CN1303235C - Dressing and smelting united technology for processing refractory copper zinc ore mixtures - Google Patents
Dressing and smelting united technology for processing refractory copper zinc ore mixtures Download PDFInfo
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- CN1303235C CN1303235C CNB2004100795363A CN200410079536A CN1303235C CN 1303235 C CN1303235 C CN 1303235C CN B2004100795363 A CNB2004100795363 A CN B2004100795363A CN 200410079536 A CN200410079536 A CN 200410079536A CN 1303235 C CN1303235 C CN 1303235C
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Abstract
The present invention relates to a process for processing hard selected Cu-Zn mixed ores in a selecting smelting combined flow path. The process firstly carries out Cu-Zn mixing selection to low grade Cu-Zn mixed sulfide ores, the obtained Cu-Zn mixed concentrate is naturally dried or partially dried by a drying kiln until water content is 7 to 12%, and then the mixed concentrate is sent into a fluidizing reactor for oxidizing roasting; furnace temperature is controlled between 930 and 1050 DEG C, products in the fluidizing reactor are roasted products which are moistened and uniformly mixed with coke, the mixture is sent back to a rotary kiln for being processed, and then the Cu and the Zn are separated; the temperature of a high temperature zone of the rotary kiln is controlled at 1100 to 1300 DEG C, and kiln end temperature is from 600 to 750 DEG C. On one hand, the process avoids zinc waste in the Cu-Zn mixed ore processing processes; on the other hand, the process finds a reasonable way for the Cu-Zn mixed ores. Ore selection process tend towards simple, the process simultaneously and greatly increases metal recovery rate, the selecting and smelting total yield of the two metals can both be increased by 15 to 20%, and the process solves the problem of resource comprehensive utilization of Cu-Zn mixed sulfide raw ores.
Description
Technical field the present invention relates to the dressing and smelting united technology for processing refractory copper zinc ore mixtures of the smelting technology of sulphide ores in the non-ferrous metal field, particularly a kind of novelty.
Background technology is along with the utilization of continually developing of Mineral resources, and the rich ore of single metal gradually reduces, and is obliged to go to handle many metal mixed ore deposit of various difficult choosings.
The large-scale copper zinc that geological prospecting in recent years and mining are found mixes the sulfuration mineral deposit, the cupric grade that wherein has up to 1～3%, contain zinc and reach about 10%, and be rich in gold and silver and a small amount of plumbous.But because the contained various mineral of ore are the xenomorphic-granular structure, copper, gold are composed and are stored in chalcopyrite, kustelite and the zink sulphide, and silver is composed and is stored in freibergite, copper glance and the lead glance, and various in addition mineral granularities are very thin, mutually parcel.Because of contained mineral embedding cloth is fine and closely woven, cause ore grinding and ore dressing difficulty in the copper zinc mixing sulfide ore, and ore dressing process can't effectively separate to the main metallic copper in the mixed ore with zinc, metal recovery rate is lower.
The traditional treatment method of copper zinc mixing sulphide ores is " protect copper lose zinc ", promptly pass through ore dressing after, the output copper ore concentrates, zinc then is present in the copper ore concentrates as impurity element.
Place's copper zinc vulcanizing mine of somewhere, Yunnan recent findings for example, its resource reserve surpasses 100,000 metal tons, and the average grade that this copper zinc mixes the sulfuration ore body is Cu:2.21%; Zn:9.0%; Pb:2.63%; Au:1.27g/t; Ag:157.35g/t.Because of ore institute cupric zinc grade is all very high, as still adopting the beneficiation method of " protect copper and lose zinc ", the contained zinc of mineral just can not get reclaiming.Therefore the initial stage once was devoted to the sorting of copper zinc, sorting beneficiation method typical test result such as table 1:
Table 1
| Element | Cu％ | Zn％ | Au(g/t) | Ag(g/t) |
| Head grade | 6.21 | 18.08 | 2.83 | 161.55 |
| The copper ore concentrates grade | 16.27 | 4.51 | 4.52 | 239 |
| Tailings grade | 0.46 | 1.09 | 1.22 | 47.29 |
| Metal recovery rate (%) | 66.34％ | 6.31％ | 40.28％ | 37.43％ |
Above beneficiation test has been selected copper in the ore body, ore that zinc content is the highest, but mineral processing index still non-constant.It is low that the copper ore concentrates that is obtained contains copper grade, and it is higher to contain zinc (impurity), and the concentration ratio of gold and silver is less than two times, and gold and silver all enter mine tailing in a large number.The rate of recovery of various metals is all very low, does not meanwhile obtain zinc ore concentrate.More than the sorting of test explanation copper zinc mixed ore is not succeeded.The relevant expert thinks that this Mine Cu zinc mixed ore does not have sophisticated industrial technique of preparing to utilize.
