Review of copper pyrometallurgical practice today and tomorrow
澳大利亚布朗斯炭质页岩铜镍钴矿工艺矿物学研究
澳大利亚布朗斯炭质页岩铜镍钴矿工艺矿物学研究闫朋;安鹏升;刘志超;潘宏伟;徐亮;赵光洲【摘要】Process mineralogy was conducted on a carbonaceous shale copper-cobalt-nickel ore from Browns area in Aus-tralia to confirm appropriate mineral processing technology to synthetically recover its valuable elements. The results show that:①It is a typical sedimentary type carbonaceous shale polymetallic ore,mineral composition is complex,main metal minerals are chalcopyrite,bornite,cobalt-nickel sulfide ore and so on. The valuable elements such as cobalt and nickel are isomorphous or mechanical inclusive in cobalt-nickel sulfide ore,pyrite and gangue minerals. Major gangue minerals are carbon,muscovite and halloysite.②Symbiotic relationship between different minerals are miscellaneous. It was also found widespread metasomatic tex-ture and disseminated structure,which results to good floatability of carbonaceous minerals easily enter to sulfide concentrates, meanwhile,parts of fine cobalt-nickel ores are encapsulated in chalcopyrite,thus they are easy to enter t o copper concentrate when floating.③Chalcopyrite and pyrite belongs to the category of fine grained dissemination,sulfur nickel and cobalt is fine-particles embedded category. Based on process mineralogy research results,technical route of stage grinding and stage separa-tion to recover copper,cobalt,nickel successively was recommended,the remaining tailings can as potassium fertilizer.%为了确定澳大利亚布朗斯地区炭质页岩铜钴镍矿资源合适的选矿工艺,对该地区有代表性矿样开展了工艺矿物学研究.结果表明:①矿石为典型的沉积型炭质页岩多金属矿,矿物组成复杂,主要金属矿物为黄铜矿、斑铜矿、硫钴镍矿等,矿石中钴、镍等有价元素以类质同象的形式或呈机械夹杂物分布于硫镍钴矿、黄铁矿及脉石矿物中,脉石矿物主要为炭质、白云母、多水高岭石等.②矿石中各矿物间共生关系复杂,普遍存在着交代结构和相互浸染构造,致使部分可浮性较好的炭质矿物易浮选进入硫化矿精矿中,同时部分微细粒硫钴镍矿被黄铜矿包裹,浮选时易进入铜精矿中.③矿石中黄铜矿和黄铁矿属中细粒嵌布范畴,硫镍钴矿属细粒—微粒嵌布范畴.根据矿石工艺矿物学特征,建议采用阶段磨矿—阶段选别的工艺依次回收铜、钴、镍、硫,尾矿可作为钾化肥.【期刊名称】《金属矿山》【年(卷),期】2017(000)004【总页数】5页(P91-95)【关键词】炭质页岩;铜钴镍矿;工艺矿物学【作者】闫朋;安鹏升;刘志超;潘宏伟;徐亮;赵光洲【作者单位】津出入境检验检疫局化矿金属材料检测中心,天津300457;津出入境检验检疫局化矿金属材料检测中心,天津300457;津出入境检验检疫局化矿金属材料检测中心,天津300457;津出入境检验检疫局化矿金属材料检测中心,天津300457;津出入境检验检疫局化矿金属材料检测中心,天津300457;津出入境检验检疫局化矿金属材料检测中心,天津300457【正文语种】中文【中图分类】TD912炭质页岩作为沉积岩中黏土岩类的一种[1]，含有大量分散的炭化有机质，并在成矿过程中受到风化和沉积作用[2]，使原矿的矿物种属、矿石结构构造趋于复杂化。
Recovery of Copper from Spent Solid Printed
Journal of Environmental Science and Management 15(1): 17-27 (June 2012)ISSN 0119-1144 Recovery of Copper from Spent Solid Printed-Circuit-Board (PCB) Wastes of a PCB Manufacturing Facility by Two-Step Sequential Acid Extraction and Electrochemical DepositionMonet Concepcion C. Maguyon1, Catalino G. Alfafara2, Veronica P. Migo3, Jovita L. Movillon4 and Carmelita M. Rebancos5ABSTRACTThe recovery of copper from solid printed circuit board (P CB) waste, by sequential acid dissolution and electrochemical deposition, was investigated as a resource recovery strategy for a local PCB-manufacturing facility.The ¿ rst stage acid dissolution process extracts the embedded copper metal from the solid PCB matrix in the form ofcopper ions, and the second-step electrolysis converts the copper ions back to its purer metal form. The copper metalcan then be processed for possible reuse, or sold for income generation. For the acid treatment, the best extractantwas found to be concentrated nitric acid added at a waste loading ratio of 120 mg PCB waste per mL of acid, and4 hr contact time. Six-hour electrochemical deposition experiments (of the acid extracts from the best dissolutionconditions) showed that a copper removal ef¿ ciency of 98% (from the acid extract) could be achieved. The chargedose of the electrochemical deposition process was computed to be 11.987 coulombs mg-1 of copper removed fromthe acid extract. From preliminary cost estimates, the reuse of the spent nitric acid from the acid treatment step isrecommended to minimize the total copper recovery cost.Key words: electrodeposition, printed circuit board, copper, semiconductor, electronicsINTRODUCTIONModern human productivity has become increasingly reliant on electronic equipment for enhancing productivity and for satisfying the hunger for information. The use of computers, mobile phones, e-book readers, and electronic analytical instruments has become an indispensable part of modern human society. The demand for electronic devices has driven technology to produce more of these devices. The pace of innovation has also gone so fast, that within a span of just a few short years, the devices become obsolete. This has lead to a signi¿ cant increase in the generation of electronic wastes coming from the manufacture and use of electronic products (Huang et al 2009; He et al 2006; Lee et al 2007; Bereketli et al 2011).One essential component in the production of electrical and electronic equipment (EEE) is the printed circuit board (PCB) (Zhou and Qiu 2010; Guo et al 2010). The printed circuit board (PC B) serves as a platform where electrical components (i.e. semiconductor chips and capacitors) are structured and electrically connected (LaDuo 2006). About $1 T sales from electronic products per year depends on PC B manufacture (LaDuo 2006). According to Guo et al (2010), the average rate of PC B manufacture increased to about 8.7% worldwide, 10.8% in Southeast Asia and 14.4% in China. In 2003, Japan manufactured about 29% of PCB worldwide followed by China (17%) and the United States (15%) (LaDuo 2006).The selection of materials for the manufacture of PCBs depends on the application (Hall and Williams 2007). Typically produced PCBs are made up of polymer ¿ lms (Hall and Williams 2007), glass, or ceramic substrates (LaDuo 2006). Fiberglass mat impregnated with a À ame-resistant epoxy resin is also used for selected commercial applications (Hall and Williams 2007; LaDuo 2006). PCBs also contain signi¿ cant amounts of metals (i.e. copper, iron, nickel, silver, gold, palladium). Copper, which is used to form the electrical circuit on the PCB, is the dominant metal species (Hall and Williams 2007; Zhou and Qiu 2010). Hence, wastes generated from PCB manufacture cannot be simply land¿ lled due to its hazardous nature and the valuable materials present in PCB waste. Toxic substances in PCB wastes (i.e. cadmium, mercury, lead, etc) should be treated prior to disposal. On the other hand, the valuable metals such as