Separation and recovery of copper in Cu-As-bearing copper electrorefining black slime by oxidation acid leaching and sulfide precipitation

A new hydrometallurgical route for separation and recovery of Cu from Cu-As-bearing copper electrorefining black slime was developed. The proposed process comprised oxidation acid leaching of Cu-As-bearing slime and selective sulfide precipitation of Cu from the leachate. The effects of various process parameters on the leaching and precipitation of Cu and As were investigated. At the first stage, Cu extraction of 95.2% and As extraction of 97.6% were obtained at 80 ℃ after 4 h with initial H2 SO4 concentration of 1.0 mol/L and liquid-to-solid ratio of 10 mL/g. In addition, the leaching kinetics of Cu and As was successfully reproduced by the Avrami model, and the apparent activation energies were found to be 33.6 and 35.1 kJ/mol for the Cu and As leaching reaction, respectively, suggesting a combination of chemical reaction and diffusion control. During the selective sulfide precipitation, about 99.4% Cu was recovered as CuS, while only 0.1% As was precipitated under the optimal conditions using sulfide-to-copper ratio of 2.4:1, time of 1.5 h and temperature of 25 ℃.

Acid precipitation coupled electrodialysis to improve separation of chloride and organics in pulping crystallization mother liquor

Inefficient separation of inorganic salts and organic matters in crystallization mother liquor is still a problem to industrial wa stewater treatment since the high salinity significantly impedes organic pollutant degradation by oxidation or incineration.In the study,acidification combined electrodialysis(ED)was attempted to effectively separate Cl-ions from organics in concentrate pulping wastewater.Membrane’s rejection rate to total organic carbon(TOC)was 85%at wastewater intrinsic pH=9.8 and enhanced to 93%by acidifying it to pH=2 in ED process.Negative-charged alkaline organic compounds(mainly lignin)could be liberated from their sodium salt forms and coagulated in acidification pretreatment.Neutralization of the organic substances also made their electro-migration less effective under electric driving force and in particular improved separation efficiency of chloride and organics.After acid-ED coupled treatment(pH=2 and J=40 mA·cm-2)[TOC]remarkably reduced from 1.315 g·L-1 to 0.048 g·L-1 and[Cl-]accumulated to 130 g·L-1 in concentrate solution.Recovery rate of NaCl was 89%and the power consumption was 0.38 kW·h·kg-1 NaCl.Irreversible fouling was not caused as electric resistance of membrane pile maintained stably.In conclusion,acidic-ED is a practical option to treat salinity organic wastewater when current techniques including thermal evaporation and pressure-driven membrane se paration present limitations.

Influence of some agricultural practices on the soil acidification in acid precipitation areas

Both acid precipitation and unreasonable agricultural practices are notorious artificial factors resulting in soil acidification. To sort out reasonable agricultural practices favorable to abating soil acidification, the task of this study was directed to a long-term field trial in Chongqing, dudng which chemical fertilizer, organic fertilizer were applied to different crop rotations and the soil pH value was measured. The results indicated that all treatments decreased pH value in the 0 to 20 cm soil layer after ten years. Problems were more serious when chlorine-containing fertilizer, excessive chemical fertilizer and mixed fertilizer were applied. It is demonstrated that balance rates of N, P and K fertilizers, application of muck in field are advantageous to abating soil acidification. Oil plants affect soil acidification more than cereal in different crop rotation.