Because the screening test of copper zinc is not succeeded, when the industrialness beneficiation test, recovered to adopt traditional " protect copper and lose zinc " beneficiation method, test-results such as table 2:
Table 2
| Element | Cu％ | Zn％ | Au(g/t) | Ag(g/t) |
| Head grade | 2-3 | 3-5 | 1.5 | 50 |
| The copper ore concentrates grade | 15 | 12 | 1.5 | 150 |
| Metal recovery rate | 90％ | 0 | About 20% | 60％ |
Above mining processing industry test, lose zinc owing to protect copper, the recovery rate in ore-dressing of copper is improved, yet abandoned content in the raw ore is reached the zinc about 10%, the utilization of lead resource, caused very big waste, and copper ore concentrates master grade is not greatly improved, wherein contained 12% zinc is then as impurity element, when selling copper ore concentrates, need make button and live together reason, further influence benefit.
As mentioned above, more than two kinds of beneficiation methods all can not reach the copper in the comprehensive recovery copper zinc mixed ore and the purpose of zinc, therefore have to adopt copper zinc to mix the ore-dressing technique of choosing.Though the metal recovery rate of this ore-dressing technique can improve a lot, copper zinc can not separate in ore dressing process, and the grade of copper, zinc is all lower in the copper and zinc bulk concentrate that is obtained, and directly the difficulty of Ye Lianing is bigger, and the cost of smelting is also than higher.
The deficiency that summary of the invention exists at above-mentioned prior art, the present invention proposes a kind of dressing and smelting united technology for processing refractory copper zinc ore mixtures of novelty, this technology is being carried out on the basis of the mixed choosing of copper zinc copper zinc mixing sulfuration raw ore, method separating copper and zinc with pyrometallurgical smelting, avoided on the one hand in the copper zinc mixed ore treating processes for the waste of zinc resource, found rational outlet for copper and zinc bulk concentrate on the other hand, make ore dressing process be tending towards the simple while, improved metal recovery rate greatly, the smelting total yield that selects of two kinds of metals all can improve 15～20%, and has solved the comprehensive utilization of resources problem that copper zinc mixes the sulfuration raw ore preferably.
The dressing and smelting united processing refractory copper zinc ore mixtures novel process that the present invention proposes, its step is as follows:
At first low-grade copper zinc mixing sulfide ore is carried out copper zinc and mix choosing, the copper and zinc bulk concentrate that obtains is sloughed part moisture to moisture 7～12% through seasoning or drying kiln, advance fluidizing reactor oxidizing roasting, Control for Kiln Temperature is between 930 ℃～1050 ℃, the fluidizing furnace product be behind the calcining humidification with the coke uniform mixing, send rotary kiln back to and handle, enter that the compound of rotary kiln is moisture should to be controlled in 18%; Control the thermal zone temperature of rotary kiln at 1100～1300 ℃, kiln end temperature in the vaporization at high temperature process of rotary kiln, be controlled the rotary kiln negative pressure at 0～40Pa at 600～750 ℃.
Above-mentioned copper and zinc bulk concentrate is its Chemical Composition Cu:5～18% by mass percentage, Zn:15～35%, and S:＞22%, all the other are gangue content and trace element.
Above-mentioned the roasting ore deposit is added wet treatment is to spray into a certain amount of water equably toward calcining the inside, advances rotary kiln through the roasting ore deposit behind the humidification and 50% coke uniform mixing and carries out reduction volatilization, reaches copper, the isolating purpose of zinc.
