Recycle of Wastewater from Lead-Zinc Sulfide Ore Flo-tation Process by Ozone/BAC Technology

Lead-zinc sulphide ore contains lead sulphide (galena), and zinc sulphide (sphalerite). In the first flotation stage, galena is rendered hydrophobic with an organic collector such as xanthate, while sphalerite is kept from floating by depressants, and in the second flotation stage, activator was used to activated zinc flotation. Since the organic regent used are different in the two flotation stage, wastewater from the second zinc flotation stage can’t be directly recycled to the first lead flotation stage. Wastewater from flotation process for concentrating lead-zinc sulphide ore often containing organic compounds such as diethyldithiocarbamate(DDTC), xanthate, terpenic oil(2# oil) and thionocarbamate esters (Z-200), are environmentally hazardous. Their removal from contaminated water and the reuse of the water is one of the main challenges facing lead-zinc sulphide ore processing plants. In this study, synthetic wastewater containing DDTC, xanthate, 2# oil and Z-200 at concentrations ranging from 21 to 42 mg/L was fed into an Ozone/Biological activated carbon (BAC) reactor. Analyses of the effluent indicated a chemical oxygen demand (COD) removal over 86.21% and Total organic carbon (TOC) removal over 90.00% were achieved under Hydraulic retention time (HRT) of 4h and O3 feeding concentration of 33.3mg/L. The effluent was further recycled to the lab scale lead concentrating process and no significant difference was found in compare with fresh water. Furthermore, lead-zinc sulphide mineral concentrating process was carried out at lab scale. The produced wastewater was treated by Ozone/BAC reactor at O3 feeding concentration of 16.7mg/L and HRT of 4h. The effluent analysis showed that TOC removal was 74.58%. This effluent was recycled to the lab scale lead-zinc sulphide mineral concentrating process and the recovery of lead was not affected. The results showed that by using Ozone/BAC technology, the lead-zinc sulphide mineral processing wastewater could be recycled.

Separation of sulfide lead-zinc-silver ore under low alkalinity condition

A complex lead-zinc-silver sulfide ore containing 2.98% Pb, 6.49% Zn and 116.32×10^-4 % Ag （mass fraction） from Yunnan Province, China, was subjected to this work. Research on mineral processing was conducted according to the properties of the lead-zinc-silver ore. Under low alkalinity condition, the lead minerals are successfully separated from the zinc minerals with new reagent YZN as zinc depressant, new reagent BPB as lead collector, CuSO4 as zinc activator and ethyl xanthate as zinc collector. The associated silver is mostly concentrated to the lead concentrate. With the process utilized in this work, a lead concentrate of 51.90% Pb with a recovery of 82.34% and a zinc concentrate of 56.96% Zn with a recovery of 81.98% are produced. The silver recovery in the lead concentrate is 80.61%. Interactions of flotation reagents with minerals were investigated, of which the results indicate that the presence of proper amount of Na2S can precipitate Pb^2＋ and has a sulfidation on oxidized lead minerals. The results also show that NazCO3 and YZN used together as combined depressants for sphalerite can signally improve the depressing effect of new reagent YZN on sphalerite.

Development in selective flotation of galena from lead-zinc-iron sulfide ores in China

A new technique for the flotation separation of lead zinc iron sulfide ores has been developed and applied to several mills in China. It is characterized by the matching of relationships among pulp pH, pulp potential, flotation collector inside grinding mill. The flotation separation of galena and sphalerite has been accomplished without the addition of any conventional depressant of sphalerite such as zinc sulphate. Lime is used as a regulator and stabilizer of pulp pH and potential. Diethyldithiocarbamate (DDTC), not xanthate, is determined as a collector for the selective flotation of galena from the Pb Zn Fe sulfide ores. The laboratory scale tests, the plant scale tests and the plant operations have all shown that the best separation results can be achieved at pH of 12.4～12.6, the pulp potential of 160～180 mV. The operation practice in the four plants has confirmed that compared with conventional flotation flowsheet, our new technology can greatly improve the flotation results, reduce the flotation time and the number of flotation cell, and increase the stability of operation and the adaptability to changes in ore properties. All these advantages have made this four plants more profitable.

Infrared thermography for prediction of spontaneous combustion of sulfide ores

The method of infrared thermography to predict the temperature of the sulfide ores has a large error. To solve this problem, the temperature of the sulfide ores is measured by thermal infrared imager and recording thermometric instrument contrastively. The main factors, including emissivity, distance, angle and dust concentration that affect the temperature measurement precision, are analyzed. The regression equations about the individual factors and comprehensive factors are obtained by analyzing test data. The application of the regression equations improves the precision of the thermal infrared imager. The geometric information lost in traditional infrared thermometry is determined by visualization grid method and interpolation method, the relationship between the infrared imager and geometry information is established. The geometry location can be measured exactly.

