CN1067113C - Pollution-free fire smelting method for Cu-Ni sulphide mine - Google Patents
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- CN1067113C CN1067113C CN98116475A CN98116475A CN1067113C CN 1067113 C CN1067113 C CN 1067113C CN 98116475 A CN98116475 A CN 98116475A CN 98116475 A CN98116475 A CN 98116475A CN 1067113 C CN1067113 C CN 1067113C
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Abstract
The present invention provides a pollution-free fire smelting method for Cu-Ni sulfide ores. The present invention integrates the unique advantages of hot plasma heating and microwave heating and integrates the processes of calcination, matte formation, blowing, slag depletion, etc. of a traditional fire method for copper sulfide or Cu-Ni sulfide ore concentrate via making use of strong activity of the oxygen of air plasma at high temperatures and the heat release because of the oxidation and the slagging of the sulfide ores. Coarse copper or converter mattes are prepared in one step, waste slag is also obtained in one step, and sulfur dioxide in high temperature tail gas is converted into elemental sulfur via catalytic reduction and is recovered by an industrial microwave oven. Therefore, the present invention greatly simplifies smelting processes and devices, saves energy and resources, basically eliminates air pollution because of harmful gases and effectively protects natural ecological environment.
Description
The present invention relates to the pollution-free pyrogenic process smelting process of a kind of copper, Ni sulphide mine.
Traditional processing copper sulfide concentrate or copper nickel vulcanised ore concentrate are produced in the pyrometallurgical smelting method of blister copper or high ice nickel, except that the oxidation roasting--and Blast Furnace Method refining " black copper " (the sulfur-bearing in the blister copper＞0.6%S), all traditional technologys all are to walk to make sulfonium (matte) melting--the progressively enrichment route of blowing.Sulphide ores matte smelting technology has Blast Furnace Method, reflection oven process, electric furnace smelting process, flash oven process, oxygen top blown smelting process and smelting bath smelting process etc.For improving the grade of sulfonium, before matte smelting, add roasting (taking off partly sulphur in advance) operation.For cutting down the consumption of energy, improve metal recovery rate, alleviate SO
2Gas is to the pollution of environment, and newly-built big factory adopts the technology of flash stove or oxygen-enriched air smelting and acid exhaust.Produce blister copper or high ice nickel by matte (sulfonium), all adopt and bessemerize, and then slag is handled separately.The common drawback that these traditional methods exist is: technical process is long, equipment is huge, area of mill site is big, the building equipment investment is big, production run expense height, comprehensive energy consumption height, environmental pollution be seriously (even under the supporting situation of acid exhaust, also have a large amount of SO inevitably
2Gas evolution and atmosphere pollution), low (as Blast Furnace Method, reflection oven process, electric furnace process etc., make in melting has 40% fixedly sulphur loss to some valuable element rate of recovery in the sulfonium process; And for example nickel is smelted, smelting comprehensive recovery＜44% of electric furnace--converter process cobalt, smelting comprehensive recovery＜55% of flash stove--converter process cobalt), waste containing metal height or the like.Compare with other traditional method in addition, the melting of flash stove--bessemerize blister copper or the high ice nickel method of producing, though have the advantages such as the rate of recovery that made full use of sulphur oxidation and iron slag making heat release and improved sulphur, but its working cost height, process control condition requires high, equipment is huge especially, the slag metal-containing height, and still have SO inevitably
2Deficiencies such as gas evolution contaminate environment also are conspicuous.Obtained " microwave desulfurization plasma smelting of nickel matte " (patent No. is 8810320.1) of China Patent Right,, still had following shortcoming in practice though make sulphide ores smelting technology technology on the basis of traditional method, obtain revolutionary breakthrough:
(1) control of the granularity of the feed stock for blast furnace of industrial microwave oven desulfurization and moisture content requires tighter;
(2) in the sweetening process, feed the H in the industrial microwave oven reactor
2The desulfurization chemical reaction that O (steam) participates in is a thermo-negative reaction, so consumes energy;
(3) also directly produce in the process of elementary sulfur (arsenic) in microwave heating desulfurization (arsenic), process control condition requires tight, and the factor of influence is more relatively, and operator are difficult for grasping.
