CN1025963C - Extraction method for copper with bottom-blown molten pool and its installation - Google Patents

Extraction method for copper with bottom-blown molten pool and its installation Download PDF

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CN1025963C
CN1025963C CN 92106990 CN92106990A CN1025963C CN 1025963 C CN1025963 C CN 1025963C CN 92106990 CN92106990 CN 92106990 CN 92106990 A CN92106990 A CN 92106990A CN 1025963 C CN1025963 C CN 1025963C
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oxygen
copper
smelting
reactor
arsenic
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CN1072962A (en
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陈汉荣
贺善持
林廷芳
蒋继穆
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BEIJING NONFERROUS METALLURG D
SHUIKOUSHAN MINE ADMINISTRATION
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BEIJING NONFERROUS METALLURG D
SHUIKOUSHAN MINE ADMINISTRATION
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Abstract

The present invention relates to a new method for smelting copper in a molten pool. A rotary horizontal cylindrical reactor is used. The present invention is characterized in that materials containing copper or arsenic copper and arsenic gold or silver are mixed with fusing agents, coal powder and return dust to be granulated, and then granules are autogenously smelted in a reactor whose bottom is matched with a jet oxygen-enriched lance to produce sulphide and slag and realize the separation of the slag from the sulphide; generated flue gas containing sulfur dioxide and arsenic trioxide is made into acid after being purified; smelting slag is discarded after electrothermic impoverishment or is used as an ironmaking raw material after ore dressing impoverishment; copper sulphide is blown by a P-S converter to generate blister copper. The present invention has the advantages of low energy consumption, long service life of a furnace, high concentration of flue gas SO2, high adaptability to raw materials, high recovery ratio and easy implementation.

