钾长石粉酸浸除铁的实验研究

在利用钾长石粉合成沸石分子筛和制取碳酸钾技术中，铁的存在会降低沸石的白度。对北京平谷、天津蓟县、内蒙白云鄂博三地钾长石粉进行硫酸酸浸除铁实验，获得最大铁浸出率分别为88．6％、93．2％和64．6％，且前两地钾长石粉中铁的浸出行为相似，酸浸除铁效果均优于白云鄂博钾长石粉。采用正交实验法研究硫酸浓度、酸浸温度和时间对除铁效果的影响，表明三者对不同地区钾长石粉酸浸除铁效果的影响程度各不相同。钾长石酸浸除铁反应开始时，铁的溶解极快，反应速率主要由化学反应控制；其后溶解相对缓慢，反应速率则由扩散作用控制。     

Iron isotope fractionation during leaching of granite and basalt by hydrochloric and oxalic acids

Transport of iron (Fe) within hydrothermal and soil environments involves the transferral into aqueous solutions by leaching of complex, polyminerallic rocks. Understanding the isotope fractionation mechanisms during this process is key for any application of the Fe-isotope system to biogeochemical studies. Here, we reacted biotite granite and tholeiite-basalt with 0.5 M hydrochloric acid and 5 mM oxalic acid solutions at ambient temperature. Solution aliquots were recovered over a seven-day period and analysed for major and trace element concentrations and Fe isotopic compositions. In all experiments, Fe initially released into solution was isotopically lighter, with Δ⁵⁶Fe_{solution-rock} as low as −1.80‰ in the granite-hydrochloric acid system. The oxalic acid experiments showed similar patterns but smaller fractionation. In all experiments, the Δ⁵⁶Fe_{solution-rock} reduced over time, which would be in line with the formation of a leached layer as proposed before [Brantley S. L., Liermann L. J., Guynn R. L., Anbar A., Icopini G. A., and Barling J. (2004) Fe isotopic fractionation during mineral dissolution with and without bacteria. Geochim. Cosmochim. Acta68(15), 3189-3204]. Granite and basalts reacting with hydrochloric acid reached apparent steady-state values of −0.60 ± 0.15‰ and −0.40 ± 0.20‰, respectively, whilst experimental values with oxalic acid were −1.0 ± 0.15‰ and −0.50 ± 0.15‰. During the granite experiments, alteration of biotite to chlorite, followed by dissolution of chlorite, were likely the dominant processes, whilst in the basalt experiments, dissolution of pigeonite was likely the principal source of Fe. Variations in pH during the hydrochloric acid experiments were minimal, remaining below 0.5 at all times. In oxalic acid solutions, the pH increased to over 4, leading likely to precipitation of secondary minerals and adsorption/co-precipitation of Fe onto mineral surfaces. These processes could contribute to the greater fractionation observed in the final stages of the oxalic acid experiments. Our results highlight the importance of mineralogy and fluid composition on the Fe-isotope systematics during weathering. The fractionation processes identified for granites and basalts are in line with those inferred from field observations in soils, sediments, groundwater and hydrothermal deposits and from laboratory studies of single-mineral leaching.     

An XPS study of the dissolution kinetics of chrysotile in 0.1 N oxalic acid at different temperatures

The dissolution of chrysotile is studied in regard to the surfaces analysis by photoelectron spectrometry. After leaching of chrysotile (Provenance: Thetford; about 200 mg of fibers of 1 cm length) in nonstirred 0.1 N oxalic conditions, the composition of the mineral surfaces is determined by XPS; kinetic curves of dissolution are given in the range 22–80°C. Two conditions for the rate-limiting step are involved for the explanation of the dissolution: diffusion of Mg²⁺ through the fibrous gel or dissociation of chrysotile. By the former, some values of the diffusion coefficient are proposed: D varies from 5·10^?19 cm²s^?1 to 5·10^?16 cm²s^?1, in the range 22–80°C. By the second model, the leaching rate is estimated from 3 Å (22°C) per h to 250 Å (80°C) per h. For the 2 models, the activation heat energy is in the range 15–20 Kcal.     