The object of the present invention is to provide and a kind ofly can simplify technical process, cut down the consumption of energy, make the pyrometallurgical smelting method of resources conservationization, and fundamentally solve sulphide ores and smelt SO in the sweetening process
2The inevitable property of obnoxious flavour effusion atmosphere pollution.
The distinct advantages of thermal-arrest plasma heating of the present invention and micro-wave energy heating is an one, the strong activity of utilizing the oxygen under air or the oxygen enrichment plasma high-temperature (8000-30000K) to have, and sulphide ores is smelted oxidation heat liberation and slag making heat release, roasting, the processes such as sulfonium, blowing, slag making and slag depletion of making of traditional smelting processes such as copper sulfide concentrate or copper nickel vulcanised ore concentrate are integrated and carry out, one step was produced blister copper or high ice nickel, and the disposable waste that obtains.SO in the high-temperature tail gas
2Being catalysed and reduced into elementary sulfur through industrial microwave oven reclaims.
Technical scheme of the present invention is finished by following process steps:
A, the moisture content behind batching (by the theoretical calculation result of revising with practice) mixing are directly added desulfurization melting on the charge bank of plasma furnace smelting zone less than 4% raw material by airtight feed bin, melt contact arc district, plasma furnace molten bath temperature is 2000-2600 ℃, it is pressurized air or the oxygen rich gas current-carrying of 0.45-0.5MPa that plasma gun adopts gauge pressure, one step was produced blister copper or high ice nickel, and the disposable waste that obtains;
B, in the plasma furnace smelting zone or the slag depletion district add CaCO
3Depletion agent and C reductive agent carry out dilution to slag, and plasma torch is with N
2Current-carrying, the disposable waste that obtains;
The SO that C, smelting zone air plasma oxidation sweetening or dearsenification produce
2Gas or As
2O
3Gas enters the industrial microwave oven reactor with high-temperature furnace gas, and microwave catalysis is reduced into elementary sulfur or arsenic under 600-800 ℃ of temperature, enters the collector sedimentation with tail gas again and reclaims free of contamination tail gas emptying.
Plasma torch control voltage is direct current 50-80V.
Smelting zone in the steps A " charge bank " is in order to protect the smelting furnace furnace wall; make it directly not accept the plasma high-temperature radiation; influence lining life design, be deposited in earlier after furnace charge is added on the domatic furnace bottom and the solid charge stores that forms to the molten bath intermediate, inclined.Furnace charge is constantly fusing under the heat conducting heating of fusion high-temperature liquid state material in the hyperthermia radiation of smelting zone plasma body and molten bath, zone that directly contacts with plasma arcs in the molten bath (melt temperature is greater than 2500 ℃) and contiguous melt, under the heat of plasma body, the slag making heat release of the vigorous oxidation of sulfonium and iron in addition, make this zone and formed very big thermograde on every side, and the metal of formation bottom (or high ice nickel) layer, the matte in middle layer (perhaps low nickel matte) layer, melt liquids such as the slag layer on upper strata, and has excellent flowing, in addition under the impact of plasma arcs column pressure, make the melt in this zone form intensive vortex movement up and down, consolidating in the melt--between liquid phase, liquid--gas and solid--causes a kind of very good and contact condition between gas phase, therefore improved heat and mass speed greatly, helped enhancing productivity.Produce following chemical reaction at the smelting zone furnace charge:
Furnace charge is gone into after accepting the furnace high-temperature radiant heat on the charge bank, with pyrite (FeS
2) sulfide that exists of form produces following decomposition reaction before fusing:
The oxidizing reaction of other sulfide:
(cobalt and nickel sulfide are by same reaction oxidation)
(oxide compound of cobalt and nickel is by same reaction sulfuration)
In smelting, nickel has following reaction:
The slag making reaction:
Under the situation that has competent silicon-dioxide to exist, little following reaction:
So, the desulfurization under air (or oxygen enrichment) plasma melting, the one, react very rapid, the 2nd, the utilization ratio of oxygen is almost 100%, this just makes exhaust gas volumn greatly reduce, with blast furnace--and converter process copper metallurgy, nickel are compared, and exhaust gas volumn of the present invention only is 1/9 of a preceding method.This not only saves energy consumption greatly, and helps the back microwave treatment in step.
