in oxidation deferrization process, the theoretical required quality of oxygen element is 28.57% with the percentage ratio of ferrum element quality, namely in anode refining process, if imagined ferrum oxidation removal only according to the oxygen element carried in blister copper, the initial oxygen content carried in blister copper, removing and meet oxidation sweetening to outside the requirement of oxygen element, remaining part at least percentage ratio with the initial ferrum element quality in blister copper is 28.57%.
And according to metallurgy of copper and practical production experience, oxygen content in the blister copper liquation that blowing end point obtains will not remain how many: when adopting suspension converting process, such as flash blowing, oxygen content in the blister copper liquation that blowing end point obtains is in most cases below 0.0050%, and sulfur content is 0.25%～0.45%, iron content, 0.50%～0.80%, belongs to oxygen very low, and sulfur is significantly high, and the pattern that ferrum is significantly high；When adopting molten bath converting process, such as P-S bessemerizes, Ausmelt furnace blowing etc., and the oxygen content in the blister copper liquation that blowing end point obtains is between 0.05%～0.1%, and sulfur content is 0.1%～0.5%, iron content, 0.010%～0.10%, also belongs to the pattern that oxygen low-sulfur is high.
Therefore, for adopting suspension converting process, such as flash blowing, during output blister copper liquation, due to the blister copper liquation of its output, to belong to oxygen very low, and sulfur is significantly high, and the pattern that ferrum is significantly high, the initial oxygen content carried in blister copper is far smaller than the initial sulfur content carried in blister copper, namely the initial oxygen content carried in blister copper is far smaller than the oxidation sweetening process theoretical requirement to oxygen element, this initial oxygen content is far from being enough for above-mentioned initial sulfur content is reduced to the requirement to sulfur content of the target anode copper, so, for suspension converting process, sulfur oxidation removal is do not meet above-mentioned metallurgical thermodynamics principle only according to the oxygen element carried in blister copper by imagination, can not realize,
Further, according to metallurgy of copper general knowledge, it must be that oxygen is very low that the inherent structure design of suspension converting furnace (such as flash converting furnace) and the design of suspension converting process thereof just determine the blister copper liquation of its output, and sulfur is significantly high, and the pattern that ferrum is significantly high, optimize the terminal point control of suspension converting process howsoever, be impossible to the blister copper liquation of its output is changed over the pattern that oxygen high-sulfur is low.Therefore, for suspension converting process, the terminal point control of suspension converting process is optimized howsoever, it is contemplated that by the initial oxygen element carried in blister copper by sulfur and ferrum oxidation removal, it is achieved autoxidation or non-oxidation anode refining, all can not realize.
Further, according to metallurgy of copper general knowledge, it is little that blister copper liquation entrainments the amount of oxygen in air in stirring roll procedure, and whole Entrainment Velocity is also very slow.If blister copper liquation achieves that by the oxygen entrainmented in air obtains anode copper from refining process, that can place greatly a stove blister copper liquation in atmospheric environment, allow their own oxygen uptake complete refining process, need not artificial refining operation, silently await and can be obtained by the anode copper that target is wanted.Obviously, this is a kind of imagination vision simply, and this is if it is can not realize.It is therefore contemplated that by the stirring rolling degree improving the blister copper liquation in anode furnace, allow the oxygen that blister copper liquation entrainments in air to supplement the deficiency of oxygen element in anode refining process, complete anode refining process, also can not realize.
Furthermore, for the oxygen content blister copper of theoretical requirement slightly above oxidation sweetening and oxidation deferrization, although it meets above-mentioned metallurgical thermodynamics condition, but, this oxygen content for being removed to target anode copper to the requirement of sulfur content and iron content or far from being enough by sulfur and ferrum, reason is: according to formula (1), wants sulfur content is removed to less than 0.0050%, then formula (1) must be promoted to carry out to the right as far as possible；And according to the principles of chemistry, in order to allow a chemical reaction carry out to the right as far as possible, then the amount of the reactant on the left of being positioned at have to be larger than aequum during its chemical reaction equilibrium；Obviously, sulfur is the object element being removed, and its content can not be too big, it is impossible to aequum during more than its molecular balance, then be only left oxygen content, then oxygen content must be bigger, it is necessary to aequum during more than its molecular balance；Give an example: such as: carry out anode refining at normal atmospheric pressure, 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 nowIt is the 10% of a normal atmosphere, i.e. 10.1KPa, if sulfur content is down to 0.003%, when, after formula (1) molecular balance, correspondingly the aequum of oxygen content is 0.65%, according to above-mentioned theory, in order to sulfur content is down to 0.003%, the initial oxygen content in blister copper have to be larger than 0.65%, or when oxygen is re-blow in the external world in aoxidizing operation process, oxygen content in blister copper is risen above 0.65%, and this oxygen content is the actual oxygen demand of oxidation sweetening.Obviously, the oxygen content that the blister copper liquation of current suspension converting process and molten bath converting process institute output carries all can not meet the actual oxygen demand of above-mentioned oxidation sweetening, the more impossible actual oxygen demand meeting above-mentioned oxidation sweetening and oxidation deferrization.
To sum up, no matter it is suspension converting process, or molten bath converting process, in order in anode refining process by sulfur and ferrum oxidation removal, output sulfur content and iron content reach the anode copper of target call, external oxygen element must be supplemented, it is necessary to extraneous winding-up oxygen-containing gas, it is necessary to carry out oxidation operation in anode refining process.
Furthermore, according to metallurgical principles, a metallurgical reaction, only meet above-mentioned two metallurgical thermodynamics condition, or inadequate, also need to meet metallurgy kinetics principle, namely there is good metallurgy kinetics condition.For anode refining, liquation is carried out stirring fully or flowing by good metallurgy kinetics condition exactly.