Comparison of hot hydroxylamine hydrochloride and oxalic acid leaching of stream sediment and coated rock samples as anomaly enhancement techniques

A hot hydroxylamine hydrochloride (H-Hxl) extraction in 25% acetic acid is compared with the commonly used oxalic acid extraction as a method of anomaly enhancement for Cu and Zn in samples from two very different metal deposits and climatic environments. Results obtained on minus-80-mesh stream sediments from an area near the Magruder massive sulfide deposit in Lincoln County, Georgia, where the climate is humid subtropical, indicate that H-Hxl enhances the anomaly for Cu by a factor of 2 and for Zn by a factor of 1.5, compared to the oxalic method. Analyses of Fe oxide-coated rock samples from outcrops overlying the North Silver Bell porphyry copper deposit near Tucson, Arizona, where the climate is semi-arid to arid, indicate that both techniques effectively outline the zones of hydrothermal alteration.The H-Hxl extraction can also perform well in high-carbonate or high-clay environments, where other workers have suggested that oxalic acid is not very effective. Therefore, the H-Hxl method is recommended for general exploration use.     

低温条件下有机酸对铁、铜的淋滤实验研究

水／岩作用实验研究表明，在低温条件下柠檬酸、草酸和酒石酸对岩石中的铁、铜都有很高的淋滤率。这表明，在表生地质作用过程中有机酸对成矿元素有很强的活化能力。实验研究同时发现，有机酸对成矿元素的活化能力受其分解温度的限制，由于大部分有机酸的分解温度都在２５０℃以下，因而有机酸对成矿元素的活化仅限于低温条件。本次研究还显示，判断一种岩石能否成为矿源层，不能简单的以其中成矿元素的含量高低作为标准，其中更关键的因素是元素在岩石中的存在形式，如果成矿元素在岩石中难以活化的形式存在，那么含量再高也无法提供成矿物质     

草酸的稳定性及CO_2包裹体压力计实验研究

应用金刚石压腔(diamond-anvil cell)实验技术,对草酸的稳定性进行了研究。草酸在高压低温条件下可以稳定存在,而在低压高温条件下将分解为CO2、H2O等气体。当成矿流体遇到破裂带或裂隙而发生减压沸腾时,可以使成矿流体中的有机络合物迅速发生分解产生大量CO2,从而造成金属元素在有利的空间沉淀、富集成矿。同时,实验研究了高温高压条件下CO2的物理化学性质,得到了CO2包裹体压力计的测定方程:P(MPa)=271.517·(Δν1381.93-0.010987·ΔT)+0.1,式中Δν1381.93(cm-1)为待测包裹体中CO2的拉曼位移相对于常温常压下CO2的拉曼位移1381.93cm-1之差,ΔT(℃)为待测包裹体的温度与常温(23℃)之差,P(MPa)为待测包裹体的内压。由上式计算拉曼位移ν的标准偏差为±0.2cm-1,压力P的误差为±54MPa。该压力标定方程适用于在高压下温度范围为23℃≤T≤390℃的压力标定。     

The kinetics of iodide oxidation by the manganese oxide mineral birnessite

The kinetics of iodide (I⁻) and molecular iodine (I₂) oxidation by the manganese oxide mineral birnessite (δ-MnO₂) was investigated over the pH range 4.5-6.25. I⁻ oxidation to iodate proceeded as a two-step reaction through an I₂ intermediate. The rate of the reaction varied with both pH and birnessite concentration, with faster oxidation occurring at lower pH and higher birnessite concentration. The disappearance of I⁻ from solution was first order with respect to I⁻ concentration, pH, and birnessite concentration, such that −d[I⁻]/dt = k[I⁻][H⁺][MnO₂], where k, the third order rate constant, is equal to 1.08 ± 0.06 × 10⁷ M⁻² h⁻¹. The data are consistent with the formation of an inner sphere I⁻ surface complex as the first step of the reaction, and the adsorption of I⁻ exhibited significant pH dependence. Both I₂, and to a lesser extent, sorbed to birnessite. The results indicate that iodine transport in mildly acidic groundwater systems may not be conservative. Because of the higher adsorption of the oxidized I species I₂ and , as well as the biophilic nature of I₂, redox transformations of iodine must be taken into account when predicting I transport in aquifers and watersheds.     