Description

Extraction method for copper with bottom-blown molten pool and its installation
The present invention relates to the bath smelting copper-smelting method.
Flash smelting and bath smelting are the copper smelting by pyrometallurgy novel methods of current two big class broad research and application, because the raw material of smelting bath smelting process need not depth drying, study more active, be used for industrial novel process Noranda process has been arranged, Wa Niukefufa (vertical copper water jacket stove), Mitsubishi process (fixed stove), silver method (reverberatory furnace) or the like.The major equipment of Noranda process is a barrel type reactor (Fig. 6) that exactly likes pierce smith converter, establish an air draft eye [30] along one side of cylinder, air or oxygen-rich air blast matte layer [34] from the eye of wind, the reactor molten bath is by slag blanket [35], matte layer [34], blister copper layer [37] is formed, blister copper settling pit near the reactor middle part is divided into blowing district, molten bath and negative area with reactor, granulation wet concentrate and flux are thrown the slag surface with pneumatic spray gun continuously from charge cavity [40], slag is discharged continuously from slag notch [33], blister copper is interrupted from copper outlet [36] emits, flue gas is discharged from the fire door [31] of settling pit top, the burner at reactor two ends [32] and [39] gas-firing or oil plant, (metallurgical industry press publishes: " external metallurgy of copper collected works " to replenish the necessary heat of melting, 1973, P159-166; " copper extracts metallurgical ", 1980, P178, P182-186).Noranda process is compared with the reflection oven process, and advantage is melting and blows and carry out continuously that fuel consumption reduces in same reactor; But output contains SO 2The flue gas of 8-15%, suitable relieving haperacidity.But also there is obvious weak point in this method, it adopts the single face side-blown, gas-liquid mixed is irregular, there is the melting dead angle, the single face side-blown is again easily to refractory materials in the stove, particularly partly produce the serious infringement of washing away near the eye of wind, reduce lining life, cause degree of enrichment to be difficult to improve (only can reach about 30%), the utilization ratio of oxygen also only about 96%, be difficult to realize natural melting, both caused slag cupric height (can reach 12%), the copper direct yield is low, causes the blister copper sulfur-bearing up to 1-2% again, need consume more air and long oxidization time when making the anode furnace refining, and flue gas SO 2The further raising of concentration also is restricted, and the relieving haperacidity cost is difficult to be reduced.The direct output blister copper of this method, it is tight that not only the control requirement is gone up in operation, and the existence of metallic copper, is easy to some impurity in the raw material, and for example As, Sb, Bi are dissolved in the metallic copper, undoubtedly obstruction are produced the anode copper that quality is fit to electrorefining.Therefore, this method only is fit to the low copper material of melting foreign matter content, is difficult to the foreign matter content height, particularly contains the melting of the high copper material of arsenic.The reactor used row's device mouth of this method near melting blowing district, must cause the dust rate height near the middle part, and mechanical dirt rate (by returning dirt) reaches about 3% in the industrial production.
The objective of the invention is in order to provide a kind of and Wa Niukefufa, Mitsubishi process and silver method to finish differently, overcome the new bath smelting copper-smelting method of above-mentioned Noranda process weak point again.It can realize pyritic smelting, and energy consumption is low, and the stove longevity is long, the slag cupric is low, sulfur dioxide in flue gas concentration height, processing parameter are easy to control, and be wide to adaptability to raw material, it is low both can to handle foreign matter content, can handle the foreign matter content height again, particularly contain the high copper material of arsenic, but both Treatment of Copper be low, the copper material that but Treatment of Copper is high again, and bottom blowing molten bath copper-smelting method and the device thereof high to recovery of gold and silver in the material.
For achieving the above object, copper-smelting method of the present invention adopts the bottom blowing bath smelting, it is with copper-contained material, or contain the arsenical copper material, or in above-mentioned two kinds of materials one or both and contain arsenic gold and silver material and flux, coal dust, after returning the mixed granulation of dirt, in being furnished with the reactor of jet oxygen enriching lance, the bottom carries out pyritic smelting, finish and make the sulfonium slag making, and realizing that the slag sulfonium separates, the output content of sulfur dioxide is high, or contains the flue gas of gaseous state white arsenic simultaneously, relieving haperacidity after purifying, smelting slag or after the electric heating dilution, abandon, or after the ore dressing dilution, make iron-smelting raw material, copper matte regulus is bessemerized the output blister copper through P-S.
