Detection of Al, Mg, Ca, and Zn in copper slag by LIBS combined with calibration curve and PLSR methods

The precise measurement of Al, Mg, Ca, and Zn composition in copper slag is crucial for effective process control of copper pyrometallurgy. In this study, a remote laser-induced breakdown spectroscopy(LIBS) system was utilized for the spectral analysis of copper slag samples at a distance of 2.5 m. The composition of copper slag was then analyzed using both the calibration curve(CC) method and the partial least squares regression(PLSR) analysis method based on the characteristic spectral intensity ratio. The performance of the two analysis methods was gauged through the determination coefficient(R^(2)), average relative error(ARE), root mean square error of calibration(RMSEC), and root mean square error of prediction(RMSEP). The results demonstrate that the PLSR method significantly improved both R^(2) for the calibration and test sets while reducing ARE, RMSEC, and RMSEP by 50% compared to the CC method. The results suggest that the combination of LIBS and PLSR is a viable approach for effectively detecting the elemental concentration in copper slag and holds potential for online detection of the elemental composition of high-temperature molten copper slag.

Copper slag assisted coke reduction of phosphogypsum for sulphur dioxide preparation

The reduction of phosphogypsum(PG)to lime slag and SO_(2)using coke can effectively alleviate the environmental problems caused by PG.However,the PG decomposition temperature remains high and the product yield remains poor.By adding additives,the decomposition temperature can be further reduced and PG decomposition rate and product yield can be improved.However,the use of current additives such as Fe_(2)O_(3)and SiO_(2)brings the problem of increasing economic cost.Therefore,it is proposed to use solid waste copper slag(CS)as a new additive to reduce PG to prepare SO2,which can reduce the cost and meet the environmental benefits at the same time.The effects of proportion,temperature and thermostatic time on PG decomposition are investigated by experimental and kinetic analysis combined with FactSage thermodynamic calculations to optimize the roasting conditions.Finally,the reaction mechanism is proposed.It is found that adding CS to the coke and PG system can increase the rate of PG decomposition and SO_(2)yield while lowering the PG decomposition temperature.For example,when the CS/PG mass ratio increases from 0 to 1,PG decomposition rate increases from 83.38%to 99.35%,SO_(2)yield increases from 78.62%to 96.81%,and PG decomposition temperature decreases from 992.4℃to 949.6℃.The optimal reaction parameters are CS/PG mass ratio of 1,Coke/PG mass ratio of 0.06 at 1100℃for 20 min with 99.35%PG decomposition rate and 96.81%SO_(2) yield.The process proceeds according to the following reactions:2CaSO_(4)+ 0.7C + 0.8Fe_(2)SiO_(4)→0.8Ca_(2)SiO_(4)+ 0.2Ca_(2)Fe_(2)O_(5)+ 0.4Fe_(3)O_(4)+2SO_(2)+ 0.7CO_(2)Finally,a process for decomposing PG with coke and CS is proposed.

Properties of Sustainable High Strength Concrete with Waste Copper Slag

The present work investigates copper slag as a substitute for river sand in high-strength concrete.The concrete mixtures were manufactured with 10%,30%,50%,70%,and 100%of copper slag to evaluate the mechanical and durability properties.The experimental results indicate that replacing copper slag above 50%affects the performance characteristics of the concrete due to its high angularity and lower water absorption characteristics.The strength of concrete with 50%copper slag is improved by 5.6%,whereas the strength of concrete with 100%copper slag is reduced by 2.75%at 28 days.However,increased curing to 90days improves the strength of the former by 7.16%and reduces the latter by only 0.23%.The water absorption,porosity,and rapid chloride penetration of the concrete mixtures with 100%copper slag are increased by 10.44%,13.20%,and 19.56%compared to control concrete.Micro-structural investigations through SEM infer higher replacement of copper results in higher void formation due to its reduced water absorption.