Above-mentioned copper and zinc bulk concentrate at first enters fluidizing reactor and carries out oxidation sweetening.
Method provided by the invention is in separating copper, zinc process, ZnS in the copper and zinc bulk concentrate, CuS and blast the airborne oxygen reaction of fluidizing furnace, obtain the oxide compound and the sulfur dioxide gas of copper, zinc, the flue gas that contains sulfurous gas send sulfate system relieving haperacidity, and the main chemical reactions formula is as follows:
Along with the rotation of rotary kiln, different chemical reactions at high temperature takes place with reductive agent C and CO in the ZnO in the calcining, CuO.ZnO is reduced into gaseous state Zn by coke, and zinc fume enters dust collecting system with flue gas, and is oxidized to ZnO in this process, then is captured down in dust collecting system.CuO and the part metallic copper that is reduced out are non-volatile in this process, and they are stayed in the kiln slag with the compound that ferric oxide, silicon-dioxide etc. are combined into complexity, reach copper, the isolating purpose of zinc.The main chemical reactions formula is as follows:
By boiling roaster and rotary kiln evaporation, zinc is enriched in the flue dust, and flue dust contains the zinc grade can reach 50～70%, and the zinc concentration ratio reaches more than 2.3, and the rate of recovery of zinc can reach 90%; Copper is being turned round in the kiln slag from collection, and revolution kiln slag cupric grade can reach more than 15%, and the concentration ratio of copper reaches more than 1.5, and the rate of recovery of copper also can reach 90%.
The higher-grade oxide powder and zinc that is obtained is sent to zinc hydrometallurgy, and the revolution kiln slag of cupric about 15% then is all operable copper metallurgy raw materials of various copper smelting by pyrometallurgy methods.
Owing to adopt technology provided by the invention,, make copper, zinc recovery rate in ore-dressing all reach comparatively ideal numerical value simultaneously with regard to making the beneficiation flowsheet in dressing-works be easy to control.Select factory's output copper and zinc bulk concentrate industrial production example as shown in table 3 as certain.
Table 3
| Element | Cu％ | Zn％ | Au(g/t) | Ag(g/t) |
| Head grade | 2-3 | 10 | 1.5 | 50 |
| The copper and zinc bulk concentrate grade | 10 | 28 | 1.5 | 150 |
| Metal recovery rate | 90％ | 90％ | 30％ | 60％ |
As can be seen from the above table, owing to allow dressing-works output copper and zinc bulk concentrate, improved the rate of recovery of main metallic copper and zinc greatly, two kinds of metal recovery rates all reach 90%.Contrast during the single copper ore concentrates of this beneficiation flowsheet and output (protect copper lose zinc), the recovery rate in ore-dressing of copper metal all reaches 90%, but the recovery rate in ore-dressing of latter's zinc metal also reaches 90%, the former then with the zinc metal as impurity.
Adopt the present invention to handle copper and zinc bulk concentrate and obtained to supply next step to smelt the copper ore concentrates (revolution kiln slag) and the oxide powder and zinc of flow processing, the rate of recovery of copper and zinc all reaches more than 80%.Compare with original two kinds of beneficiation flowsheets, both reclaimed zinc, improved the rate of recovery of two kinds of metals again, metal recovery rate can improve 15～20%; And the grade of copper, zinc can be enriched to a higher level in the product, can directly be used as the raw material of copper, zinc smelting.
The present invention compared with prior art, the effect comparison of separating copper zinc sees Table 4.
Table 4
| Process selecting | Copper zinc sorting flow process | Protect copper and lose the zinc flow process | Combined process flow of the present invention |
| Output product and the rate of recovery | Single product, copper ore concentrates cupric 16.27%, the Cu rate of recovery 66.34%, copper ore concentrates contains zinc 4.51%, zinc recovery 0, Zn does not obtain zinc ore concentrate as impurity. | Single product, copper ore concentrates cupric 15%, the Cu rate of recovery 90%, copper ore concentrates contains zinc 12%, zinc recovery 0, zinc is as impurity. | Two kinds of products, copper ore concentrates (revolution kiln slag) cupric 15%, copper recovery: 90% * 90%=81%, higher-grade ZnO powder contains Zn65%, zinc recovery: 90% * 90%=81%. |
| The benefit contrast | Copper ore concentrates is because of containing zinc 4.51%, lived together reason by button during sale, the zinc loss abandons the Cu rate of recovery 66.34% in the ore. | Copper ore concentrates is because of containing Zn12%, lived together reason by button during sale, the zinc loss abandons the Cu rate of recovery 90% in the ore. | Realized that copper zinc separates, copper recovery 81% in the copper ore concentrates, and zinc recovery 81% in the oxide powder and zinc. |
Embodiment describes in further detail the present invention below in conjunction with embodiment.
