CN108425021A - A kind of blister copper pyrogenic process continuous refining process - Google Patents

A kind of blister copper pyrogenic process continuous refining process Download PDF

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Publication number
CN108425021A
CN108425021A CN201810305477.9A CN201810305477A CN108425021A CN 108425021 A CN108425021 A CN 108425021A CN 201810305477 A CN201810305477 A CN 201810305477A CN 108425021 A CN108425021 A CN 108425021A
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CN
China
Prior art keywords
copper
continuous refining
liquid
gas
zoneofoxidation
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CN201810305477.9A
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Chinese (zh)
Inventor
郝小红
张振民
曹珂菲
冯双杰
崔大韡
李栋
林屹
许欣
周钢
孔令卓
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China ENFI Engineering Corp
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China ENFI Engineering Corp
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Priority to CN201810305477.9A priority Critical patent/CN108425021A/en
Publication of CN108425021A publication Critical patent/CN108425021A/en
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B15/00Obtaining copper
    • C22B15/0026Pyrometallurgy
    • C22B15/006Pyrometallurgy working up of molten copper, e.g. refining

Abstract

The present invention provides a kind of blister copper pyrogenic process continuous refining process, which includes:Continuously blister copper is added in zoneofoxidation, melting obtains copper liquid;It is passed through oxidizing gas to copper liquid, copper is made to aoxidize and the copper liquid after oxidation is made to flow into progress reduction reaction in reducing zone;The combustible gas that reducing zone generates is burnt when flowing through zoneofoxidation;Copper liquid after reduction is flowed continually out through putting copper mouth, and the flue gas of generation is discharged with the flue gas of zoneofoxidation from outlet flue together.By being carried out at the same time oxidation, reduction reaction process in continuous refining furnace, exhaust gas volumn is small, can shorten the activity duration, improves utilization rate of equipment and installations, effectively solves SO2In serious pollution problem caused by smoke discharge amount is big and traditional handicraft the problem of blister copper involucrum cold burden.Exhaust gas volumn and smoke components are relatively stablized simultaneously, and the combustible fumes that reducing zone generates can be burnt secondary use in oxidized area before discharging, so that reduction fume afterheat is effectively utilized, have many advantages, such as that low energy consumption, environmental-friendly, exhaust gas volumn is small, production efficiency is high.

