CN1540007A - Decoppering refining agent in use for fire refining of non-ferrous metal with low melting point and technical procedure - Google Patents
Decoppering refining agent in use for fire refining of non-ferrous metal with low melting point and technical procedure Download PDFInfo
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- CN1540007A CN1540007A CNA2003101108301A CN200310110830A CN1540007A CN 1540007 A CN1540007 A CN 1540007A CN A2003101108301 A CNA2003101108301 A CN A2003101108301A CN 200310110830 A CN200310110830 A CN 200310110830A CN 1540007 A CN1540007 A CN 1540007A
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Abstract
A copper-removing refining agent for refining low-smelting-point non-ferrous metal is NaOH and S. Its copper-removing process includes smelting the non-ferrous metal at 280 deg.C, adding NaOH while stirring until it is fused and floating on the surface of metal, adding S, heating to 650-680 deg.C, stirring for 30 min, cooling to 450-500 deg.C for generating slag, and removing the slag. Its advantages are high copper-removing efficiency and short time.
Description
The technical field is as follows:
the invention relates to a decoppering refining agent in the fire refining of low-melting point nonferrous metal and a process thereof, belonging to the technical field of fire refining in nonferrous metallurgy.
Background art:
the traditional method for removing copper by fire refining of low-melting-point nonferrous metals such as bismuth, lead, tin and the like is a copper removal method by adding sulfur. However, the conventional refining method of adding sulfur and removing copper has the following disadvantages: (1) when sulfur is added at a temperature above the melting point of the metal, the sulfur is extremely easy to burn violently, so that the consumption of the sulfur is increased, and the safety of operators is threatened; (2) the copper removal efficiency is low, when the copper content of the crude metal is reduced from 0.0 x% to 0.001-0.0005%, multiple times of sulfurization, stirring for two hours each time and long-time heating and cooling are required, and the unit equipment productivity and labor productivity in the copper removal process are very low; (3) the copper slag has high content of target metal and low metal recovery rate in the copper removing process. Taking fire refining of bismuth as an example, the slag after adding sulfur and removing copper contains 55-70% of bismuth, and the slag after removing copper takes away a large amount of bismuth, so that the direct yield of bismuth is reduced.
Through the literature search, the public reports of the same technology as the invention are not found.
The invention content is as follows:
the invention aims to overcome the defects of the prior art and provide a copper removal technology in the fire refining of low-melting-point nonferrous metals, which has high copper removal efficiency and high direct yield of target metals.
The principle of the invention is as follows:
the main reactions of the copper removal and refining of the low-melting metal are as follows:
according to the calculation of free energy of formation of the compound, at a lower temperature (280 ℃. + -.) the affinity of sulfur to Bi, Sn, Pb is greater than that to copper, and this time it is favorable for sulfur to be absorbed by the host metal (Bi, Sn, Pb) to form the intermediate sulfide (Bi)2S3SnS, PbS), and at higher temperatures (e.g., 650 ℃. + -.) the affinity of sulfur for copper is greater than that for the target metal (Bi, Sn, Pb), which facilitates reactions (1), (2), and (3) to the right, converting the intermediate sulfide formed at low temperatures into copper sulfide into a slag phase. The addition of NaOH not only reduces the slag phaseThe dissolution of the target metal also reduces the specific gravity of the slag phase and reduces the melting of the slag phasePoint, is in favor of Cu2The separation of S slag and metal is more beneficial to the separation of target metal (bismuth, tin and copper) and slag, greatly reduces the mechanical entrainment of slag relative to the target metal and improves the direct recovery rate of metal. In addition, the addition of NaOH reduces Cu2The activity or concentration of S in slag phase is favorable for Cu2S enters a slag phase, so that the copper removal efficiency is improved.
The copper-removing refining agent consists of industrial NaOH and sulfur; wherein, the addition of the industrial NaOH is 1.0-2.0% of the total amount of the crude metal, and the addition of the sulfur is 1.25 times of the total amount of the crude metal.
The copper removing process comprises the steps of adding sodium sulfide at low temperature, removing copper at high temperature, cooling and fishing slag, namely: adding industrial NaOH accounting for 1.0-2.0% of the total amount of the crude metal at 280 ℃, wherein the water content of the NaOH is 25-30%, stirring until the NaOH is melted and floats on the surface of the metal, pressing sulfur which is 1.25 times of the copper content of the crude metal, heating to 650-680 ℃, starting a stirrer for stirring for 30 minutes, standing, reducing the temperature to 450-500 ℃, and fishing slag when refined scum is crusted and separated from the metal melt.