Silicon isotopic fractionation during adsorption of aqueous monosilicic acid onto iron oxide

The quantification of silicon isotopic fractionation by biotic and abiotic processes contributes to the understanding of the Si continental cycle. In soils, light Si isotopes are selectively taken up by plants, and concentrate in secondary clay-sized minerals. Si can readily be retrieved from soil solution through the specific adsorption of monosilicic acid () by iron oxides. Here, we report on the Si-isotopic fractionation during adsorption on synthesized ferrihydrite and goethite in batch experiment series designed as function of time (0-504 h) and initial concentration (ic) of Si in solution (0.21-1.80 mM), at 20 °C, constant pH (5.5) and ionic strength (1 mM). At various contact times, the δ²⁹Si vs. NBS28 compositions were determined in selected solutions (ic = 0.64 and 1.06 mM Si) by MC-ICP-MS in dry plasma mode with external Mg doping with an average precision of ±0.08‰ (±2σ_SEM). Per oxide mass, ferrihydrite (74-86% of initial Si loading) adsorbed more Si than goethite (37-69%) after 504 h of contact over the range of initial Si concentration 0.42-1.80 mM. Measured against its initial composition (δ²⁹Si = +0.01 ± 0.04‰ (±2σ_SD)), the remaining solution was systematically enriched in ²⁹Si, reaching maximum δ²⁹Si values of +0.70 ± 0.07‰ for ferrihydrite and +0.50 ± 0.08‰ for goethite for ic 1.06 mM. The progressive ²⁹Si enrichment of the solution fitted better a Rayleigh distillation path than a steady state model. The fractionation factor ²⁹ε (±1σ_SD) was estimated at −0.54 ± 0.03‰ for ferrihydrite and −0.81 ± 0.12‰ for goethite. Our data imply that the sorption of onto synthetic iron oxides produced a distinct Si-isotopic fractionation for the two types of oxide but in the same order than that generated by Si uptake by plants and diatoms. They further suggest that the concentration of light Si isotopes in the clay fraction of soils is partly due to sorption onto secondary clay-sized iron oxides.     

Magnesium recovery from magnesite tailings by acid leaching and production of magnesium chloride hexahydrate from leaching solution by evaporation

The recovery of magnesium from magnesite tailings in aqueous hydrochloric acid solutions by acid leaching was studied in a batch reactor using hydrochloric acid solutions. Subsequent, production of magnesium chloride hexahydrate (MgCl₂.6H₂O) from leaching solution was also investigated. The effects of temperature, acid concentration, solid-to-liquid ratio, particle size and stirring speed on the leaching process were investigated. The pseudo-second-order reaction model seemed to be appropriate for the magnesium leaching. The activation energy of the leaching process was estimated to be 62.4 kJ mol^− 1. Finally, MgCl₂.6H₂O in a purity of 91% was produced by evaporation of leaching solution obtained at a temperature of 40 °C, 1.0 M acid, solid-to-liquid ratio of 10 g/L, particle size of 100 µm, stirring speed of 1250 rpm and leaching time of 60 min.     

苹果酸对含铊黄铁矿的淋滤实验研究

在２５￣５５℃低温条件下研究了苹果酸对广东云浮含铊黄铁矿的准动态淋滤,模拟考察了Ｔ１、Ｃｄ和Ｐｂ三种有毒元素随矿山开采和环境介质等因素作用而进入环境的情况。结果表明,云浮矿中Ｔ１的含量大大超过地壳背景值,越细的料级中含量越高。从淋滤结果可以推测,在矿山开采过程中,在环境介质的淋滤作用下,Ｔ１进入环境的速率远比Ｃｄ和Ｐｂ快。在介质浓度、作用时间和温度等影响淋滤结果诸因素中,温度的影响尤为明显。     

Investigation of zinc extraction from different leach residues by acid leaching

With different properties, zinc is one of the most important non-ferrous metals and it is used in various application areas, especially as an anti-corrosion agent. In Turkey, zinc production was based on zinc carbonate ores (ZnCO₃), at Çinkur plant from establishment to 1997 due to high reserves of zinc carbonate. After that, zinc concentrate coming from Iran was used in this plant over the last two decades. Thus, two different leach residues called as Turkish leach residue (TLR) and Iranian leach residue (ILR) were accumulated more than one million ton in Çinkur stock piles. In this study, it is aimed to investigate zinc recovery for each leach residue by use of sulphuric acid (H₂SO₄) and to compare the TLR and the ILR. Initially, detailed chemical, mineralogical and thermal analyses of these different leach residues were carried out. In order to investigate the effect of acid concentration and reaction duration on zinc recovery, leaching experiments were carried out at following conditions: 95 °C, 100 g/L pulp density and 600 rpm stirring rate. According to the characterization results, the chemical compositions for both residues are nearly similar; however, experimental results show that zinc recovery per cent of the ILR was higher than that of TLR for all experimental durations and acid concentrations. This may be due to the presence of Zn-containing compounds in the both residues at different percentages.     

