CN1603433A - 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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- CN1603433A CN1603433A CN 200410079536 CN200410079536A CN1603433A CN 1603433 A CN1603433 A CN 1603433A CN 200410079536 CN200410079536 CN 200410079536 CN 200410079536 A CN200410079536 A CN 200410079536A CN 1603433 A CN1603433 A CN 1603433A
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Abstract
One kind elects to smell the union flow to process difficultly to choose the copper zinc mix ore craft, this craft first carries on the correspondence to the low-grade copper zinc mix curing ore to mix chooses, the copper zinc mix ore concentrate which obtains to be dry after the nature or takes off the partial moisture contents after the dry cellar to to contain water in 7~~12%, enters the ebullition calciner oxidizing roasting, the furnace temperature control between 930deg.C~~1050deg.C, after the ebullition furnace output thing namely bakes the granulated substance to humidify with the coke even mix, delivers rotation cellar processing, achieved separates copper and the zinc goal, the control rotation cellar high temperate zone temperature in 1100deg.C~~1300deg.C, the cellar tail temperature in 600deg.C~~750deg.C, The craft on the one hand has avoided to the copper zinc mix ore treating processes in to the zinc resources waste, on the other hand had found the reasonable outlet for the copper zinc mix ore concentrate, while enable the dressing process to tend to simple, greatly enhanced the metal returns-ratio, two kind of metals elect to smelt the total returns-ratio to be possible to enhance 15~~20%, and has solved the copper zinc mix curing undressed ore resources comprehensive utilization problem well.
Description
The invention relates to a smelting technology of sulfide ores in the field of nonferrous metals, in particular to a novel process for treating refractory copper-zinc mixed ores by a combined dressing and smelting process.
Background artas mineral resources are continuously developed and utilized, the amount of single-metal rich ores is gradually reduced, and various refractory multi-metal mixed ores have to be treated.
In large copper-zinc mixed sulfide ore deposits discovered in geological exploration and mining in recent years, the copper content is as high as 1-3%, the zinc content is about 10%, and the large copper-zinc mixed sulfide ore deposits are rich in gold, silver and a small amount of lead. However, because various minerals contained in the ore are in a special granular structure, copper and gold are generated in chalcopyrite, bullion and sphalerite, silver is generated in tennantite, chalcocite and galena, and the various minerals are fine in granularity and mutually wrapped. The mineral in the copper-zinc mixed sulfide ore is embedded densely, so that ore grinding and ore dressing are difficult, main metal copper and zinc in the mixed ore cannot be effectively separated in the ore dressing process, and the metal recovery rate is low.
The traditional treatment method of the copper-zinc mixed sulfide ore is 'copper conservation and zinc loss', namely, copper concentrate is produced after ore dressing, and zinc exists in the copper concentrate as an impurity element.
For example, a copper-zinc sulfide ore recently discovered somewhere in Yunnan has a resource reserve of more than 10 ten thousand metal tons, and the average grade of the copper-zinc mixed sulfide ore body is Cu: 2.21 percent; zn: 9.0 percent; pb: 2.63 percent; au: 1.27 g/t; ag: 157.35 g/t. Because the grade of copper and zinc contained in the ore is very high, if a beneficiation method of 'preserving copper and losing zinc' is still adopted, the zinc contained in the ore cannot be recovered. Therefore, copper-zinc separation was initially pursued, and typical test results of the separation beneficiation method are shown in table 1:
TABLE 1
| Element(s) | Cu％ | Zn％ | Au(g/t) | Ag(g/t) |
| Raw ore grade | 6.21 | 18.08 | 2.83 | 161.55 |
| Copper concentrate grade | 16.27 | 4.51 | 4.52 | 239 |
| Grade of tailings | 0.46 | 1.09 | 1.22 | 47.29 |
| Recovery of metals (%) | 66.34％ | 6.31％ | 40.28％ | 37.43％ |
The ore with the highest copper and zinc contents in the ore body is selected in the ore dressing test, but the ore dressing index is still very poor. The obtained copper concentrate has low copper-containing grade, high zinc (impurity) content, less than twice of the enrichment ratio of gold and silver, and a large amount of gold and silver enter tailings. The recovery of the various metals is very low and at the same time no zinc concentrate is obtained. The above experiments indicate that the separation of copper-zinc mixed ores is unsuccessful. The experts of the field consider that no mature industrial beneficiation technology is available for the copper-zinc mixed ore of the mine.