gold and copper should be recovered in order to prevent resource depletion.Traditional methods of recycling waste PCBs includes mechanical (i.e. multi-crushing, grinding, electrostatic separation, gravity-, density-based and magnetic separation) and hydrometallurgical methods (Duan et al, 2009;1 Assistant Professor, Department of Chemical Engineering, College of Engineering and Agro-Industrial Technology (CEAT), University of the Philippines Los Banos, College, Laguna 4031, Philippines E-mail: mcmaguyon0182@ (corresponding author)2 Associate Professor, Department of Chemical Engineering, CEAT, UPLB3 Research Associate Professor, National Institute of Molecular Biology and Biotechnology, UPLB4 Professor, Department of Chemical Engineering, CEAT, UPLB5 Professor, School of Environmental Science and Management, UPLBLi et al 2009; Eswaraiah et al 2008; Yoo et al 2009; Veit et al 2005). Hall and Williams(2007) determined the applicability of pyrolysis to convert the organic portion of PCB waste into liquid fuel. In their process, a wide variety of metals from the PCB remained in the char (residue) and further processing is required to recover each metal. Oishi et al (2007), on the other hand, employed a three-step process (leaching, solvent extraction and electrodeposition) to recover copper from scrap PCB from electronic equipments. These methods, however, are employed for PCBs from scrap electronics discarded by end-users. No or little information is available for treatment of wastes from the manufacture of PCBs particularly from the etching and lamination steps. Hence, this study was conceptualized.In this study, the technical feasibility of recovering copper from solid PCB waste sheets from the lamination step in the manufacturing process (Figure 1) was explored. The technical solution perceived to be useful in recovering copper from PC B waste was a combination of acid treatment followed by electrodeposition. Electrodeposition has an advantage over other conventional metal removal and recovery methods since in this process copper can be recovered in its metal form (Cu0). Some studies have proven the electrochemical method to be effective in removing metals from industrial wastewaters such as semiconductor wastewater (Aquino 2005) and gold smelting efÀ uent (Vivas 2007). However, since the PCB waste is in solid form, the copper and other metals present in the waste must be dissolved ¿ rst by acid treatment prior to electrodeposition. Initially, a screening experiment for the acid treatment of solid PCB waste was done by testing different combinations of acid types, waste loadi ng (expressed as mg PCB waste mL-1 acid) and soaking times using a 23 full factorial design. The concentration (in mg l-1) of copper in the acid extract after acid treatment was evaluated to determine the suitable acid for extraction as well as the effects of varying the operating conditions (i.e. waste loading and soaking time). Subsequently, a general factorial design with two factors (i.e. waste loading and soaking time) was done using the suitable acid for extraction to determine the optimum waste loading and soaking time combination. The electrodeposition process, on the other hand, was evaluated with respect to residual copper concentration of the electrolyte. The charge dose of the electrodeposition process was also calculated to determine operational and scale-up factors.MATERIALS AND METHODSPreparation and Elemental Analysis of Printed Circuit Board (PCB) WasteThe solid printed circuit board (PCB) waste used in the experiment was obtained from a local PCB manufacturing ¿rm. Solid PC B waste sheets were shredded into smaller chips, approximately 5 mm x 3 mm in size, before acid treatment to maximize the PCB-acid contact area. A sample of the PC B waste sheet is shown in Figure 1. Elemental analysis of the shredded solid PC B waste was done using X-Ray Fluorescence (XRF) spectroscopy and scanning electron microscopy. The residue obtained from the acid treatment step was analyzed for gold content using Energy Dispersive X-Ray (EDX) analysis.Preparation of Different Oxidizing Agents (Acids) for the Acid Treatment StepC oncentrated (65% wt) nitric acid and aqua regia (a 1:3 volume mixture of concentrated nitric acid and concentrated (36% wt) hydrochloric acid) were compared to determine the suitable acid for oxidation and dissolution of the copper metal embedded in the solid PCB waste.Acid TreatmentInitially, a screening experiment (23 full factorial design) was employed to select the suitable acid for copper extraction from PCB waste. Batch experiments were carried out in 1-L erlenmeyer Àasks using two different types of acids (HNO3and aqua regia). Fifteen and 75 g of shredded PCB waste were soaked in a constant volume of acid (500 mL) corresponding to waste load values of 30 and 150 mg PC B waste mL-1 acid, respectively. Samples of acid extracts were obtained after 1 hr and 24 hours contact time and subjected to copper analysis using atomic absorption spectrophotometry. Statistical analysis and cube plot were generated using Design Expert ® Version 8.0.6 to determine the suitable acid for copper extraction.Subsequently, a general factorial design with two (2) factors (i.e. waste load and contact time) was conducted using the best acid for extraction based on the screening experiment. Varying amounts (15, 30, 60 and 75 g) of PCB waste were18Recovery of Copper from Spent Solid PCB wastesFigure 1. Printed circuit board waste.Journal of Environmental Science and Management Vol. 15. No. 1 (June 2012)19soaked in a constant volume of acid (500 mL) corresponding to waste loads of 30, 60, 120 and 150 mg PCB waste mL-1 acid. Samples were taken at regular intervals during the acid treatment step for copper analysis. The copper concentration of the acid extract at different waste load values was plotted against time to determine the practical operating conditions for acid treatment.Copper ElectrodepositionBatch electrolysis set-up. The experimental set-up for the electrodeposition is presented in Figure 2. Electrolysis was conducted in a 500-mL beaker reactor with magnetic stirrer. Working volume was 400 mL. The operating current was supplied by a DC power source with a variable