The slag depletion district of step B, except that adding depletion agent and reductive agent, the using plasma heat tracing can make this stripping section produce two effects like this, and the one, make the melt in the molten bath keep tranquil relatively, help the metal sedimentation, reduce slag metal-containing; The 2nd, add depletion agent CaCO
3With reductive agent C, following chemical reaction is taken place:
(silicate of cobalt and nickel carries out same reduction reaction)
Slag depletion in nickel is smelted, press sulfur content: the amount of slag amount=3/1000 adds vulcanizing agent S, help the capture and the sedimentation of dispersive copper in the slag, nickel, cobalt metal, slag after the dilution (waste) contains heavy metal and is respectively 0.13%Cu, 0.055%Ni, 0.O11%Co, precious metal and platinum metals then 100% enter blister copper or high ice nickel, and it is minimum that the slag containing metal is dropped to.
Among the step C, the SO that smelting zone air (or oxygen enrichment) plasma desulfuration or dearsenification produce
2Gas or As
2O
3Gas enters the industrial microwave oven reactor with high-temperature furnace gas, and the high temperature carbon-coating in reactor under the katalysis of micro-wave energy, is realized following reduction reaction:
Element S after being reduced or As gas enter collector and deposit after lowering the temperature, and regularly emit, and realize that the tail gas of emptying does not contain the purpose of pollutent.It is just to be elementary sulfur (vapour) state and to exist entering the industrial microwave stokehold that sulphur in the furnace gas has part, this is because of air or the oxygen of squeezing in the molten bath in the oxygen enrichment plasma body exhausts (mating under the proper situation) in the molten bath, and the pyrite (FeS in the furnace charge that adds
2) S that goes out of the thermal dissociation result of anaerobic and its effect.
The technical process of one of prior art as shown in Figure 1;
Technical process of the present invention as shown in Figure 2.
Plasma body of the present invention--the micro-wave energy heating system as shown in Figure 3.
Wherein, 1 is plasma electrical source, and it anodal 2 is connected with the furnace bottom of plasma melting stove 5, and negative pole 3 is connected with plasma torch 4,6 for being located at the slag-drip opening on the plasma furnace, 7 is that metal (or high ice nickel) is emitted the insulation molten bath, which is provided with discharge outlet, and 8 is the slag depletion district, 10 are melting (blowing) district, separate with fire-resisting partition 9 between slag depletion district and the smelting zone, 11 is metal level, and 12 is matte or low matte layer, 13 is slag layer, 14 is the furnace gas funnel uptake, and 15 is microwave source, and 16 is resonator cavity, 17 are the microwave heating reactor, 18 is elementary sulfur or arsenic collector, and 19 is the cleaning of off-gas flue, and 20 is the exhaust emissions blower fan.