Leaching of nickel-molybdenum sulfide ore in membrane biological reactor

The bioleaching of molybdenum from its sulfide ore using a Mo-resistant thermophilic bacterium sulfolobus metallics combined with a membrane biological reactor（MBR） was studied.The experimental results showed that the concentration of Mo can be controlled by filter of the membrane in MBR and the toxicity of Mo to microorganism is decreased in the process of bioleaching.It was also evidenced that there were different leaching rates of Ni and Mo when the concentration of Mo was different.After leaching for 20 d in the MBR at Mo concentration of 395 mg/L,the leaching rates of Ni and Mo reached the maximum of 79.57% and 56.23% respectively under the conditions of 100 g/L of mineral density,65 ℃,pH=2 and 1.0 L/min of the aeration rate.While 75.59% Ni and 54.33% Mo were leached out in column without membrane under the same conditions.

Self-heating tendency evaluation of sulfide ores based on nonlinear multi-parameters fusion

In order to reveal the nonlinear dynamics characteristics of unsteady self-heating process of sulfide ores, nine different kinds of sulfide ore samples from a pyrite mine in China were taken as experimental materials and their self-heating characteristics were measured in laboratory. Furthermore, the measured temperature was studied by integrating wavelet transform, nonlinear characteristic parameters extraction and fuzzy comprehensive evaluation. The results indicate that only the ore samples 1, 2, 6 and 9 have obvious self-heating phenomenon, and their self-heating initiative temperatures are 220 ℃, 239 ℃, 220 ℃ and 220 ℃, respectively, which means that they are difficult to produce self-heating under normal mining conditions. The correlation dimension of self-heating process is fraction and the maximum Lyapunov exponent is positive, which means that it is feasible to study the self-heating process based on chaotic dynamics theory. The nonlinearities of self-heating process of these four samples （ore samples 1, 2, 6 and 9） are 0.8227, 0.7521, 0.9401 and 0.8827 respectively and the order of the samples according to these results is： sample 6, sample 9, sample 1, sample 2, which is consistent with the measured results of self-heating characteristics. Therefore, the nonlinearity method can be used to evaluate the self-heating tendency of sulfide ores, and it is an effective verification of the reliability of measured results.

REE Geochemistry of Sulfides from the Huize Zn-Pb Ore Field, Yunnan Province: Implication for the Sources of Ore-forming Metals

REE abundances in sulfides from the Huize Zn-Pb ore field were determined with the ICPMS after preconcentration. The REE abundances in 26 sulfide samples （including pyrite, galena and sphalerite） are very low, with the ~REE ranging from 1.6×10^-9 to 166.8×10^-9. Their LREE/HREE ratios range from 7.6 to 98, showing LREE enrichment relatively. The JEu values are below 1, indicating that they were deposited from an Eu-depleted and reducing fluid-system. Similar to the ore-hosting carbonate strata, calcite separates from carbonate veinlets filling in the fractures or faults crosscutting the carbonate strata also show clear Eu-depletion. This indicates that the carbonate veinlets and their parent fluid was possibly sourced from the strata and inherited the REE geochemical features of the strata. Therefore, REE-geochemical characteristics of both the sulfides and calcites, which were deposited from an ore-forming hydrothermal system, are similar to those of carbonate strata, and strongly suggest that the ore metals were mainly sourced from carbonate strata.

Bioleaching of low-grade copper sulfide ores by Acidithiobacillus ferrooxidans and Acidithiobacillus thiooxidans

The grown conditions of Acidithiobacillus ferrooxidans and Acidithiobacillus thiooxidans were investigated,and then experiments were conducted to research the bioleaching behaviors of crude ore of copper sulfide and hand-picked concentrates of chalcopyrite by Acidithiobacillus ferrooxidans and Acidithiobacillus thiooxidans.The experimental results show that the bacteria grow best when the temperature is(30±1) °C and the pH value is 2.0.The bacteria concentration is 2.24×107 mL-1 in this condition.It is found that the copper extraction yield is affected by the inoculum size and the pulp density and the extraction yield increases as the inoculum size grows.The bioleaching rates reach their highest point in sulfide copper and chalcopyrite with a pulp density of 5% and 10%,respectively.Column flotation experiments of low-grade copper sulfide ores show that the bioleaching recovery reaches nearly 45% after 75 days.