Copper smelter slag treatment by ammonia solution:Leaching process optimization

The feasibility of copper smelter slag processing by ammonia solution treatment was investigated. The central composite rotatable design(CCRD) and approximation method were used to determine the optimum conditions of zinc and copper recovery to a solution. The experimental design was done at five levels of the four operating parameters which were the initial concentration of NH–3, the initial Cl ions concentration, leaching time and solid/liquid ratio. Two mathematical models describing dependence of metal recovery on the operating parameters were obtained. The models are successful in predicting the responses. It was found that optimal parameters for zinc and copper recovery are as follows(values for copper are given in brackets): initial CNH3 17.1%(19.9%), initial CCl– 160 g/L(160 g/L), leaching process duration 4.56 h(4.13 h), solid/liquid ratio 0.39(0.53). The maximum Zn and Cu recoveries to solution, obtained experimentally under the conditions, are 81.16% and 56.48%, respectively.

Recovery of copper from copper slag using a microbial fuel cell and characterization of its electrogenesis

The microbial fuel cell, which can convert the chemical energy of organic matter into electricity via the catalytic action of microorganisms, is a novel environmentally friendly technology for wastewater treatment and energy generation. The electrical energy generated by the microbial fuel cell can be used as an alternative to a traditional external power source required to extract copper via electrolytic treatment. A dual-chamber microbial fuel cell(DMFC) for the treatment of copper slag sulfuric acid leach liquor was constructed. The electrogenesis performance of the DMFC and its ability to extract copper from the copper slag leachate were investigated. The results demonstrated that the maximum voltage was 540 mV when the DMFC achieved steady-state operation. The removal rate of copper ions was greater than 80.0%, and the maximum value was 92.1%. Moreover, X-ray diffraction and scanning electron microscopy were used to characterize the cathodal products. The results showed that the product deposited onto the cathode was copper and that its morphology was similar to that of the electrolytic copper powder. The DMFC can generate electricity and recover copper from copper slag simultaneously.

Recovery of iron from copper slag by deep reduction and magnetic beneficiation

Aiming at recovering iron from high-iron-content copper slag, this article introduced a combination technol- ogy of deep reduction and magnetic beneficiation, investigated the iron recovery efficiency and optimized the technical conditions. When coke powder with 86wt% fixed carbon was used as a reductant, iron was successfully extracted from the copper slag. Under the optimized condition of the coke powder content of 14wt%, the calcium-to-silicon mass ratio （Ca/Si） of 0.2, the roasting temperature of 1300℃, the roasting time of 3 h, the grinding time of 20 min, and the magnetic field intensity of 61 kA-m-1, the iron recovery rate of the copper slag can reach 91.82%, and the extracted iron powder has an iron grade of 96.21%. With the characteristics of high iron grade and low impurity content, the extracted iron powder can be used as high-quality raw materials of weathering steel.

Preparation of Granulated Adsorption Material of Water-quenched Slag/rectorite Composite for Removal of Cu(Ⅱ)Ions from Copper Smelter Wastewater

The preparation of granulated adsorption material of water-quenched slag/rectorite composite and the treatment of Cu （ Ⅱ ）-containing copper smelter wastewater with the adsorption material were studied. The experimental results showed that under the conditions with the mass ratio of water-quenched slag to rectorite of 1：1, 10% additive of industrial starch （IS）, and 50% water, and a calcination temperature of 400 ℃, the granulated adsorption material prepared had a density of 1.06 kg/m^3, a porosity of 62.29%, water absorption rate of 58.82%, and compressive strength of 2.22 MPa. The efficiency of wastewater treatment was the best, whereas the rate of spallation loss was low. Under the conditions of natural pH, with the addition of the granulated adsorption material of 0.05 g/mL, a reaction time of 40 minutes, and temperature of 25 ℃, the efficiency of the granulated adsorption material for the removal of Cu （ Ⅱ ） ions from the copper smelter wastewater attained 98.2%, and the quality indexes of the wastewater after treatment conformed with the first level of integrated wastewater discharge standard （GB8978-1996）. The reclamation of the used granulated adsorption material was carried out by de-sorption of the Cu （ Ⅱ） ions from the surface with 1 mol/L sodium chloride solution. The de-sorption rate was 96.4%, and the adsorption material can be reused many times to treat copper smelter wastewater.