Effects of precipitation variation on severe acid rain in southern China

Acid rain has been recognized as a serious environmental problem in China since the 1980s, but little is known about the effects of the climatic change in regional precipitation on the temporal and spatial variability of severe acid rain. We present the effects of the regional precipitation trend change on the area and intensity of severe acid rain in southern China, and the spatio-temporal distribution characteristics of SO2 and NO2 concentrations are analyzed on the basis of SO2 and NO2 column concentration data. The results are as follows. （1） The emission levels of SO2 and NO2 have reached or passed the precipitation scavenging capacity in parts of southern China owing to the emission totals of SOz and NO2 increasing from 1993 to 2004. （2） Notable changes in the proportion of cities subject to severe acid rain occurred mainly in the south of the middle-lower reaches of the Yangtze River during 1993-2004. With an abrupt change in 1999, the severe acid rain regions were mainly located in central and western China during 1993-1999 and moved obviously eastward to the south of the lower-middle reaches of the Yangtze River with the proportion of cities subject to severe acid rain increasing significantly from 2000 to 2004. （3） The spatial distribution and variation in the seasonal precipitation change rate of more than 10 mm/10a are similar to those of severe acid rain in southern China. An abrupt change in 1999 is seen for winter and summer precipitation, the same as for the proportion of cities subject to severe acid rain in southern China. The significant increase in summer storm precipitation from 1991 to 1999 mitigated the annual precipitation acidity in the south of the Yangtze River and reduced the area of severe acid rainfall. On the other hand, the decrease in storm rainfall in summer expanded the area of severe acid rainfall in the south of the Yangtze River in 2000-2006. Therefore, the change in seasonal precipitation is an important factor in the severe acid rain regions moving eastward and expanding in southern China.

Interaction between uranium and humic acid (Ⅱ): complexation, precipitation and migration behavior of U(Ⅵ) in the presence of humic substances

The complexation, precipitation, and migration behavior of uranium in the presence of humic acid (HA) or fulvic acid (FA) were investigated by cation exchange, ultrafiltration and dynamic experiment, respectively. The results showed that (i) complex equilibrium between the uranium and humic substances was achieved at approximately 72 h, (ii) the coordination number varied from 1:1 to 1:2 ( U(Ⅵ) : humic acid) as pH increased from 3 to 6; and (iii) , while the complex stability constant decreased when temperature increased, but increased with pH value. We found that the precipitation of uranyl could only be observed in presence of HA, and the precipitation was influenced by conditions, such as pH, uranium concentration, temperature, and the HA concentration. The maximum precipitation proportion up to 60% could be achieved in the condition of 40 mg/L HA solution at pH 6. We further observed that the migration behavior of uranium in soil in the presence of humic acid (HA) or fulvic acid (FA) was different from that in the presence of inorganic colloid, and the effect of humic substances (HS) was limited.

A STUDY ON BUFFERING CAPACITY OF THE FOREST SOIL AGAINST ACIDIC PRECIPITATION IN SEVERAL AREAS OF CHINA

Soil samples from several forest areas in China were analyzed by X-ray powder diffractometry after mineral separation and enrichment. The density gradient separation method with sequential extraction by acetone-methylene iodide mixtures was applied for the separation of fine sand fraction of soil samples. The clay fraction (【 2μm) was separated from silt fraction of soil samples prior to examination. Mineral components in some fine sand and clay samples were compared, and their weathering potentiality and buffering capacity against acidic precipitation were discussed.

Sulfide precipitation flotation for treatment of acidic mine waste water

Sulfide precipitation flotation of copper iron bearing acidic waste water from a large copper mine and the stimulated waste water were studied. The pH of the waste water was 2.2, with 130 mg/L Cu 2+ and 500 mg/L Fe 3+ (Fe 2+ ). Results show that, when Na 2S was added as precipitating agent, sodium butylxanthate as collector and at pH 2.0, the removal of copper could be as high as 99.7% and the residual copper decreased to 0.2 mg/L, however, almost no iron was removed. When the floated solution was neutralized to pH=8.0, more than 98% iron was precipitated and the residual iron was less than 10 mg/L. In experiment on actual mine effluents, after the use of precipitate flotation technology to recover copper and pH neutralization to precipitate iron, the treated waste water does meet the emission standards for sewage and valuable floating copper graded 37.12%. The chemical calculation and mechanism of solution were also presented.