The decoppering refining agent and the decoppering process are suitable for decoppering refining of bismuth, tin and lead, and the decoppering frequency is determined according to the copper content of the crude metal.
Compared with the conventional refining of adding sulfur and removing copper, the invention has the following advantages: (1) the primary copper removal efficiency is improved by 4-5 times compared with the conventional copper removal by adding sulfur; (2) compared with the conventional copper removal by adding sulfur, the copper removal only consumes 1/4-1/6 of the time of adding sulfur and removing copper, so that the productivity and labor productivity of unit equipment are greatly improved; (3) the slag yield is low, and the slag contains less metal, so that the direct yield of the target metal is high; (4) the energy consumption is reduced to 1/4-1/5; (5) the safety is good, and the violent oxidation combustion of sulfur cannot be generated; (6) due to the addition of NaOH, impurities such As Fe, As, Sb and the like are removed in the copper removing process, so that the time and consumption for removing Fe, As and Sb in the next refining step are reduced.
The specific implementation mode is as follows:
example 1 (high efficiency decoppering refining of crude bismuth):
taking 3T crude bismuth with copper content of 0.034%, heating and melting in a refining pot, reducing the temperature to 280 ℃ by pressing fire, adding industrial NaOH (45 kg, wherein 10 kg is the last slag after last copper removal) accounting for 1.5% of the weight of the crude bismuth, reducing the surface temperature of metal after adding the NaOH, properly and manually stirring to ensure that the temperature is uniform from top to bottom, adjusting the temperature of a slag phase and the metal to 280 ℃, adding sulfur (1.3 kg) with copper content of 1.25 times of the crude bismuth, inserting the sulfur into the slag phase by a clamp, immediately covering the sulfur by viscous scum, and preventing the sulfur from being oxidized and combusted, and regarding granular or powdery sulfur. After the addition, the mixture is rapidly stirred, so that the mixture is coated by slag phase and can also prevent oxidation combustion. And after slightly manually stirring, heating to 680 ℃ by adding fire, starting the stirrer, stirring for 30 minutes, stopping the machine, standing, cooling to 450 ℃, wherein the slag is encrusted, the brittle and hard slag shell is broken, the slag can be fished by a strainer, the slag yield is 28.6 kg, the bismuth content of the firstly fished slag is 1.5-3.5% (weight is 18.6 kg), the slagis intensively treated as copper slag, the bismuth content of the later fished slag is 4.5-10.6% (weight is about 10 kg), and the bismuth is added again as an additive added with NaOH next time so as to recover excessive bismuth in the slag. The amount of NaOH added for copper removal in the second refining is 1 percent, namely 30 kg (containing 10 kg of returned high-bismuth slag), and the amount of sulfur added is 1.25 times (namely 0.10 kg) of the amount of copper contained in the crude bismuth. The operation is the same as the first copper removal. After two times of adding sodium sulfate to remove copper, the copper content in bismuth is reduced to 0.0006% (lower than the requirement of No. 1 refined bismuth).
Example 2 (high efficiency decoppering refining of crude bismuth):
the operation process and the implementation mode are the same as example 1, taking 3T crude bismuth, wherein the copper content is 0.806%. The difference is that: 1.5 percent of NaOH (45 kg of NaOH is 10 kg of NaOH returned to the high-bismuth slag) is added in the first copper removal, and the sulfur addition amount is 1.25 times (24.2 kg) of the copper content of the crude bismuth; and 1.0 percent of NaOH (30 kg, wherein 10 kg is high bismuth return slag) is added for the second copper removal, and the sulfur content is 1.25 times (0.5 kg) of the copper content of the crude bismuth.
The change of the impurity copper in the bismuth in the above two examples with the refining process is shown in Table 1. The technical and economic indexes of bismuth refining and copper removal are shown in table 2.