Present embodiment is raw materials used to be to mix the copper and zinc bulk concentrate that choosing obtains with copper zinc mixing sulfide ore through copper zinc, and chemical ingredients (by mass percentage) is as follows: Zn:27.33%, Cu:5.15%, S:33.23%, Pb:2.46%, SiO
2: 2.06%, all the other are gangue content and trace element.Copper and zinc bulk concentrate is sloughed part moisture through seasoning or drying kiln, keeps advancing the material of fluidizing furnace moisture 7～12%.The fluidized bed roasting temperature is mainly looked concentrate and is contained Pb and SiO
2And decide, if contain Pb＞2.5% or SiO
2＞5%, the fluidized bed roasting temperature will be controlled low, prevents that these low-melting materials from forming caking in stove, makes the fluidizing furnace cisco unity malfunction, and furnace temperature generally is controlled between 930 ℃～1050 ℃.If above two kinds of substances content are lower, can suitably improve the boiling roaster temperature, this moment, the not only residual sulphur of calcining of output was low, and the granularity of particle output calcining when lower than temperature is big, all helps the production of subsequent handling rotary kiln.
950～970 ℃ of present embodiment control fluidized bed roasting temperature, the chemical ingredients of output calcining is as follows: Zn:31.08%, Cu:6.57%, S:1.58%; Boiling siege ability reaches 5.8 tons/meter
2Day.Metal recovery rate: zinc recovery 99%, copper recovery 98.8%.
In the fluidized bed roasting process, the granularity of the calcining that comes out from the fluidizing furnace overflow port is thicker, and it is generally thinner from the gather dust granularity of the roasting dirt that facility takes down of flue gas back warp, fly upward loss when reducing rotary kiln into, generally all will carry out pre-treatment before advancing rotary kiln, simple way is a humidification, promptly sprays into a certain amount of water equably toward the calcining the inside, fly upward loss when reducing blanking, advance that the kiln material is moisture to be controlled in 18%.Reducing the best bet that flies upward is to granulate, and needs to drop into the granulation facility.
Enter rotary kiln allocate 50% coke into through the calcining after the pre-treatment after, control rotary kiln temperature is at 600～750 ℃, the thermal zone temperature of rotary kiln this moment can reach 1100～1300 ℃, under this temperature, chemical reaction takes place in the stove, with the form volatilization of steam, in the Rotary Kiln back segment or the process of gathering dust, be oxidized to zinc oxide again after zinc oxide is reduced, promptly obtain high-grade oxide powder and zinc through dust collecting system again.Cupric oxide or the metallic copper that is reduced of part then with furnace charge in ferric oxide, silicon-dioxide etc. stay and discharge by kiln hood in the slag, so just realized separating of copper and zinc.
In the vaporization at high temperature process of rotary kiln, control the rotary kiln negative pressure at 0～40Pa, the partial roasting ore deposit directly enters dust collecting system with flue gas and causes the oxide powder and zinc cupric higher when preventing that negative pressure is excessive, and the rate of recovery of copper reduces.
The oxide powder and zinc of present embodiment output contains zinc＞65%, kiln slag cupric＞9.38%.Handle through fluidized bed roasting and revolution Rotary Kiln, smelt total yield: zinc recovery＞90%; Copper recovery＞90%.