The device that the present invention adopts is that its reactor of improved Shuiko mountain method of smelt lead device (CN85105034A) is can be along the horizontal barrel type reactor of central shaft rotation, inner lining refractory, top is provided with charging opening, flue gas discharge opening, and the bottom is provided with oxygen rifle hole, siphon port one end of inserting the spray oxygen-blowing gun and is provided with overflow cinder spout.But the present invention is located at siphon port, overflow cinder spout and flue gas discharge opening the bellend away from oxygen rifle district (front end) of reactor, copper matte regulus and smelting slag following current are flowed, and the bellend diameter suitably amplified, make the length-to-diameter ratio of bellend littler by 0.2~0.4 than oxygen rifle district length-to-diameter ratio.The setting of bellend has improved the melt situation of smelting furnace, has improved the technico-economical comparison of melting, promotes separating of copper matte regulus and slag, reduces the slag cupric.The reactor that has overcome Shuiko mountain method of smelt lead is located at oxygen rifle district with flue gas discharge opening and siphon port, overflow cinder spout is located at the rear end, cause the big defective of mechanical dust quantity in the flue gas, make the metallurgical reaction kinetics and the thermodynamic(al)equilibrium of bottom blowing bath smelting more reasonable, created condition for realizing pyritic smelting.The present invention also adopts bitubular tubular type or single hose jet oxygen enriching lance winding-up oxygen-rich air.The pipe core outer wall of the logical industrial oxygen of bitubular tubular type is a gear shape, and circumferential weld passes to air conservation oxygen rifle, than the logical nitrogen save energy of Shuiko mountain method of smelt lead, has improved the degree of enrichment of going into furnace gases again, helps pyritic smelting.The present invention is used for handling when containing the arsenical copper material, flue gas removes after the routine that waste heat boiler and thermoelectric dust-precipitator are isolated solid-state flue dust and heavy metal flue dust purifies, also need through pervaporation quench tower and cold dust precipitator, gaseous state white arsenic in the flue gas is reclaimed with thick white arsenic form, and the flue gas that reaches the relieving haperacidity standard send acid making system relieving haperacidity.
Fig. 1 is a process flow sheet of the present invention.
Fig. 2 is a reactor of the present invention longitudinal section synoptic diagram.
Fig. 3 is a single hose jet oxygen enriching lance longitudinal diagram of the present invention.
Fig. 4 is a bitubular tubular type jet oxygen enriching lance longitudinal diagram of the present invention.
Fig. 5 is an evaporation quench tower front view of the present invention.
Fig. 6 is the reactor longitudinal section synoptic diagram of Noranda process.
Technical process of the present invention is: cupric (or also containing the arsenic gold and silver) concentrate, flux, coal dust (about 3%) and the particle diameter b that returns the moisture 8-10% that the furnace charge a of dirt after mixed make through nodulizer [2] add continuously from the charging opening [8] on reactor [1] top that (charging opening is provided with two in the reactor; one is standby), oxygen-rich air is blown into the molten bath continuously by four jet oxygen enriching lances in four oxygen rifle holes [13] of insertion reaction device bottom and carries out pyritic smelting.Matte d emits from siphon port [12], send P-S to bessemerize into blister copper, and blister copper is electrolysis after refining, and the output electrolytic copper and the anode sludge reclaim gold and silver from the anode sludge.Smelting slag c emits continuously from overflow cinder spout [11], or discards after the electrothermal front bed dilution, and the matte of electrothermal front bed output is incorporated among the matte d of reactor output and handled; Or after slow cooling, carry out ore grinding-flotation, and the output copper ore concentrates returns the Preblend system PBS batching, and flotation tailings can be used as iron-smelting raw material, and is also discardable.The high flue gas of sulfurous gas that contains of output is discharged by flue gas discharge opening [10], reclaims used heat through waste heat boiler (3), and thermoelectric dust-precipitator (4) send acid making system relieving haperacidity after isolating solid-state flue dust (mechanical dirt) and heavy metal dirt.If when handling arsenic-containing material, the flue gas that thermoelectric dust-precipitator is discharged also needs through evaporation quench tower (5) and cold dust precipitator (6) captures and output slightly in vain behind the arsenic, contain the flue gas that arsenic reaches the relieving haperacidity standard, delivers to acid making system relieving haperacidity again.Also be provided with nozzle opening (7) and (9) on the reactor, when blow-on, spray into oil fuel in reactor, melting batch after the working of a furnace is normal, promptly stops oil spout, and whole fusion process carries out under self-heat condition fully continuously.When the present invention uses bitubular tubular type jet oxygen enriching lance, the pipe core outer wall is left some grooves, become gear shape, industrial oxygen and air are that the oxygen inlet (16) and the lateral air intlet (17) of the pipe core of gear shape enters the oxygen rifle from outer wall respectively, under certain pressure, industrial oxygen is through pipe core, and air is jetted to reactor from the oxygen muzzle of oxygen rifle front end simultaneously through the circumferential weld of binocular tube.When using single hose jet oxygen enriching lance, after industrial oxygen and air entered the mixing section mixing of oxygen rifle from the air intlet (14) of the lateral oxygen inlet in rear end (15) and rear end respectively, the oxygen muzzle from front end under certain pressure was jetted to reactor.When changing the oxygen rifle, only need the rotational response device, make the oxygen muzzle exceed the top of the slag in molten bath, promptly replaceable, extremely convenient.