According to above-mentioned analysis conclusion, the invention provides a kind of shallow oxidation anode refining system without reduction for processing high impurity crude copper, including for containing containing copper container, refining furnace 1, feed tube 2, drain pipe 3, vacuum pump, driving gas tube 201, top blast nozzle 4, carrying out the condenser that cools down and for lifting the lowering or hoisting gear of refining furnace for the flue gas produced in antianode refining process of blister copper liquation；
The profile of refining furnace 1 is vertical type columnar, inner hollow forms cavity, refining furnace 1 includes steel shell and builds the refractory lining at steel shell inner surface by laying bricks or stones, the top of refining furnace 1 is provided with the gas outlet 101 for being connected with vacuum pump, the gas outlet 101 of refining furnace 1 connects with the air inlet of condenser, and the gas outlet of condenser connects with vacuum pump；
Feed tube 2 and drain pipe 3 all include steel-made inner shell, be arranged on the refractory lining of the inner surface of steel-made inner shell and be arranged on the refractory material outer lining of outer surface of steel-made inner shell；
Feed tube 2 and drain pipe 3 are fixedly installed on the diapire of refining furnace 1 and are tightly connected with the diapire of refining furnace 1, cavity in refining furnace 1 is interconnected with the cavity passage in feed tube, cavity in refining furnace 1 is interconnected with the cavity passage in drain pipe 3, and all devices being connected with refining furnace 1 all carry out encapsulation process to prevent from destroying the vacuum state in refining furnace 1 at the position being connected with refining furnace 1；
Gas tube 201 is driven to be arranged on feed tube 2 with driving gas with pressure of jetting in the copper melt in feed tube 2；
Top blast nozzle 4 be arranged on the roof of refining furnace 1 and can along the roof of refining furnace 1 slide up and down for by top blast nozzle 4 to blow oxygen-containing gas in the copper melt in refining furnace 1 in the way of top-blown gas；
Top blast nozzle 4 is the multilamellar internal and external casing structure of the hollow pipe including multiple inside and outside suit, top blast nozzle 4 include by inside and outside the cavity in hollow pipe or adjacent two suit hollow pipe tube wall between cavity formed and for carrying the first oxygen-containing gas passage of oxygen-containing gas, the first oxygen-containing gas passage connects with the compressed air source unit of oxygen-containing gas；
That top blast nozzle 4 also includes being formed by cavity between the tube wall of the hollow pipe of suit inside and outside adjacent two and for top blast nozzle carries out the cool cycles aquaporin of cooling protection, cool cycles aquaporin connects with apparatus for supplying cool water；
The gas outlet of top blast nozzle 4 is positioned at more than the upper liquid level of the copper melt of refining furnace and with the upper liquid level of copper melt in a distance.
The mode of operation of above-mentioned anode refining system is:
1) first melted blister copper liquation is joined in the Sheng copper container for containing blister copper liquation, it is preferred that by chute, blister copper liquation is introduced Sheng copper container from copper converting stove, it is preferred that introduce in Rotary Anode Furnace；Then the feed tube 2 being arranged on refining furnace 1 diapire and drain pipe 3 are immersed in and contain the upper liquid level certain depth below of copper melt in copper container, it is then turned on the vacuum pump that connects with refining furnace 1 by the cavity vacuum state in refining furnace 1, now in refining furnace 1, contains the cavity passage along feed tube 2 and drain pipe 3 of the copper melt in copper container under the effect of atm difference between vacuum residual voltage and external atmosphere pressure and rise in the cavity flowing into refining furnace 1；
2) by driving gas tube 201 to jet in the copper melt in feed tube 2 driving gas with pressure, then under the drive of atm difference and driving gas, contain the copper melt in copper container constantly risen by feed tube 2 in inflow refining furnace 1, then the copper melt in refining furnace 1 is constantly flowed out by refining furnace 1 again through drain pipe 3 and is back in Sheng copper container, is containing copper container, feed tube 2, is forming circulating of copper melt between refining furnace 1 and drain pipe 3；
Simultaneously, in refining furnace 1, by top blast nozzle in the copper melt in the way of top-blown gas, oxygen-containing gas blowed to refining furnace, element sulphur in copper melt is oxidized to the gaseous oxygen compound of sulfur by the oxygen element in oxygen-containing gas, ferrum element in copper melt is oxidized to the oxide of ferrum by the oxygen element in oxygen-containing gas, it is achieved the oxidation operation process of desulfurization deferrization；
Simultaneously, a part for whole content of impurity element included in the copper melt in refining furnace 1 is directly volatilized with elemental form, the remainder of whole content volatilizees with oxide form after being oxidized to oxide by oxygen-containing gas, while realizing the oxidation operation process of desulfurization deferrization, realize the refining process of simultaneously imurity-removal element, impurity element include in lead, zinc, arsenic, antimony, bismuth and tin element one or more or all；
Meanwhile, the vacuum residual voltage level in refining furnace 1 is controlled so that when the sulfur content in copper melt reaches target anode copper to the requirement of sulfur content, the oxygen content realizing molecular balance with this sulfur content also reaches the requirement to oxygen content of the target anode copper；
3) step 2) carry out a period of time after, the component of the copper melt after sample examination anode refining and content, if result of laboratory test reaches the requirement to sulfur content and iron content of the target anode copper, then first abolish the vacuum state in refining furnace 1, then the feed tube 2 being arranged on refining furnace 1 diapire and drain pipe 3 are departed 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 the requirement of any one in both sulfur or ferrum, continue anode refining, until result of laboratory test reaches the requirement to sulfur content and iron content of the target anode copper；Anode refining terminate to obtain the content of sulfur, ferrum and oxygen reach the anode copper liquation of target call, containing SO2Flue gas and slag.The content of the sulfur of above-mentioned output, ferrum and oxygen reaches the anode copper liquation of target call and flow to Copper Anode Plate Casting system through chute, is cast into positive plate.
In the present invention, before anode refining terminates, it is positioned at above-mentioned Sheng copper container, and the copper melt circulated in refining furnace 1, feed tube 2 and drain pipe 3 is blister copper liquation, because anode refining does not terminate, it is meant that the above-mentioned copper melt of sample examination is not reaching to the requirement to sulfur content and iron content of the target anode copper.
In the present invention, above-mentioned oxygen-containing gas is preferably air or oxygen-enriched air, and in oxygen-enriched air, the percent by volume of oxygen is 25%～95%.
In the present invention, in the copper melt of sample examination, sulfur content and iron content reach the requirement to sulfur content and iron content of the target anode copper is mark reference, terminal time as oxidation operation, as for whether lead impurity element, zinc, arsenic, antimony, bismuth and/or tin element reach ideal value, the present invention does not make hard requirement, because not removing clean above-mentioned impurity element, it is possible to removed further in follow-up electrorefining processes.
In the present invention, above-mentioned driving gas is nitrogen or argon, it is preferred to nitrogen.
In the present invention, namely above-mentioned vacuum residual voltage refers to the pressure of the remaining under vacuum conditions gas of refining furnace 1 internal cavity, the same with the meaning of noun vacuum.Preferably, step 2) in vacuum residual voltage be 100Pa～1000Pa.
In the present invention, the above-mentioned Sheng copper container for containing blister copper liquation is preferably Rotary Anode Furnace 5, in actual production, Rotary Anode Furnace 5 need to be made adaptability structural modification, to adapt to coordinate the use of refining furnace 1, including offering the opening entering for refining furnace 1 or going out on the furnace wall of Rotary Anode Furnace 5.