Simulating study on the effect of acid precipitation on forest soil weathering

The effect of acid rain on the forest soils in China was discussed on the basis of simulating studies. The soils were collected from five typical areas, including Chongqing in Sichuan Province and Guiyang in Guizhou Province, where there has been heavier acid rain in southwest China, and Huitong in Hunan Province, Zhouzhi in Shaanxi Province, and Xinglong in Hebei Province, all of which were selected as control. Field investigation and sampling were made in the typical forests in all the above five areas. The relationship between pH values in precipitation and rates of soil weathering, the difference between the rates of soil weathering in different areas, and the cause of such a difference, have been worked out. The prediction was also conducted on the supply dynamics of nutrient and toxic elements in various forest ecosystems which were affected by acid deposition in order to understand the long-term effects of acid precipitation on the forest ecosystems studied.

A MORPHOLOGICAL STUDY OF POLY(DIVINYLBENZENE-co-ACRYLIC ACID) IN CROSSLINKING PRECIPITATION POLYMERIZATION

Divinylbenzene-80 （DVB-80） and polar monomer acrylic acid （AA） having hydrogen bonding at a total monomer loading of 5 vol% were precipitated-copolymerized in a variety of organic solvents with 2,2＇-azobis（isobutyronitrile） （AIBN） as initiator. The experiments were investigated from a two-dimensional matrix, i.e., the actual crosslinking degree of DVB varying from 0 to 80% and the solvent composition varying from 0 to 100% of toluene mixture with acetonitrile, when the mixture of acetonitrile and toluene was used as the reaction solvent. Under various reaction conditions, six distinct morphologies including soluble polymers, swellable microgels, coagulum, irregular microparticles, and nano-/micrometer microspheres were formed and the structures of these polymer architectures were described. A morphological map was utilized to discuss the effects of both crosslinking degree of DVB and composition of solvent on the transitions between morphology domains. The results demonstrated that the microspheres are formed by an internal contraction due to the marginal solvency of the continuous phase and the crosslinking of the polymer network through the covalent bonding from DVB as well as the interchain hydrogen-bonding between the carboxylic acid units.

studies on the Mechanism of Producing Tungstic Acid by Complex-Homogeneous Precipitation Method

A new method of producing tungstic acid with a yield over 98% at room temperature and low acidity is advanced and referred to as Complcx -Homogeneous Precipitation Method. If combined with the treatment of activated charcoal in recovering the remnant tungsten left in the filter liquor, a perfect closed technological process can be obtained. The key to this method is to prevent the formation of pseudo-metatungstatc during scdium rungstate being acidified directly with the aid of the complexing-protecting agent H2O2, The perexo-mtermediate, which was prepated and identified as dipcroxytetratnngstate by IR and Raman analysis by comparison with diperorytetramolybdate, can be decomposed by SO2 tapidly and quantitatively. The tungstic acid precipitate can be filtered and washed easily. The related mechanisin is studied.

An evaluation of quality assurance to monitor acid precipitation by using ion balance in Guizhou，China

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PREPARATION OF POLY(ETHYLENEGLYCOL-co-ACRYLIC ACID) MICROSPHERES WITH DIVINYLBENZNE AS CROSSLINKER BY DISTILLATION-PRECIPITATION POLYMERIZATION

Monodisperse poly（poly（ethyleneglycol） methyl ether acrylate-co-acrylic acid） （poly（PEGMA-co-AA）） microspheres were prepared by distillation-precipitation polymerization with divinylbenzene （DVB） as crosslinker with 2,2＇- azobisisobutyronitrile （AIBN） as initiator in neat acetonitrile without stirring. Under various reaction conditions, four distinct morphologies including the sol, microemulsion, microgels and microspheres were formed during the distillation of the solvent from the reaction system. A 2D morphological map was established as a function of crosslinker concentration and the polar monomer AA concentration, in comonomer feed in the transition between the morphology domains. The effect of the covalent crosslinker DVB on the morphology of the polymer network was investigated in detail at AA fraction of 40 vol%. The ratios of acid to ethylene oxide units presenting in the comonomers dramatically affected the polymer-polymer interaction and hence the morphology of the resultant polymer network. The covalent crosslinking by DVB and the hydrogen bonding crosslinking between two acid units as well as between the acid and ethylene oxide unit played key roles in the formation of monodisperse polymer microspheres.