Smelting chlorination method applied to removal of copper from copper slags

In order to reasonably utilize the iron resources of copper slags, the smelting chlorination process was used to remove copper from copper slags. Higher holding temperature and O2 flow rate are beneficial to increasing copper removal rate. However,the Cu2O mode is formed by the reaction of surplus O2 and CuCl with O2 flow rate increasing over 0.4 L/min, causing CuCl volatilization rate and copper removal rate to decrease. The resulting copper removal rate of 84.34% is obtained under the optimum conditions of holding temperature of 1573 K, residence time of 10 min, Ca Cl2 addition amount of 0.1(mass ratio of CaCl2 and the copper slag) and oxygen flow rate of 0.4 L/min. The efficient removal of copper from copper slags through chlorination is feasible.

Hydrophobic-surface of copper from converter slag in the flotation system

The converter slag from a smeltery in Daye contains 2.01% copper.The floatability of copper has a significant influence on the flotation of converter slag.Flotation tests,contact angle tests and FTIR were conducted to assess the influences of pH and different flotation concentrators on its hydrophobic process,mechanism and flotation.The results show that since chemisorptions are formed on the surface,hydrophobicity of copper is highly enhanced by xanthate,butylamine dithiophosphate and Z-200.The hydrophobic-surface of copper becomes worse with low recovery in strong acid and alkali situation.When pH value is 10,butylamine dithiophosphate and butyl xanthate are used as the mixed-collector,the grade of copper is 40.01%and that of tailings is 0.37%.

Chemical looping gasification of sewage sludge using copper slag modified by NiO as an oxygen carrier

Chemical looping gasification(CLG) provides a novel approach to dispose the sewage sludge.In order to improve the reactivity of the calcined copper slag,NiO modification is considered as one of the good solutions.The copper slag calcined at 1100℃ doped with 20 wt% NiO(Ni20-CS) was used as an oxygen carrier(OC) in sludge CLG in the work.The modification of NiO can evidently enhance the reactivity of copper slag to promote the sludge conversion,especially for sludge char conversion.The carbon conversion and valid gas yield(V_(g)) increase from 67.02% and 0.23 m^(3)·kg^(-1) using the original OC to 78.34% and 0.29 m^(3)·kg^(-1) using the Ni20-CS OC, respectively.The increase of equivalent coefficient(Ω) facilitates the sludge conversion and a suitable Ω value is determined at 0.47 to obtain the highest valid gas yield(0.29 m^(3)·kg^(-1)).A suitable steam content is assigned at 27.22% to obtain the maximum carbon conversion of 87.09%,where an acceptable LHV of 12.63 MJ·m^(-3) and Vg of 0.39 m^(3)·kg^(-1)are obtained.Although the reactivity of Ni20-CS OC gradually decreases with the increase in cycle numbers because of the generation of NiFe_(2) O_(4-δ) species,the deposition of sludge ash containing many metallic elements is beneficial to the sludge conversion.As a result,the carbon conversion shows a slight uptrend with the increase of cycle numbers in sludge CLG.It indicates that the Ni20-CS sample is a good OC for sludge CLG.

Investigation on the Copper Content of Matte Smelting Slag in Peirce-Smith Converter

The copper contents and its existing forms in the slags during the slag-making stage of Peirce-Smith converters in Guixi Smelter, Jiangxi Province, China have been investigated. The investigation was based on plant trials with the corresponding thermodynamic calculations and kinetic considerations. From the plant data, the total copper content in the slags was in the range of 2% to 8% (mass fraction). The mechanical entrainment of matte drops has been found to be the main cause of the copper loss. The suspension index, defined as the ratio of the mass fraction of copper in suspended matte drops in the slag to that in bulk of the matte phase, has been adopted to quantify the matte entrainment. The values of this parameter estimated in this work have been found mainly within a range of 2.5%-8.0%. The Fe3O4 content in the slag has been estimated to be the most important factor, among others, influencing the separation of slag with matte and, consequently, the copper loss from the slag.

