CN1034960A - A kind of fire refining technique of raw copper of nitrogen-blow - Google Patents
A kind of fire refining technique of raw copper of nitrogen-blow Download PDFInfo
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- CN1034960A CN1034960A CN 88105024 CN88105024A CN1034960A CN 1034960 A CN1034960 A CN 1034960A CN 88105024 CN88105024 CN 88105024 CN 88105024 A CN88105024 A CN 88105024A CN 1034960 A CN1034960 A CN 1034960A
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Abstract
The invention belongs to the method for refining of metal, particularly for the pyrorefining of blister copper.Principal character of the present invention is when carrying out pyrorefining for the higher ore deposit blister copper of quality, top at converter, refining furnace or copper-clad is blown into nitrogen with spray gun in fused blister copper solution, to reach the purpose of impurity such as the sulphur that removes in the copper liquid, oxygen, the anode copper of output better quality.The present invention have the activity duration short, fuel consumption is few, uses no or little reductive agent, equipment is simple, is easy to advantages such as realization.
Description
The invention belongs to the refining of metal, particularly a kind of pyrorefining method of blister copper.
In the production process of copper, the pyrorefining of blister copper is an important link.The purpose of pyrorefining is to provide chemical ingredients and physical specification all qualified positive plate for cupric electrolysis production.At present, the blister copper of most copper works all will carry out pyrorefining in the world, and then carries out electrolysis, the electrolytic copper that output is suitable for using.The pyrorefining method mainly is made up of oxidation and two stages of reduction.Its refinery practice is to treat that purified blister copper solution packs in the refining furnace, to spray into air under certain condition in the fused blister copper.Copper in airborne oxygen and the melt reacts, and generates Red copper oxide, and is dissolved in the copper liquid.Impurity reaction in Red copper oxide and the copper liquid, the generation oxide compound volatilizees with flue gas and removes or remove with the flux slag making.In oxidation stage, remove though impurity such as sulphur are oxidized, and the oxygen level in the copper liquid has increased, exist the antianode casting and the electrolysis of crossing polyoxy are harmful to., also will reduce behind oxidation stage for this reason, generally adopt heavy oil to make reductive agent, spray in the stove, the copper with oxidized is reduced into metallic copper.It is long that this kind technology exists the activity duration, and fuel and reductive agent consume problem of higher.
Once reported on " JOVRNal OF METALS " (1982.12 and 1983.12) that people such as P.Goyal installed the porous plug gas permeable brick in the bottom of rotary refining furnace, in the process of pyrorefining blister copper, test by the nitrogen blowing desulfurization in copper liquid of porous plug gas permeable brick, this kind method is after nitrogen flushing, also need to reduce with hydrogen, still need consume more reductive agent, and the equipment more complicated, industrial being not easy to realized.
The object of the present invention is to provide a kind of refinery process time short, fuel and reductive agent consumption are few, and equipment is simple, is easy to the method at the pyrorefining blister copper of industrial application.
The present invention proposes on the basis in the higher analysis of output blister copper quality that some ore deposit copper smelting plant converter for copper matte are blown, research.My ore deposit blister copper quality is higher, and its copper content is 98.6～99.5%, and except that sulphur content was high slightly, other impurity was all lower.Near the foreign matter content that anode copper allows, abroad the copper content of some national ore deposit blister coppers is also 99.0～99.7%.
The chemical ingredients of anode copper requires:
Impurity Pb Sn Ni As Sb Bi O
2
%＜ 0.2 0.075 0.5 0.04 0.03 0.04 0.1～0.05
Some factory's blister copper chemical ingredients (%) of China
Composition Cu S O Ni Fe Pb
Shen Ye 98.62 0.08 0.42 0.1 0.046 0.25
Daye 99.49 0.04 0.22 0.05 0.0475 0.05
Zhongtiao Shan Mountain 99.01 0.041 0.52 0.14 0.0026 0.009
Composition Zn As Sb Bi
Shen Ye 0.028 0.10 0.04 0.016
Daye 0.002 0.04 0.02 0.008
Zhongtiao Shan Mountain 0.0005 0.004 0.0005 0.0005
Some the ore deposit blister copper pyrorefining of above analysis revealed mainly to as if sulphur, rather than other impurity that is difficult to remove.