Locating method of fire source for spontaneous combustion of sulfide ores

in order to achieve a more efficient way to accurately detect the position of the fire source of spontaneous combustion underground mine, a simple fire source locating method, based on infrared scanning system which can determine the point where the highest temperature on the surface of igniting ores occurs, was proposed. First, the differential equations that describe heat flow in ore body were presented and the relationship between the surface temperature distribution and the depth and intensity of inner fire source was established with a relatively simple heat transfer model. With the solution of equation, the expression of the relationship between the surface temperature distribution and the inner fire source was deduced and the mathematical-physical model of heat transfer process was set up. Then, with the model, visualization of fire source on the basis of MATLAB simulation platform was realized. The results show that： 1） within 10 m, when the detecting depth is less than 2 m, the temperature perturbation on ores surface can change rapidly, and then slowly; after 4 m, in contrast, it changes very little, and is even close to zero at 10 m; 2） When it is close to self-ignition duration and the detective depths are 2, 5 and 10 m, respectively, the maximum temperature differences are correspondingly 0.5, 0.04 and 0.005 ℃ in the scope of 1 m×1 m; under the same condition, the maximum temperature differences are 1.391, 0.136 and 0.018 ℃, respectively, in the scope of 2 m×2 m. Therefore, this system can be used to measure the temperature differences on the surface of ore body and determine the highest temperature point directly. Also, it is possible to determine the depth of fire source and its intensity by locating method of fire source indirectly.

Ore Genesis of the Kalatongke Cu-Ni Sulfide Deposits, Western China: Constraints from Volatile Chemical and Carbon Isotopic Compositions

The Kalatongke Cu-Ni sulfide deposits located in the East Junggar terrane, northern Xinjiang, western China are the largest magmatic sulfide deposits in the Central Asian Orogenic Belt （CAOB）. The chemical and carbon isotopic compositions of the volatiles trapped in olivine, pyroxene and sulfide mineral separates were analyzed by vacuum stepwise-heating mass spectrometry. The results show that the released volatiles are concentrated at three temperature intervals of 200-400°C, 400-900°C and 900-1200°C. The released volatiles from silicate mineral separates at 400-900°C and 900-1200°C have similar chemical and carbon isotopic compositions, which are mainly composed of H2O （av. ~92 mol%） with minor H2, CO2, H2S and SO2, and they are likely associated with the ore-forming magmatic volatiles. Light δ13CCO2 values （from -20.86‰ to -12.85‰） of pyroxene indicate crustal contamination occurred prior to or synchronous with pyroxene crystallization of mantlederived ore-forming magma. The elevated contents of H2 and H2O in the olivine and pyroxene suggest a deep mantle-originated ore-forming volatile mixed with aqueous volatiles from recycled subducted slab. High contents of CO2 in the ore-forming magma volatiles led to an increase in oxygen fugacity, and thereby reduced the solubility of sulfur in the magma, then triggered sulfur saturation followed by sulfide melt segregation; CO2 contents correlated with Cu contents in the whole rocks suggest that a supercritical state of CO2 in the ore-forming magma system under high temperature and pressure conditions might play a key role in the assemblage of huge Cu and Ni elements. The volatiles released from constituent minerals of intrusion 1# have more CO2 and SO2 oxidized gases, higher CO2/CH4 and SO2/H2S ratios and lighter δ13CCO2 than those of intrusions 2# and 3#. This combination suggests that the higher oxidation state of the volatiles in intrusion 1# than intrusions 2# and 3#, which could be one of key ore-forming factors for large amounts of ores and high contents of Cu and Ni in intrusion 1#. The volatiles released at 200-400°C are dominated by H2O with minor CO2, N2＋CO and SO2, with δ13CCO2 values （-25.66‰ to -22.98‰） within the crustal ranges, and are considered to be related to secondary tectonic-hydrothermal activities.

Evaluation of spontaneous combustion tendency of sulfide ore heap based on nonlinear parameters

To explore a new evaluation method for spontaneous combustion tendency of different areas in sulfide ore heap, ore samples from a pyrite mine in China were taken as experimental materials, and the temperature variations of the measuring points of simulated ore heap were measured. Combined with wavelet transform and nonlinear parameters extraction, a new method for spontaneous combustion tendency of different areas in sulfide ore heap based on nonlinear parameters was proposed and its reliability was verified by field test. The results indicate that temperature field evolution of the simulated ore heap presents significant spatial difference during self-heating process. Area with the maximum increasing extent of temperature in sulfide ore heap changes notably with the proceeding of self-heating reaction. Self-heating of sulfide ore heap is a chaotic evolution process, which means that it is feasible to evaluate spontaneous combustion tendency of different areas by nonlinear analysis method. There is a relatively strong correlation between the maximum Lyapunov exponent and spontaneous combustion tendency with the correlation coefficient of 0.9792. Furthermore, the sort of the maximum Lyapunov exponent is consistent with that of spontaneous combustion tendency. Therefore, spontaneous combustion tendency of different areas in sulfide ore heap can be evaluated by means of the maximum Lyapunov exponent method.