In the present invention, by being arranged on feed tube 2 drive gas tube 201 to driving gas with pressure of jetting in the copper melt in feed tube 2.
The kind of the above-mentioned lowering or hoisting gear for lifting refining furnace 1 and specification are not limited by the present invention, adopts lowering or hoisting gear of the prior art to meet lifting this function of refining furnace, it is possible to be jacking, it is also possible to be lifting.
In the present invention, it is higher that high impurity crude copper means the content of impurity element in blister copper, impurity element include in lead, zinc, arsenic, antimony, bismuth and tin element one or more or all, the content of impurity element exceedes the Copper making industry general claimed range to its content.In the present invention, in actual production, above-mentioned high impurity crude copper not necessarily includes whole above-mentioned six kinds of impurity elements, it is possible to include one or more of above-mentioned six kinds of impurity elements, it is also possible to include whole above-mentioned six kinds of elements.In actual production, even if above-mentioned high impurity crude copper-clad is containing a certain kind of six kinds of above-mentioned impurity elements, but the content of this impurity element is likely to and less than industry universal standard, but the content of other contained certain impurity element exceedes industry universal standard.In actual production, as long as impurity element contained in above-mentioned blister copper is one of above-mentioned six kinds of impurity elements and this impurity content exceedes industry universal standard, this blister copper is just for high impurity crude copper.
In the present invention accessible high impurity crude copper, the preferred higher limit of the percentage by weight of above-mentioned six kinds of impurity elements that may be present is: lead≤1.4%, zinc≤0.05%, arsenic≤1.0%, antimony≤0.1%, bismuth≤0.5%, stannum≤0.1%.
The invention provides a kind of shallow oxidation anode refining system without reduction for processing high impurity crude copper, apparently, this anode refining system is not to process high impurity crude copper, process the ratio in numerous functions that high impurity crude copper is only this anode refining system more prominent a bit；Since this anode refining system can process high impurity crude copper, it is clear that it also is able to the normal blister copper of processing element content.
The operation principle of above-mentioned anode refining system provided by the invention is:
(1). according to metallurgical thermodynamics, the dominant response formula of oxidation sweetening is: [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 the above free space of copper melt liquid level2The dividing potential drop 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, then can obtain formula (3):Wherein, k is constant coefficient.Visible, when temperature andAfter certain, sulfur content and the product of oxygen content in copper melt are a definite value.Just because of this, when sulfur content is reduced to only small desired value by oxidation sweetening, oxygen content automatic trim, inevitably become very big, result exceedes normal range.Such as: carry out anode refining at normal atmospheric pressure, 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 nowBe the 10% of a normal atmosphere, i.e. 10.1KPa, if sulfur content is down to 0.003%, then correspondingly oxygen content is increased to 0.65%.
According to above-mentioned, at a certain temperature, the product of the sulfur content in copper melt and oxygen content withPartial pressure is linear relationship, if willPartial pressure reduces, then the product of the sulfur content in copper melt and oxygen content it also reduces, if the desired value now continuing to keep aoxidizing operation final sulfur content is constant, then then can reduce with the oxygen content of this sulfur content trim.Based on this theory, if willPartial pressure reduces, when sulfur content is reduced to only small desired value by oxidation sweetening, although oxygen content also can automatic trim, but will not become very big as original, but one withPartial pressure reduces the less value that degree matches.Such as: carry out anode refining at normal atmospheric pressure, 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 nowBe the 10% of a normal atmosphere, i.e. 10.1KPa, if sulfur content is down to 0.003%, then correspondingly oxygen content is increased to 0.65%.When inciting somebody to actionDifferential 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 content is 0.065%；When inciting somebody to actionDifferential pressure drop is to the 1/100 of above-mentioned 10.1KPa, i.e. 101Pa, then when sulfur content is down to 0.003%, correspondingly equilibrium oxygen content is then 0.0065%；When inciting somebody to actionDifferential 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%, correspondingly equilibrium oxygen content is then 0.00065%.Above-mentioned correspondingly equilibrium oxygen content 0.065%, 0.0065% or 0.00065% is only theoretical value, in actual production, due to the impact of other factors, correspondingly the actual value of equilibrium oxygen content is hardly possible is reduced to above-mentioned respective horizontal, but bigger than above-mentioned theoretical value.
(2). according to above-mentioned, the product of oxidation sweetening is SO2Gas, the present invention utilizes vacuum pump constantly by SO2Gas is taken away 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). the principle that copper melt circulates: when the feed tube 2 being arranged on refining furnace 1 bottom surface and drain pipe 3 being immersed in the upper liquid level certain depth below containing copper container inner melt, it is then turned on the vacuum pump that connects with refining furnace 1 by the cavity vacuum state in refining furnace 1, in refining furnace 1, now under the effect of atm difference between vacuum residual voltage and external atmosphere pressure, contains liquation in copper container rise along the cavity flowing into refining furnace 1 along the cavity passage of feed tube 2 and drain pipe 3；Blister copper liquation now does not circulate；For making blister copper liquation circulate, jet in the liquation in feed tube 2 driving gas with pressure, owing to expanded by heating and pressure decline after driving gas to enter the liquation in feed tube 2, cause isothermal expansion, in feed tube 2, moment produces substantial amounts of nuclei of bubbles and expands rapidly, the gas-powered blister copper liquation expanded rises, under the drive of atm difference and driving gas, contain the liquation in copper container constantly risen by feed tube 2 in inflow refining furnace 1, then the liquation in refining furnace 1 is constantly flowed out by refining furnace 1 again through drain pipe 3 and is back in Sheng copper container, containing copper container, feed tube 2, circulating of liquation is formed between refining furnace 1 and drain pipe 3.
According to above-mentioned principle (1), in the present invention, owing to inciting somebody to actionPartial pressure reduces, when sulfur content is reduced to only small desired value by oxidation sweetening, although oxygen content also can automatic trim, but will not become very big as original, but one withnullPartial pressure reduces the less value that degree matches，So，The initial oxygen content carried in copper melt and later stage is made to be re-blow oxygen content that oxygen-containing gas supplemented almost fully for oxidation sweetening and oxidation deferrization by the external world，There is not much left for oxidation operation terminal oxygen content，The oxygen-containing gas re-blow in the external world will not do substantial amounts of idle work as original，The oxygen-containing gas amount that the external world that in the present invention, oxidation operation consumes supplements only accounts for the 10%～30% of the oxygen-containing gas amount that the oxidation operation of former anode refining consumes，The oxygen-containing gas amount consumed compared to the oxidation operation of former anode refining decreases 70%～90%，So the present invention is a kind of shallow oxidizing anode refine，Improve the real oxygen-containing gas ratio for oxidation sweetening in oxygen-containing gas，Decrease the oxygen-containing gas ratio making idle work，Decrease the actually used amount of oxygen-containing gas in anode refining process，Decrease oxygen-containing gas waste，Reduce the production cost of anode refining.
