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CN-121992190-A - Cascade treatment and multi-metal collaborative recovery process for micro-particle wrapped sulfur concentrate

CN121992190ACN 121992190 ACN121992190 ACN 121992190ACN-121992190-A

Abstract

The invention relates to a step treatment and multi-metal collaborative recovery process of a micro-particle wrapped sulfur concentrate, which comprises (1) acid complexing strengthening desilication pretreatment, (2) two-stage temperature-control atmosphere roasting, namely one-stage low-temperature reducing atmosphere vulcanization volatilizing dearsenification, two-stage medium-temperature oxidizing atmosphere pore-forming desulfurization, (3) selective copper extraction by reductive ammonia, and (4) non-cyanide gold and silver leaching. The cascade treatment and multi-metal collaborative recovery process constructs a complete technical chain from 'source blocking secondary wrapping' to 'arsenic and sulfur recycling' to 'multi-metal cascade recovery', so that gold and silver recovery rates are respectively stabilized at 90% and above 80%, copper recovery rate is above 88%, iron concentrate grade is >62%, arsenic is less than or equal to 0.10%, sulfur is less than or equal to 1.0%, arsenic and sulfur recycling rate is >95%, comprehensive utilization rate of resources is improved by more than 35%, and comprehensive breakthrough of four dimensions of recovery rate of valuable elements, product quality, environmental protection benefit and economy in refractory sulfur concentrate is realized.

Inventors

  • Zhou Guanglang
  • LIAO JINCHUAN
  • DUAN SHENGHONG
  • LI YAMIN
  • ZHOU DONGYUN

Assignees

  • 云南黄金矿业集团股份有限公司

Dates

Publication Date
20260508
Application Date
20260306

Claims (9)

  1. 1. The step treatment and multi-metal collaborative recovery process for the micro-particle coated sulfur concentrate is characterized by comprising the following steps of: (1) The acidic complexation strengthening desilication pretreatment comprises the steps of pulping the micro-particle wrapped sulfur concentrate to a concentration of 30% -35%, adding oxalic acid to adjust the pH value to 6-6.8, and then sequentially adding a composite inhibitor, a composite collector and a foaming agent for flotation desilication to obtain desilication sulfur concentrate, wherein the composite inhibitor is a mixture of sulfonated CMC (sulfonated carboxymethyl cellulose) and acidified modified sodium silicate, the composite collector is a mixture of isobutyl xanthate and butylammonium black drug, and the foaming agent is No. 2 oil; (2) Two-stage temperature-controlled atmosphere roasting, namely uniformly mixing desilication sulfur concentrate obtained in the step (1) with a vulcanizing agent, then sending the mixture into a rotary kiln for one-stage roasting, roasting for 1.5-2.5 hours in a weak reducing atmosphere (nitrogen protection) with the oxygen content of 0.5% -1.0%, carrying out thermal decomposition and vulcanization reaction on the toxic sand to generate volatile As 2 S 3 smoke SO As to realize dearsenification, and obtaining dearsenification calcine; (3) Reducing ammonia to extract copper selectively, namely pulping the oxidized calcine obtained in the step (2) to 35% -40%, adding ammonia water, ammonium carbonate and sodium sulfite, leaching for 1.5-2.5 hours under the condition of 45-60℃, pH 9.5.5-10.5, enabling copper to enter a solution in a copper ammonia complex ion manner, realizing selective leaching of copper, and obtaining copper-rich leaching solution and ammonia leaching tailings after solid-liquid separation; (4) And (3) non-cyanide leaching gold and silver, namely, pulping the ammonia leaching tailings obtained in the step (3) to a concentration of 30% -35%, adding lime to adjust the pH value to 11-11.5, pre-alkaline leaching for 3-5 hours at normal temperature to remove residual ammonia and fix harmful impurities, and then adding a non-cyanide gold leaching agent to leach for 24-30 hours to enable gold and silver to enter noble liquid in a complex ion form, wherein the leached tailings are iron concentrate.
  2. 2. The process for cascade treatment and multi-metal collaborative recovery of micro-particle coated sulfur concentrate according to claim 1, wherein the oxalic acid consumption in the step (1) is 1.5-2.5 kg/t.
  3. 3. The step treatment and multi-metal collaborative recovery process for the micro-particle wrapped sulfur concentrate is characterized in that oxalic acid is added and stirred for 8-12 min, a composite inhibitor is added and stirred for 5-8 min, a composite collector is added and stirred for 3-5 min, a foaming agent 2# oil is added and stirred for 1-2 min in the step (1), and the flotation is a one-time roughing and two-time scavenging process.
  4. 4. The step treatment and multi-metal collaborative recovery process for the micro-particle coated sulfur concentrate is characterized by comprising the steps of (1) adding 290-350 g/t sulfonated CMC, 440-500 g/t acidified modified water glass, 125-135 g/t isobutyl xanthate, 45-55 g/t butylammonium black drug, 38-45 g/t 2# oil, adding 145-175 g/t sulfonated CMC, 210-250 g/t acidified modified water glass, 62-68 g/t isobutyl xanthate, 23-33 g/t butylammonium black drug, 19-23 g/t 2# oil, and adding 72-90 g/t sulfonated CMC, 105-125 g/t acidified modified water glass, 28-34 g/t isobutyl xanthate, 12-17 g/t butylammonium black drug and 9-12 g/t 2# oil through one-time rough cleaning.
  5. 5. The process for cascade treatment and multi-metal collaborative recovery of micro-particle wrapped sulfur concentrate according to claim 1, wherein the vulcanizing agent in the step (2) is elemental sulfur powder with the dosage of 15-25kg/t, and nitrogen is introduced into the rotary kiln at a speed of 350-450 Nm < 3 >/t.
  6. 6. The step treatment and multi-metal collaborative recovery process for the micro-particle wrapped sulfur concentrate according to claim 1 is characterized in that the As 2 S 3 flue gas in the step (2) is recovered by a dust collection and condensation system to obtain a high-purity As 2 S 3 product, and the SO 2 flue gas is recovered by a dust collection and acid making system to prepare sulfuric acid.
  7. 7. The process for cascade treatment and multi-metal collaborative recovery of micro-particle wrapped sulfur concentrate according to claim 1, wherein the ammonia water in the step (3) is 80-100 kg/t, ammonium carbonate is 35-45 kg/t, and sodium sulfite is 5-10kg/t.
  8. 8. The process for cascade treatment and multi-metal collaborative recovery of micro-particle wrapped sulfur concentrate according to claim 1, wherein the lime dosage in the step (4) is 4-6 kg/t.
  9. 9. The process for cascade treatment and multi-metal collaborative recovery of micro-particle wrapped sulfur concentrate according to claim 1, wherein the non-cyanide gold leaching agent in the step (4) is a cyano-like environment-friendly gold leaching agent or a lime sulphur gold leaching agent, and the dosage of the non-cyanide gold leaching agent is 3-5 kg/t.