Investigation of chemical suppressants for inactivation of sulfideores

In order to investigate the effective control method of sp ontaneous com bustion in the mining of sulfide ore deposits. This paper presents the testing r esults of several selected chemicals (water glass, calcium chloride, calcium oxi de, magnesium oxide and their composites) as oxidation suppressants for sulfide ores. A weight increment scaling method was used to measure suppressant performa nce, and this method proved to be accurate, simple and convenient. Based on a large number of experiments, the test results show that four types of chemical mixtures demonstrate a good performance in reducing the oxidation rate of seven active sulfide ore samples by up to 27% to 100% during an initial 76 d period. T he mixtures of water glass mixed with calcium chloride and magnesium oxide mixed with calcium chloride can also act as fire suppressants when used with fire spr inkling systems.

Bioleaching of complex polymetallic sulfide ores by mixed culture

Bacterial leaching of single sulfide minerals and polymetallic sulfide ores was operated in shake flasks and small-scaled columns.The results show that bioleaching of jamesonite is not accessible,the iron extraction rate of pyrrhotite bioleaching reaches 98.2% after 26 d,and the zinc extraction rate of marmatite bioleaching reaches 92.3%,while the corresponding iron extraction reaches only 13.6% after 29 d.Pulp density has a significant effect on metal extraction of pyrrhotite and marmatite bioleaching.The corresponding metal extraction rate decreases with the increase of pulp density.For the polymetallic sulfide ores,zinc extraction of 97.1% is achieved after bioleaching in shake flasks for 10 d,while only 7.8% is obtained after bioleaching in small-scaled column.Analytical results of scanning electron microscopy(SEM) and energy dispersive X-ray analysis(EDX) reveal that large amount of calcium sulfate is formed on the mineral surface.

Bioleaching of low-grade copper sulfide ore by extremely thermoacidophilic consortia at 70℃in column reactors

The effects of introducing M.sedula derivatives having different Cu^2+-resistance on bioleaching capacity of a defined consortium(consisting of A.brierleyi DSM1651 and M.hakonensis HO1-1)were studied in column reactors at 70℃.Introducing M.sedula copA mutant,a copper sensitive derivative,only had negligible effects on bioleaching.While introducing M.sedula ARS50-2,a Cu^2+resistant strain,substantially consolidated bioleaching process,with 27.77%more copper recovered after 58 d of bioleaching.Addition of M.sedula ARS50-2 likely enhanced the sulfur oxidation capacity of consortium after the 24th day under the Cu^2+stress.The majority of extreme thermoacidophiles were attached on minerals surface as indicated by quantitative PCR(qPCR)data.Successions of microbial community of extremely thermoacidophilic consortia that attached on surface of minerals were different from those in leachate.M.hakonensis HO1-1 was the dominant species attached on minerals surface in each column reactor throughout bioleaching process.The sessile M.sedula ARS50-2 remained as a major species till the 34th day.A.brierleyi DSM1651 was the most abundant planktonic species in leachate of each column reactor.These results highlight that higher Cu^2+-resistance is a beneficial trait for extreme thermoacidophiles to process copper minerals.

Mechanism of Mg2+ dissolution from olivine and serpentine: Implication for bioleaching of high-magnesium nickel sulfide ore at elevated pH

To inhibit the dissolution of Mg^2+ during the bioleaching process of high-magnesium nickel sulfide ore, the effect of major bioleaching factors on the dissolution of Mg^2+ from olivine and serpentine was investigated and kinetics studies were carried out. The results indicated that the dissolution rate-controlling steps are chemical reaction for olivine and internal diffusion for serpentine. The most influential factor on the dissolution of Mg^2+ from olivine and serpentine was temperature, followed by p H and particle size. A novel method of bioleaching at elevated pH was used in the bioleaching of Jinchuan ore. The results showed that elevated pH could significantly reduce the dissolution of Mg^2+ and acid consumption along with slightly influencing the leaching efficiencies of nickel and cobalt. A model was used to explain the leaching behaviors of high-magnesium nickel sulfide ore in different bioleaching systems. The model suggested that olivine will be depleted eventually, whereas serpentine will remain because of the difference in the rate-controlling steps. Bioleaching at elevated pH is a suitable method for treating high-magnesium nickel sulfide ores.