voltage ranging from 0 volt to 30 volts (Wheeler WSPS-817, Taiwan).In the electrolysis experiment, a stainless steel cathode and a sintered platinum anode were used as the electrode system. The dimensions of the electrodes were about 5 cm x 15 cm. A rubber spacer, approximately 5 mm thick, was placed in between the electrodes to prevent short circuiting. Copper electrodeposition experiments at different dilutions of acid extracts. The acid extract obtained from acid treatment of solid PCB waste using the best operating conditions was used as the electrolyte in the electrodeposition experiments at different dilutions. Electrodeposition of copper using the raw concentrated solution could not be done due to problems associated with severe acidic conditions which could potentially dissolve the metal electrodes and generation of large amounts of oxidants during electrolysis as a consequence of high concentration of chloride (Cl-) ions in the acid extracts. Thus, several dilution factors were tried to determine a practical dilution that would favor copper electrodeposition. Distilled water was used to dilute the raw concentrated acid extracts using dilution factors of 2, 3.5, 5 and 10. The resulting diluted solution served as the electrolyte or “plating bath” in the electrodeposition process operated at 3A for 6 hours. Samples were taken at regular intervals during electrolysis and tested for copper concentration using atomic absorption spectrophotometry. The result of the experiment was used to assess the practical dilution factor for copper electrodeposition.Copper electrodeposition experiments at different operating currents. The diluted acid extracts prepared using the optimized acid treatment conditions and dilution factor was electrolyzed at different operating currents (1A, 2A and 3A). Samples were taken at regular time intervals and analyzed for copper content using atomic absorption spectrophotometry. The results of the experiment were used to obtain useful engineering relationships for a scaled up process (i.e. charge dose).Data Analysis. Residual copper concentration during electrodeposition of acid extracts were plotted against time for dilution of 2, 3.5, 5 and 10. The trends from the time pro¿les were observed and evaluated. Also, the time for copper concentration to level off during electrodeposition was determined for each dilution. The maximum copper removal was also determined.Residual copper concentration time course for electrodeposition of diluted acid extract (using the optimum dilution factor) at different operating currents 1A, 2A and 3A were constructed to evaluate the effect of operating current on copper removal . Using the time course plot for currents 1A, 2A, and 3A, the time required for copper recovery to level-off was determined for each current. Secondary effects of electrolysis, which includes pH and temperature of the electrolyte were also monitored.Using the experimental data, the copper charge dose for electrodeposition of acid extracts (under optimum acid treatment conditions and dilution factor) was determined. The charge dose has been de¿ ned as the amount of electricity required to remove a target pollutant. It has been used as an empirically derived factor for scale-up and operation of electrolytic reactors (Alfafara et al 2003). C harge dose is de¿ ned as the amount of charge required to remove unit mass of pollutant with unit of coulombs (Alfafara et al 2002). It can be calculated using Equation (1).Figure 2. Copper electrodeposition experimental set-up.(1)where: Q = charge dose , C/mg pollutant removed I = electrical current, A t = time, sCo = initial concentration of pollutant, mg L -1 C = ¿ nal concentration of pollutant, mg L -1 V = volume of beaker, LThe copper charge dose was then used to calculate the energy requirement of the process using Equation (2):nickel (1.39% wt), and a non-metallic element, sulfur (0.74% wt). Aside from copper, there were some valuable metals in the waste including silver (Ag), nickel (Ni) and titanium (Ti). Metallic gold may possibly be also present in the waste since gold is used in the manufacturing process (Zhou and Qiu 2010). However, since the actual concentration of gold in the waste may not be within the XRF limits of detection, metallic gold may not have been detected. To con¿ rm the presence of gold in the waste, the scanning electron microscopy was used. The presence of metallic gold (Au) in the PCB waste was qualitatively con¿ rmed. The differences in the composition of PCB manufacturing waste and PCB from scrap electronic equipments were also revealed (Table 1). PC B manufacturing waste mainly consists of copper (96.62% wt) while the PCB from scrap electronics contains copper at a relatively lower percentage (26% wt and 47.68% wt). This may be attributed to the presence of other electronic components (i.e. resistors, capacitors) and solder (tin, lead) present in PCB from scrap electronics which may contain different metallic compositions. Also, electronic scraps consist largely of non-metallic components (65% wt) and consequently, relatively lower metallic components (35% wt) (Park and Fray 2009).From T able 1, several potentially hazardous components were also present in the PC B manufacturing20E is the voltage in volts and Q is the charge dose in Coulombs mg -1 copper.RESULTS AND DISCUSSIONAnalysis of Potential Pollutants in Solid Printed Circuit Board (PCB) WasteThe shredded solid printed circuit board (PC B) manufacturing waste was analyzed for elemental components using X-Ray Fluorescence (XRF) spectroscopy. There were 21 elements embedded in the waste (T able 1). Based on masspercentage, copper was found as the dominant metalspecies(96.62% wt), followed by another metallic element,(2)ElementPCB manufacturing waste aPCB from scrap electronicsOishi et al (2007)Hall and Williams (2007)Copper (Cu)96.622647.68Nickel (Ni) 1.39 1.5 2.09Sulfur (S)0.74------Cobalt (Co)0.610.0580.00Rubidium (Rb)0.38------Thorium (Th)0.06------Calcium (Ca)0.06--- 4.94Mercury (Hg)0.04---0.00Selenium (Se)0.02------Barium (Ba)0.02---0.12Tellurium (Te)0.01------Molybdenum (Mo)0.010.012---Antimony (Sb)0.010.160.00Cesium (Cs)0.01------Chromium (Cr)0.01---0.01Tin (Sn)4.34x10-3 4.9---Titanium (Ti) 3.79x10-3---0.00Palladium (Pd) 3.75x10-3---0.00Silver (Ag) 2.31x10-30.063 1.27Vanadium (V) 1.83x10-3------Scandium (Sc)8.67x10-4------Table 1. Elemental composition (%w/w) of PCB manufacturing waste and PCB from scrap electronics.Recovery of Copper from Spent Solid PCB wastesaExperimental datawaste. Although copper (the dominant species) is considered valuable due to its widespread applications in coinage, water pipes, roof coverings, pigments and dyes and cooking utensils, it can cause adverse health effects such as damage in a variety of organ systems and even death at high concentrations (Corradi 2011). Vapor or water-soluble salts of mercury is considered as an acutely hazardous element since it corrodes membranes of the body. Acute mercury poisoning can cause bleeding of gums, vomiting and stomach pain. It also causes irreversible damages to the brain, liver and kidney (Microsoft Encarta P remium 2006). Low-exposure to mercury can also negatively affect reproductive health (Wirth 2010). Chromium, on the other hand, is a carcinogenic metal in its hexavalent form.Copper was the most dominant metal (96.62% wt of total metals in PCB waste) among the 21 metals embedded in the printed circuit board waste and this paper focused on the extraction and recovery of copper from the solid PCB manufacturing waste.Copper Extraction by Acid TreatmentSelection of Acid Extractant and Extraction Conditions. Demir et al (2004) and Park and Fray (2009) suggest that nitric acid (HNO 3) and aqua regia, respectively, can be used to extract copper from PCB wastes. The use of aqua regia in the acid treatment step was also deemed advantageous for the extraction of gold from the waste. According to Park and Fray (2009), gold can be selectively extracted from the diluted acid (aqua regia) extracts using toluene. However, the extraction of gold from PCB waste was not covered in this paper.The reaction between HNO 3 and copper from PC B waste during acid treatment was characterized by the evolution of brown gas and green color of the resulting solution. Based on the known reaction between copper metal and nitric acid shown in Equation 3 (Park and Fray 2004), the brownish gas was most likely, nitrogen dioxide (NO 2).Initially, metallic copper could be oxidized by NO 3- ions from nitric acid to Cu 2+ ions accompanied with the evolution of brownish nitrogen dioxide (NO 2) gas. The copper ions produced may have subsequently reacted with chloride ions (Cl -) from hydrochloric acid to produce a greenish copper chloride (CuCl 2) liquid. An excess amount of chloride ions could then possibly react with CuCl 2 to produce a yellowish complex ion (CuCl 42-).A 23 full factorial screening experiment were used to compare HNO 3 and aqua regia based on the concentration of copper in the acid extracts. Higher concentration of copper in the acid extracts is more desirable since it means that more copper was stripped from the PCB waste. Consequently, more copper can be recovered from the PCB waste by electrodeposition of the acid extract. The cube plot for the screening experiment done to compare the two acids is illustrated in Figure 3. The cube plot shows that HNO 3 is more effective in extracting copper from the solid PCB matrix since higher copper concentrations were observed in the HNO 3 side (right face). One-hour acid treatment at 150 mg PCB waste mL -1 acid, for example, resulted to copper concentration of 65,078 mg l -1 for HNO 3 which is much higher than that obtained for aqua regia (19,868 mg l -1). An increase in waste loading (bottom to top face) increases the amount of copper extracted. For instance, copper concentration increased from 10,938 mg l -1 (30 mg PC B waste mL -1 acid) to 62,078 mg l -1 (150 mg PCB waste mL -1 acid) after 1 hour contact time using HNO 3. On the other hand, increasing the soaking time from 1 hour to 24 hours (front to back face) increases the amount of copper extracted from the waste. For example, the copper concentration increased from 19,868 mg l -1 (1 hour) to 48,460 mg l -1 (24 hours) for acid treatment at 150 mg PCB waste mL -1 acid using aqua regia, At Į=0.05, the ANOV A result indicates that the model is signi¿ cant at p-value of <0.0001. It alsoJournal of Environmental Science and Management Vol. 15. No. 1 (June 2012)21(3)The resulting greenish solution could be due to oxidation and dissolution of copper ions in nitric acid. It also indicates that copper ions in the acid extract were in its Cu 2+ form. On the other hand, the reaction between copper and aqua regia was characterized by the formation of a yellowish-green solution and evolution of brownish gas. Equations 4 to 6 show the mechanism for oxidation of copper (Cu 0) from solid PCB waste to Cu 2+ions using aqua regia.(6)(5)(4)Figure 3. Cube plot for the acid treatment of solid PCB wasteusing HNO 3 a nd a qua regia a t different wa ste loa dings (30 a nd 150 mg PCB wa ste mL -1 acid)and soaking times (1 and 24 hours).indicates that the three factors (i.e. acid type, waste loading and soaking time) as well as the 2-factor interactions signi¿ cantly affect the amount of copper extracted from the PCB waste.HNO3 was used in the acid treatment for the extractionof copper from the solid PC B waste since higher copper concentrations were obtained using HNO3.Effect of Acid Treatment Time and Waste Loading. The time pro¿ le for concentration of copper extracted from PCB waste in nitric acid (HNO3) at different waste loadings between 30 mg PCB mL-1 nitric acid to 150 mg PCB mL-1 nitric acid is plotted in Figure 4.At waste loadings of 30 and 60 mg PC B wastemL-1 HNO3, an initial increase in copper concentrationwas observed followed by a level-off at a certain copper concentration, after approximately 1-hr operation. A similar trend was observed for the waste loading of 120 mg PCBwaste mL-1 HNO3. However, the level-off period startedafter 4 hours treatment.Operating at 150 mg PC B waste mL-1 HNO3 wasteload, on the other hand, resulted to an initial rise in copper concentration until a peak copper concentration was reached after approximately 2-hr treatment. This was followed by an abrupt À uctuation until the copper concentration leveled off after approximately 8-hr operation. This À uctuation