Effect of Vortex Stirring on the Dilution of Copper Slag

In order to solve the problem that the vulcanizing agent utilization rate is low and the dilution effect of copper slag is poor,the vortex stirring dilution method was used to improve the conditions of the dilution kinetics and copper recovery.The water model was used to simulate the effect of copper slag dilution.Under the premise of keeping the Reynolds number consistent,silicone oil and glass beads were used instead of copper slag and vulcanizing agent.Based on the relationship between voltage and concentration,the PC6D dual-channel particle concentration measuring instrument was used to study the stirring speed and the insertion depth of the stirring paddle in model experiments,and the suitable conditions were speed 250 rpm and insertion depth 70 mm.The fire dilution of copper slag was done under the conditions.After stirring and sedimentation,the Fe_(3)O_(4) in slag decreased from 22.58% to 4.65%,and the copper content of the slag decreased from 2.94% to 0.34%.The copper recovery was 88.44%.

Recovery of Copper and Cobalt from Converter Slag with a New Flotation Method Using H_(2）S

In this study,two different samples were obtained from Küre Copper factory.It was determined that the samples contain:the sample of K.C.F.(Küre Copper Factory),0.70%Cu and 0.5%Co.This sample was firstly grounded at-100 mesh dimension.Flotation was done according to previously obtained optimum flotation conditions.The flotation yield of Cu and Co in concentrate phase was found to be low by collective flotation.Even when the samples were grounded at-160 mesh,no change was observed in the flotation result.Especially,Co could not float under the flotation conditions of the non-sulfurized samples.There,a new flotation method was applied which was not applied until now.For this aim,the samples were firstly sulphurised under the steam of H2S+H2O.By this method,the amount of Cu and Co in the samples get rich.According to the obtained results,the optimum reactions for flotation and sulphurization were determined.In the first sulphurization conditions for the sample of K.C.F.,the yield of flotation for the Co and Co were found to be 98.27%and 68.07%,respectively.The results indicate that Cu can be floated at low yield in the original samples.On the other hand,Co cannot float under these conditions.

Thermodynamic Study on Process in Copper Converters(The slag-making stage)

The so-called Goto's model was modified by introducing a parameter of the oxygen efficiency from industrial trials, as well as the selected and newly re-assessed thermodynamic data. The application of the model to copper converters in Guixi Smelter has been carried out by the combination of thermodynamic calculations with the mass and heat balance using the plant data obtained in industrial trials for many heats. For the slag-making stage, good agreements have been reached betWeen the calculated and measured temperature, blowing time as well as the contents for main elements in the matte and the slag. Relativel}'' large deviations for contents of Zn and Pb in the slag may be caused by the complex chemical composition of the real molten slag, which ma}; result in a large difference of γzn. and γPb,adopted with their real values. It is noted that the model can simulate the slag-making stage of copper converting process in industrial Pierce-Smith converters well.

Effect of copper slag recovery on hydrometallurgical cut-off grades considering environmental aspects

Determining the hydrometallurgical cut-off grades specifies the destination of low grade materials and this is subjected to more benefits in mining. Copper production rate is considered as one of the fundamental issues in hydrometallurgical cut-off grades determination. Slags are remarked as one of the main sources of copper. It is not only regarded as a waste but also identified as another resource extracting base metals. Slags are characterized by copper high grade. Thus, slag copper recovery can be led to different cut-off grades and net present value(NPV). The current research scrutinizes the effect of slag recovery by both flotation and hydrometallurgical methods on the hydrometallurgical cut-off grades. For this purpose, the optimum cut-off grade algorithms of hydrometallurgical methods are developed by considering associated environmental parameters, incomes and also the costs. Then, their optimum amounts are calculated with NPV maximization as an objective function. The results indicate that considering slag copper recovery in the hydrometallurgical cut-off grade algorithms reduces the environmental costs caused by slag dumping and leads to more NPV by 9%.