Acid equilibrium during bioleaching of alkaline low-grade sulfide copper ore

This article reports the study on acid equilibrium during bioleaching of alkaline low-grade copper sulfide ore. Adding auxiliary agents 1# （sulfur） and 2# （pyrite） makes bacterial leaching of copper and acid production carried out simultaneously because the auxiliary agents can be oxidized by bacteria and the oxidation products involve acid. The acid required for dissolving alkaline gangue during bacterial leaching is produced, and acid equilibrium is reached during the ore bio-leaching. The recovery of copper reaches more than 95%.

Co-extraction of valuable metals and kinetics analysis in chlorination process of low-grade nickel-copper sulfide ore

To efficiently co-extract Ni and Cu from low-grade nickel-copper sulfide ore,chlorination roasting with NH;Cl followed by a water leaching process was investigated.The results show that 98.4%Ni and 98.5%Cu can be synchronously extracted when the ore particle size is 75-80μm,the roasting time is 2 h,the mass ratio of NH;Cl to ore is 1.6:1 and the roasting temperature is 550°C.The evolution behavior of various minerals was elucidated using X-ray diffraction(XRD)coupled with scanning electron microscopy(SEM).The kinetics of the chlorination process based on the differential thermal and thermogravimetric analysis(DTA-TG)data was analyzed by Kissinger method and Flynn-Wall-Ozawa(FWO)method.The chlorination process of low-grade nickel-copper sulfide ore mainly contains two stages:the decomposition of NH;Cl and the chlorination of ore.The maximum apparent activation energies(Ea)at two stages are determined to be 114.8 and 144.6 kJ/mol,respectively.The condensed product of exhaust gas is determined to be ammonium chloride,which can be recycled as the reactant again,making the process economic and clean.

Application of response surface methodology in optimization of bioleaching parameters for high-magnesium nickel sulfide ore

The response surface methodology(RSM)was used to optimize the operating parameters during the bioleaching of Jinchuan high-magnesium nickel sulfide ore.The particle size,acid addition,pulp density and inoculation amount were chosen as the investigated parameters.To maximize the leaching efficiency of nickel,copper,cobalt and minimize the dissolution of magnesium and iron ions,the model suggested a combination of optimal parameters of particles less than 0.074 mm being 72.11%,sulfuric acid addition being 300 kg/t,pulp density being 5%and inoculation amount being 12.88%.Under the conditions,the average results of three parallel experiments were 89.43%of nickel leaching efficiency,36.78%of copper leaching efficiency,84.07%of cobalt leaching efficiency,49.19%of magnesium leaching efficiency and 0.20 g/L of iron concentration.The model indicated that the most significant factor in response of the leaching efficiency of valuable metal is the particle size,and the most significant factor in response to the leaching efficiency of harmful ions(Mg2+)is the amount of sulfuric acid addition.And according to the suggested models,no significance of the interaction effect between particle size and acid addition was shown.Under the optimized parameters suggested by models,the valuable metals could be separated from harmful ions during the bioleaching process.

Effect of technological factors on bacterial leaching of low-grade Ni-Cu sulfide ore

The bioleaching of a low grade Ni Cu sulfide ore from Jinchuan Mine with Thiobacillus ferrooxidans (TF5) and Thiobacillus thiooxidans (TT) was investigated. The effect of pH, the initial cell numbers of bacteria, the pulp density and the ratio of TF5 and TT on leaching was described, and the favorable bioleaching conditions for the ore were experimentally confirmed. The aeration leaching, agitation leaching with air bubbling, and column leaching were respectively tested. The highest recovery was achieved in the aeration leaching. After leaching for 20?d with pulp density of 15%, the extractions of Ni, Cu and Co were respectively 95.4%, 48.6% and 82.6%.

STUDY ON GREY FORECASTING MODEL OF COPPER EXTRACTION RATE WITH BIOLEACHING OF PRIMARY SULFIDE ORE

A model GM （grey model） （1,1） for forecasting the rate of copper extraction during the bioleaching of primary sulphide ore was established on the basis of the mathematical theory and the modeling process of grey system theory. It was used for forecasting the rate of copper extraction from the primary sulfide ore during a laboratory microbial column leaching experiment. The precision of the forecasted results were examined and modified via ＂posterior variance examination＂. The results show that the forecasted values coincide with the experimental values. GM （1,1） model has high forecast accuracy; and it is suitable for simulation control and prediction analysis of the original data series of the processes that have grey characteristics, such as mining, metallurgical and mineral processing, etc. The leaching rate of such copper sulphide ore is low. The grey forecasting result indicates that the rate of copper extraction is approximately 20% even after leaching for six months.