Use anode refining system provided by the invention real oxygen-containing gas ratio for oxidation sweetening in improve oxygen-containing gas, while decreasing the oxygen-containing gas ratio making idle work, also achieve unforeseeable technique effect: in the liquation obtained after oxidation operation, oxygen content can meet the target anode copper normal requirement to oxygen content, follow-up without carrying out reduction operation, achieve real nothing reduction anode refining, principle is: according to above-mentioned principle (1), in the present invention, if willPartial pressure reduces, when sulfur content is reduced to only small desired value by oxidation sweetening, although oxygen content also can automatic trim, but will not become very big as original, but one withPartial pressure reduces the less value that degree matches；Further, if the vacuum residual voltage level controlled in refining furnace 1, willPartial pressure is reduced to certain reasonable interval, make when the sulfur content in copper melt reaches target anode copper to the requirement of sulfur content, although oxygen content also can automatic trim, but not over the target anode copper normal requirement scope to oxygen content, since oxygen content has met the target anode copper normal requirement to oxygen content in the copper melt obtained after oxidation operation, then follow-up without carrying out reduction operation again.
Use anode refining system provided by the invention real oxygen-containing gas ratio for oxidation sweetening in improve oxygen-containing gas, while decreasing the oxygen-containing gas ratio making idle work, also achieve the unforeseeable technique effect of another one: in the present invention, when not carrying out reduction operation, in the anode copper liquation that anode refining terminal obtains, oxygen content can reach the 1/100～1/10 of former anode refining terminal oxygen content, reduces 1 to 2 orders of magnitude than former anode refining terminal oxygen content.It should be evident that the reduction degree of 1 to 2 orders of magnitude is for metallurgy industry, being very significant technological progress, namely the present invention achieves the Advantageous Effects of highly significant.Apparently, the less anode copper liquation of oxygen content is conducive to output surface quality and the better positive plate of internal soundness, the carrying out of follow-up electrorefining can be more beneficial for, the quantum of output of the sedimentation earth of positive pole and the floating earth of positive pole can be significantly reduced, reduce cathode plate surface particle, improve the current efficiency of electrorefining, improve internal soundness and the surface quality of the cathode plate of electrorefining output.
Use anode refining system provided by the invention real oxygen-containing gas ratio for oxidation sweetening in improve oxygen-containing gas, while decreasing the oxygen-containing gas ratio making idle work, also achieve the unforeseeable technique effect of another one: in the present invention, in oxidation sweetening deferrization process, owing to formula (1) is to carry out at vacuum state so that the product SO of formula (1)2nullGas is constantly pumped，Formula (1) reaction does not reach poised state all the time，All the time carry out to the right，Oxidation sweetening is made to have good metallurgical thermodynamics condition，And copper melt big cycle volume circulate，Oxidation sweetening deferrization is made to have good metallurgy kinetics condition，The oxidation operation process time can be reduced within 1 hour，Major part heat can reduce within 40 minutes，Add the present invention can realize without reduction anode refining，Therefore anode refining process time (not including feed time and casting time) can be reduced within 1 hour by the present invention，Major part heat can reduce within 40 minutes，And pole, Yuanyang refining process (not including feed time and casting time) required time is generally 2 hours，So，Present invention significantly reduces the time needed for anode refining process，Reduction amplitude is about 50%～66.67%，Considerably improve production efficiency and rhythm of production.
Use anode refining system provided by the invention real oxygen-containing gas ratio for oxidation sweetening in improve oxygen-containing gas; while decreasing the oxygen-containing gas ratio making idle work; also achieve the unforeseeable technique effect of another one: generally possibly together with impurity elements such as lead, zinc, arsenic, antimony, bismuth and/or tin elements in blister copper; anode refining is except desulfurization and deferrization, in addition it is also necessary to by the elimination as far as possible of above-mentioned impurity element.In recent years owing to Copper making ability is acutely expanded, the supply of high-quality copper concentrate becomes more and more nervous, and copper concentrate becomes " high impurity " gradually.High impurity, the content being primarily referred to as the impurity elements such as the lead in copper concentrate, zinc, arsenic, antimony, bismuth and/or stannum is higher.High impurity copper concentrate is smelting and after blowing, the blister copper of output is exactly generally high impurity crude copper.For above-mentioned impurity element, prior art openly adopts simple vacuum distilling technique (not extraneous oxygen-containing gas of re-blowing) the above-mentioned blister copper liquation removing impurities of refine.When adopting simple vacuum distilling technique (not extraneous oxygen-containing gas of re-blowing) the above-mentioned blister copper liquation of refine, as long as temperature, vacuum and refining time are suitable, lead in above-mentioned impurity element, zinc and bismuth element can become gaseous state volatilization, well removed, the content of three all can be down to less than 0.0050% with comparalive ease, the removal efficiency of lead and bismuth is all more than 95%, and the removal efficiency of zinc is more than 85%；Arsenic in above-mentioned impurity element, antimony and tin element are then difficult to become gaseous state volatilization, removal effect is very poor, removal efficiency is only 10%～30%, reason is: the affinity of arsenic and antimony and copper is all stronger, it is easily formed stable arsenic-copper compound and antimony-copper compound, stable arsenic-copper compound and antimony-copper compound volatility under vacuum conditions are very weak, thus the volatilization limiting arsenic and two kinds of elements of antimony removes, the boiling point of simple substance stannum is 2270 DEG C, it is difficult to from copper, separate stannum evaporate very close to, simple vacuum distilling refine with the boiling point of copper.And the present invention is on the basis of above-mentioned simple vacuum distilling technique, improve, oxygen-containing gas is blowed to the liquation in refining furnace 1 under vacuum state in refining furnace 1, a part for whole content of lead in above-mentioned impurity element, zinc and bismuth element is directly volatilized with elemental form, the same with simple vacuum distilling technique, the remainder of whole content volatilizees with oxide form after being oxidized to oxide by above-mentioned oxygen-containing gas, the volatility of this oxide is also better, without influence on elimination speed and the elimination degree of plumbous, zinc and bismuth element；nullArsenic in above-mentioned impurity element、A part for whole content of antimony and tin element still directly can be volatilized with elemental form，The same with simple vacuum distilling technique，The remainder of whole content volatilizees with oxide form after being oxidized to oxide by above-mentioned oxygen-containing gas，Arsenic is oxidized to arsenic oxide by oxygen-containing gas，Arsenic is freed from arsenic-copper compound，Thus breaking away from the serious negative influence that arsenic element is volatilized by original arsenic-copper compound，Antimony is oxidized to sb oxide by oxygen-containing gas，Antimony is freed from antimony-copper compound，Thus breaking away from the serious negative influence that antimony element is volatilized by original antimony-copper compound，Stannum is oxidized to stannum oxide by oxygen-containing gas，The boiling point of stannum oxide is 1430 DEG C，In this boiling point and anode refining process the temperature 1250 DEG C of copper melt very close to，Make stannum oxide can volatilize ratio more thoroughly，Arsenic oxide、The volatility of sb oxide and stannum oxide is all relatively good，Thus considerably improving arsenic、The elimination speed of antimony and three kinds of elements of stannum and elimination degree，Arsenic and antimony can be removed to less than 0.01%，The removal efficiency of arsenic can be increased to more than 95%，The removal efficiency of antimony can be increased to more than 75%，Stannum can be removed to less than 0.0050%，The removal efficiency of stannum is increased to more than 90%.Therefore, the present invention is while realizing shallow oxidation nothing reduction operation, achieve the unforeseeable technique effect of another one: achieve the refining process of imurity-removal Element Lead, zinc, arsenic, antimony, bismuth and six kinds of impurity elements of stannum simultaneously, make the anode refining method provided by the invention both can the blister copper of refine normal level range, it is also possible to process the blister copper of high impurity content.