Changes in soil microbial community response to precipitation events in a semi-arid steppe of the Xilin River Basin, China

In the context of climate change, precipitation is predicted to become more intense at the global scale. Such change may alter soil microbial communities and the microbially mediated carbon and nitrogen dynamics. In this study, we experimentally repackaged precipitation patterns during the growing season(from June to September) of 2012 in a semi-arid temperate steppe of the Xilin River Basin in Inner Mongolia of China, based on the 60-year growing season precipitation data. Specifically, a total amount of 240 mm simulated precipitation was assigned to experimental plots by taking the following treatments:(1) P6(6 extreme precipitation events, near the 1^(st) percentile);(2) P10(10 extreme precipitation events, near the 5^(th) percentile);(3) P16(16 moderate precipitation events, near the 50^(th) percentile); and(4) P24(24 events, 60-year average precipitation, near the 50^(th) percentile). At the end of the growing season, we analyzed soil microbial community structure and biomass, bacterial abundance, fungal abundance and bacterial composition, by using phospholipid fatty acid(PLFA), real-time quantitative polymerase chain reaction(RT-qPCR) and 16S rRNA gene clone library methods. The extreme precipitation events did not change soil microbial community structure(represented by the ratio of PLFA concentration in fungi to PLFA concentration in bacteria, and the ratio of PLFA concentration in gram-positive bacterial biomass to PLFA concentration in gram-negative bacterial biomass). However, the extreme precipitation events significantly increased soil microbial activity(represented by soil microbial biomass nitrogen and soil bacterial 16S rRNA gene copy numbers). Soil fungal community showed no significant response to precipitation events. According to the redundancy analysis, both soil microbial biomass nitrogen and soil ammonium nitrogen(NH_4-N) were found to be significant in shaping soil microbial community. Acidobacteria, Actinobacteria and Proteobacteria were the dominant phyla in soil bacterial composition, and responded differently to the extreme precipitation events. Based on the results, we concluded that the extreme precipitation events altered the overall soil microbial activity, but did not impact how the processes would occur, since soil microbial community structure remained unchanged.

Soil respiration response to precipitation reduction in a grassland and a Mongolian pine plantation in semi-arid northeast China

Climate change is predicted to alter global precipitation regimes.However,the response of soil carbon and nitrogen cycles and soil microorganisms to precipitation reduction is poorly understood but is dependent on ecosystem type.To evaluate the impacts of reduced precipitation on soil respiration,soil inorganic nitrogen(i.e.,NH4^+–N and NO3^-–N),nitrogen mineralization,and soil microbial community composition,a precipitation manipulation experiment was initiated in a Mongolian pine plantation and a naturally restored grassland in semi-arid northeast China.Precipitation reduction led to decreases of soil respiration rates by 14 and 8%in 2014 and 2015 in the Mongolian pine plantation but no changes in the grassland.Soil inorganic nitrogen,ammonification and nitrification rate,and soil phospholipids fatty acids were not significantly changed by reduced precipitation but significantly differed between the two ecosystems and among growing seasons.Our results suggest that the impacts of precipitation reduction on soil respiration were different between the Mongolian pine plantation and the grassland,and that ecosystem type and growing season had more pronounced impacts on soil carbon and nitrogen cycles.