Claims (4)
1, a kind of dressing and smelting united technology for processing refractory copper zinc ore mixtures, it is characterized in that: copper zinc mixing sulfide ore mixes choosing through copper zinc and obtains copper and zinc bulk concentrate, slough extremely moisture 7～12% concentrate of part moisture through seasoning or drying kiln, enter fluidizing furnace oxidizing roasting, the control furnace temperature is between 930 ℃～1050 ℃, the calcining of output through humidification and with the coke uniform mixing after, moisturely be controlled at 18% and enter rotary kiln with interior compound and make copper, zinc separates, control the thermal zone temperature of rotary kiln at 1100～1300 ℃, kiln end temperature is at 600～750 ℃, and kiln tail negative pressure is controlled at 0～40Pa.
2, dressing and smelting united technology for processing refractory copper zinc ore mixtures according to claim 1, it is characterized in that: obtain copper and zinc bulk concentrate through the mixed choosing of copper zinc and be Cu 5～18% by mass percentage, Zn 15～35%, S＞22%, and all the other are gangue content and trace element.
3, dressing and smelting united technology for processing refractory copper zinc ore mixtures according to claim 1, it is characterized in that: the calcining of fluidizing reactor output carries out reduction volatilization through entering rotary kiln afterwards with 50% coke uniform mixing behind the humidification, reaches copper, zinc separation.
4, dressing and smelting united technology for processing refractory copper zinc ore mixtures according to claim 1 is characterized in that: copper and zinc bulk concentrate at first enters fluidizing reactor and carries out oxidation sweetening.
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102021317B (en) * | 2010-12-16 | 2012-07-04 | 葫芦岛锌业股份有限公司 | Oxidizing roasting process by blending high fluorine chlorine zinc oxide complex material |
| PE20161083A1 (en) | 2014-01-31 | 2016-11-19 | Goldcorp Inc | PROCESS FOR THE SEPARATION OF AT LEAST ONE METAL SULFIDE FROM A MIXED SULFIDE ORE OR CONCENTRATE |
| CN107805721A (en) * | 2017-09-06 | 2018-03-16 | 昆明理工大学 | A kind of selecting smelting combination method of difficult copper zinc vulcanizing mine |
| CL2019003246A1 (en) * | 2019-11-13 | 2020-04-17 | Univ Concepcion | A process to produce metallic copper from copper concentrates without generating waste |
| CN112342404A (en) * | 2020-10-19 | 2021-02-09 | 云南云铜锌业股份有限公司 | Wet zinc smelting pretreatment method for high-impurity secondary roasted ore, zinc calcine and application |
| CN114182097B (en) * | 2021-12-08 | 2024-03-12 | 西安建筑科技大学 | Method for cooperatively recycling copper-zinc-containing oxide and zinc sulfide |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU954468A1 (en) * | 1980-12-24 | 1982-08-30 | Специальное конструкторское бюро тяжелых цветных металлов при Институте "Гинцветмет" | Method for oxygen-weighted cyclone and electrothermic processing of sulfide materials |
| SU1705383A1 (en) * | 1990-03-26 | 1992-01-15 | Всесоюзный научно-исследовательский горно-металлургический институт цветных металлов | Method of rotary kiln fuming of zinc and iron containing waste slags |
| CN1124297A (en) * | 1994-12-08 | 1996-06-12 | 景治熙 | Technique for producing metal by directly smelting sulphide ore |
| CN1275629A (en) * | 2000-04-21 | 2000-12-06 | 沈阳冶炼厂 | Method for treating high zinc infusible fine copper ore |
-
2004
- 2004-10-29 CN CNB2004100795363A patent/CN1303235C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU954468A1 (en) * | 1980-12-24 | 1982-08-30 | Специальное конструкторское бюро тяжелых цветных металлов при Институте "Гинцветмет" | Method for oxygen-weighted cyclone and electrothermic processing of sulfide materials |
| SU1705383A1 (en) * | 1990-03-26 | 1992-01-15 | Всесоюзный научно-исследовательский горно-металлургический институт цветных металлов | Method of rotary kiln fuming of zinc and iron containing waste slags |
| CN1124297A (en) * | 1994-12-08 | 1996-06-12 | 景治熙 | Technique for producing metal by directly smelting sulphide ore |
| CN1275629A (en) * | 2000-04-21 | 2000-12-06 | 沈阳冶炼厂 | Method for treating high zinc infusible fine copper ore |
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