Because the copper-zinc separation test is unsuccessful, the traditional 'copper-preserving and zinc-losing' ore dressing method is adopted during the industrial ore dressing test, and the test results are shown in the table 2:
TABLE 2
| Element(s) | Cu％ | Zn％ | Au(g/t) | Ag(g/t) |
| Raw ore grade | 2--3 | 3--5 | 1.5 | 50 |
| Copper concentrate grade | 15 | 12 | 1.5 | 150 |
| Recovery of metals | 90％ | 0 | About 20 percent | 60％ |
In the above mineral processing industrial test, the recovery rate of copper mineral processing is improved due to the loss of zinc and copper by the retention of copper, but the utilization of zinc and lead resources with the content of about 10% in the raw ore is abandoned, which causes great waste, and the main grade of copper concentrate is not greatlyimproved, wherein the zinc with the content of 12% is used as an impurity element, and impurity removing treatment is needed when the copper concentrate is sold, which further affects the benefit.
As described above, neither of the two beneficiation methods can achieve the purpose of comprehensively recovering the copper wall and the iron wall and the zinc in the copper-zinc mixed ore, so that a beneficiation process of copper-zinc mixed beneficiation has to be adopted. Although the metal recovery rate of the beneficiation process can be greatly improved, copper and zinc cannot be separated in the beneficiation process, the grade of copper and zinc in the obtained copper-zinc bulk concentrate is low, the direct smelting difficulty is high, and the smelting cost is high.
The invention aims at the defects of the prior art, and provides a novel process for treating refractory copper-zinc mixed ore by a combined dressing and smelting process, which separates copper and zinc by a pyrometallurgical method on the basis of carrying out copper-zinc mixed dressing on copper-zinc mixed sulfide raw ore, so that on one hand, the waste of zinc resources in the treatment process of the copper-zinc mixed ore is avoided, on the other hand, a reasonable way is found for the copper-zinc mixed concentrate, the beneficiation process tends to be simple, the metal recovery rate is greatly improved, the total dressing and smelting recovery rate of two metals can be improved by 15-20%, and the problem of comprehensive utilization of the resources of the copper-zinc mixed sulfide raw ore is better solved.
The invention provides a new process for treating refractory copper-zinc mixed ore by a combined dressing and smelting process, which comprises the following steps:
firstly, carrying out copper-zinc mixed separation on low-grade copper-zinc mixed sulfide ores, naturally drying the obtained copper-zinc mixed concentrate or removing partial water in a drying kiln until the water content is 7-12%, carrying out oxidizing roasting in a fluidized bed roaster at the furnace temperature of 930-1050 ℃, uniformly mixing the fluidized bed roaster product, namely roasted sand, with coke after humidifying, sending the mixture back to a rotary kiln for treatment, and controlling the water content of the mixture entering the rotary kiln to be within 18%; the temperature of a high-temperature zone of the rotary kiln is controlled to be 1100-1300 ℃, the temperature of the kiln tail is controlled to be 600-750 ℃, and the negative pressure of the kiln tail of the rotary kiln is controlled to be 0-40 Pa in the high-temperature volatilization process of the rotary kiln.
The copper-zinc bulk concentrate comprises the following chemical components in percentage by mass: 5-18%, Zn: 15-35%, S: more than 22 percent, and the rest is gangue components and trace elements.
The above-mentioned humidification treatment of roasted ore is that a certain quantity of water is uniformly sprayed into the roasted ore, and the humidified roasted ore and 50% coke are uniformly mixed, and fed into rotary kiln to make reduction and volatilization so as to attain the goal of separating copper from zinc.