It is as follows also to find to contain the oxygen situation in the blister copper:
Blowing degree (O) % (S) %
Blowing suitable 0.321 0.042
Over-blowing 0.561 0.035 a little
Can see in the above-mentioned analysis that the blister copper oxygen level of bessemerizing output is 8～16 times more than of sulphur content, has surpassed the theoretical value of oxidation desulfur reaction needs.
Based on this analysis, the present invention adopts the rare gas element method of carrying to create conditions from the thermodynamics and kinetics aspect, impels the dissolved oxygen of blister copper own to incite somebody to action wherein sulphur oxidation and removes.Like this, just can cancel the operation of these two opposition of oxidation-reduction in the current technology.
Main points of the present invention be with the fused blister copper pack into copper-clad, the blowing converter, rotary refining furnace or fixed refining furnace.To be 99.99% nitrogen with purity by spray gun spray into temperature from the top is 1100 ℃-1250 ℃ the blister copper solution.
The used spray gun of jetting is the consumable formula, and two kinds of single hole spray gun and multihole lances are arranged.The single hole spray gun is an immerseable, adopts internal diameter 5-15mm, and external diameter 25-35mm steel pipe is made, and immerses melt end skin and is surrounded by high-temperature refractory.Multihole lance is the several jet pipes of many peaces at the spray gun top, helps air-flow and disperses.
The general technology parameter
Winding-up temperature: 1100 ℃-1250 ℃;
Winding-up time: 5-25 minute;
Nitrogen flow: 0.1-1NM
3/ TminCu;
Gun insertion depth: 0.7-0.8H(H is a pool depth);
Injection method: top blast;
Nitrogen gas purity: more than 99.99%.
Ingredient requirement
Composition Cu Ni Fe Pb As Sb Bi
% 98.5 0.0 0.02 0.0 0.00 0.0005 0.001
-99.5 -0.5 -0.03 -0.2 -0.03 -0.03 -0.04
Carry out all can in copper-clad, blowing converter, rotary refining furnace and fixed refining furnace with this kind method refining blister copper.
Embodiment 1. is shown in Fig. 1 (Fig. 1 is at top blast nitrogen refining synoptic diagram in the copper-clad), in refining process, the nitrogen that is contained in the nitrogengas cylinder (1,2,3) is blown in the blister copper solution that is contained in the copper-clad (8) by the spray gun (9) that is inserted on the copper-clad lid (7) through nitrogen flow variable valve (4), tensimeter (5), spinner-type flowmeter (6).Top blast nitrogen refining blister copper in copper-clad except that the general technology parameter, requires copper-clad top to keep the headroom of 300-400mm.Gun insertion depth makes nozzle apart from wrapping the end greater than 200mm.
Embodiment 2, shown in Fig. 2 (Fig. 2 is for carrying out nitrogen top blast refining blister copper synoptic diagram in the converter), in refining process, be contained in nitrogen process nitrogen flow variable valve (4), tensimeter (5), spinner-type flowmeter (6) in the nitrogengas cylinder (1,2,3), be blown in the blister copper solution that is contained in the converter (7) by spray gun (8,9).Top blast nitrogen refining blister copper is except that the general technology parameter in converter, requires two spray guns are intersected to insert in the stoves, and spray gun becomes 30-45 ° of angle layout with furnace bottom, Spray gun nozzle apart from furnace bottom greater than 200mm.
Adopt nitrogen top blast method of refining, directly nitrogen is sprayed into temperature and be in 1100 ℃-1250 ℃ the blister copper solution, promoted the effect of sulphur and oxygen in the copper liquid, generate SO
2Gas is discharged with nitrogen bubble, reaches the purpose that removes sulphur and oxygen in the copper liquid.So just effectively utilize the reaction of sulphur in the oxygen of blister copper itself and the blister copper, avoided too much oxygen to enter in the fused blister copper, produced peroxidation, caused the loss of copper.
Nitrogen top blast refining technique of raw copper has simple, industrial being easy to of equipment to be realized; Activity duration is short; Can use no or little reducing agent; The advantages such as a large amount of fuel savings of energy.
Use process of the present invention, can obtain high-quality anode copper, the blister copper sulfur-bearing Can be down to 0.0005～0.002%, contain oxygen and can be down to 0.2%. Copper surface and inside after the spray refining are provided with pore, and chemical composition and physical specification meet the requirements.