Chemistry and source identification of wet precipitation in a rural watershed of subtropical China

South China is one of the regions severely suffering from acid rain in the world.However,few systematic studies of rural precipitation chemistry have been performed in comparison with the extensive studies on their urban counterparts of this region.In order to characterize the current acid rain status and identify its possible sources in the rural area of South China,we analyzed precipitation collected event by event from a rural forested watershed in southern Anhui Province between March 2007 and February 2010.The results showed that the concentrations of major ions within precipitation in the studied rural area were significantly lower than those reported for the urban areas of the same latitude in China.Nevertheless,the precipitation acidity(with an average pH value of 4.49) and the frequency of acid rain(95%) were considerably high.The relatively high ratio of(SO42+ NO 3)/(Ca2+ +NH4+) was the main cause of acid rain in this rural area,as SO 2 and NO x were the main precursors of acid rain,while Ca2+ and NH4+acted as the dominant neutralizers to the acidity.Source identification indicated that Ca2+ and Mg2+ mainly were derived from alkaline dust,SO42,NO 3 and NH4+originated mainly from anthropogenic sources such as industrial and agricultural activities,most Na +,Cl,K + and some of Mg2+ were derived from the sea.The results suggested that the major ions within precipitation in the rural area of South China were related to the meso-scale and long-range transport of particles and aerosols in the air.

VARIATION OF PH IN ATMOSPHERIC PRECIPITATION IN CITIES OF JILIN PROVINCE

Through statistical analysis on data of atmospheric precipitation samples of 8 cities from 1992 to 1997,this paper discussed temporal and spatial variations of pH in atmospheric precipitation in Jilin Province, China Monitored pH value in the 8 representative cities was converted into hydrogen ion consistency and average condsistency was calculated by weighting precipitation, then mean pH value was calculated according to average hydrogen ion consisteney. Results show that atmospheric precipitaion of cities in Jilin Province is basically. neutral, but in Tumem and Hunchun cities atmospheric precipitation is seriously acid. The average pH value of atmospheric precipitation of the eastern cities of Tumen and Hunchun in many years is 5. 12 and 5. 38 respectively, and the atmospheric precipiboon acidity in the two cities is quite serious with the extreme low pH is 3. 91 and 4. 28 respectively. Most of the acid precipitation occurred in summer and autumn seasons in the 8 monitored cities, so that the low pH value of atmoopheric pmeipitation occurred in summer and autunm seasons and high pH value occurred in winter ed spring seasons. The temporal and spatial variations of pH in atmospheric precipitation in Jilin Province are attributed to both local sources and peripheral sources, and are related to both natural and artificial factors.

Chemical characteristics of precipitation and wet deposition of major ions in Liaozhong County of Liaoning Province,Northeast China

The chemical characteristics of precipitation were analyzed based on the chemical composition of principal ionic within acid rain(from February 2007 to January 2008)of Liaozhong Meteorological Station located in Malong Village in Liaozhong County of Northeast China,meteorological conditions on the corresponding period ground,and variation of several air pollutants concentration.The results indicated that:(1)The precipitation average pH value of all samples was4.76;the frequency of acid rain during the observation period was 70.7%;the frequency was 82.8%in summer and autumn.(2)In the chemical composition of precipitation,the primary anions were SO_4^(2-)and NO_3^-;the primary cations were NH_4^+and Ca^(2+).(3)All concentration of anions was higher in summer and winter,but relatively low in spring and autumn.This showed that the relationship between regional rainfall acidification and pollution was not significant.(4)Rainwater acidity and nearly floor gaseous pollution concentration were different from each other,and pH and NO_x,CO,NO_2 and O_3concentrations showed significant negative correlation,but was not obvious with SO_2 concentration.However,the pH and alkaline pollutants,such as particulate,was positively correlative.