Description

A kind of blister copper pyrogenic process continuous refining process
Technical field
The present invention relates to non-ferrous metallurgy technology field, more particularly to a kind of blister copper pyrogenic process continuous refining process.
Background technology
The fire metallurgy process of copper generally comprises three copper concentrate melting, Copper Matte Converting and blister refining steps.Copper matte regulus is blown Refine output the general cupric 98.5~99.5% of blister copper, remaining impurity element have sulphur, oxygen, iron, arsenic, antimony, zinc, tin, lead, bismuth, nickel, Cobalt etc. usually also contains rare metals and the noble metals such as selenium, tellurium, gold and silver.Impurity element can be to the electric conductivity and mechanicalness of copper Harmful effect can be generated, and the valuable elements such as rare metal and noble metal then need synthetical recovery, improve resource utilization.Copper fire Method refining refer in the case where melt hot conditions, it is removing mineral products blister copper and sulphur in reclaimed copper, iron, lead, zinc, nickel, arsenic, antimony, tin, secret With the impurity such as oxygen, the pyrometallurgic copper process of output blister copper.
Blister copper pyro-refining includes mainly aoxidizing and restoring two processes.Oxidation stage is that at high temperature, oxidant is sent Enter in molten raw, the Cu in melt is oxidized to Cu first2O, Cu2O makes its oxidation with the effect of other metallic impurity elements again, raw At metal oxide in copper liquid solubility very little, and proportion is lighter, can rapid emersion liquid level form clinker and be discharged.Oxygen After the completion of change, the oxygen in copper liquid can be precipitated in solidification in the form of Cu2O, is distributed on the crystal boundary of Cu, is caused to endanger to electrorefining Evil, need to carry out reduction deoxidation.Reduction phase is that at high temperature, reducing agent is sent into copper liquid, reducing agent and the Cu in melt2O Deoxidation is reacted, after oxygen content drops to a certain degree in copper liquid, you can cast.
For traditional blister copper fire refining process, In Crystal Solid Copper material or liquid are generally handled using refining reverberatory furnace The production process of blister copper, each heat is divided into charging, (copper material) fusing, (copper water) oxidation, (copper water) reduction and casting (anode plate) five stages.Due to the congenital limitation by reverberatory furnace furnace type structure, either hand stock or mechanized charging, Charging rate is relatively slow, and the concurrent heating of whole process and the lower thermal efficiency of reverberatory furnace cause the fuel cost of anode plate to occupy It is high not under.After the completion of traditional 5 stages of reverberatory furnace, it is further continued for next furnace period operation, productivity is low, and production cost is high.
Invention content
In view of the deficienciess of the prior art, the object of the present invention is to provide a kind of blister copper pyrogenic process continuous refining process, it should Technique can realize the melting continuously from blister copper to anode copper, have low energy consumption, environmental-friendly, exhaust gas volumn is small, production efficiency is high etc. Advantage.
To achieve the goals above, the technical solution adopted by the present invention is as follows:
A kind of blister copper pyrogenic process continuous refining process, includes the following steps:
Continuously blister copper is added in the zoneofoxidation of continuous refining furnace, melting obtains copper liquid;
Into zoneofoxidation, copper liquid is passed through oxidizing gas, so that copper is aoxidized and is aoxidized impurity element and generates refinement oxide slag;
Refinement oxide slag is discharged, and the copper liquid after oxidation is made to flow into reducing zone;
It is passed through reducing agent to reducing zone, the copper liquid after oxidation is made to carry out reduction reaction;
The combustible gas that reducing zone generates is burnt when flowing through zoneofoxidation;
Copper liquid after reduction is flowed continually out through putting copper mouth, and the flue gas of generation is arranged with the flue gas of zoneofoxidation from outlet flue together Go out.
Further, in-furnace temperature is maintained at 1150-1250 DEG C.
Further, the flow velocity for oxidizing gas being passed through to zoneofoxidation is supersonic jet.
Further, oxidizing gas is passed through to zoneofoxidation by one or more spray gun, every gun traffic is about 85Nm3/h。
Further, the oxygen-enriched air that oxidizing gas is compressed air or oxygen concentration is 21%-50% percents by volume.
Further, the oxygen content that control flows into the copper liquid of reducing zone is 0.5~1.0%.
Further, the oxygen content of the copper liquid of control outflow reducing zone is 0.05-0.2%.
Further, the reducing agent is natural gas, liquefied petroleum gas, ammonia, propane, fine coal, one kind in heavy oil or more Kind, preferably natural gas or liquefied petroleum gas.
Further, further include blasting nitrogen or inert gas into copper liquid in reducing zone.
Further, the copper liquid through putting the outflow of copper mouth is cast outside stove.
Blister copper pyrogenic process continuous refining process provided by the present invention, by being carried out at the same time oxidation in continuous refining furnace, going back Former process, shortens the activity duration, improves utilization rate of equipment and installations, while the continuous refining process of the present invention can also carry out reducing zone Gas burning recycles, and effectively reduces energy consumption, reduces smoke discharge amount, reduces pollution, has environmental-friendly, automatization level High, the advantages that production efficiency is high.
Description of the drawings
Fig. 1 is the structural schematic diagram of the blister copper pyrogenic process continuous refining furnace of one embodiment of the present invention;
Fig. 2 is the flow chart that continuous refining is carried out using the blister copper pyrogenic process continuous refining furnace of the present invention.