The present invention compared with prior art has following advantage:
(1) plasma heating
1. can under anticyclonic condition, obtain than big long continuous high temperature (8000-30000K) air-flow more than five times of chemical combustion heat;
2. the energy height of plasma arcs is concentrated and (can be focused on 1.1 * 10
7Watt/cm
2, be more than hundred times of common welding arc), more than the stream scooter supersonic speed of current-carrying gas, its heat transfer rate is big more than 10 times than the traditional heating method in the heatable substance process;
3. the plasma arcs torch can be adjusted its working parameter at any time according to the variation and the needs of production technique, helps realizing the technology purpose;
4. in chemical reaction process, reactant is under the high temperature of plasma heating, activated reactant molecule, make some be difficult under the Heating temperature of traditional heating method to realize or under this temperature irrealizable chemical reaction be achieved, in addition under the high temperature of plasma heating, self intensive stirring action and reactant under the high-temperature liquid state that causes by the plasma arcs torch, self molecular thermalmotion of product, strengthened the mass transfer velocity of chemical reaction greatly, thereby improved the chemical reaction velocity of heated reactant greatly, therefore, plasma heating shows as extra high production efficiency aborning;
5. the plasma electrical source output rating designs under the situation of correlation parameter operational coordination in proper and the production at plasma torch and heating correlation parameter, can be converted into heat effect in 100% ground.Therefore, wait the comprehensive energy consumption of daughter heating very low;
6. plasma heating does not have the pollution to product such as fuel combustion and consumption of electrode, and plasma arcs is the surface heating to material, material is promptly molten in heat following moment of plasma arcs, therefore, the plasma heating dust rate almost is zero, and exhaust gas volumn greatly reduces, and the thermosteresis of taking away because of flue gas also just significantly reduces like this, so help improving and control quality product and environment protection;
7. plasma heating is not owing to exist the frequent lifting problem of electrode, thereby is easy to realize and guarantee the sealing and the atmosphere control thereof of technology stove;
8. plasma heating, because the efficient height, production technique is simplified, and its attached auxiliary facility greatly reduces, and therefore, floor space is few, and the one-time investment of building equipment is little, and is easy to realize that production technique controls automatically.
(2) micro-wave energy adds
1. microwave has the selectivity heating to material, therefore is able to abundant application in industries such as mining and metallurgys;
2. micro-wave energy has the intensive katalysis to the chemical reaction of inhaling the ripple material;
3. the temperature rise of micro-wave energy heatable substance is very rapid, and the temperature rise speed of inhaling the ripple material can only make traditional heat transfer theory and HEAT TRANSFER LAW add at micro-wave energy and pine for not exclusively being suitable for the nanosecond time measurement;
4. micro-wave energy has certain penetration to heated material, is the direct heat release of molecule of inhaling the ripple material, therefore, heated material show as be heated very even;
5. any pollution of bringing to heated material because of no thermal source or exothermic material of micro-wave energy heatable substance, so the unusual cleaning of micro-wave energy heating;
6. comprehensive energy consumption is saved in the micro-wave energy heating;
7. micro-wave energy heating efficiency height (production with economy).
The present invention has greatly simplified the technological process of production in sum, has reduced comprehensive energy consumption, reduce process control condition, and it is minimum that slag metal-containing is reduced to, and greatly improves metal recovery rate, makes valuable resource be able to the economized utilization.
In addition, because earlier being converted into the sulphur in sulphide ores or the sulphur arsenic ore deposit or arsenic, the present invention is easy to evaporable high-temperature gas sulfurous gas (SO
2) or white arsenic (As
2O
3), introduce industrial microwave again and can be catalysed and reduced into elementary sulfur or arsenic recovery in the reactor.Therefore, not only simplify the structure of the industrial microwave oven of system sulphur, arsenic, and made full use of the oxidation heat liberation in sulphide ores, sulphur arsenic ore deposit, greatly saved the energy.Sulfurous gas be if reduction with carbon under routine heating must just begin reduction when temperature is 1100 ℃ in addition, and will could reduce complete in the following charcoal layer greater than 1300 ℃ in temperature.Just can be fully in the time of 700 ℃ and adopt micro-wave energy to add hotbed of carbon temperature with the sulfur dioxide gas reduction.Therefore, fundamentally solved SO
2Obnoxious flavour helps the conservation of nature ecotope to the problem of topsoil.
Table 1 is that the economic and technical norms of the high ice of produced in several ways nickel compare.