And (3) firstly, feeding the copper-zinc bulk concentrate into a fluidized bed roaster for oxidative desulfurization.
In the process of separating copper and zinc, ZnS and CuS in copper-zinc bulk concentrate react with oxygen in air blown into a fluidized bed furnace to obtain copper and zinc oxides and sulfur dioxide gas, and the flue gas containing sulfur dioxide is sent to a sulfuric acid system to prepare acid, wherein the main chemical reaction formula is as follows:
with the rotation of the rotary kiln, ZnO and CuO in the calcine and reducing agents C and CO are subjected to different chemical reactions at high temperature. ZnO is reduced into gaseous Zn by coke, zinc steam enters a dust collecting system along with flue gas, is oxidized into ZnO in the process, and is captured in the dust collecting system. In the process, CuO and part of reduced metallic copper are not volatilized, and the CuO and the part of reduced metallic copper are combined with iron oxide, silicon dioxide and the like to form complex compounds which are left in kiln slag, thereby achieving the purpose of separating copper and zinc. The main chemical reaction formula is as follows:
through the roasting in a fluidized bed furnace and the volatilization in a rotary kiln, zinc is enriched in the smoke dust, the zinc-containing grade of the smoke dust can reach 50-70%, the zinc enrichment ratio can reach more than 2.3, and the recovery rate of the zinc can reach 90%; copper is separated and collected in rotary kiln slag, the copper-containing grade of the rotary kiln slag can reach more than 15%, the copper enrichment ratio reaches more than 1.5, and the copper recovery rate can also reach 90%.
The obtained high-grade zinc oxide powder is sent to a wet-process zinc smelting method, and the rotary kiln slag containing about 15 percent of copper is a copper smelting raw material which can be used in various pyrometallurgical copper smelting methods.
The process provided by the invention can easily control the beneficiation flow of the beneficiation plant, and simultaneously, the copper and zinc beneficiation recovery rate can reach ideal values. An example of industrial production of copper-zinc bulk concentrates from a certain concentration plant is shown in table 3.
TABLE 3
| Element(s) | Cu％ | Zn％ | Au(g/t) | Ag(g/t) |
| Raw ore grade | 2-3 | 10 | 1.5 | 50 |
| Grade of copper-zinc bulk concentrate | 10 | 28 | 1.5 | 150 |
| Recovery of metals | 90％ | 90％ | 30％ | 60％ |
It can be seen from the above table that the recovery rates of the main metals copper and zinc are greatly improved as the ore dressing plant is allowed to produce the copper-zinc bulk concentrate, and the recovery rates of both metals reach 90%. Compared with the process of producing single copper concentrate (retaining copper and losing zinc), the beneficiation recovery rate of copper metal reaches 90%, but the beneficiation recovery rate of zinc metal reaches 90%, and the zinc metal is taken as an impurity in the former.
The method for treating the copper-zinc bulk concentrate obtains the copper concentrate (rotary kiln slag) and the zinc oxide powder which can be treated by the next smelting process, and the recovery rates of copper and zinc are both more than 80%. Compared with the two original ore dressing processes, the recovery rate of zinc and the recovery rate of two metals are improved, and the metal recovery rate can be improved by 15-20%; and the grades of copper and zinc in the product can be enriched to a higher level, and can be directly used as raw materials for copper and zinc smelting.
Compared with the prior art, the effect of separating copper and zinc is shown in Table 4.