Wherein, the reference numerals are as follows:
1:Furnace body;
101:Zoneofoxidation;
102:Reducing zone;
2:Charge door;
3:Outlet flue;
4:Partition wall;
5:Put copper mouth;
61:Oxidation spray gun;
62:Restore spray gun;
7:Slag-drip opening.
Specific implementation mode
Technical scheme of the present invention is described further below according to specific embodiment.Protection scope of the present invention is unlimited In following embodiment, these examples are enumerated merely for exemplary purpose without limiting the invention in any way.
Fig. 1 is the structural schematic diagram of the blister copper pyrogenic process continuous refining furnace of one embodiment of the present invention, as shown in Figure 1, slightly Pyrometallurgical continuous refining furnace includes furnace body 1, charge door 2, outlet flue 3, puts copper mouth 5 and slag-drip opening 7, and the copper mouth 5 of putting is preferably Copper mouth is put in siphon.There is in furnace body 1 interconnected zoneofoxidation 101 and reducing zone 102, can be carried out at the same time blister copper oxidation and Reduction process.The outlet flue 3 is set to the top of the furnace body, and the charge door 2 is set to the side wall of zoneofoxidation 101, institute It states and puts the side wall that copper mouth 5 is set to reducing zone 102, slag-drip opening 7 is set to zoneofoxidation and reducing zone, and can divide according to actual needs It is arranged not on the side wall of zoneofoxidation and reducing zone one or more.
Furnace body 1 is formed by refractory material laying, furnace cavity by partition wall 4 by zoneofoxidation 101 and reducing zone 102 every It opens, i.e. the setting of partition wall 4 is between charging zoneofoxidation 101 and reducing zone 102.The partition wall 4 is fixed on the both sides side wall of furnace body 1, It is not contacted with the bottom wall of furnace body 1 and roof, i.e., has gap between partition wall 4 and the bottom of furnace body 1, which can be according to reality Border production needs that height is arranged, it is sufficient to copper liquid be allow to flow through.For example, when partition wall volume is height × width x length:1100mm When × 460mm × 280mm, it is about height × width x length that gap, which can be arranged,:200mm×400mm×460mm.By above-mentioned partition wall and The setting in gap can be such that blister copper hot material fluid is continuously added in stove, ensure the influence of refinery practice nonfertilization refining workshop section, to Refinery practice can be made to be carried out continuously, realize blister copper continuous feed, anode copper direct casting, shorten total activity duration, raising is set Standby utilization rate and production efficiency.
Also there is gap, the gap upper furnace can be made to form a unified gas between partition wall 4 and the top of furnace body 1 Space so that the flue gas generated in refining process by by collect in the upper furnace space of furnace body 1, jointly from 1 top of furnace body Outlet flue 3 be discharged, enable reaction generate flue gas merging treatment, smoke components, exhaust gas volumn and the flue-gas temperature of formation are all More stable, subsequent smoke processing system is simple, and can be with recovery waste heat.Outlet flue 3 is preferably provided at the top of zoneofoxidation 101 Portion is more preferably disposed at zoneofoxidation 101 and leans on top side wall, and when reduction reaction carries out to a certain extent, what reducing zone generated can Burned to be used when burning gases flow through zoneofoxidation by the gap of partition wall 4 and roof of the furnace, reduction fume afterheat obtains Effective utilization, can substantially reduce energy consumption.
It is respectively equipped with oxidation spray gun 61 and reduction spray gun in the roof of the furnace of zoneofoxidation 101 and reducing zone 102 and/or bottom 62, the oxidation spray gun 61 and reduction spray gun 62 can be water cooled lance, and can be respectively set multiple.Oxidation spray gun 61 is to zoneofoxidation 101 spray into oxidant, such as compressed air or oxygen concentration are the oxygen-enriched air of 21%-50% percents by volume (V%), are passed through The addition of oxidant controls oxidation depth, that is, controls copper liquid oxygen content.Oxygen-enriched air effluxvelocity is high, is Supersonic rapid fire Stream, but stock very little is flowed, every gun traffic is about 85Nm3/ h, so melt can be injected without causing big splash.Also Former spray gun 62 sprays into reducing agent, such as natural gas, liquefied petroleum gas, ammonia, propane, fine coal, heavy oil to reducing zone 102, by also The addition of former agent controls reduction depth, that is, controls copper liquid oxygen content.Oxidant and reduction are sprayed into melt by spray gun Agent, melt agitation is abundant, and zoneofoxidation 101 and reducing zone 102 control oxidizing atmosphere and reducing atmosphere, mass-and heat-transfer item respectively Part is good, and the utilization rate of Oxidizing and Reducing Agents is high, while technique and its plant automation are horizontal high, can automatically control oxidation Agent, reducing agent spray into situation.Oxidation spray gun 61 and reduction spray gun 62 and the angle of horizontal plane are 90 °, and usually not close The position of partition wall 4 is installed, to ensure that Melt Stability flows.
The side wall and/or roof of reducing zone 102 are equipped with and put copper mouth 5, and copper mouth, the copper after continuous refining are put in preferably siphon Liquid can be put copper mouth by this and continuously be discharged, then carry out casting process.Due in stove without casting process, without casting and Empty stove soak in short-term, and fume afterheat is fully used, energy consumption can be significantly reduced than traditional work.
Be additionally provided with slag-drip opening 7 on the side wall of zoneofoxidation 101 and reducing zone 102, the oxidizing slag that oxidation process generates periodically from Slag-drip opening 7 is discharged.Slag-drip opening 7 is generally proximal to the setting of partition wall 4, and the clinker of emersion liquid level can be discharged, in order to avoid dirt is caused to copper liquid Dye, while slag-drip opening 7 also can be used as sampling observation panel, so that operator observes the state of copper liquid in charging zoneofoxidation 101 at any time, Oxygen content or sampling observation can be monitored on-line.