Originally above-mentioned condenser only has the function of cooled flue gas, and when needing distillation elimination containing a large amount of lead impurity element, zinc, arsenic, antimony, bismuth and stannum in blister copper liquation, condenser should also have the function of condensing gaseous metal.Kind and the specification of this condenser are not limited by the present invention, adopt condenser of the prior art to meet above-mentioned functions.
In the present invention, containing copper container, feed tube 2, circulating of liquation is formed between refining furnace 1 and drain pipe 3, the such big cycle volume ground flowing of liquation is that the non-metallic inclusion in elimination copper melt improves extremely advantageous dynamic conditions, improve collision probability and the agglomeration of non-metallic inclusion in copper melt, non-metallic inclusion after agglomeration is easier to rely on the buoyancy of self to float, it is mixed in the slag blanket of copper melt upper surface, thus considerably improving nonmetal elimination speed and elimination degree in copper melt, improve the cleanliness factor of the anode copper liquation obtained after anode refining terminates.
In one embodiment of the invention, top blast nozzle 4 also include by inside and outside the cavity in hollow pipe or adjacent two suit hollow pipe tube wall between cavity formed and for carrying the compressed gas passage of the compressed gas being mixed with slag former powder, compressed gas passage connects with gas powder feedway.Sprayed in the copper melt to refining furnace 1 by the compressed gas being blended with slag former powder in the way of top spray gas by top blast nozzle 4.
Adding slag former in the copper melt in refining furnace 1, after slag former and oxidation operation, the oxide generation slag making that obtains react, obtains refining slag, and refining slag floats, formation refine slag blanket in liquid level place on the copper melt in Sheng copper container.Slag former owing to adding can react with the oxide of ferrum that obtains after oxidation operation and the oxide generation slag making of above-mentioned impurity element, therefore the product content of oxidation reaction can be significantly reduced, break the former poised state of oxidation reaction, oxidation reaction is promoted to carry out to the right, such as, for above-mentioned formula (2), slag former can react with the oxide generation slag making of ferrum that obtains after oxidation operation, generate slag phase, such as silicic acid scum, significantly decrease the oxide content of ferrum in copper melt, break the former poised state of formula (2), formula (2) is promoted constantly to carry out to the right, thus improve elimination speed and the elimination degree of oxidation deferrization.nullThe present invention is further，Select in refining furnace 1, join in copper melt slag former，Owing to above-mentioned oxygen-containing gas blows in copper melt in refining furnace 1，Oxidation reaction in copper melt mainly carries out in refining furnace 1，The above-mentioned oxide also main generation in refining furnace 1 coordinating slag making with slag former，Namely the oxide participating in slag making generates in refining furnace 1，Then slag former adds in refining furnace 1，The two kinds of materials participating in slag making are respectively positioned in refining furnace 1，Slag former falls in copper melt and can react with the oxide generation slag making in copper melt rapidly，There is higher reaction rate and complete degree of reaction，Addition place and feed postition unlike other slag formers，Such as slag former joins in the copper melt contained in copper container outside refining furnace 1，Also need to wait for oxide slowly to spread in the copper melt that the scale of construction is huge with slag former，Final diffusion collides and slag making just can be occurred together to react，Slag making response speed is relatively low and slag making reaction is very not thorough，So arrange，Considerably improve elimination speed and the elimination degree of oxidation deferrization removing impurities matter.Preferably, slag former is quartz particles or powder.
Anode refining process needs certain time, and within this time period, the temperature of copper melt can inevitably decline, it is therefore desirable to copper melt is heated additional heat.Rotary Anode Furnace 5 anode refining blister copper process general in current industry, Rotary Anode Furnace 5 is a horizontal oval cylindrical barrel body, copper melt in Rotary Anode Furnace 5 is heated insulation by the burner adopting burn combustible thing and oxygen-containing gas, burner and charging aperture are arranged at the one end on the length direction of Rotary Anode Furnace 5, exhanst gas outlet is arranged on the other end on Rotary Anode Furnace 5 length direction, burner is so arranged, there is Railway Project: 1. so mode of heating is similar to the pattern of " broad irrigation ", the heat that burner produces is let drift, the heat that burner produces is not applied in the place of real needs fully, heat waste phenomenon is serious, heat utilization ratio is relatively low；2. first the heat that burner produces will heat in copper melt liquid level space above, then the heat in upper space passes to the copper melt of lower section in the way of radiant heat transfer, heat transfer modes has and only has this one of radiant heat transfer pattern in this process, and according to metallurgical thermodynamics principle, radiant heat transfer pattern is minimum one of several of heat transfer efficiency in numerous heat transfer modes, therefore, there is the problem that heat utilization ratio is low and heat transfer rate is less in current mode of heating；3. for the container of this long cartridge type of Rotary Anode Furnace 5, only the one end on the length direction in Rotary Anode Furnace 5 arranges burner is irrational, obviously, better near the copper melt heating and thermal insulation effect of burner, from burner more away from copper melt, heating and thermal insulation effect is more poor, and for the whole copper melts in Rotary Anode Furnace 5, heating and thermal insulation effect is extremely uneven.It should be evident that there is the current mode of heating of above-mentioned multiple problem, it is unfavorable for solving the above-mentioned technical problem mentioned in the present invention, the carrying out being unfavorable in anode refining process the processes such as desulfurization deferrization removing impurities matter.