was observed only at the highest loading (150 mg PC Bwaste mL-1 HNO3). Repeat experimental runs also showedthe same À uctuation only at the highest loading. Complex interactions (which may be related to equilibrium shifts due to Cu2+ accumulation and reduction in the reaction system) were indicated by the observation at higher loadings; these may need further investigation.For practical purposes, the waste loading at 120 mgPC B waste mL-1 HNO3 at a soaking time of4 hours waschosen as a practical acid extraction condition, because the À uctuations in copper concentration at 150 mg PCB wastemL-1 HNO3 loading stabilized only after 8 hours. Operatingat lower waste load values of 30 and 60 mg PCB waste mL-1HNO3 would entail shorter treatment time (approximately 1hour). However, it would require large volumes of nitric acid to extract copper from PCB waste. Although the treatment time required for copper concentration to level-off at 120 mgPCB waste mL-1 HNO3 is longer (approximately4 hours) ascompared to lower waste load values (30 and 60 mg PCBwaste mL-1 HNO3), operating at a waste load of 120 mg PCBwaste mL-1 HNO3 would require lesser amount of acid toextract copper from the waste. Hence, waste loading of 120 mg mL-1 was chosen as the practical working waste loading (despite a higher copper extracted at 150 mg mL-1), and a reasonably high amount of copper was leached from the PCB wastes.Electrodeposition of CopperThe electrolytes used in the electrodeposition step were the acid extracts obtained using nitric acid added at 120 mg PCB waste mL-1 acid waste loading and 4 hours soaking time. The copper concentration of the raw concentrated acid extracts was found to be approximately equal to 51, 950 mg l-1. The acid extract was also found to be highly acidic having a pH value of 0.0. Based on Equation 3, copper is in its ionic form (C u2+) in the acid extracts obtained from the acid treatment step using HNO3as oxidizing agent. To recover copper from the electrolyte, ionic copper (C u2+) should therefore be reduced to metallic copper (Cu0) using the electrodeposition process.Effect of Dilution of Electrolyte. Electrodeposition using raw concentrated acid extracts from nitric acid treatment step as electrolyte was not tried since the solution was found to be still reactive (as evidenced by emission of brownish gas from the electrolyte container) and highly acidic (pH 0.0). A highly acidic solution could react with the metal electrodes used in electrodeposition. Hence, the electrodeposition process was tested for acid extracts diluted at dilution factors of 2, 3.5, 5 and 10, operated at a constant current of 3A for 6 hours. The result of the electrolysis time course is drawn in Figure 5. Dilution factors of 2, 3.5, 5 and 10 were referred in the graph (and this section) as DF 2, DF 3.5, DF 5 and DF 10, respectively.The horizontal plot for residual copper concentration at DF 2 indicates that there was no signi¿ cant copper deposition at the cathode. At DF 3.5, on the other hand, there was some decrease in residual copper concentration. However, the “level-off” concentration of copper in the acid extract is still relatively high (~13,000 mg l-1) after 6 hours of electrolysis. At comparatively low dilution values (DF 2 and DF 3.5), there was little or no deposition of copper at the cathode. This could be due to formation of chlorine-based oxidants during electrolysis (Alfafara et al 2003) and extremely acidic pH of the acid extract. C hlorine-based oxidants may have been formed from the naturally-occurring chloride ions in the acid solution. Both conditions promote a highly oxidative environment which could cause dissolution of the deposited metals back to Cu2+ ions. Further dilution at higher DF values (DF 5 and DF 10), could have possibly reduced the concentration of the chloride ions and the acidity of the electrolyte which made copper removal by electrodeposition feasible.Residual copper concentration decreased over time for DF 5 and DF 10 and leveled off at a certain copper concentration (Figure 5). The residual C u2+ concentration pro¿ les for DF 5 and DF 10 during the ¿ rst 135 minutes of22Recovery of Copper from Spent Solid PCB wastes23electrolysis were also observed to be parallel. The initial rates of copper removal (-dCu/dt, from 0 minutes to 135 minutes), for DF 5 and DF 10 were then calculated using linear regression, and these were found to be the same (about 32 mg Cu liter-minute -1). This could be further explained using Faraday’s Law of Electrolysis, as given by the following equation:The derivative shows that the rate of copper removal is a constant [dm/dt=(1/nF)]. Since the operating current for DF 5 and DF 10 were the same, then based on Faraday’s Law, the rate of copper removal (as indicated by the slope of the plots in Figure 5) should be the same. This similarity of slope was observed for the ¿ rst 135 minutes of electrolysis. However, beyond 135 minutes deviation from Faraday’sLaw was observed. The graphs tended to level off and were not anymore parallel. Furthermore, the level off time for DF 10 (270 minutes) was earlier than DF 5 (315 minutes)as shown in Figure 5. This can be attributed to dilutioneffects which include lower C u 2+concentration and lowerCl - ions concentration in the electrolyte. Shorter electrolysis time would be required to remove smaller amount of copper ions from the electrolyte. Whereas, the concentration of chlorine-based oxidants during electrolysis would be lowerFigure 4. Copper concentration time courses for acid treatment of solid PCB waste using nitric acid (HNO3) as copper-dissolving and oxidizing agent at different waste loadingsJournal of Environmental Science and Management Vol. 15. No. 1 (June 2012)(7)where m is moles of metal deposited on the cathode, I is current, t is time, n is the number of electrons in the redox equation and F is the Faraday’s constant.The derivative of Equation (7) gives the rate of copperremoved from the solution, and deposited at the cathode. Figure 4. Residual copper concentration time courses at different dilution factors and operating current of 3A.。
第15届国际普兰西会议上难熔金属独领风骚
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南非帕拉博鲁瓦超大型氧化铁型铜(金)矿床