Fig. 2 is the flow chart that continuous refining is carried out using the blister copper pyrogenic process continuous refining furnace of the present invention, as shown in Fig. 2, slightly Pyrometallurgical continuous refining process includes the following steps:
Step S101 is continuously added to from charge door 2 by blister copper in the zoneofoxidation 101 of continuous refining furnace, and melting obtains Copper liquid;
Step S102 is passed through oxidizing gas by oxidation spray gun 61, so that the copper liquid in stove is aoxidized and aoxidizes impurity element Generate refinement oxide slag;
Refinement oxide slag is discharged in step S103, the underclearance stream that the copper liquid after oxidation passes through the partition wall 4 of continuous refining furnace Enter in reducing zone 102;
Step S104:It restores spray gun 62 and sprays into reducing agent, the copper liquid after oxidation is made to carry out reduction reaction;
Step S105:The combustible gas that reducing zone 102 generates is flowed through by the partition wall 4 of continuous refining furnace with roof of the furnace It burns when zoneofoxidation 101;
Step S106:Copper liquid after reduction is through putting the outflow of copper mouth, and the flue gas of generation is with the flue gas of zoneofoxidation from outlet flue 3 one With discharge.
Since zoneofoxidation 101 and reducing zone 102 are interconnected and in same furnace body 1, can be carried out continuously oxidation, restore Journey ensure that continuous refining process is not influenced by workshop section, to realize the continuous refining of blister copper.
In step S101, in-furnace temperature is controlled at 1150~1250 DEG C.
In step s 102, the oxidizing gas that oxidation spray gun sprays into can be compressed air or oxygen concentration is 21-50V%'s Oxygen-enriched air.Cu is oxidized to form Cu first2O, Cu2O reacts generation with impurity element (such as other metallic elements) again can be with copper The refinement oxide slag or impurity element of liquid separation are oxidized to be combined to form refinement oxide slag with flux again after metal oxide. Oxygen-enriched air effluxvelocity is supersonic jet, and every gun traffic is about 85Nm3/ h due to its effluxvelocity height, but flows stock Very little, so melt can be injected without causing big splash.
In step s 103, refinement oxide slag is continuously or discontinuously discharged by slag-drip opening 7, and the copper liquid after aoxidizing later passes through The underclearance of the partition wall 4 of continuous refining furnace flows into reducing zone 102.Copper liquid after oxidation flows into before reducing zone 102, control Oxygen content after oxygenerating in copper liquid is 0.5~1.0%.Oxidation can be controlled by compressed air or the amount of blasting of oxygen-enriched air Depth, that is, control copper liquid oxygen content, at slag-drip opening 7 can on-line checking oxygen content, or sampling observation.
In step S104, reducing agent is added into copper liquid by restoring spray gun 62, the copper liquid after oxidation is made to be restored Reaction.Reducing agent used is one or more in natural gas, liquefied petroleum gas, ammonia, propane, fine coal, heavy oil, and copper liquid is embezzled The Cu of sum2O is reacted with reducing agent generates Cu.
In step S105, when reducing agent such as natural gas, liquefied petroleum gas etc., melted through restoring 61 continuous high speed of spray gun and spraying into When pond carries out reduction reaction, the combustible gas such as CO that reducing zone generates burns, the heat of releasing adds when flowing through zoneofoxidation 101 To utilize, energy consumption can be reduced.In addition, reducing agent can also be blasted together into stove by restoring spray gun 62 and will not be reacted with copper Gas, as nitrogen or inert gas improve mass-and heat-transfer condition, strengthening smelting response intensity to stirring melt.
In step s 106, the copper liquid after reduction is flowed continually out by the copper mouth of putting of reducing zone 102, flows out it in copper liquid Before, the oxygen content of the copper liquid after control reduction is 0.05-0.2%.The flue gas of generation is with the flue gas of zoneofoxidation 101 from outlet flue 3 It is discharged together.Since oxidation, reduction reaction are carried out continuously, continuous-stable, flue gas continuous-stable are reacted, and exhaust gas volumn is small, solution Having determined, traditional refining furnace exhaust gas volumn fluctuation is big, and smoke components each stage also differs the problem of bringing.
In conclusion the blister copper pyrogenic process continuous refining process of the present invention can realize the melting continuously from blister copper to anode copper, Oxidation, reduction reaction process are carried out at the same time when operation, and exhaust gas volumn is small, can shorten the activity duration, are improved utilization rate of equipment and installations, are effectively solved Certainly SO2In serious pollution problem caused by smoke discharge amount is big and traditional handicraft the problem of blister copper involucrum cold burden.Exhaust gas volumn simultaneously Relatively stablize with smoke components, the combustible fumes that reducing zone generates oxidized area can be burnt secondary use before discharging, make reduction cigarette Gas waste heat is effectively utilized, and can be significantly reduced than traditional work without casting and empty stove soak, energy consumption in short-term. In short, the blister copper pyrogenic process continuous refining furnace of the present invention has low energy consumption, environmental-friendly, automatization level is high, production efficiency is high etc. Advantage.
Those skilled in the art should be noted that embodiment described in the invention is only exemplary, can be Various other replacements, changes and improvements are made in the scope of the present invention.Thus, the present invention is not limited to the above embodiments, and only It is defined by the claims.