For this, in one embodiment of the invention, top blast nozzle 4 also includes that the cavity between the tube wall by the hollow pipe being set with inside and outside the cavity in hollow pipe or adjacent two is formed and for transporting combustible gases fuel gas passage, and fuel gas passage connects with the compressed air source unit of fuel gas.
In anode refining process, when the cavity in refining furnace 1 is in vacuum state, by top blast nozzle 4 by the way of top-blown gas to winding-up fuel gas in refining furnace 1, then it is sufficiently mixed with the oxygen-containing gas of the first oxygen-containing gas passage conveying, then fuel gas and oxygen-containing gas are lighted burning, copper melt in refining furnace 1 is carried out supplementary heating process by the combustion reaction liberated heat utilizing fuel gas and oxygen-containing gas, utilize the combustion reaction liberated heat of fuel gas and oxygen-containing gas that the dross thing formed after splash copper melt cooling on refining furnace 1 inwall is carried out fusing removing to process.
Preferably, fuel gas is natural gas or coal gas.
nullThe present invention，When cavity in refining furnace 1 is in vacuum state，By top blast nozzle 4 by the way of top-blown gas to winding-up fuel gas and oxygen-containing gas in refining furnace 1，Fuel gas and oxygen-containing gas are lighted burning，Copper melt in refining furnace 1 is carried out supplementary heating process by the combustion reaction liberated heat utilizing fuel gas and oxygen-containing gas，So heating，Owing to oxidation operation all carries out in refining furnace 1 and completes，And also all carried out in refining furnace 1 by the combustion heating of top blast nozzle 4，Heat supplier and heat need Fang Jun in refining furnace 1，Therefore the heat produced can be transferred to this part copper liquation carrying out oxidation operation in refining furnace 1 fully and directly，The heat amount produced significantly reduces compared to before improving，But this part copper liquation for carrying out oxidation operation process in refining furnace 1 is enough，A small amount of and sufficient heat is adopted only this part copper liquation carrying out oxidation operation accurately to be supplemented，The heat produced all is used in the place of needs，Avoid the heating mode of original " broad irrigation "，Inexcessive，Do not waste，Improve heat utilization ratio，Decrease the consumption of combustible and oxygen-containing gas；Unnecessary heat can be delivered to refining furnace 1 along with the big cycle volume of copper melt flows in refining furnace 1, pass to the copper melt at all the other positions of Rotary Anode Furnace 5, copper melt in Rotary Anode Furnace 5 was carried out preheating insulation before entrance refining furnace 1 carries out oxidation operation, 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 compared to radiant heat transfer want high many, therefore the present invention is except the relatively low heat transfer modes of this heat transfer efficiency of radiant heat transfer, also there is the heat transfer modes that this heat transfer efficiency of convection heat transfer' heat-transfer by convection is higher, thus considerably improving the heat transfer efficiency of mode of heating of the present invention；Owing to this part copper liquation carrying out oxidation operation in refining furnace 1 is only directly heated insulation by the present invention, it should be apparent that, do not have the phenomenon that above-mentioned heating is uneven.To sum up, the mode of heating of the present invention ensure that the copper melt the carrying out oxidation operation requirement to temperature, and what improve oxidation operation carries out speed and performance level.
After entering the vacuum environment in refining furnace 1 doped with the copper melt driving gas, and when re-blowing extraneous oxygen-containing gas, copper melt in refining furnace 1 will not be circulate imperturbably, but violent splash, so, inevitably with regard in the copper melt splash of some to the inwall of refining furnace 1, owing to the temperature of refining furnace 1 upper space and upper inside wall is relatively low, the copper melt meeting cooled and solidified of liquid, in the course of time, just forms dross thing one layer hard in the inner wall surface of refining furnace 1.Apparently, this cold conditions dross thing antianode refining process and to service life of refining furnace 1 all without positive role, such as: owing to dross thing is contained within the elements such as higher sulfur, ferrum, oxygen, lead, zinc, arsenic, antimony, bismuth, after anode refining terminates, this dross thing can cause the anode copper liquation having reached target component requirement to return sulfur, Hui Tie, return oxygen etc., causes sulfur, ferrum or oxygen element in anode copper liquation again to raise；Dross thing can corrode the refractory lining of refining furnace 1；Dross thing also can reduce the dischargeable capacity of refining furnace 1.For this, in the present embodiment, in anode refining process, when the cavity in refining furnace 1 is in vacuum state, by top blast nozzle 4 by the way of top-blown gas to winding-up fuel gas and oxygen-containing gas in refining furnace 1, fuel gas and oxygen-containing gas are lighted burning, the combustion reaction liberated heat of fuel gas and oxygen-containing gas is utilized to be purged processing to the dross thing formed after splash copper melt cooling on refining furnace 1 inwall, the temperature improving refining furnace 1 internal upper part space and upper inside wall prevents the copper melt cooled and solidified of splash from forming dross thing, thus decreasing the generation of dross thing；The temperature improving refining furnace 1 internal upper part space and upper inside wall makes dross thing melted by heat again become liquid, inwall along refining furnace 1 flows downward, again it is back in the copper melt circulated, complete anode refining process, thus decreasing the quantity of the dross thing generated, thus reducing a series of negative influences that above-mentioned dross thing brings.
In one embodiment of the invention, top blast nozzle 4 also include the cavity in hollow pipe or inside and outside adjacent two suit hollow pipe tube wall between cavity formed and for the second oxygen-containing gas passage of the oxygen-containing gas of gas fuel burning with carrying, the second oxygen-containing gas passage connects with the compressed air source unit of oxygen-containing gas.In the present embodiment, the oxygen-containing gas of the second oxygen-containing gas passage conveying is served only for coordinating above-mentioned gas fuel burning, it is not involved in the anode refining process of the oxygen-containing gas of the first oxygen-containing gas passage conveying, realize special gas special, each it is independent of each other mutually, according to actual needs, the oxygen-containing gas that oxygen-containing gas and the first oxygen-containing gas passage of the second oxygen-containing gas passage conveying is carried oxygen-containing dense on can be different.