Evaporation quench tower of the present invention is straight tubular void tower, the top is provided with smoke inlet (19) and nozzle (18), water atomizes rapidly from nozzle high pressure ejection back, atomized water and flue gas coflow, and evaporation rapidly, make the flue gas fast cooling arrive it more than dew point, do not make smoke condensation, only make the crystallization of gaseous state white arsenic, discharge from the lateral exhanst gas outlet of tower (20) then, enter cold dust precipitator and accept arsenic dirt, the thick white arsenic of output.Tower bottom is provided with the cleaning ash discharging hole.The water pressure that feeds nozzle must be enough to make the water of ejection to atomize fully, and atomized water can all be evaporated when flowing through quench tower, in order to avoid influence cold dust precipitator normal running.The major technique condition that realizes bottom blowing of the present invention molten bath pyritic smelting is: the oxygen material compares 180-230Nm 3/ t, bath temperature 1200-1250 ℃, industrial oxygen and air pressure are all 0.5-0.8MPa, feed the air of oxygen rifle and the ratio of oxygen (empty oxygen ratio) 0.5-1.0, go into the oxygen-rich concentration 40-70%O of furnace gases 2, thermoelectric dust-precipitator outlet (quench tower import) temperature 250-300 ℃, 120-140 ℃ of cold dust precipitator inlet temperature, 90-100 ℃ of cold dust precipitator temperature out.When smelting slag adopts the electric heating dilution, Fe/SiO 2Ratio is 0.8-1.0, when adopting the ore dressing dilution, and Fe/SiO 2Than being 1.6-2.0.
The technical qualification and the index of the embodiment of the invention see Table 1.
Shuikoushan copper smelting process of the present invention is a bottom blowing molten bath pyritic smelting copper-smelting method, and its advantage is: 1. adopt the round shape closed reactor, and compact construction, surface-area is little, helps saving heat energy; 2. adopt the bottom-blown smelting mode, slow down melt to the washing away of bricking, the stove longevity reached more than 300 days, and coefficient of oxygen utilization can improve the degree of enrichment of melting up to 100%, realizes pyritic smelting, and energy consumption is low, and the slag cupric is low, only 1-3%; 3. exhaust gas volumn is little, and sulfur dioxide in flue gas concentration height reaches more than 20%, and mechanical dirt rate is little, 1-1.5% only, and gas cleaning and sulfur dioxide recovery cost are low; 4. be furnished with the arsenic of catching device, can handle outside the copper material that contains arsenic 3-5%, arsenic-removing rate reaches more than 90%, and arsenic flue dust (thick white arsenic) grade can reach 95%As 2O 3, further purifying technique is simple, cost is low; 5. processing parameter is easy to control, is convenient to realize automatization control; 6. wide to adaptability to raw material, it is low both can to handle foreign matter content, can handle the foreign matter content height again, particularly contain the high copper material of arsenic, but both Treatment of Copper was low, but the copper material that Treatment of Copper is high again, be particularly conducive to and handle the material that contains gold and silver, can obtain the gold recovery more than 95%.
Reactor of the present invention also can be used for the smelting of heavy metals such as lead, nickel.Receipts arsenic device evaporation quench tower of the present invention and cold dust precipitator also can be used for the industrial sector that needs capture the gaseous state white arsenic in the flue dust, and both comprehensively reclaiming arsenic was protected environment again.
The technical qualification of the embodiment of the invention and index
Embodiment 1 embodiment 2 embodiment 3 embodiment 4
The copper ore concentrates copper ore concentrates
1, raw material contains arsenical copper concentrate copper ore concentrates
Gold sulphur concentrate gold ore
Composition: Cu% 9.41 21.19 25.00 5.71
As% 3.15 3.58 0.02 0.54
Fe% 27.10 24.95 21.50 20.33
S% 33.31 36.06 34.51 26.50
Au g/t 3.8 14.25
2, technical qualification
Oxygen-rich concentration %O 240 65 70 65.6
The oxygen material is than the m of N → 5. 3/ t 205 220 180 200
Bath temperature ℃ 1,220 1,200 1,230 1200
Slag type Fe/SiO 20.8 1.6 1.8 0.8
Thermoelectric dust-precipitator temperature out ℃ 260 280 250 250
Cold dust precipitator inlet temperature ℃ 120 130 120
Cold dust precipitator temperature out ℃ 90-100 90-100 90-100
3, technical indicator
Copper recovery % 97.04 98.16 98.5 96.56
Gold recovery % 95.29 98.646
Waste cupric % 0.4 0.33 0.35 0.36
Matte grade: Cu% 36.7 49.05 50 24.58
As% 0.18 0.20 0.07
Arsenic-removing rate % 90.57 92.00 80
The fire door flue gas contains SO 2% 22.50 26 27.10 25.10