The effects of pH, ionic strength, and iron-fulvic acid interactions on the kinetics of non-photochemical iron transformations. II. The kinetics of thermal reduction

A combination of flow-injection analysis and kinetic analysis was used to examine the speciation of iron(II) and iron(III) in fulvic acid solutions as a function of pH, ionic strength, and time. This methodology was used to follow a shift in iron speciation from faster to slower reacting species over a timescale of several days. This speciation data shows that both iron(II) and iron(III)-fulvic acid complexes are important iron species in humic-containing natural waters and that their amounts and their rates of transformation to colloidal iron are controlled primarily by the kinetics of thermal (dark) reduction and iron(II) oxidation. The kinetic analysis methodology also yielded the rate constants for the thermal reduction of iron by the fulvic acid. These rate constants decrease with increasing pH and are independent of ionic strength. While thermal reduction was found to be too slow to produce large amounts of steady state iron(II) at circumneutral pH, it does provide a mechanism for iron redox cycling in the absence of photochemical or biochemical processes.     

Study on treatment of wastewater from acid in-situ leaching of uranium ore with sulfate reducing bacteria

Synthetic surfactants are among the most widely used chemicals in the world （around 10 millions of tons are produced per year）, mainly as key components in detergent formulation, apart from other applications such as wetting agents or emulsifiers. Coastal ecosystems receive large quantities of these compounds and, after a relatively fast partial degradation in water, the remaining quantities end up in the sediments due to their high affinity for organic carbon in the particulate phase. We therefore focused our studies on sediments because they can be assumed to play an important environmental role acting as a sink for these contaminants. Moreover, because of their widespread use and source specificity, surfactants can usefully be employed as molecular indicators in sediments for more general contamination caused by human activities. This work deals with the vertical distribution in sediment cores of the main anionic surfactants, both linear alkylbenzene sulfonates （LAS） and alkyl ethoxysulfates （AES）, and non-ionic surfactants, including nonylphenol polyethoxylates （NPEOs） and alcohol polyethoxylates （AEOs）. In the case of LAS their degradation metabolites sulfophenyl carboxylic acids （SPCs） are also studied. The processes considered are degradation, sorption and diffusion occurring along the sedimentary column for the different homologues contained in the commercial surfactant mixtures. The most hydrophobic surfactants such as NPEOs and AEOs remain strongly attached to the particulate phase whereas polar metabolites such SPCs tend to be present in the pore water. Highest values of surfactants are found near the surface and, in most cases, there is a decrease in their concentration down the sediment core. Furthermore, the reduction in the average length of the ethoxylated chain in polyethoxylated surfactants, as well as the increase in the concentrations of SPCs at depths showing redox potential from -300 to -400 mV, suggests that surfactants may be degraded anaerobically in the sediment. In the case of LAS, these field results are compared with the data from laboratory experiments carried out in order to determine sorption capacity and anaerobic degradation.     

The complexation of iron by marine humic acid

Cation exchange capacity measurements, performed before and after removal of humic acid from Narragansett Bay sediments, indicate that low concentrations of these organic substances strongly influence the ability of the sediment to react with metal ions. Atomic absorption and spectrophotometric methods allow quantitative determination of the extent of reaction between a naturally occurring humic acid and iron in artificial seawater. Humic acid-iron complexes are formed whose solubilities depend on the humic acid-iron ratio used in the experiment. This study suggests that humic acid is a transporting agent for trace metals in a marine environment.     

碱熔除铁氟化物置换容量法测定铁矿石中的三氧化二铝

试样经氢氧化钠碱熔,过滤分离铁等元素,将滤液酸化、DETA络合、氟化钠置换,再用硫酸铜标准溶液回滴释放出来的EDTA,从而实现对铝的测定,通过本方法对铁矿石标准物质及样品的测定,结果的相对标准偏差在0.93%~2.95%之间,且铁矿石标准物质测定值与认定值相符。     

Speciation of adsorbed arsenate on the surface of hydrous iron oxide

Adsorption of arsenate on hydrous iron oxide is an important process controlling geochemical cycling of arsenic in environment as well as the fate of arsenic-bearing mining wastes. The widely accepted view on the mechanism of adsorption is that arsenate is adsorbed via bidentate binuclear inner-sphere complexation. In this study, we characterized the arsenate-hydrous iron oxide sorption solids synthesized at pH=3-8 using Fourier transformed infrared spectroscopy （FTIR） and X-ray diffraction （XRD）. It has been determined that poorly crystalline ferric arsenate developed on the surface of iron oxide when arsenate was sorbed at acidic pH, while at alkaline pH the adsorption of arsenate was via bidentate complexation.     

