Leaching Behavior of Silver in Reduction Acid Leaching Process of Mn-Ag Paragenesis Ore AITranslate

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Basic Information:

DOI：10.13373/j.cnki.cjrm.XY24090016

Chinese Library Classification Number:TD865

Citation Information:

Manganese-silver ore is an important precious metal strategic resource in China，it often associated with copper，gold，iron，and other minerals. Under the weathering and other environmental effects，Cu²⁺，Ag⁺，Pb²⁺，and other cations can enter the manganese minerals’ tunnel structure，which forming a multi-metal paragenesis ore with extremely complex mineralogical properties. Therefore，it is difficult to study mineralogy，beneficiation-metallurgy technology and engineering in the utilization of such resources. These situations had led to a low-level development and comprehensive utilization rate of multi-metals for a long time. The ore sample came from Fe-Mn-Ag polymetallic ore in Yunnan，China. Raw ore was prepared by crushing，grinding，and high gradient magnetic separation （HGMS），the research object was obtained. This article conducted chemical multi-element analysis，mineral liberation analyzer （MLA）mineral composition analysis，silver phase analysis，potential-pH （E_h-pH）relationship analysis，solution chemistry analysis，and scanning electron microscopy-energy dispersive spectrometer （SEM-EDS）analysis. The article systematically studied the main mineral types and contents in ores，the chemical phase composition of silver，the influence of acidic leaching pH on silver recovery，the leaching E_h-pH relationship of iron and manganese，the precipitation conditions of iron hydroxide，the mineral composition analysis of acid leaching residue，the particle size composition and metal distribution of silver in acid leaching residue，and the reaction relationship characterized between silver sulfate and iron colloids by SEM-EDS. The results showed that Ag content in the sample was 66.81×10⁻⁶，Mn content was 2.58%，and Fe content was 43.58%. The content of Mn and Ag were low relatively，and the main element was Fe. Most of the minerals in the sample were limonite，with a content of 70.18%，followed by manganese minerals with a content of 9.17%. The content of visible silver mineral was low，and the main gangue minerals were quartz and dolomite. The distribution rate of silver combined with manganese was 75.47%，while the distribution rate of silver combined with limonite was 6.78%. The content of native silver and silver sulfide were low. When pH of acid leaching was 3，the actual recovery rate of silver reached its highest value，and as pH further decreased，the silver recovery rate decreased significantly. E_h-pH relationship of Fe and Mn in this reaction system was calculated by hydrocarbon system calculator （HSC）chemistry software. Mn²⁺ in the acid leaching solution had a wide range solubility，even in alkaline environments，so it would not have a significant impact on the material composition of the acid leaching solution. Under conditions of insufficient acid dosage，Fe would form Fe（OH）SO₄ and Fe（OH）₃ colloids or precipitates. Under conditions of excessive acid，iron colloids would react with H⁺ and SO₄²⁻to form Fe₂（SO₄）₃，which was soluble. At the same time，Fe²⁺ or Fe³⁺ would be hydrolyzed to form Fe（OH）₂ and Fe（OH）₃ precipitates. According to solution chemistry calculations，the theoretical pH at which Fe（OH）₃ began to precipitate was about 1.48，and the theoretical pH at precipitated completely was about 2.82. Based on the above analysis，a principle model for the coagulation of silver sulfate by iron colloids had been designed. Through the study of acid leaching residue，it was found that FeOOH-colloid （colloidal hydroxide iron oxide）was a new substance in the acid leaching reaction，with a mineral content of 7.54%. Further analysis showed that the products were the final substance of the aging reaction of colloidal precipitates，such as Fe（OH）₃. Ag distribution rate in acid leaching residue was mainly concentrated in the fine particle size of -0.020 mm，especially in -0.010 mm particle size，where Ag content was as high as 432×10⁻⁶. This phenomenon indicated a significant enrichment effect，and the particle size of newly formed silver sulfate was finer generally. In SEM images，a large amount of FeOOH-colloid could be observed in the acid leaching residue，which was dispersed by ultrasonic waves，but no silver was found. The overall particle size of FeOOH-colloid was extremely fine，even reaching the micro-nano scale. In the agglomerative state of the sample （without ultrasonic waves treated），EDS could detect the points with high silver content. Ag content was 4%~15% and sulfur trioxide content was 4%~11%，which proved the presence of silver sulfate. EDS surface scanning analysis revealed that Ag element was extremely dispersed in the iron colloid，with high brightness clusters appearing in some positions. The two-dimensional spatial scale of silver reached the nanometer level. At the same time，the results showed that the iron colloid can adsorb silver sulfate precipitation. These findings provided some theoretical supports for the efficient utilization of refractory manganese silver resources.