TABLE 4
| Flow of Program for programming Selecting Selecting | Copper-zinc separation process | Copper-protecting and zinc-losing process | Combined process of the invention |
| Product produced by birth Go out Product produced by birth Article (A) And go back to Harvesting machine Rate of change | Single product Copper concentrate contains 16.27 percent of copper The Cu recovery rate is 66.34 percent The zinc content of the copper concentrate is 4.51 percent Zinc recovery rate 0 Zn as impurity Zinc concentrate is not obtained | Single product Copper concentrate contains 15 percent of copper The recovery rate of Cu is 90 percent The copper concentrate contains 12 percent of zinc Zinc recovery rate 0 Zinc as an impurity | Two products Copper concentrate (rotary kiln slag) contains 15 percent of copper And (3) copper recovery rate: 90%. times.90%. 81% The high-grade ZnO powder contains Zn 65% And (3) zinc recovery rate: 90%. times.90%. 81% |
| Effect of (1) Benefit to To pair Ratio of | The copper concentrate contains Zn4.51% The utility model is processed by the impurity-removing treatment when in sale, discarding loss of zinc in ore The Cu recovery rate is 66.34 percent | The copper concentrate contains 12 percent of zinc The utility model is processed by the impurity-removing treatment when in sale, discarding loss of zinc in ore The recovery rate of Cu is 90 percent | Realizes the separation of copper and zinc The recovery rate of copper in the copper concentrate is 81 percent The recovery rate of zinc in the zinc oxide powder is 81 percent |
The present invention will be described in further detail with reference to examples.
The raw material used in the example is copper zincThe copper-zinc bulk concentrate obtained by copper-zinc bulk separation of the mixed sulfide ore comprises the following chemical components (in percentage by mass): zn: 27.33%, Cu: 5.15%, S: 33.23%, Pb: 2.46% of SiO2: 2.06 percent, and the balance of gangue components and trace elements. And (3) removing partial water from the copper-zinc bulk concentrate through natural drying or a drying kiln, and keeping the water content of the material entering the fluidized bed furnace at 7-12%. The boiling roasting temperature mainly depends on the Pb and SiO contained in the concentrate2And if Pb is greater than 2.5% or SiO2The boiling roasting temperature is controlled to be lower than 5 percent, the substances with low melting points are prevented from forming agglomeration in the furnace, the boiling furnace can not work normally, and the furnace temperature is generally controlled between 930 ℃ and 1050 ℃. If the contents of the two substances are lower, the roasting temperature of the fluidized bed furnace can be properly increased, the produced roasted product has low residual sulfur, and the granularity of the produced roasted product is larger when the particle ratio is lower than the temperature, so that the production of the rotary kiln in the subsequent process is facilitated.
In the embodiment, the boiling roasting temperature is controlled to be 950-970 ℃, and the produced roasted product comprises the following chemical components: zn:31.08%, Cu: 6.57%, S: 1.58 percent; the capacity of the fluidized bed furnace reaches 5.8 tons/m2Day. And (3) metal recovery rate: the zinc recovery rate is 99 percent, and the copper recovery rate is 98.8 percent.
In the boiling roasting process, the granularity of the roasted sand coming out of an overflow port of the boiling furnace is coarse, the granularity of the roasted dust collected from flue gas by a dust collection facility is generally fine, and in order to reduce the flying loss in the rotary kiln, the roasted sand is generally pretreated before entering the rotary kiln, the simple method is humidification, namely a certain amount of water is uniformly sprayed into the roasted sand, the flying loss in the blanking process is reduced, and the water content of the kiln feeding material is controlled within 18 percent. The best way to reduce fly-over is granulation, which requires investment in granulation facilities.
Adding 50% of coke into the pretreated calcine, then feeding the calcine into a rotary kiln, controlling the temperature of the kiln tail of the rotary kiln to be 600-750 ℃, controlling the temperature of the high-temperature zone of the rotary kiln to be 1100-1300 ℃, carrying out chemical reaction in the kiln at the temperature, reducing the zinc oxide, volatilizing the reduced zinc oxide in the form of steam, oxidizing the reduced zinc oxide into zinc oxide at the rear section of the volatilization kiln or in the dust collection process, and then obtaining the high-grade zinc oxide powder through a dust collection system. The copper oxide or the partially reduced metallic copper and the iron oxide, silicon dioxide and the like in the furnace burden are remained in the slag and discharged from the kiln head, so that the separation of copper and zinc is realized.
In the high-temperature volatilization process of the rotary kiln, the negative pressure of the kiln tail of the rotary kiln is controlled to be 0-40 Pa, so that the situation that when the negative pressure is too large, part of roasted ore directly enters a dust collecting system along with flue gas, the copper content of zinc oxide powder is high, and the recovery rate of copper is reduced is prevented.