Claims (8)
1, a kind of method of nitrogen-blow pyrorefining blister copper is characterized in that satisfying in the refining process certain processing parameter and ingredient requirement, the high pure nitrogen of jetting to fused blister copper liquid from the top of stove or bag.
2, the method for nitrogen-blow pyrorefining blister copper as claimed in claim 1 is characterized in that said certain processing parameter is:
1. jet temperature: 1100-1250 ℃;
2. jet the time: 5-25 minute;
3. nitrogen flow: 0.1-1NM
3/ Tmin Cu;
4. gun insertion depth: 0.7-0.8H((H is a pool depth).
3, the method for nitrogen-blow pyrorefining blister copper as claimed in claim 1 is characterized in that said ingredient requirement is: contain Cu98.5-99.5% in the blister copper; Ni0.0～0.5%; Fe0.02-0.03%; Pb0.0-0.2%; As0.0-0.03%; Sb0.0005-0.03%; Bi0.001-0.04%.
4,, it is characterized in that when refining process carries out in copper-clad, requiring copper-clad top to keep the headroom of 300-400mm as the method for claim 1,2,3 described nitrogen-blow pyrorefining blister coppers; Its gun insertion depth requires nozzle apart from wrapping the end greater than 200mm.
5, as the method for claim 1,2,3 described nitrogen-blow pyrorefining blister coppers, it is characterized in that, when refining process carries out in converter, require two spray guns intersections are inserted in the stove, spray gun becomes 30-45 ° of angle to arrange with furnace bottom, the nozzle of spray gun apart from furnace bottom greater than 200mm.
6, as the method for claim 1,2,3 described nitrogen-blow pyrorefining blister coppers, it is characterized in that when refining process carries out in rotary refining furnace, requirement with two spray guns respectively from the oxidation mouth of rotary refining furnace with go back that stomodaeum is vertical to be inserted in the stove, the nozzle of spray gun is greater than 200mm apart from furnace bottom.
7, as the method for claim 1,2,3 described nitrogen-blow pyrorefining blister coppers, it is characterized in that when refining process carries out in fixed refining furnace, requiring to insert the molten bath from fire door with reclinate spray gun, nozzle apart from furnace bottom greater than 200mm, in the winding-up process, the molten bath is stirred in all around.
8, the method for nitrogen-blow pyrorefining blister copper as claimed in claim 1 is characterized in that its purity of said high pure nitrogen is more than 99.99%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88105024 CN1017263B (en) | 1988-02-09 | 1988-02-09 | Nitrogen-blow fire refining technique of raw copper |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88105024 CN1017263B (en) | 1988-02-09 | 1988-02-09 | Nitrogen-blow fire refining technique of raw copper |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1034960A true CN1034960A (en) | 1989-08-23 |
| CN1017263B CN1017263B (en) | 1992-07-01 |
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ID=4833257
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 88105024 Expired CN1017263B (en) | 1988-02-09 | 1988-02-09 | Nitrogen-blow fire refining technique of raw copper |
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| Country | Link |
|---|---|
| CN (1) | CN1017263B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106282598A (en) * | 2016-08-29 | 2017-01-04 | 金川集团股份有限公司 | A kind of control sulfur nitrating refinery practice |
| CN110093628A (en) * | 2019-04-30 | 2019-08-06 | 云南铜业股份有限公司西南铜业分公司 | A kind of copper electrolyzing refining method generating core-shell structure copper anode mud |
-
1988
- 1988-02-09 CN CN 88105024 patent/CN1017263B/en not_active Expired
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106282598A (en) * | 2016-08-29 | 2017-01-04 | 金川集团股份有限公司 | A kind of control sulfur nitrating refinery practice |
| CN110093628A (en) * | 2019-04-30 | 2019-08-06 | 云南铜业股份有限公司西南铜业分公司 | A kind of copper electrolyzing refining method generating core-shell structure copper anode mud |
| CN110093628B (en) * | 2019-04-30 | 2021-06-08 | 云南铜业股份有限公司西南铜业分公司 | Copper electrolytic refining method for generating core-shell structure copper anode mud |
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| Publication number | Publication date |
|---|---|
| CN1017263B (en) | 1992-07-01 |
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