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局部锈蚀圆钢管混凝土短柱轴压承载力试验研究
第 55 卷第 1 期2024 年 1 月中南大学学报(自然科学版)Journal of Central South University (Science and Technology)V ol.55 No.1Jan. 2024局部锈蚀圆钢管混凝土短柱轴压承载力试验研究陈梦成1, 2，罗苏昌1，黄宏1, 2，方苇1, 2，许开成1, 2，钱文磊1(1. 华东交通大学 省部共建轨道交通基础设施性能监测与保障国家重点实验室，江西 南昌，330013；2. 华东交通大学 土木工程建筑学院，江西 南昌，330013)摘要：钢管混凝土(CFST)在服役环境中被腐蚀，导致其钢结构承载力降低，严重威胁到结构的服役性能和使用寿命。
首先，采用机加工车铣方法制作模拟局部锈蚀的人工缺陷，然后以钢管外表面局部环向贯通锈蚀位置、锈蚀钢管体积损失率、锈蚀外表面面积损失率(简称锈蚀面积损失率，下同)为试验参数，对45根局部锈蚀圆CFST 短柱试件进行轴压承载力试验；其次，分析锈蚀位置、锈蚀钢管体积损失率、面积损失率和壁厚损失率对锈蚀试件承载力、刚度和延性的影响，揭示锈蚀CFST 试件破坏机理和承载力退化机制；最后，针对局部锈蚀圆CFST 短柱构件轴压承载力提出一个简化实用计算公式。
研究结果表明：各试件具有类似的破坏特征，主要呈明显的腰鼓状破坏，且发生在锈蚀区；随着锈蚀钢管体积损失率增大，锈蚀CFST 柱的承载力、刚度和延性均出现不同程度的降低；在锈蚀钢管体积损失率和面积损失率相同的情况下，就局部锈蚀位置影响而言，中部影响最大；就锈蚀程度表征参数影响而言，锈蚀钢管体积损失率影响最大，面积损失率次之，壁厚损失率最小；本文提出的简化实用公式可为圆钢管混凝土构件全寿命设计提供参考依据。
关键词：圆钢管混凝土短柱；局部锈蚀；轴压承载力；退化机制中图分类号：TU938.9 文献标志码：A 文章编号：1672-7207（2024）01-0317-13Experimental studies on axial compressive bearing capacity ofcircular CFST stub columns with localized corrosionCHEN Mengcheng 1, 2, LUO Suchang 1, HUANG Hong 1, 2, FANG Wei 1, 2, XU Kaicheng 1, 2, QIAN Wenlei 1(1. State Key Laboratory of Service-Performance Monitoring and Protecting for Rail Transit Infrastructures, EastChina Jiaotong University, Nanchang 330013, China;2. School of Civil Engineering and Architecture, East China Jiaotong University, Nanchang 330013, China)Abstract: During the service period, the load bearing capacity of concrete filled steel tubular(CFST) structures decreases over time under corrosive environment, seriously threatening the service performance and service life of the structures. Firstly, a turn milling machining method was used to manufacture an artificial defect to simulate a收稿日期： 2023 −02 −25； 修回日期： 2023 −04 −25基金项目(Foundation item)：国家自然科学基金资助项目(52278180，51878275) (Projects(52278180, 51878275) supported by theNational Natural Science Foundation of China)通信作者：陈梦成，博士，教授，从事钢混组合结构设计理论及其耐久性和安全性等研究；E-mail ：****************.cnDOI: 10.11817/j.issn.1672-7207.2024.01.026引用格式： 陈梦成, 罗苏昌, 黄宏, 等. 局部锈蚀圆钢管混凝土短柱轴压承载力试验研究[J]. 中南大学学报(自然科学版), 2024, 55(1): 317−329.Citation: CHEN Mengcheng, LUO Suchang, HUANG Hong, et al. Experimental studies on axial compressive bearing capacity of circular CFST stub columns with localized corrosion[J]. Journal of Central South University(Science and Technology), 2024, 55(1): 317−329.第 55 卷中南大学学报(自然科学版)localized through-circumferential corrosion on the outer surface of steel tube. After this, axial compression load bearing capacity experiments were conducted on 45 circular CFST stub columns with localized through-circumferential corrosion by varying the corrosion position, volume loss ratio and external surface area loss ratio (area loss ratio for short, similarly hereinafter) of corroded steel tube. Secondly, the effects of localized corrosion position, volume loss ratio, area loss ratio and wall-thickness loss ratio on the axial load bearing capacity, stiffness and ductility of locally corroded CFST stub column were discussed, and the failure and load bearing capacity degradation mechanisms of the corroded specimens were revealed. Finally, a simplified practical calculation formula was established for the axial bearing capacity of CFST stub columns with localized corrosion. The results show that the corroded specimens have similar responses. Obvious outward bulging failure is predominated and occurs in the corrosion region. With increasing corrosion volume loss ratio, the bearing capacity, stiffness and ductility of the specimen with localized corrosion decrease at different level. Given the same corrosion volume loss ratio and area loss ratio, as for the impact of localized corrosion position, the largest impact appears in the specimen with localized through-circumferential corrosion at its mid-part; as for the effect of corrosion level indexes, the largest impact is that of volume loss ratio, followed by that of area loss ratio, and the minimum impactis that of wall-thickness loss ratio. The proposed prediction model can provide a reference framework for the life-cycle design of CFST columns.Key words: circular CFST stub columns; localized corrosion; axial compression load bearing capacity; degradation mechanism钢管混凝土结构具有承载能力高、塑性和韧性好、施工方便、经济效益高等优点，多用于高层建筑、大跨度桥梁、海洋平台、锅炉塔架、电视台等土木工程结构中[1−4]。
Some thoughts on gold-rich porphyry copper deposits
At Bajo de La Alumbrera in the Faral16n Negro district, Catamarca province, northwest Argentina, an oval dacite porphyry stock of late Miocene age emplaced in comagmatic andesitic volcanic rocks representing an eroded stratovolcano has been shown to contain a copper-gold orebody. Although the mineralized stock is quartz-bearing, volcanic rocks in the Farall6n Negro district have been assigned to the shoshonitic suite (Dostal et al., 1977). Geological work (Sillitoe, 1973 unpub, rept. ; Gonz~lez, 1975) has revealed a near-perfect zonal arrangement of alteration-mineralization, with propy litic and sericitic-argillic zones disposed around a potassium silicate core, 900 x 600 m in surface dimensions (Fig. 2). Most of the ore, which assays 0.58 % Cu and 0.63 gm/tonAu, is confined to the potassium silicate facies, much of which lies within the stock. Potassium silicate alteration is characterized by biotite, quartz, anhydrite, magnetite and subordinate K-feldspar, but irregular patches, the largest 300 x 150 m in diameter, in the central part of the potassium silicate zone exhibit intensive veining and replacement by quartz and magnetite (commonly I0 vol. %), accompanied by lesser coarse-grained
秘鲁南部地区斑岩型铜矿成矿模式探讨