Dephosphorization of phosphorus-rich manganese ores by selective leaching with dilute hydrochloric acid

Leaching of three high-phosphorus manganese ore samples from central India with dilute hydrochloric acid (0.1–0.6 M) has been found to reduce their phosphorus contents below the specified limit of 0.12%. Various process parameters, such as concentration of acid, liquid/solid ratio, temperature and period of leaching, particle size of ore etc., have been investigated in detail and optimum values have been worked out on the laboratory scale. Both liquid/solid ratio (slurry concentration) and temperature of leaching appear to be critical process parameters. While the increase in liquid/solid ratio above 3–4 has no beneficial effect, leaching temperature above 50°C has an adverse effect on the extent of dephosphorization. Grain size of ore finer than 100 mesh (B.S.) in general gives satisfactory dephosphorization. Laboratory-scale results have been, in general, supported by bench-scale work which shows that phosphorus can be effectively removed from high-phosphorus manganese ores of central India by leaching in dilute hydrochloric acid at ambient temperature. Comparative performance of the dilute solutions of all the three mineral acids as leaching agents has been discussed.     

深层温压条件下有机酸热稳定性模拟研究

深层、超深层中有机酸的分布特征及其热稳定性对储层物性有着重要影响。采用高温高压水—岩模拟装置对储层中典型一元和二元有机酸（乙酸和乙二酸）的分解反应进行了模拟,对动力学参数进行了计算,并分析其影响因素。结果显示:乙二酸比乙酸更容易分解,且分解反应的速率更高;乙酸和乙二酸分解反应的起始温度分别为230 ℃和180 ℃,其反应速率随着温度的升高而急剧增加。反应体系中高pH值和钾长石的存在明显提高了乙酸和乙二酸分解反应的反应速率,但对起始温度影响较小。高流体压力和静岩压力均会抑制乙酸和乙二酸的分解,在提高有机酸分解反应起始温度的同时降低分解反应速率。从地质意义上来讲,相对高压、低地温的地层环境更有利于有机酸的保存,因此具有低地温梯度的沉积盆地形成深层—超深层优质储层的可能性更高。     

柱子淋洗模拟研究磷酸铁膜抑制黄铁矿氧化效果

自然室温条件下用柱子淋洗模拟研究了接氧化亚铁硫杆菌（Ｔｈｉｏｂａｃｉｌｌｕｓ ｆｅｒｒｏｏｘｉｄａｎｓ,简称Ｔ．Ｆ菌）时磷酸铁膜抑制黄铁矿氧化的效果。试验结果首次指出：用ＫＨ２ＰＯ４与Ｈ２Ｏ２淋洗黄铁矿,在其表面形成的磷酸铁膜不能抑制黄铁矿的生物氧化,反而在一定程度上加速其氧化进程。经包膜后的黄铁矿矿石柱子间歇循环淋洗一年后的收集液中ＳＯ４＾２－累积量高达３３７５６．１ｍｇ;为对照组的１．６倍,是     

Purification of diatomite powder by acid leaching for use in fabrication of porous ceramics

This study presents an investigation of the purification of a raw diatomite by acid leaching conducted in hot solution (75 °C and 5 M HCl) for long periods up to 240 h, evaluates the use of these purified powders in the fabrication of porous materials, and examines their porosities. The treatment for 1 h increased the specific surface area of diatomite from 189 m²/g to 222 m²/g, but the SiO₂ content of 78.66% was still low. Material leached for a relatively short time shows an amorphous phase with quartz and plagioclase phases and the plagioclase is removable at longer leaching times during which no disruptive effect on the fine microscopic pores of the particles was observed. Thus, the diatomite based powders have potential use in the fabrication of porous coating as a membrane-separating layer: sintering at a relatively high temperature (1300 °C) still showed a significantly high apparent porosity of 48%.