Description

Cascade treatment and multi-metal collaborative recovery process for micro-particle wrapped sulfur concentrate Technical Field The invention belongs to the technical field of mineral processing recovery, and particularly relates to a step treatment and multi-metal collaborative recovery process for micro-particle wrapped sulfur concentrate, which is particularly suitable for treating high-arsenic refractory sulfur concentrate containing gold, silver, copper and iron. Background The micro-particle coated high-arsenic sulfur concentrate is a typical difficult-to-treat resource facing the gold smelting industry in China, wherein the occurrence state of valuable elements of gold, silver, copper and iron and harmful elements of arsenic and sulfur is complex, main carriers of gold and silver are pyrite and arsenopyrite, the embedded granularity is extremely fine (< 5 mu m), the dissociation degree of monomers is low, more than 50% exists in a sulfide coating form, compact coating is formed, and the co-occurrence relationship with arsenic is close. The conventional regrinding and re-leaching process is difficult to damage the wrapping structure, so that the leaching rates of gold and silver are only 40% and 20% -25%, respectively, and a great deal of valuable metals are lost. Aiming at the problems, although the leaching rate of gold and silver is improved to 65% -70% and 30% -40% by the improved roasting-cyanidation technology, the effective recovery is not realized, the iron concentrate after roasting has high arsenic and sulfur content (about 1.02% of arsenic and about 2.56% of sulfur), the iron grade is lower (57% -58%), the copper is not effectively recovered, and the comprehensive utilization of resources is not sufficient. The main technical bottleneck is that the traditional one-stage oxidation roasting is used for strengthening sulfur and arsenic removal, and high-temperature (700 ℃) oxidation conditions are generally adopted, but the conditions are easy to cause three problems. Firstly, the material is easy to sinter to form a compact smooth surface, but is not in an ideal porous structure, so that contact reaction of cyanide medicament and gold and silver particles is seriously hindered, secondly, feO in the material can react with SiO 2 to generate low-melting silicate such As fayalite and the like, so that dissociated and bare micro-particle gold and silver are re-wrapped and sealed by a molten glass phase to form a 'secondary wrapping' effect, leaching of gold and silver is further limited, thirdly, newly generated As 2O3 can react with Fe 2O3 in high-temperature oxidizing atmosphere to generate stable ferric arsenate, and arsenic is solidified in calcine, so that the arsenic content of iron concentrate exceeds the standard, and the product quality is seriously influenced. In addition, as 2O3 smoke dust generated by roasting is extremely toxic arsenic-containing smoke dust, and has the disadvantages of complex treatment flow, high cost and secondary pollution risk. Therefore, it is needed to develop an integrated technology capable of solving the above problems systematically, namely, high-efficiency dissociation of the fine particle inclusion, harmless removal of arsenic and sulfur, and multi-metal cascade recovery, so as to achieve the dual goals of comprehensive utilization of resources and green clean production. Disclosure of Invention The invention aims to provide a step treatment and multi-metal collaborative recovery process of micro-particle wrapped sulfur concentrate, which systematically solves the core problems of secondary wrapping, arsenic pollution, copper loss, iron resource waste and the like of the traditional process through the whole flow innovation of acid complexation strengthening desilication, low-temperature vulcanization volatilizing arsenic removal, medium-temperature oxidation pore-forming desulfurization, reductive ammonia leaching copper-non-cyanide gold and silver leaching. In order to achieve the above purpose, the present invention adopts the following technical scheme: a step treatment and multi-metal collaborative recovery process for micro-particle coated sulfur concentrate comprises the following steps: (1) The acidic complexation strengthening desilication pretreatment comprises the steps of pulping the micro-particle wrapped sulfur concentrate to a concentration of 30% -35%, adding oxalic acid to adjust the pH value to 6-6.8, and then sequentially adding a composite inhibitor, a composite collector and a foaming agent for flotation desilication to obtain desilication sulfur concentrate, wherein the composite inhibitor is a mixture of sulfonated CMC (sulfonated carboxymethyl cellulose) and acidified modified sodium silicate, the composite collector is a mixture of isobutyl xanthate and butylammonium black drug, and the foaming agent is No. 2 oil; Aiming at the core pain point that active ferrous oxide (FeO) can react with SiO 2 to generate fayalite and cause gold