The zinc oxide powder produced by the embodiment contains more than 65% of zinc and the kiln slag contains more than 9.38% of copper. And (3) treating by a boiling roasting and rotary volatilizing kiln, wherein the total recovery rate of smelting is as follows: the recovery rate of zinc is more than 90 percent; the copper recovery rate is more than 90 percent.
Claims (4)
1. A process for treating refractory copper-zinc mixed ore by a dressing-smelting combined process is characterized by comprising the following steps: copper-zinc mixed sulfide ore is subjected to copper-zinc mixed separation to obtain copper-zinc mixed concentrate, part of water is removed through natural drying or a drying kiln to obtain concentrate containing 7-12% of water, the concentrate is put into a fluidized bed furnace for oxidizing roasting, the furnace temperature is controlled to be 930-1050 ℃, the produced roasted sand is humidified and uniformly mixed with coke, the mixture containing the water within 18% enters a rotary kiln to separate the copper and the zinc, the temperature of a high-temperature zone of the rotary kiln is controlled to be 1100-1300 ℃, the temperature of a kiln tail is controlled to be 600-750 ℃, and the negative pressure of the kiln tail is controlled to be 0-40 Pa.
2. The process for treating refractory copper-zinc mixed ore by the dressing-smelting combined flow according to claim 1, which is characterized in that: and (3) carrying out copper-zinc mixed separation to obtain copper-zinc mixed concentrate, wherein the copper-zinc mixed concentrate comprises 5-18% of Cu, 15-35% of Zn, more than 22% of S and the balance of gangue components and trace elements in percentage by mass.
3. The process for treating refractory copper-zinc mixed ore by the dressing-smelting combined flow according to claim 1, which is characterized in that: the calcine produced by the fluidized bed roaster is humidified and then uniformly mixed with 50% coke, and then enters the rotary kiln for reduction and volatilization, so that the separation of copper and zinc is achieved.
4. The process for treating refractory copper-zinc mixed ore by the dressing-smelting combined flow according to claim 1, which is characterized in that: the copper-zinc bulk concentrate firstly enters a fluidized bed roaster for oxidative desulfurization.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102021317A (en) * | 2010-12-16 | 2011-04-20 | 葫芦岛锌业股份有限公司 | Oxidizing roasting process by blending high fluorine chlorine zinc oxide complex material |
| US9885095B2 (en) | 2014-01-31 | 2018-02-06 | Goldcorp Inc. | Process for 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 |
| 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 |
| CN115066390A (en) * | 2019-11-13 | 2022-09-16 | 康塞普西翁大学 | Method for producing copper metal from copper concentrate without producing waste |
| 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 |
Family Cites Families (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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- 2004-10-29 CN CNB2004100795363A patent/CN1303235C/en not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102021317A (en) * | 2010-12-16 | 2011-04-20 | 葫芦岛锌业股份有限公司 | Oxidizing roasting process by blending high fluorine chlorine zinc oxide complex material |
| 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 |
| US9885095B2 (en) | 2014-01-31 | 2018-02-06 | Goldcorp Inc. | Process for separation of at least one metal sulfide from a mixed sulfide ore or concentrate |
| US10370739B2 (en) | 2014-01-31 | 2019-08-06 | Goldcorp, Inc. | Stabilization process for an arsenic solution |
| US11124857B2 (en) | 2014-01-31 | 2021-09-21 | Goldcorp Inc. | Process for separation of antimony and arsenic from a leach solution |
| 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 |
| CN115066390A (en) * | 2019-11-13 | 2022-09-16 | 康塞普西翁大学 | Method for producing copper metal from copper concentrate without producing waste |
| CN115066390B (en) * | 2019-11-13 | 2023-08-04 | 康塞普西翁大学 | Method for producing copper metal from copper concentrate without producing waste |
| EP4059884A4 (en) * | 2019-11-13 | 2023-12-27 | Universidad De Concepcion | Method for producing copper metal 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 |
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