In one embodiment of the invention, fuel gas passage and the second oxygen-containing gas passage are integral type structure, and the integral structure of fuel gas passage and the second oxygen-containing gas passage and the first oxygen-containing gas passage are split-type structural, the integral structure of fuel gas passage and the second oxygen-containing gas passage can slide up and down relative to the first oxygen-containing gas passage in the vertical direction.So arrange, can separately regulate top blast nozzle 4 in the distance size playing in anode refining process between gas outlet and the upper liquid level of lower section copper melt of the first oxygen-containing gas passage, can separately regulate the distance size between gas outlet and the upper liquid level of copper melt of top blast nozzle 4 fuel gas passage and second oxygen-containing gas passage in heating process, separately regulate above-mentioned distance size to meet respective real world applications needs, each independent, it is independent of each other mutually, improves practicality and the treatment effect of top blast nozzle 4.
In one embodiment of the invention, the side lower of refining furnace 1 is provided with side-blown nozzle 6 and blows oxygen-containing gas in the way of blowing by submergence below the upper liquid level of the copper melt in refining furnace 1, and the gas outlet of side-blown nozzle 6 is positioned at below the upper liquid level of the copper melt of refining furnace 1；
Side-blown nozzle 6 is the multilamellar internal and external casing structure of the hollow pipe including multiple inside and outside suit, side-blown nozzle 6 include by inside and outside the cavity in hollow pipe or adjacent two suit hollow pipe tube wall between cavity formed and for carrying the oxygen-containing gas passage of oxygen-containing gas, oxygen-containing gas passage connects with the compressed air source unit of oxygen-containing gas；
That side-blown nozzle 6 also includes being formed by cavity between the tube wall of the hollow pipe of suit inside and outside adjacent two and blow and spray mouth 6 for offside and carry out the cool cycles aquaporin of cooling protection, cool cycles aquaporin connects with apparatus for supplying cool water.So arranging, side-blown nozzle 6 is matched with top blast nozzle 4, while top blast nozzle 4 top blast oxygen-containing gas, supplements oxygen-containing gas to the copper solution in refining furnace 1 in the way of the side-blown oxygen-containing gas of submergence, and the two cooperates, and has better effect and efficiency.
In one embodiment of the invention, side-blown nozzle 6 also include by inside and outside the cavity in hollow pipe or adjacent two suit hollow pipe tube wall between cavity formed and for carrying the compressed gas passage of the compressed gas being mixed with slag former powder, compressed gas passage connects with gas powder feedway.So arranging, side-blown nozzle 6 is matched with top blast nozzle 4, and while top blast nozzle 4 top blast slag former, to supplement slag former to the copper solution in refining furnace 1 in the way of submergence is side-blown, the two cooperates, and has better effect and efficiency.
nullIn one embodiment of the invention，The concrete structure of top blast nozzle 4 is: top blast nozzle 4 is the multilamellar internal and external casing structure of the hollow pipe including multiple inside and outside suit，Including the fuel gas pipe set gradually from inside to outside、Second oxygen-containing gas pipe、First oxygen-containing gas pipe、Compressed gas pipe and cooling water pipe，Hollow cavity in fuel gas pipe forms above-mentioned fuel gas passage，Cavity between the tube wall of fuel gas pipe and the second oxygen-containing gas pipe forms above-mentioned the second oxygen-containing gas passage for carrying the oxygen-containing gas coordinating gas fuel burning，Cavity between the tube wall of the second oxygen-containing gas pipe and the first oxygen-containing gas pipe forms above-mentioned the first oxygen-containing gas passage for carrying oxygen-containing gas，Cavity between first oxygen-containing gas pipe and the tube wall of compressed gas pipe forms above-mentioned compressed gas passage，Cavity between compressed gas pipe and the tube wall of cooling water pipe forms above-mentioned cool cycles aquaporin.
In one embodiment of the invention, the concrete structure of side-blown nozzle 6 is: side-blown nozzle 6 is the multilamellar internal and external casing structure of the hollow pipe including multiple inside and outside suit, including the oxygen-containing gas pipe set gradually from inside to outside, compressed gas pipe and cooling water pipe, hollow cavity in oxygen-containing gas pipe forms above-mentioned oxygen-containing gas passage, cavity between the tube wall of oxygen-containing gas pipe and compressed gas pipe forms the above-mentioned compressed gas passage for carrying the compressed gas being mixed with slag former powder, cavity between compressed gas pipe and the tube wall of cooling water pipe forms above-mentioned cool cycles aquaporin.
The present invention is directed to and want to solve the technical problem that, provide multiple laddering technical scheme, multiple laddering technical schemes are mutually combined superposition, cooperate, mutually promote, forming an overall plan, the technique effect of acquirement is much better than the technique effect of an any of the above described technical scheme, and synergistic effect is notable.
The method and apparatus of the not detailed description of the present invention is prior art, repeats no more.
In this specification, each embodiment adopts the mode gone forward one by one to describe, and what each embodiment stressed is the difference with other embodiments, between each embodiment same or similar part mutually referring to.
The explanation of above example is only intended to help to understand method and the core concept thereof of the present invention.It should be pointed out that, for those skilled in the art, under the premise without departing from the principles of the invention, it is also possible to the present invention carries out some improvement and modification, these improve and modify in the protection domain also falling into the claims in the present invention.
Described above to the disclosed embodiments, makes professional and technical personnel in the field be capable of or uses the present invention.Multiple amendment for these embodiments is apparent from for those skilled in the art, and generic principles defined herein can without departing from the spirit or scope of the present invention, realize in other embodiments.Therefore, the present invention is not intended to be limited to the embodiments shown herein, and is to fit to the widest range consistent with principles disclosed herein and features of novelty.