秘鲁南部地区斑岩型铜矿成矿模式探讨胡中岳;杨树暄;王家杰;安幼林;王欢【摘要】In a general way ,porphyry copper deposits exist not only alteration zoning ,but also mineralization types and li-thologiczoning .There are three layers in the vertical structure characteristics:The upper part is crackle breccia zone ,the central part is explosive breccia or concealed explosive breccia zone ,the lower part is porphyry zone .Their corresponding mineralization types also can be divided into three types basically:the upper part is stockwork ( net vein-vein) minerali-zation,the central part is the mineralized breccia form mineralization , the lower part is disseminated mineralization . Through the study of typical deposits ,the authors can establish a model of porphyry copper deposits .Originated from the upper mantle ,the magma is mixed and reacted with other hydrothermal fluid ( tectonic hydrothermal fluid , atmospheric precipitation ,etc.) in the proper place in the process of differentiation and rising ,and mineralized material is precipitated and mineralized corresponding to produce different types of deposits .Its spatial distribution of bottom-up is roughly:por-phyry molybdenum deposits-porphyry copper molybdenum deposits-porphyry copper deposits-porphyry copper gold depos-its+stockwork type copper gold deposits-breccia type copper gold deposits +stockwork type copper gold deposits +vein type copper gold deposits-stockwork type gold copper deposits+vein type gold copper deposits +vein type gold deposits .%一般斑岩型铜矿不仅存在蚀变分带，还存在矿化类型及岩性分带。
19246640_华北克拉通南缘卢氏多金属矿集区硫化物Rb-Sr_定年及地质意义
１０００ ０５６９／２０１９／０３５（０７） ２０１３ ２５ＡｃｔａＰｅｔｒｏｌｏｇｉｃａＳｉｎｉｃａ 岩石学报ｄｏｉ：１０ １８６５４／１０００ ０５６９／２０１９ ０７ ０５华北克拉通南缘卢氏多金属矿集区硫化物Ｒｂ Ｓｒ定年及地质意义张哲铭１，２，３ 曾庆栋１，２，３ 高帅１，２，３ 褚少雄１，２ 李德亭１，２ 程占东４ 马留锁４ 郭云鹏１，２ＺＨＡＮＧＺｈｅＭｉｎｇ１，２，３，ＺＥＮＧＱｉｎｇＤｏｎｇ１，２，３ ，ＧＡＯＳｈｕａｉ１，２，３，ＣＨＵＳｈａｏＸｉｏｎｇ１，２，ＬＩＤｅＴｉｎｇ１，２，ＣＨＥＮＧＺｈａｎＤｏｎｇ４，ＭＡＬｉｕＳｕｏ４ａｎｄＧＵＯＹｕｎＰｅｎｇ１，２１ 中国科学院地质与地球物理研究所，中国科学院矿产资源研究重点实验室，北京 １０００２９２ 中国科学院地球科学研究院，北京 １０００２９３ 中国科学院大学，北京 １０００４９４ 卢氏县国土资源局，卢氏 ４７２２００１ ＫｅｙＬａｂｏｒａｔｏｒｙｏｆＭｉｎｅｒａｌＲｅｓｏｕｒｃｅｓ，ＩｎｓｔｉｔｕｔｅｏｆＧｅｏｌｏｇｙａｎｄＧｅｏｐｈｙｓｉｃｓ，ＣｈｉｎｅｓｅＡｃａｄｅｍｙｏｆＳｃｉｅｎｃｅｓ，Ｂｅｉｊｉｎｇ１０００２９，Ｃｈｉｎａ２ ＩｎｓｔｉｔｕｔｉｏｎｓｏｆＥａｒｔｈＳｃｉｅｎｃｅ，ＣｈｉｎｅｓｅＡｃａｄｅｍｙｏｆＳｃｉｅｎｃｅｓ，Ｂｅｉｊｉｎｇ１０００２９，Ｃｈｉｎａ３ ＵｎｉｖｅｒｓｉｔｙｏｆＣｈｉｎｅｓｅＡｃａｄｅｍｙｏｆＳｃｉｅｎｃｅｓ，Ｂｅｉｊｉｎｇ１０００４９，Ｃｈｉｎａ４ ＬｕｓｈｉＣｏｕｎｔｒｙＢｕｒｅａｕｏｆＬａｎｄａｎｄＲｅｓｏｕｒｃｅ，Ｌｕｓｈｉ４７２２００，Ｃｈｉｎａ２０１９ ０２ １１收稿，２０１９ ０６ ０１改回ＺｈａｎｇＺＭ，ＺｅｎｇＱＤ，ＧａｏＳ，ＣｈｕＳＸ，ＬｉＤＴ，ＣｈｅｎｇＺＤ，ＭａＬＳａｎｄＧｕｏＹＰ ２０１９ ＴｈｅＲｂ ＳｒｉｓｏｔｏｐｉｃｄａｔｉｎｇｏｆｓｕｌｆｉｄｅｓａｎｄｇｅｏｌｏｇｉｃａｌｓｉｇｎｉｆｉｃａｎｃｅｏｆｔｈｅＬｕｓｈｉｐｏｌｙｍｅｔａｌｌｉｃｏｒｅ ｃｏｎｃｅｎｔｒａｔｅｄａｒｅａｉｎｓｏｕｔｈｅｒｎｍａｒｇｉｎｏｆｔｈｅＮｏｒｔｈＣｈｉｎａＣｒａｔｏｎ ＡｃｔａＰｅｔｒｏｌｏｇｉｃａＳｉｎｉｃａ，３５（７）：２０１３－２０２５，ｄｏｉ：１０ １８６５４／１０００ ０５６９／２０１９ ０７ ０５Ａｂｓｔｒａｃｔ ＴｈｅｒｅａｒｅａｌｏｔｏｆＡｕ，ＭｏａｎｄＰｂ ＺｎｐｏｌｙｍｅｔａｌｌｉｃｏｒｅｄｅｐｏｓｉｔｓｄｅｖｅｌｏｐｅｄｉｎＱｉｎｌｉｎｇｍｅｔａｌｌｏｇｅｎｉｃｂｅｌｔ，ｓｏｕｔｈｅｒｎｍａｒｇｉｎｏｆｔｈｅＮｏｒｔｈＣｈｉｎａＣｒａｔｏｎ ＴｈｅＬｕｓｈｉｐｏｌｙｍｅｔａｌｌｉｃｏｒｅ ｃｏｎｃｅｎｔｒａｔｅｄａｒｅａｉｓｌｏｃａｔｅｄｉｎｅａｓｔｅｒｎｐａｒｔｏｆｔｈｉｓｂｅｌｔ，ｗｈｉｃｈｉｎｃｌｕｄｉｎｇＹｅｃｈａｎｇｐｉｎｇＭｏ Ｗｄｅｐｏｓｉｔ，ＢａｂａｏｓｈａｎＦｅ Ｃｕｄｅｐｏｓｉｔ，ＬｏｕｆａｎｇＡｇ Ｃｕｄｅｐｏｓｉｔ，ＬｉｕｇｕａｎＰｂ Ｚｎｄｅｐｏｓｉｔ，ａｎｄｓｏｏｎ ＬｏｕｆａｎｇＡｇ Ｃｕｄｅｐｏｓｉｔｉｓａｈｙｄｒｏｔｈｅｒｍａｌｌｏｄｅｐｏｌｙｍｅｔａｌｌｉｃｄｅｐｏｓｉｔ，ｉｔｏｃｃｕｒｓｗｉｔｈｉｎｔｈｅａｍｐｈｉｂｏｌｅｐｌａｇｉｏｇｎｅｉｓｓｏｆＴａｉｈｕａＧｒｏｕｐ，ａｎｄｔｈｅｏｒｅｂｏｄｉｅｓｉｎｔｈｉｓｄｅｐｏｓｉｔａｒｅｃｏｎｔｒｏｌｌｅｄｂｙｔｈｅｓｔｒｕｃｔｕｒａｌａｌｔｅｒａｔｉｏｎｆｒａｃｔｕｒｅｚｏｎｅｓ ＴｗｏｓｔａｇｅｓｏｆｍｉｎｅｒａｌｉｚａｔｉｏｎａｒｅｉｄｅｎｔｉｆｉｅｄｉｎＬｏｕｆａｎｇｄｅｐｏｓｉｔ：ｑｕａｒｔｚ ｐｙｒｉｔｅ ｃｈａｌｃｏｐｙｒｉｔｅａｎｄｑｕａｒｔｚ ｐｙｒｉｔｅ ｇａｌｅｎａ ｓｐｈａｌｅｒｉｔｅ ｃａｌｃｉｔｅａｓｓｅｍｂｌａｇｅｓ ＴｈｅｆｏｒｍｅｒｉｓｔｈｅＣｕｍｉｎｅｒａｌｉｚａｔｉｏｎｓｔａｇｅ，ｗｈｉｌｅｔｈｅｌａｔｔｅｒｉｓｔｈｅＰｂ Ｚｎｍｉｎｅｒａｌｉｚａｔｉｏｎ ＬｉｕｇｕａｎＰｂ Ｚｎｄｅｐｏｓｉｔｉｓａｓｋａｒｎｄｅｐｏｓｉｔ，ｗｈｏｓｅｏｒｅｂｏｄｉｅｓｏｃｃｕｒｗｉｔｈｉｎｔｈｅｓｋａｒｎｂｅｌｔｂｅｔｗｅｅｎｄｏｌｏｍｉｔｅｏｆｔｈｅＧｕａｎｄａｏｋｏｕＧｒｏｕｐａｎｄｇｒａｎｉｔｅｐｏｒｐｈｙｒｙｏｒｃｒｙｐｔｏｅｘｐｌｏｓｉｖｅｂｒｅｃｃｉａ ＴｗｏｓｔａｇｅｓｏｆｍｉｎｅｒａｌｉｚａｔｉｏｎａｒｅｉｄｅｎｔｉｆｉｅｄｉｎＬｉｕｇｕａｎｄｅｐｏｓｉｔ：ｄｉｏｐｓｉｄｅ ｔｒｅｍｏｌｉｔｅ ａｃｔｉｎｏｌｉｔｅ ｇａｒｎｅｔ ｍａｇｎｅｔｉｔｅａｎｄｇａｌｅｎａ ｓｐｈａｌｅｒｉｔｅ ｐｙｒｉｔｅ ｅｐｉｄｏｔｅ ｓｅｒｐｅｎｔｉｎｅ ｑｕａｒｔｚ ｃａｌｃｉｔｅ Ｔｈｅｆｏｒｍｅｒｉｓｔｈｅｍａｇｎｅｔｉｔｅｍｉｎｅｒａｌｉｚａｔｉｏｎｓｔａｇｅ，ａｎｄｔｈｅｌａｔｔｅｒｉｓｔｈｅＰｂ Ｚｎｍｉｎｅｒａｌｉｚａｔｉｏｎｓｔａｇｅ ＴｈｅｒｅｓｕｌｔｓｏｆｃｈａｌｃｏｐｙｒｉｔｅｉｓｏｃｈｒｏｎｄａｔｉｎｇｉｎｄｉｃａｔｅｔｈａｔｔｈｅＲｂ ＳｒｉｓｏｃｈｒｏｎａｇｅｏｆｔｈｅＬｏｕｆａｎｇＡｇ Ｃｕｄｅｐｏｓｉｔｉｓ１２７ ８±３ １Ｍａ（２σ，ＭＳＷＤ＝１ １），ａｎｄｔｈｅｉｎｉｔｉａｌ８７Ｒｂ／８６Ｓｒｏｆｗｈｉｃｈｉｓ０ ７１０９９８±０ ００００６８；ＴｈｅＲｂ ＳｒｉｓｏｃｈｒｏｎａｇｅｏｆｐｙｒｉｔｅｉｎＬｉｕｇｕａｎＰｂ Ｚｎｄｅｐｏｓｉｔｉｓ１２４ ８±１ ６Ｍａ（２σ，ＭＳＷＤ＝１ ４），ａｎｄｔｈｅｉｎｉｔｉａｌ８７Ｒｂ／８６Ｓｒｏｆｗｈｉｃｈｉｓ０ ７１１０７４±０ ００００６４ ＴｈｅａｇｅｄａｔａｉｎｄｉｃａｔｅｔｈａｔｔｈｅｈｙｄｒｏｔｈｅｒｍａｌｐｏｌｙｍｅｔａｌｌｉｃｄｅｐｏｓｉｔｓｉｎＬｕｓｈｉｐｏｌｙｍｅｔａｌｌｉｃｏｒｅ ｃｏｎｃｅｎｔｒａｔｅｄａｒｅａｗｅｒｅｆｏｒｍｅｄｉｎＥａｒｌｙＣｒｅｔａｃｅｏｕｓ，ｗｈｉｃｈｉｓａｓｓｏｃｉａｔｅｄｗｉｔｈＥａｒｌｙＣｒｅｔａｃｅｏｕｓｉｎｔｒｕｓｉｖｅｍａｇｍａｔｉｓｍ Ｃｏｍｂｉｎｉｎｇｗｉｔｈｒｅｇｉｏｎａｌｇｅｏｌｏｇｉｃａｌｄａｔａ，ｉｔｃａｎｂｅｃｏｎｃｌｕｄｅｄｔｈａｔｔｈｅｐｏｌｙｍｅｔａｌｌｉｃｄｅｐｏｓｉｔｓｉｎｔｈｉｓａｒｅａｗｅｒｅｆｏｒｍｅｄｉｎａｔｅｃｔｏｎｉｃｓｅｔｔｉｎｇｒｅｌａｔｅｄｔｏｃｒａｔｏｎｄｅｓｔｒｕｃｔｉｏｎｈａｐｐｅｎｅｄｉｎＥａｒｌｙＣｒｅｔａｃｅｏｕｓＫｅｙｗｏｒｄｓ ＬｏｕｆａｎｇＡｇ Ｃｕｄｅｐｏｓｉｔ；ＬｉｕｇｕａｎＰｂ Ｚｎｄｅｐｏｓｉｔ；Ｒｂ Ｓｒｄａｔｉｎｇ；Ｐｙｒｉｔｅ；Ｃｈａｌｃｏｐｙｒｉｔｅ；Ｌｕｓｈｉｏｒｅ ｃｏｎｃｅｎｔｒａｔｅｄａｒｅａ摘 要 华北克拉通南缘秦岭成矿带发育大量金矿、钼矿及铅锌多金属矿床。
英文论文翻译 生烃潜力评价
利比亚东苏尔特盆地生烃潜力及有机地球化学评价唐正浩译（地球科学学院地球化学2010-2班）摘要本文对东苏尔特盆地上白垩统苏尔特组、他格非特组、瑞克博组、拉赫马特组、巴希组以及下白垩统巴希组和努比亚组的，取自阿迈勒、Gialo、Nafoora和Sarir地区的11口井（6C1-59，6J1-59，6R1-59，KK1-65，OO2-65，M1-51，KK1-65，B-96，B-95，B-99，E1-NC-59）的93块岩石切片进行有机地球化学评价。
通过批量的地球化学参数和分析色谱-质谱（GC-MS）图的生物标志化合物特征，以找出多样性的非海相岩相夹层，包括砂岩，粉砂岩，页岩和砾岩。
这样的岩石是很好的烃源岩，并含有从一般到很好的有机质，其中优秀烃源岩的总有机碳(TOC)含量丰富，达到5.16％。
所研究的样品从天然气到生油有机质，氢指数(HI)介于11-702 mgHC/gTOC之间，其中天然气的氢指数(HI)<150 mgHC /gTOC，大多数生油有机质的的氢指数(HI)300，氧指数(OI)介于3-309 mgCO2 /gTOC之间，由此可以说明所分析的有机质属于II/III型干酪根。
苏尔特组和拉赫马特组源岩生油窗的成熟度变化范围从成熟到过成熟，由此可以推断它的产率(PI)介于0.07-1.55之间，Tmax 介于425-440之间，成熟度Ro%介于0.46-1.38之间，其他组的成熟度属于低成熟和高成熟。
一些样品的低PI值可能表明大部分烃类以经从岩石中排出并运移出去。
为了调查样本的热演化程度和古沉积条件，分析了单独的21个岩样的抽提物的生物标志化合物比值。
姥鲛烷/植烷比值0.65 -1.25和DBT/ P比值 0.04-0.47表明了缺氧和沉积烃源岩的低氧条件。
通过占主导地位的C27和同样占主导地位的C28甾烷的同系物中分子组成的分布的研究，可以看出研究样品的有机物来自于海洋藻类。
岩石样品中的海相页岩和碳酸盐岩也高C19TT/C23TT比，C24TeT/C23TT值相对较低。
赞比亚ICHIMPE铜钴矿矿床特征及成因
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基底 为卢 富布 （ ｕｕ ｕ 超 群 和姆 瓦 （ ｖ ） Ｌ ｆｂ ） Ｍｕ ａ 超 群 。卢 富 布超 群岩 性 为 花 岗片 麻 岩 、 片岩 、 片麻 岩 ， 距 今 １ ￣２ ３ ５亿 年 。姆 瓦超 群 岩性 主要 为 石英 云母 片岩 ， 今 ９ １ 距 ～ ３亿 年［ 。 １ ］ 加丹 加超 群 不 整 合接 触 于基 底 之 上 ， 成 于 ５ 形
Ｉ ＨＩ Ｅ铜钴 矿床 位 于赞 比亚铜 矿 带 中 部 的 Ｃ ＭＰ 谦 比西 盆地 东缘 （ 图 １ ， 铜 矿 带 是 世 界 著 名铜 见 ）该 矿 带“ 中非铜 矿带 ” 的一 部分 。 赞 比亚 铜矿带 主要 受轴 向北西 的 卡富埃 复式 大 背 斜控 制 。背斜 两翼 形 成 西 南 、 东 两个 次 级 向斜 北 盆 地 系列 ， 中以西 南 向斜 为 主体 ， 其 由恩 昌加 、 比 谦
Ａｂ ｔ ａ ｔ ｓ ｒ ｃ ：Ｔｈ ＣＨＩ ＰＥ Ｃｕ Ｃｏ Ｄｅ ｏ ｉ ｉ ａ ｔ ｐ ｃ ｌ ｅ ｏ ｉ ｌ ｃ ｔｄ ｉ ａ ｉ Ｃ ｎ ｏ ＤＲＣ）Ｃｕ Ｃｏ ｍｅ ａｌ ｇ ｎ ｃ ｅＩ Ｍ — ｐ ｓｔ ｓ ｙ ｉａ ｐ ｓｔ ｏ ａ ｅ ｎ Ｚ ｍｂ ａ ｏ ｇ （ ｄ － — ｔｌ ｅ ｉ ｏ ｂ ｌ Ｏｒ ｏ ｉｓ ｏ ｃ ｒｉ ｒ — ｅ ｒｎ ｏ ｍａ ｉｎ ｎ ｔ ｅ ｌｗｅ ａ ｏ ｐ Ｉ ｒ ｅ Ｏ ｐ ｏ ｔ ｕ ｔ ｅ ｘ ｌ ｒ ｔ ｎ ｅｔ ． ｅ ｂ ｄ ｅ ｃ ｕ ｏ ｅ ｂ ａ ｉ ｇ ｆ ｒ ｔ ｓ ｉ ｈ ｏ ｒ Ｒｏ ｎ Ｇｒ ｕ ． ｎ ｏ ｄ ｒ ｔ ｒ ｍｏ ｅ ｆ ｒ ｈ ｒｅ ｐ ｏ ａ ｉ ｎ ｏ ｏ ａ ｄ ｅ ａ ｕ ｔ ｎ ｏ ｈ ｓ ａ ｅ ，ｂ ｓ ｄ ｏ ｈ ｕ ｎ ｖ ｌ ａ ｉ ｆｔ ｉ ｒ ａ ｏ ａ ｅ ｎ ｔ ｅ ｓ ｍｍａ ｙ ｏ ｒ ｖ ｏ ｓ ｓｕ ｉｓ ｈ ｓ ｐ ｐ ｒ ｂ ｉｆｙ ｄ ｓ ｒｂ ｓ ｔ ｅ ｇ ｏ ｏ ｉ ａ ｒ ｆ ｐ ｅ ｉｕ ｔ ｄ ｅ ，ｔ ｉ ａ ｅ ｒｅ ｌ ｅ ｃ ｉ ｅ ｈ ｅ ｌ ｇ ｃ ｌ ｂ ｃｇｏ ｎ ａ ｋ ｒ ｕ ｄ，ｇ ｏ ｏ ｉａ ｈ ｒ ｃ ｅ ｉｔ ｓｏ ｒ － ｅ ｒｎ ｏ ｍａ ｉ ｎ ｎ ｅ ｏ ｉ，ａ ｄ ｄ ｓ ｕ ｓ ｓｄ ｐ ｓｔ ｅ ｅ ｉ ａ ｄ ｍｅ — ｅ ｌｇ ｃ ｌｃ ａ ａ ｔ ｒｓ ｉ ｆ ｅ ｂ ａ ｉ ｇ ｆ ｒ ｔ ｓａ ｄ ｄ ｐ ｓｔ ｎ ｉｃ ｓ ｅ ｅ ｏ ｉ ｇ ｎ ｓｓ ｎ ｔ ｃ ｏ ｏ
夏季高温时硫铝酸盐水泥-硅酸盐水泥二元体系的早期性能
新型建筑材料2020.120引言硫铝酸盐水泥具有早强、高强、抗冻、抗渗、耐久性良好等优点[1-3]，广泛应用于抢修、修补工程中[4-5]。
王培铭和范胜华[6]的研究指出，低温环境延缓了硫铝酸盐水泥的水化，早期水化程度大幅减小，而对后期强度影响不大。
徐玲琳和杨晓杰[7]研究发现，养护温度越高，硫铝酸盐水泥水化越快，片状单硫型水化硫铝酸钙的生成时间越早、生成量越高。
陈雷等[8]研究发现，不同种类缓凝剂对快硬硫铝酸盐水泥的影响不同，酒石酸、硼酸等是比较理想的缓凝剂。
王中平等[9]研究了不同养护温度下无水石膏掺量对硫铝酸盐水泥水化的影响，5℃时无水石膏掺量越高，硫铝酸盐水泥砂浆的强度越低，40℃时一定程度上促进早期强度的提高。
有研究者将一定比例的普通硅酸盐水泥与硫铝酸盐水泥复合使用，有利于强度和弹性模量的发展[10-12]。