Embodiment 1
Handled copper ore concentrates main chemical compositions is:
Element Cu S Au Fe SiO
2CaO MgO
Composition % 25 12 200g/T 16.46 22 3.08 1.8
According to chemical ingredients and each chemical equation of above-mentioned raw materials, prepare burden flux (SiO by the calculation result with the practice correction of theory
2) the amount of allocating into carry out charge calculation by containing 10.31%CaO in the final waste.The furnace charge that adds the people smelting zone is only allocated the SiO of capacity into
2(white sand or in small, broken bits after silicon dioxide mine), after mixing drying (moisture is less than 4%) by the sealing feed hopper add the smelting zone charge bank continuously or discontinuously.Furnace charge is gone into the stokehold must perform relevant the preparation by metallurgical furnace blow-on rule, can formally start.Add other copper smelting by pyrometallurgy factory shrend waste before formally feeding intake earlier, start the plasma heating fusing, make liquid level rise to cinder notch, adjust the plasma torch pole span, its electric power output voltage is stabilized between the 50-80V can feed intake.It is the pressurized air current-carrying of 0.45-0.5MPa that plasma torch adopts gauge pressure, directly squeeze into the molten bath, pass slag blanket and enter matte (or low nickel matte) layer, be advisable and carry out plasma melting with not disturbance metal (or high ice nickel) layer, meanwhile stripping section is also devoted oneself to work, and adds CaCO
3Depletion agent and C reductive agent, plasma torch is with N
2Current-carrying, smelting zone temperature are 2000-2600 ℃.Along with the continuous desulfurization, fusing, the slag making that add furnace charge, result according to slag and the continuous sampling analysis of blister copper, the flow of unit of adjustment's time air plasma current-carrying gas and confession ore deposit magnitude relation, and adjust the depletion agent of stripping section adding and the relation of the reductive agent and the product quantity of slag, till obtaining optimal parameter.Blister copper, waste are emitted respectively.Slag depletion agent and reductive agent only add at stripping section.
Thermal source in the molten bath is from three aspects, and the one, the sulphide ores oxidation heat liberation; The 2nd, furnace charge slag making heat release; The 3rd, plasma heating.These three kinds of heats concentrate in the same molten bath, have greatly saved the energy.
High-temperature gas in the molten bath (about 1500 ℃) is introduced in the industrial microwave oven reactor by sealing insulation flue, under 600-800 ℃ of temperature, and the sulfurous gas (SO in the furnace gas
2) gas by in the reactor by micro-wave energy preheating and the warmed-up red-hot carbon layer of high-temperature furnace gas, under the micro-wave energy catalysis and the portion of energy of replenishing, be reduced into elementary sulfur fully, enter sulphur collector cooling deposition then.And furnace gas again after drip washing by the exhaust blower emptying.
Stove (cigarette) gas that the inventive method melting produces has following characteristics: A, furnace gas temperature height (1500 ℃); B, stove narrow-minded (only be traditional method 1/9); C contains mine dust hardly in the furnace gas, thereby the sulphur of industrial microwave oven reduction back output is of high grade; D goes in the furnace gas of industrial microwave stokehold to contain oligo-elements sulphur; E, SO in the furnace gas
2The concentration height is greater than 10%S.
Main economic and technical indices:
Element blister copper grade (%) waste containing metal (%) is smelted direct recovery rate (%)
Cu ＞98 ＜0.13 ＞98
Au 816g/T ＞99
S ＜0.1 ＞97
Copper nickel vulcanised ore concentrate main chemical compositions:
Element Ni Cu Fe S CaO MgO SiO
2
Composition (%) 5.06 2.36 31.23 21.05 1.58 12.4 12.43
Press the same quadrat method of embodiment 1, obtain following technico-economical comparison:
Element high ice nickel grade (%) waste containing metal (%) is smelted direct recovery rate (%)
Ni 52.87-58.25 0.055-0.013 98-99
Cu 18.20-23.73 0.13-0.11 84.77-96.51
Co 0.98-1.20 0.011-0.0098 ＞78
S 8-10 ＞96
Precious metal and platinum metals almost 100% enter high ice nickel.