Scaling and clogging treatment of aging tunnel drainage pipes in karst areas using eco-friendly acid agent

In karst areas,the drainage pipes of aging tunnels are prone to be clogged by precipitated carbonates,resulting in lining cracking and tunnel leaking.As a result,not only the driving safety will be deteriorated,but also the water pressure on the lining might also be elevated significantly.For the structural stability and service lifespan of old tunnels,it is of great importance to remove these precipitated carbonates in time.Traditional treatment methods are often destructive to some extent or not efficient enough.This study aims to experimentally develop an eco-friendly acid-based chemical cleaning method to remove carbonate precipitations efficiently.The proposed chemical cleaning agent is an aqueous solution with strong acidity,consisting of sulfamic acid,water,and additives.The factors affecting the cleaning efficiency include the acid solubility,temperature and flow rate of the cleaning agent,as well as additives.Elevating the solution temperature to 50
C or a flow rate of no less than 0.2 m/s can improve cleaning efficiency.Although the salt effect cannot work,1 wt%of polymaleic acid as a surfactant could further promote the cleaning rate.The cleaning efficiency will increase with the flow rate in a power function.The relatively low flow rate that improves the cleaning rate considerably can avoid highpressure-induced mechanical damage to tunnel drainpipes.The waste could be easily treated to acceptable levels using commercial sewage treatment products and can also be recycled in agriculture.With the chemical cleaning,the water pressure at the arch springing of the lining will reduce with the increased radius of transverse drainpipes in a power function.The proposed acid-based cleaning method,which is highly efficient,non-or low-destructive to aging tunnels,sufficiently safe for humans,and friendly enough to the environment,will offer a promising alternative to remove the precipitated carbonates in tunnel drainpipes efficiently.

低分子量有机酸(苹果酸)对方解石-氟的吸附/沉淀反应影响

低分子量有机酸常对矿物的表面反应(吸附/沉淀)产生影响,从而影响矿物的溶解、矿化等过程,进而影响环境地球化学进程中元素的迁移稳定性。苹果酸作为一种广泛存在于自然界中的有机酸,是植物通过代谢过程分泌的副产品。通过批量平衡法开展了苹果酸对方解石-氟的吸附/沉淀反应的影响研究,旨在深入理解有机酸在地球化学过程中的作用。结果表明:①初始pH值为7.7条件下,对于低浓度氟(≤5 mg·L^(-1)),随着苹果酸浓度的升高,其对氟去除的抑制作用呈增强趋势;对于中、高浓度氟(25或60 mg·L^(-1)),氟去除主导机制为CaF 2沉淀反应,苹果酸的抑制作用对其影响不大,但其表面吸附反应导致pH值升高和钙浓度下降。②初始pH值为8.3条件下,对于低浓度氟(≤20 mg·L^(-1)),苹果酸对氟去除仍有抑制作用;苹果酸与Ca 2+的络合反应促使pH值和钙浓度上升;对于中浓度氟(60 mg·L^(-1)),氟去除主导机制为CaF 2沉淀反应,20 mg·L^(-1)苹果酸已对其产生抑制作用,随着苹果酸浓度继续升高,pH值先降后升,钙浓度持续上升,彰显了苹果酸络合反应的效应;对于高浓度氟(100 mg·L^(-1)),100 mg·L^(-1)苹果酸能极大抑制CaF 2沉淀反应,对应的pH值未超过无苹果酸时,对应的钙浓度仍低于其空白背景值,暗示了CaF 2沉淀反应的主导性。③初始pH值为8.7条件下,对于低浓度氟(≤5 mg·L^(-1)),苹果酸对氟去除的抑制作用有所减弱,但其络合反应产生的效应十分显著,导致pH值和钙浓度上升;对于高浓度氟(240 mg·L^(-1)),氟去除主导机制为CaF 2沉淀反应,该反应随着苹果酸浓度的升高而受到抑制,对应的钙浓度不断上升彰显苹果酸络合反应的效应,而pH值的下降也表明了CaF 2沉淀反应的主导性。本研究深入探讨了氟元素在方解石矿物界面上的吸附、迁移和转化过程,为理解氟的迁移稳定性提供了新的视角和理论基础,同时对富含有机酸环境中方解石矿物的稳定性评估具有重要意义,也为氟在其他矿物上的迁移转化研究提供借鉴。