Optimization of Roots and Copper Slag to Reinforce Soft Soil Using Response Surface Method

In this paper,roots and copper slag were used to overcome the weakness and reinforce the mechanical property of soft soil.The experiments were designed by the Response Surface Method(RSM),the content optimizing of the root permeated copper slag mixed soil for achieving appropriate values of shear strength and the final results evaluating were also conducted by RSM.Four independent variables including moisture content(12–21%by dry weight of the mixture),slag content(10–20%by dry weight of the mixture),roots content(0–1.1%by dry weight of the mixture),and aspect ratio of roots L/d(5–40)were studied and a generalized response model was built to predict the experimental results.The optimum contents of the four independent variables were suggested as 15.41%(moisture),16.30%(copper slag),and 0.82%(roots)with an aspect ratio of 28.14,respectively.It can be concluded from the verification experiments that the predicted values of the soil mechanical property are almost equal to the experimental values,which validate the response model.Moreover,a typical subgrade model was built for proving the practical advantages of using the above-mentioned mixture as subgrade fill.

铜渣贫化回收铜的研究现状及展望

铜是现代工业不可或缺的原材料,然而我国铜资源对外依存度高,是典型的“卡脖子”资源。铜主要通过火法冶炼铜精矿制得,冶炼过程渣量大、渣含铜量高达0.5%~5%,远高于我国铜矿的可采品位(0.2%)。因此,研究铜渣贫化回收铜的工艺对提升我国资源保障能力具有重要意义。基于铜/铜锍在渣中的赋存状态、铜损的主要形式,重点综述了现阶段铜渣贫化回收铜的工艺技术,包括火法贫化法、浮选法、湿法处理等,并对未来的研究重点进行了展望。目前,电炉贫化处理量大,技术成熟,但其通常使用煤炭等作为还原剂,由于其密度小于铜渣,反应时大多漂浮渣层表面并燃烧,反应不充分,也不利于大气环保。另外,工业上常使用金属铁棒还原炉底结瘤的磁铁矿,但其密度大于铜/铜锍,在渣液中沉降速度快,对渣层的还原不彻底。因此,开发环保、高效的还原剂逐渐成为火法电炉贫化研究的重点。浮选法是处理天然铜矿的常用手段,但铜渣存在硬度高、伴生关系复杂、粒度分布不均、微细粒多等浮选难点,同时铜渣高温浮选导致捕收剂失活的问题也亟待解决。在处理低品位铜渣时,湿法浸出是常用手段,但化学试剂和废液环保问题难以解决;生物浸出具有性质稳定、对环境无污染,且浸出后金属含量较低等优点,但其浸出周期长、效率低。根据目前贫化工艺的难点,对未来贫化工艺开发与优化进行了展望,如增加外场聚集四氧化三铁以改善铜/铜锍沉降环境、开发环保高效的火法贫化还原剂、探究还原剂对不同铜渣渣型的作用机制以及开发耐高温的铜渣浮选新药剂等。

超重力强化分离铜渣中铜的数值模拟及辅助工业设计

由于当前铜冶炼工艺产生的铜渣铜含量比较高,采用传统的电炉贫化技术分离铜液滴时间长、回收率低,因此引入超重力技术对贫化过程进行改善。采用数值模拟的方法,以卧式离心机为模型基础,选用转炉铜渣作为试验对象进行研究,借助COMSOL Multiphysics软件构建模型,模拟铜渣中铜液滴的沉降过程。根据计算结果分析重力系数(G)、温度(T)对不同粒径铜液滴沉降行为的影响。结果表明,在T=1300℃、G=1的条件下,粒径低于80μm的铜液滴无法自由沉降;在恒定温度下,重力系数以及铜液滴粒径的增加均有利于铜液滴在铜渣中的沉降;温度升高会降低铜渣和铜的黏度,促进二者分离。最后,根据铜液滴的沉降数据,对离心机半径、给料速度等工业参数提出优化建议,以提升铜的回收率,降低企业生产成本。

含铜污泥搭配发热危废协同处理及综合利用技术

本文介绍了富氧侧吹熔池熔炼炉协同处理含铜污泥和发热危废的技术,该工艺具有金属回收率高、熔炼强度大、一次能源消耗低,实现了含铜污泥的有价金属的综合回收和发热危废的无害化处理。生产实践表明:处理量10万吨/a含铜污泥和发热危废,可降低煤率约10%,节约成本770万/a,产出约4000t/a的多金属合金(其中含铜55%、含镍11.9%),为企业提质增效打开了的突破口。