Claims (8)

1. the anode refining system that the shallow oxidation nothing for processing high impurity crude copper is reduced, it is characterized in that, including for containing containing copper container, refining furnace, feed tube, drain pipe, vacuum pump, driving gas tube, top blast nozzle, carrying out the condenser that cools down and for lifting the lowering or hoisting gear of described refining furnace for the flue gas produced in antianode refining process of blister copper liquation；
The profile of described refining furnace is vertical type columnar, inner hollow forms cavity, described refining furnace includes steel shell and builds the refractory lining at described steel shell inner surface by laying bricks or stones, the top of described refining furnace is provided with the gas outlet for being connected with described vacuum pump, the gas outlet of described refining furnace connects with the air inlet of described condenser, and the gas outlet of described condenser connects with described vacuum pump；
Described feed tube and described drain pipe all include steel-made inner shell, be arranged on the refractory lining of the inner surface of described steel-made inner shell and be arranged on the refractory material outer lining of outer surface of described steel-made inner shell；
Described feed tube and described drain pipe are fixedly installed on the diapire of described refining furnace and are tightly connected with the diapire of described refining furnace, cavity in described refining furnace is interconnected with the cavity passage in described feed tube, cavity in described refining furnace is interconnected with the cavity passage in described drain pipe, and the device that all and described refining furnace is connected all carries out encapsulation process to prevent from destroying the vacuum state in described refining furnace at the position being connected with described refining furnace；
Described driving gas tube is arranged on described feed tube with driving gas with pressure of jetting in the copper melt in described feed tube；
Described top blast nozzle be arranged on the roof of described refining furnace and can along the roof of described refining furnace slide up and down for by described top blast nozzle to blow oxygen-containing gas in the copper melt in described refining furnace in the way of top-blown gas；
Described top blast nozzle is the multilamellar internal and external casing structure of the hollow pipe including multiple inside and outside suit, described top blast nozzle include by inside and outside the cavity in hollow pipe or adjacent two suit hollow pipe tube wall between cavity formed and for carrying the first oxygen-containing gas passage of described oxygen-containing gas, described first oxygen-containing gas passage connects with the compressed air source unit of described oxygen-containing gas；
That described top blast nozzle also includes being formed by cavity between the tube wall of the hollow pipe of suit inside and outside adjacent two and for described top blast nozzle carries out the cool cycles aquaporin of cooling protection, described cool cycles aquaporin connects with apparatus for supplying cool water；
The gas outlet of described top blast nozzle is positioned at more than the upper liquid level of the copper melt of described refining furnace and with the upper liquid level of copper melt in a distance.
2. anode refining system according to claim 1, it is characterized in that, described top blast nozzle also include by inside and outside the cavity in hollow pipe or adjacent two suit hollow pipe tube wall between cavity formed and for carrying the compressed gas passage of the compressed gas being mixed with slag former powder, described compressed gas passage connects with gas powder feedway.
3. anode refining system according to claim 1, it is characterized in that, described top blast nozzle also includes that the cavity between the tube wall by the hollow pipe being set with inside and outside the cavity in hollow pipe or adjacent two is formed and for transporting combustible gases fuel gas passage, and described fuel gas passage connects with the compressed air source unit of described fuel gas.
4. anode refining system according to claim 3, it is characterized in that, described top blast nozzle also include the cavity in hollow pipe or inside and outside adjacent two cavity between the tube wall of the hollow pipe of suit formed and the second oxygen-containing gas passage of oxygen-containing gas for gas fuel burning described with carrying, described second oxygen-containing gas passage connects with the compressed air source unit of described oxygen-containing gas.
5. anode refining system according to claim 4, it is characterized in that, described fuel gas passage and described second oxygen-containing gas passage are integral type structure, and the integral structure of described fuel gas passage and described second oxygen-containing gas passage is split-type structural with described first oxygen-containing gas passage, the integral structure of described fuel gas passage and described second oxygen-containing gas passage can slide up and down relative to described first oxygen-containing gas passage in the vertical direction.
6. anode refining system according to claim 1, it is characterized in that, the side lower of described refining furnace is provided with side-blown nozzle and blows oxygen-containing gas in the way of blowing by submergence below the upper liquid level of the copper melt in described refining furnace, and the gas outlet of described side-blown nozzle is positioned at below the upper liquid level of the copper melt of described refining furnace；
Described side-blown nozzle is the multilamellar internal and external casing structure of the hollow pipe including multiple inside and outside suit, described side-blown nozzle include by inside and outside the cavity in hollow pipe or adjacent two suit hollow pipe tube wall between cavity formed and for carrying the oxygen-containing gas passage of described oxygen-containing gas, described oxygen-containing gas passage connects with the compressed air source unit of described oxygen-containing gas；
That described side-blown nozzle also includes being formed by cavity between the tube wall of the hollow pipe of suit inside and outside adjacent two and for described side-blown nozzle carries out the cool cycles aquaporin of cooling protection, described cool cycles aquaporin connects with apparatus for supplying cool water.
7. anode refining system according to claim 6, it is characterized in that, described side-blown nozzle also include by inside and outside the cavity in hollow pipe or adjacent two suit hollow pipe tube wall between cavity formed and for carrying the compressed gas passage of the compressed gas being mixed with slag former powder, described compressed gas passage connects with gas powder feedway.
8. anode refining system according to claim 1, it is characterised in that described Sheng copper container is Rotary Anode Furnace, described Rotary Anode Furnace includes opening that is that offer on its furnace wall and that lower into for described refining furnace or rise away.
CN201610141854.0A 2016-03-13 2016-03-13 Shallow-oxidation reduction-free anode refining system for processing high-impurity crude copper Pending CN105779786A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59226131A (en) * 1983-06-06 1984-12-19 Nippon Mining Co Ltd Vacuum refining device for crude copper
CN1324411A (en) * 1998-08-28 2001-11-28 沃斯特－阿尔派因工业设备制造有限公司 Method for producing a metal melt and corresponding multifunction lance
CN101203619A (en) * 2005-04-01 2008-06-18 传统环境服务有限公司 Operation of iron oxide recovery furnace for energy savings, volatile metal removal and slag control
CN103498058A (en) * 2013-09-09 2014-01-08 杨先凯 Technology and apparatus for removing lead, zinc, arsenic, antimony, bismuth and tin from matte
CN104561585A (en) * 2013-10-14 2015-04-29 阳谷祥光铜业有限公司 Copper concentrate smelting method and copper concentrate smelting device

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59226131A (en) * 1983-06-06 1984-12-19 Nippon Mining Co Ltd Vacuum refining device for crude copper
CN1324411A (en) * 1998-08-28 2001-11-28 沃斯特－阿尔派因工业设备制造有限公司 Method for producing a metal melt and corresponding multifunction lance
CN101203619A (en) * 2005-04-01 2008-06-18 传统环境服务有限公司 Operation of iron oxide recovery furnace for energy savings, volatile metal removal and slag control
CN103498058A (en) * 2013-09-09 2014-01-08 杨先凯 Technology and apparatus for removing lead, zinc, arsenic, antimony, bismuth and tin from matte
CN104561585A (en) * 2013-10-14 2015-04-29 阳谷祥光铜业有限公司 Copper concentrate smelting method and copper concentrate smelting device

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Application publication date: 20160720