Claims (10)

1. a kind of blister copper pyrogenic process continuous refining process, which is characterized in that include the following steps:
Continuously blister copper is added in the zoneofoxidation of continuous refining furnace, melting obtains copper liquid;
Into zoneofoxidation, copper liquid is passed through oxidizing gas, so that copper is aoxidized and is aoxidized impurity element and generates refinement oxide slag;
Refinement oxide slag is discharged, and the copper liquid after oxidation is made to flow into reducing zone;
It is passed through reducing agent to reducing zone, the copper liquid after oxidation is made to carry out reduction reaction;
The combustible gas that reducing zone generates is burnt when flowing through zoneofoxidation;
Copper liquid after reduction is flowed continually out through putting copper mouth, and the flue gas of generation is discharged with the flue gas of zoneofoxidation from outlet flue together.
2. blister copper pyrogenic process continuous refining process as described in claim 1, which is characterized in that the in-furnace temperature is maintained at 1150 ~1250 DEG C.
3. blister copper pyrogenic process continuous refining process as described in claim 1, which is characterized in that described to be passed through oxic gas to zoneofoxidation The flow velocity of body is supersonic jet.
4. blister copper pyrogenic process continuous refining process as described in claim 1, which is characterized in that by one or more spray gun to oxygen Change area and be passed through oxidizing gas, every gun traffic is about 85Nm3/h。
5. blister copper pyrogenic process continuous refining process as described in claim 1, which is characterized in that the oxidizing gas is compressed air Or the oxygen-enriched air that oxygen concentration is 21%-50% percents by volume.
6. blister copper pyrogenic process continuous refining process as described in claim 1, which is characterized in that control flows into the copper liquid of reducing zone Oxygen content is 0.5~1.0%.
7. blister copper pyrogenic process continuous refining process as described in claim 1, which is characterized in that the copper liquid of control outflow reducing zone Oxygen content be 0.05~0.2%.
8. blister copper pyrogenic process continuous refining process as described in claim 1, which is characterized in that the reducing agent is natural air-liquid It is one or more in liquefied oil gas, ammonia, propane, fine coal, heavy oil, preferably natural gas or liquefied petroleum gas.
9. blister copper pyrogenic process continuous refining process as described in claim 1, which is characterized in that further include in reducing zone to copper liquid In blast nitrogen or inert gas.
10. blister copper pyrogenic process continuous refining process as described in claim 1, which is characterized in that the copper through putting the outflow of copper mouth Liquid is cast outside stove.
CN201810305477.9A 2018-04-08 2018-04-08 A kind of blister copper pyrogenic process continuous refining process Pending CN108425021A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110760691A (en) * 2019-11-26 2020-02-07 象山旭雯钢铁科技有限公司 Fire refining blister copper machine

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Publication number Priority date Publication date Assignee Title
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CN101386918A (en) * 2008-10-30 2009-03-18 阳谷祥光铜业有限公司 Anode refining method for high sulphur raw copper
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Publication number Priority date Publication date Assignee Title
CN110760691A (en) * 2019-11-26 2020-02-07 象山旭雯钢铁科技有限公司 Fire refining blister copper machine

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