Table 1 is produced high ice nickel method economic and technical norms relatively
* relevant producer is formally not open.
Claims (2)
1, a kind of copper, Ni sulphide mine pollution-free fire smelting method utilize the heating of thermal plasma and micro-wave energy to handle, and it is characterized in that finishing by following process steps:
A, moisture content behind the batching mixing directly adds the melting of plasma furnace smelting zone less than 4% raw material by seal silo, melt contact arc district, molten bath temperature is 2000-2600 ℃, it is pressurized air or the oxygen rich gas current-carrying of 0.45-0.5MPa that plasma torch adopts gauge pressure, one step was produced blister copper or high ice nickel, and the disposable waste that obtains;
B, in the plasma furnace smelting zone or the slag depletion district add CaCO
3Depletion agent and C reductive agent carry out dilution to slag, and plasma torch is with N
2Current-carrying, the disposable waste that obtains;
C, the SO that smelting zone air plasma oxidation sweetening or dearsenification produce
2Gas or As
2O
3Gas enters the industrial microwave oven reactor with high-temperature furnace gas, and microwave catalysis is reduced into elementary sulfur or arsenic under 600-800 ℃ of temperature, enters the collector sedimentation with tail gas again and reclaims free of contamination tail gas emptying.
2, method according to claim 1 is characterized in that plasma torch power supply output control voltage is the 50-80 volt.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98116475A CN1067113C (en) | 1998-08-08 | 1998-08-08 | Pollution-free fire smelting method for Cu-Ni sulphide mine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98116475A CN1067113C (en) | 1998-08-08 | 1998-08-08 | Pollution-free fire smelting method for Cu-Ni sulphide mine |
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| CN1211630A CN1211630A (en) | 1999-03-24 |
| CN1067113C true CN1067113C (en) | 2001-06-13 |
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| CN98116475A Expired - Fee Related CN1067113C (en) | 1998-08-08 | 1998-08-08 | Pollution-free fire smelting method for Cu-Ni sulphide mine |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FI116069B (en) * | 2002-06-11 | 2005-09-15 | Outokumpu Oy | Procedure for making raw cups |
| CN102735047A (en) * | 2012-07-19 | 2012-10-17 | 昆明理工大学 | Method and equipment for depleting furnace slag of electric melting furnace of side-blowing melting pool |
| CN105328115B (en) * | 2015-10-19 | 2017-09-01 | 戴伟平 | The renovation process of cast waste sand hot plasma |
| CN107604170A (en) * | 2017-08-25 | 2018-01-19 | 金川集团股份有限公司 | A kind of method of separation and concentration noble metal in potassium cloride slag from low nickel matte |
| CN111101001B (en) * | 2020-01-16 | 2023-06-16 | 中国恩菲工程技术有限公司 | One-step nickel smelting system and one-step nickel smelting method |
| CN114485147B (en) * | 2022-01-21 | 2024-04-30 | 河南和成无机新材料股份有限公司 | Fast ignition heating method for electric arc furnace |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1031256A (en) * | 1988-05-24 | 1989-02-22 | 昆明工学院 | Microwave desulfurization plasma smelting of nickel matte |
| CN1153221A (en) * | 1996-09-24 | 1997-07-02 | 徐有生 | Cobalt-bearing oxidized ore treatment by microwave-heat plasma |
-
1998
- 1998-08-08 CN CN98116475A patent/CN1067113C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1031256A (en) * | 1988-05-24 | 1989-02-22 | 昆明工学院 | Microwave desulfurization plasma smelting of nickel matte |
| CN1153221A (en) * | 1996-09-24 | 1997-07-02 | 徐有生 | Cobalt-bearing oxidized ore treatment by microwave-heat plasma |
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