Comprehensive recovery method for tin removal slag of crude copper

A recovery method and a technology for removing tin slag, applied in the direction of improvement of process efficiency, sulfur preparation/purification, etc., can solve problems such as low softening point of blister copper slag removal, difficult processing of alloy products, and treatment of sulfur dioxide gas, etc., to achieve reduction Outsourcing, low cost, and the effect of reducing production costs

Pending Publication Date: 2022-04-22
ZHUZHOU SMELTER GRP
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AI Technical Summary

Problems solved by technology

[0003] (1) Pyromelting: A certain proportion of flux is mixed in a short kiln for smelting to produce semi-products of tin-copper alloy. Due to the large amount of impurities in the slag entering the alloy, there are certain difficulties in further processing of the alloy product
[0004] (2) Roasting-leaching method: After roasting the crude copper descaling slag, sulfuric acid is used to leaching the calcine, so that copper is opened from the tin smelting system in the form of copper sulfate products. The softening point of tin slag is low, and multi-stage roasting is required to achieve the purpose of roasting without kiln formation and sulfur removal, so that the roasting time is very long and the processing cost is high
This kind of fire method or partial fire method has the problem of sulfur dioxide gas treatment or waste gas pollution.
[0007] (5) All-wet process: Some researchers have carried out research on the full-wet treatment process of blister copper tin slag removal, which is to decompose the blister copper tin slag with hydrochloric acid, so that all the components in the slag enter the solution, and then in the solution The separation of each element in this method has the disadvantages of lengthy process flow and complicated process.

Method used

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  • Comprehensive recovery method for tin removal slag of crude copper

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0044] Step A, ball milling: the mass percent concentration is: Sn 55.15%, Cu 15.45%, S 12.41%, Ag 0.147% blister copper tin removal slag is carried out ball milling, the particle size of the crude copper tin removal tin slag after ball milling is 60 μ m (- 250 mesh) to 100%, or a particle size of 45 μm (-320 mesh) to 80%.

[0045] Step B, Oxygen-enriched leaching: Add the ball-milled crude copper descaling slag obtained in Step A into the sulfuric acid leaching solution for leaching, the leaching liquid-solid ratio = 10:1 (mass ratio), leaching temperature 99 ° C, leaching time = 18 hours, Oxygen unit consumption for oxygen-enriched leaching is 200 m 3 / t crude copper to remove tin slag, the initial concentration of Fe is 4g / L, and the activator added is ferric sulfate; the terminal acidity is 18g / L, Fe 3+ : Fe 2+ = 5:1, add 8g / L sodium persulfate half an hour before the end of the leaching, filter and separate to obtain the leaching residue and the leaching solution conta...

Embodiment 2

[0050] Step A, ball milling: after ball milling the blister copper desoldering slag with mass percent concentration: Sn 55.15%, Cu 15.45%, S 12.41%, Ag 0.147%, the obtained particle size is 58 μm up to 100%, and 44 μm up to 80%.

[0051] Step B, Oxygen-enriched leaching: Add the ball-milled crude copper descaling slag obtained in Step A into sulfuric acid leaching solution for leaching, leaching liquid-solid ratio = 20:1 (mass ratio), leaching temperature 96 ° C, leaching time = 24 hours, Oxygen unit consumption for oxygen-enriched leaching is 150 m 3 / t crude copper to remove tin slag, the initial concentration of Fe is 4g / L, and the activator added is a mixture of ferric sulfate and ferrous sulfate; the terminal acidity is 28 g / L, Fe 3+ : Fe 2+ = 4:1, add 12g / L ammonium persulfate half an hour before the end of leaching, filter and separate to obtain the leaching residue and the leaching solution containing copper sulfate, the leaching solution contains Sn 0.031g / L, and th...

Embodiment 3

[0056] Step A, ball milling: after ball milling the crude copper desoldering slag with a mass percentage concentration of: Sn 55.15%, Cu 15.45%, S 12.41%, Ag 0.147%, the obtained particle size is 59 μm up to 100%, and 43 μm up to 80%.

[0057] Step B, Oxygen-enriched leaching: Add the ball-milled crude copper descaling slag obtained in Step A into the sulfuric acid leaching solution for leaching, the leaching liquid-solid ratio = 15:1 (mass ratio), leaching temperature 98 ° C, leaching time = 21 hours, The unit oxygen consumption of oxygen-enriched leaching is 180 m 3 / t crude copper to remove tin slag, the initial concentration of Fe is 5g / L, and the activator added is ferrous sulfate; the terminal acidity is 22g / L, Fe 3+ : Fe 2+ = 4.5:1, add 10g / L potassium persulfate half an hour before the end of leaching, filter and separate to obtain leaching residue and copper sulfate-containing leaching solution, the leaching solution contains 0.025g / L of Sn, and the Cu content in th...

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Abstract

The invention discloses a comprehensive recovery method for crude copper tin removal slag. The comprehensive recovery method comprises the following steps: A, carrying out ball milling on the crude copper tin removal slag; b, adding the tin-removed slag of the crude copper subjected to ball milling into a sulfuric acid leaching solution for leaching, and filtering and separating to obtain leaching slag and a leaching solution containing copper sulfate; c, flotation is conducted, specifically, segmented flotation is conducted on the leaching residues, and sulfur concentrate and tailings are obtained when an inhibitor CaO is added and the pH value is adjusted to be 6.5-8.0 during first-segment flotation; the pH value of the second-stage flotation is 4.5-6.0, a flotation agent is added for flotation, and silver concentrate and tin concentrate are obtained; and D, iron powder reduction is conducted, specifically, reduced iron powder is slowly added into the leachate obtained in the step B, the reduction temperature is 50-60 DEG C, the end point potential is controlled to be 90-140 mv, and copper removal liquid and copper slag are obtained. According to the method, the leaching rate of copper can exceed 95%, addition of reduced iron powder is reduced, and consumption of acid in the reduction process is reduced. The comprehensive recovery of the crude copper tin removal slag has the advantages of reasonable process, low separation cost, no pollution, no toxicity and the like.

Description

technical field [0001] The invention relates to the technical fields of hydrometallurgy and chemical industry, in particular to a comprehensive recovery method for removing tin slag from blister copper. Background technique [0002] In the tin smelting process, the tin concentrate is reduced and smelted to obtain crude tin, and the crude tin is subjected to fire refining by adding sulfur and removing copper. And 10 to 18% blister copper slag (also known as sulfur slag or copper tin), also contains a certain amount of silver. Most of the tin in this slag exists in the form of hydrocassiterite, metallic tin, tin sulfide or copper-tin alloy, most of the copper exists in the form of copper metal copper and its sulfide, and there is a small amount of copper sulfate. At home and abroad, there are mainly the following methods for the treatment of such blister copper slag removal: [0003] (1) Pyromelting: A certain proportion of flux is mixed in a short kiln for smelting to produ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C22B7/04C22B15/00C22B11/00C22B25/06C01B17/06
CPCC22B7/04C22B7/007C22B15/0071C22B15/0089C22B25/04C22B25/06C22B11/044C01B17/06Y02P10/20
Inventor 廖贻鹏林文军王勇周玉琳唐亦秋陈敬阳
Owner ZHUZHOU SMELTER GRP
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