Claims (9)

1, a kind of employing can rotating horizontal barrel type reactor the bath smelting copper-smelting method, it is characterized in that it is with copper-contained material, or contain the arsenical copper material, or in the above-mentioned material one or both and contain arsenic gold and silver material and flux, coal dust and the grain ore deposit of returning behind the dirt mixing granulation add in the reactor from the charging opening [8] of reactor [1] upper front end continuously, oxygen-rich air is blown into the molten bath continuously via the jet oxygen enriching lance of configuration in the reactor bottom oxygen rifle hole [13], carry out pyritic smelting, finish and make the sulfonium slag making, and in the separation of reactor bellend realization slag sulfonium, smelting slag is discharged continuously from the overflow cinder spout [11] of bellend end, this slag or after the electric heating dilution, abandon, or after the ore dressing dilution, make iron-smelting raw material, also discardable, copper matte regulus (matte) is emitted from the siphon port [12] of bellend, bessemerizes the output blister copper through P-S again, and oxygen-enriched bottom-blowing output content of sulfur dioxide is high, or the flue gas that contains the gaseous state white arsenic is simultaneously discharged relieving haperacidity after purifying from the flue gas discharge opening [10] on reactor bellend top.
2, bottom blowing according to claim 1 molten bath copper-smelting method, output contains sulfurous gas when it is characterized in that handling arsenic-containing material, the flue gas that contains the gaseous state white arsenic simultaneously, remove after the routine that waste heat boiler and thermoelectric dust-precipitator are isolated solid-state and heavy metal flue dust purifies, also need to make the crystallization of gaseous state white arsenic through the evaporation quench tower, and the thick white arsenic of cold dust precipitator capture output, send acid making system relieving haperacidity again.
3, bottom blowing according to claim 1 molten bath copper-smelting method is characterized in that the oxygen material than being 180-230Nm 3/ t, bath temperature are 1200-1250 ℃.
4, bottom blowing according to claim 1 molten bath copper-smelting method is characterized in that the oxygen and the air pressure that spray into the molten bath through reactor bottom jet oxygen enriching lance are all 0.5-0.8MPa, and empty oxygen is than being 0.5-1.0, and going into the furnace gases oxygen-rich concentration is 40-70%.
5, bottom blowing according to claim 1 molten bath copper-smelting method is characterized in that smelting slag or is Fe/SiO 2Than being the high white residue of 0.8-1.0, after the electrothermal front bed dilution, abandon, or be Fe/SiO 2Than being the high scum of 1.6-2.0, after slow cooling-ore grinding-flotation dilution as iron-smelting raw material.
6, according to claim 1 and 2 described bottom blowing molten bath copper-smelting methods, it is characterized in that thermoelectric dust-precipitator outlet (quench tower import) temperature is 250-300 ℃, cold dust precipitator inlet temperature is 120-140 ℃, temperature out is 90-100 ℃.
7, the reactor [1] of the described bottom blowing of claim 1 molten bath copper-smelting method, it is can be along the horizontal barrel type reactor of central shaft rotation, inside is lined with refractory materials, the bottom is provided with oxygen rifle hole [13] and the siphon port [12] of inserting the spray oxygen-blowing gun, top is provided with charging opening [8] and flue gas discharge opening [10], also be provided with excessive cinder notch [11], it is characterized in that siphon port, overflow cinder spout and flue gas discharge opening all are located at the bellend away from oxygen rifle district (front end), the length-to-diameter ratio of reactor bellend is than the little 0.2-0.4 of length-to-diameter ratio in oxygen rifle district (front end), the spray oxygen-blowing gun that inserts in the oxygen rifle hole is a gear shape for the pipe core outer wall, the bitubular tubular type jet oxygen enriching lance that industrial oxygen and air are not pre-mixed in the oxygen rifle, it is provided with industrial oxygen import [16] and air intlet [17], the central duct industrial oxygen, binocular tube circumferential weld blowing air.
8, the reactor of bottom blowing according to claim 7 molten bath copper-smelting method, it is characterized in that inserting spray oxygen-blowing gun in the oxygen rifle hole and also can be the single hose jet oxygen enriching lance that industrial oxygen and air are pre-mixed in the oxygen rifle, be respectively equipped with air intlet [14] and industrial oxygen import [15] on the mixing locular wall of oxygen gun back end.
Smoke eliminator during 9, according to claim 1 and 2 described bottom blowing molten bath copper-smelting methods processing arsenic-containing materials, it is provided with waste heat boiler, thermoelectric dust-precipitator, it is characterized in that it also is provided with the evaporation cold dust precipitator of quench tower [5] [6], the evaporation quench tower is straight tubular void tower, the top is provided with smoke inlet [19] and can makes the water high pressure ejection back nozzle [18] of atomizing rapidly, and lower side is provided with exhanst gas outlet [20], and the bottom also is provided with the cleaning ash discharging hole.
CN 92106990 1992-07-04 1992-07-04 Extraction method for copper with bottom-blown molten pool and its installation Expired - Lifetime CN1025963C (en)

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CN 92106990 CN1025963C (en) 1992-07-04 1992-07-04 Extraction method for copper with bottom-blown molten pool and its installation

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CN 92106990 CN1025963C (en) 1992-07-04 1992-07-04 Extraction method for copper with bottom-blown molten pool and its installation

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CN1025963C true CN1025963C (en) 1994-09-21

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CN102102152A (en) * 2009-12-17 2011-06-22 云南冶金集团股份有限公司 Method for smelting lead by reducing lead-rich slags
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CN103031447A (en) * 2011-09-30 2013-04-10 申殿邦 Horizontal type molten pool smelting process outside furnace and dedicated device thereof
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