现阶段研究集中在低温养护时的硫铝酸盐水泥和硫铝酸盐水泥-硅酸盐水泥二元体系及硫铝酸盐水泥-硅酸盐水泥-石膏三元体系的水化进程，在环境温度较高时，硫铝酸盐夏季高温时硫铝酸盐水泥-硅酸盐水泥二元体系的早期性能李超，范树景，杭法付，叶勇（浙江忠信新型建材股份有限公司杭州研发分公司，浙江杭州310052）摘要：研究了环境温度为40℃时硫铝酸盐水泥-硅酸盐水泥二元体系砂浆早期性能（凝结时间、抗压和抗折强度）的变化规律，指出了早强剂及缓凝剂对砂浆早期宏观性能的调节作用。
结果表明，当环境温度为40℃时，未掺调凝剂情况下，随着硫铝酸盐水泥掺量的增加，二元体系凝结时间大幅度缩短，小时强度快速增长，抗压强度有所提高，28d 抗折强度呈先提高后降低趋势，在掺量为15%时出现峰值。
掺入0.1%~0.3%的缓凝剂时，有效延长了二元体系的凝结时间，延长施工开放时间，但抗折及抗压强度略有损失。
复掺缓凝剂和早强剂时，凝结时间控制在合理范围内，二元体系的小时强度和28d 抗折抗压强度都有所提高。
关键词：高温环境；二元体系；早期性能中图分类号：TU528.31文献标识码：A文章编号：1001-702X （2020）12-0060-04Early performance of sulphoaluminate cement-Portland cement binary system at high temperature in summerLI Chao ，FAN Shujing ，HANG Fafu ，YE Yong（Zhejiang Zhongxin New Building Materials Co.Ltd.，Hangzhou R&D Branch ，Hangzhou 310052，China ）Abstract ：This paper studies the change law of the early performance （setting time ，compressive strength and flexural strength ）of sulphur aluminate cement-Portland cement mortar early binary system under the environment temperature of 40℃，and points out the macro regulation effect of early strength agent and retarder on the properties of mortar at early stage.Results show that whenthe environment temperature was 40℃，under the condition without mixing coagulation agent ，with the increase of the sulfate alumi -nate cement content ，the setting time of the binary system was greatly shortened ，the hourly strength increased rapidly ，and the com -pressive strength increased.The 28d flexural strength first increased and then decreased and reached peak at 15%.When 0.1%~0.3%retarders were added ，the setting time of the binary system was effectively extended and the opening time of construction wasincreased.However ，the flexural and compressive strength were slightly lost.When the retarders and early strength agents were added at the same time ，the setting time was controlled within a reasonable range ，and both the hourly strength and 28d flexural and compressive strength of the binary system were increased.Key words ：high temperature environment ，binary system ，early performance基金项目：台州市科技计划项目（XM20190193）收稿日期：2019-12-27；修订日期：2020-04-17作者简介：李超，男，1995年生，助理工程师，主要从事保温砂浆、轻质薄层砌筑砂浆、灌浆料等的研究。
普朗斑岩铜矿包裹体、同位素研究及成矿时代
与斑 岩成矿作用特征 一致 。硫 同位 素 ８ ｃ 为 （一２２ ３ ７ ） 。 Ｓ ％ ． ３～ ． ５ ％ ，显示 单一 深 源岩 浆硫 。岩 体黑 云母 等 Ａ 一 ｒ ｒ Ａ 和矿石石英 一辉钼矿 Ｒ —Ｏ ｅ ｓ同位素年 龄为 ２ ６ ４ ～ １ ０ ． Ｍａ ２ ３±３８ ，属 岛孤 斑岩型铜矿床。 ． Ｍａ 关键词 ：斑岩型铜矿 ；成矿 流体 ；硫同位素 ；成矿 时代 ；云南普朗铜矿
同位 素 特征 等研 究成 果 ，对矿 床成 因机制 提供 新 资料 。
１ 地 质 背 景
普 朗铜矿 处 于 中咱微 陆块 东 、甘 孜 一理 塘 结 （ ） 合 带 南 段 西 则 ，二 者 夹 持 的 义 敦 岛 弧 南段 （ 缝 图
１ ，属 于 东斑 岩 （ 岩 一夕 卡岩 成 矿 ） 带 。带 内 主要 出露 上 三 叠 统 曲 嘎 寺 组 （ ， ） 图姆 沟组 （ ） ） 斑 Ｔｑ 、 Ｔｔ、
等 ，２ ０ ；曾普胜 等 ，２ ０ ，２ ０ 。成 矿 规 律 和 矿 床 地 质 特 征 也 有 较 多 的 讨 论 与 报 道 （ 玉 华 等 ， ０７ ０ ３ ０ ６） 范 ２ ０ ；李 光军 等 ，２ ０ ） ０６ ０ ５ ；矿床 的辉 钼矿 Ｒ ｅ—Ｏ 成 矿 和 矿化 关 系密 切 的钾 化 钾 长石 的 Ｋ—Ａ 年 龄 已经 获 ｓ ｒ
产 出。
矿 区外 围 安 山岩 ｃ （ ａ０）／Ｊ（ ｏ Ｎ ｏ Ｋ ０） 值 变 化在 ０ ６ ． １～１ ８之 间 ，Ｋ ０含 量相 对 较 高 ，与含 矿 超 浅 ． ： 成 岩侵 人 改造有 关 。样 品 总体 ∞ （ ａ ０） ＜∞ （ ，为 太 平 洋 型 海 底 火 山 喷 发 产 物 。此 外 ，岩 石 中 Ｎ Ｋ ０） Ｍ Ｏ、Ｃ Ｏ相 对较 高 ，主 要微 量 元 素 （ ０ ）Ｓ ５、Ｒ ０ 、Ｓ ８ 、Ｚ ０ 、Ｎ ２ ａｌ ８ ｆ ． 、 ｇ ａ １ ｃ１ ｂ １５ ｒ ４ ｒ ８ ｂ４ 、Ｂ ８ 、Ｈ ７ ６ ２ ５ Ｔ ． ｈ５ ６、Ｖ １ １ ｕ５ ７ 、Ｃ ８、Ｐ ９ ｎ８ 、Ｗ ． 、Ｓ ． 、Ｂ ． ９ ｂ４ 、Ｚ ４ １４ ｎ２ ２ ｉ ０ 、Ｍｏ０ ５ ，与 微 氏值 相 比 ，Ｒ 、Ｓ 、Ｂ ０ ． １ ｂ ｒ ａ 大离 子 亲石 元素 偏低 ，Ｎ 、Ｚ 、Ｈ 非 活 动性元 素偏 高 ，其 余则 与岛弧钙 碱性 玄 武岩元 素 特征 大体 一致 。 ｂ ｒ ｆ
萨瓦甫齐铀矿床岩石浸出液水化学对古流体的指示作用
萨 瓦 甫 齐铀 矿 床 岩石 浸 出液 水 化 学对 古流 体 的指 示作 用
林 效 宾 ，王 志 明 ，郝 伟 林 ，韩 军
（ 工业 北 京 地 质研 究 院 ，中核 集 团 铀 资源 勘 查 与评 价 技 术 重 点实 验 室 ，北 京 １０ ２ ） 核 ０ ０ ９
［ 摘要 ］萨 瓦 甫 齐 铀矿 床 位 于 新 疆 维 吾 尔 自治 区 阿克 苏 地 区 。新 构 造 运 动 使 盆 地 盖 层 变 得 陡 直 甚 至倒 转 ，承压 含 水 层 中 的地 下 水 不断 被 疏 干 ，现 今 在 垂深 ４ ５ｉ ７ ｎ以上 已 无地 下 水 活 动 ，铀 矿 体 主要 残 留在 古 层 间 氧 化 还原 过 渡 带 中 。根 据 水一 相 互 作 用 的 原 理 ，试 图通 过 研 究 岩 样 浸 出液 的水 化 学 来 获 岩 取 古 地 下 流体 的一 些基 本 特 征 。 ［ 键 词 ］萨 瓦 甫 齐铀 矿 床 ；砂 岩 型 铀 矿床 ；层 间 氧 化带 ；水 一 关 岩体 系 ；Ｅ — Ｈ 法 ｈｐ ［ 中图 分类 号 ］Ｐ １ ． ；Ｐ ９ ［ 献标 志码 ］Ａ ６ ９１ ４ ５８ 文 ［ 章 编号 ］１ ７ — ６ ６ ２ １ ） ３ ０ ５ — ７ 文 ６ ２ ０ ３ （０ １ ０ — １ ６ ０
Ｌ Ｎ ａ — ｉ Ｗ ＡＮＧ ｈ — ｎ Ｉ Ｘｉｏ ｂ ｎ， Ｚ ｉ ｍｉ ｇ， ＨＡＯ ｅ — ｉ ＨＡＮ ｕ Ｗ ｉ ｌｎ， Ｊｎ
（ Ｎ Ｃ Ｋ ｙＬ ｂ ｒｔｒ ｏ ｒｎｕ ｅｏ ｒｅ ｘ ｌｒｔ ｎａｄＥ ａｕｔ ｎＴ ｃ ｎ ｌ ｙ Ｃ Ｎ ｅ ａｏａ ｙ ｆ ａ ｉｍ Ｒ ｓｕｃｓ ｐｏａｉ ｎ ｖｌａｉ ｅｈ ｏｏ ， ｏ Ｕ Ｅ ｏ ｏ ｇ
Ｎｅ ｔｃ ｏ ｃ ａ ｔ ｉｙ， ｔ ｅ ｏ ｃ ｒ ｎ ｅ ｏ ｅ ｅ ｓ ｎｄ ｏ ｈ ｒｆ ｒ ｔｏ ｓｈ ｓｂ ｅ ｔ ｅ ｌ ｉｔｄ ａ ｄ ｅ ｅ ｏ ｅ ｔｎｉ ｃ ｉ ｔ ｖ ｈ ｃ ｕｒｅ ｃ ｆＴｉｍｉ ｒｕ ａ ｔ ｅ ｏ ｍａｉ ｎ ａ ｅ ｎ ｓｅ ｐ ｙ ｔｌｅ ｎ ｖ ｎ ｏ ｅｔｒ ｅ ｖ ｒｕ ｎ ｄ． Ｔｈ ｒ ｕ ｄ ｔ ｒ ｉ ｈ ｏ ｆｎ ｄ ａ ｉ ｓ ｉ ｃ ｎ ｅ ｕ ｎ ｌ ｒ ｉ ｅ ａ ｙ ｎｄ ｔ ｒ ｓ ｎｏ ｅ ｇ ｏ ｎ ｗａｅ ｎ ｔ ｅ ｃ ｎ ｅ ｑｕ￣ｒ ｓ ｏ ｓ ｑ ｅ ｔｙ ｄ ａｎ ｄ ｗａ ａ ｈｅｅ ｉ ｉ ｇ ｏ ｄ ｔｒ ａ ｔｖ ｔ ｓ ｎ ｈ ｒ ｃ ｓ ｖ ｒ ｈ ｖ ｒｉａ ｄ ｐ ｈ ｆ ４７ ｍ．Ｕｒ ｎ ｕ ｒ ｕｎ ｗａｅ ｃｉ ｉｉ ｉ ｔ ｅ ｏ ｋ ｏ ｅ ｔ ｅ ｅｔｃ ｌ ｅ ｔ ｏ ５ ｅ ａ ｉ ｍ ｏ ｅ ｏ ｉ ｓ ｒ ｔ ｒ ｂ ｄ ｅ ａ ｅ ｈｅ ｌｆｏ ｅ ｉ ｌ ｘ ｓｅ ｎ ｔ ｅ ｔａ ｓｔｏ ｏ ｅ ｏ ｎ ｅ ｌｙ ｒｏ ｉ ａｉ ｎ— ｅ ｃｉ ｎ ｅｔｖ ｒｍａ ｎ ｙ ｅ ｉｔｄ ｉ ｈ ｒ ｎ ｉｉｎ ｚ ｎ ｆｉ ｔｒａ ｅ ｘ ｄ ｔ ｏ ｒ ｄｕ ｔｏ ．Ｂａ ｅ ｎ ｔ ｅ ｗａｅ － ｏ ｋ ｓ ｄ ｏ ｈ ｔ ｒ ｒ ｃ
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a b
b,*
Nordic Metallurgical Consultants Inc., Sudbury, Ont., Canada P3E 5Y7 Department of Metals and Materials Engineering, University of British Columbia, 309-6350 Stores Road, UBC, Vancouver, BC, Canada V6T 1Z4
Minerals Engineering 17 (2004) 103
Corrigendum
This article is also available online at: /locate/mineng
Corrigendum to ‘‘Review of copper pyrometallurgical practice: today and tomorrow [Minerals Engineering 16 (2003) 893–919]’’ q
*
q
0892-6875/$ - see front matter Ó 2003 Elsevier Ltd. All rights reserved. doi:10.1016/j.mineng.2003.11.016
The corrected Table 1 is reproduced below:
Table 1 Worldwide summary of copper smelters Country Albania Australia Belgium Brazil Canada China Czech Republic Denmark Finland Germany India Iran Japan North Korea Mexico Norway Pakistan Philippines Portugal Russia R.S. Africa Sweden Thailand Ukraine Uganda Uzbekistan Zambia No. of units 3 7 2 2 8 41 1 1 1 5 7 2 10 3 7 1 1 1 1 14 6 1 2 1 1 1 4 Country Armenia Austria Botswana Bulgaria Chile Cuba D.R. of Congo Egypt France Hungary Indonesia Italy Kazakhstan South Korea Namibia Oman Peru Poland Romania Slovakia Spain Taiwan Turkey United Kingdom U.S.A. Yugoslavia Zimbabwe No. of units 1 2 1 3 11 1 3 1 2 1 1 1 5 3 1 1 2 4 2 1 6 2 3 3 17 1 6
Source: Non-ferrous metal works of the world, World Copper Databook.
doi of original article 10.1016/j.mineng.2003.08.002. Corresponding author. Tel.: +1 705 522 1362; fax: +1 705 522 3698. E-mail addresses: ray_moskalyk_nordic@sympoatico.ca, raymoskayk@yahoo.ca (R.R. Moskalyk), alfantaz@interchange.ubc.ca (A.M. Alfantazi).
The authors regret that in Table 1 of the above article, the number of units (copper smelters) in the U.S.A. should read 17 not 2 as originally published.