TABLE 1 change of copper content in bismuth during high efficiency decoppering
| Serial number | Crude bismuth copper (%) | Copper content after the first copper removal | Copper content after the second copper removal |
| Example 1 | 0.0446 | 0.00248 | 0.0006 |
| Example 2 | 0.806 | 0.016 | 0.0010 |
Example 3 (high efficiency copper removal for crude tin refining):
taking 4T crude tin with copper content of 0.64%, heating and melting the crude tin after the crude tin is put into a pot, adjusting the temperature of a tin melt to 280 ℃, adding industrial NaOH (40 kg, wherein 10 kg is the return amount of high-tin copper slag) with the crude tin content of 1.0%, and then adding sulfur (27 kg) with the copper content of 1.25 times of the crude tin. Firstly adding NaOH, slightly stirring to melt the NaOH into a viscous state, then pressing the NaOH into the massive sulfur by using a clamp, slightly tilting the sulfur after adding the sulfur to cover the sulfur by viscous scum so as to prevent oxidation combustion, quickly stirring the granular and powdery sulfur after adding the sulfur and mixing the granular and powdery sulfur with the scum, and also preventing the oxidation combustion, slightly manually stirring the sulfur up and down after adding the sulfur, then standing and heating the sulfur to 650 ℃, starting a mechanical stirrer to stir the sulfur for 30 minutes, standing and cooling the sulfur to scum crusting (about 450 ℃), fishing out the slag by using a strainer, wherein the tin content of the slag fished out firstly is 1.5-3.5%, the slag fished out can be centrally stacked for treatment, the tin content of the slag fished out later is up to 4.5-10%, and the slag can be returned to the next copper removal refining for adding the NaOH. After the copper is removed for one time, the copper content of the crude tin can be reduced to be below 0.01 percent (reaching the standard of No. 1 refined tin), and the technical and economic indexes of the efficient copper removal and refining of the crude tin are shown in a table 2.
Example 4 (high efficiency copper removal for lead bullion fire refining):
the method comprises the following steps of taking 4T crude lead with 1.6 percent of copper, melting the crude lead in a refining pot, adding industrial NaOH (namely 80 kg, wherein 15 kg is returned from the high lead slag after copper removal at the last time) according to 2.0 percent of the crude lead, adding sulfur (namely 64 kg) according to 1.25 percent of the copper content of the crude lead, carrying out the first crude lead copper removal refining according to the operation process of example 3, and reducing the copper content of the crude lead to 0.054 percent after the first copper removal refining and not reaching the copper content standard of No. 1refined lead, so that the second high-efficiency copper removal is necessary. The second copper removal is carried out by adding industrial NaOH with 1.5 percent of crude lead content (namely 60 kilograms, wherein 15 kilograms is the high lead return slag refined last time), adding sulfur (2.7 percent of copper content is 0.054 percent) according to 1.25 percent of copper content in lead, and then carrying out the second copper removal operation of crude lead refining according to the operation of the example 3, after the second copper removal, the copper content of the crude lead is reduced to be less than 0.001 percent, so as to reach the copper content standard of No. 2 lead, and the copper removal of the refining can be finished. The technical and economic indexes of the high-efficiency copper removal refining of the crude lead are shown in the table 2.
TABLE 2 technical economic indices for efficient refining of crude (bismuth, tin, lead) copper
| Metal | Copper removing process | For the first time Copper removing effect Percentage ratio% | Need to make Copper removal Number of times | Copper removing assembly Time (small) Time) | Total slag rate ％ | The slag content is high Metal (%) | Copper removing device Distance direct collecting Percentage ratio% | Safety feature |
| Bismuth (III) | Sulfurizing to remove copper | 5～20％ | 6 | 20--24 | 25 | 67.16 | 83.2％ | Is not safe |
| Inventive example 1 | ～94.5％ | 2 | 4 (Liansheng) Temperature reduction) | 4.5 | 1.6～4.5％ Average is 2.6% | 96.5％ | Security | |
| Inventive example 2 | ＞98％ | 2 | 4 | 5.5 | 1.5～4.2％ Average 2.58 percent | 98.6％ | Security | |
| Tin (Sn) | Sulfurizing to remove copper | 10～25％ | 4 | 16～20 | 20～25％ | Average 75% | 85％ | Is not safe |
| Inventive example 3 | ～98.4％ | 1 | 2.5 | 5.1％ | 1.5～3.5％ Average is 2.5% | 95％± | Security | |
| Lead (II) | Sulfurizing to remove copper | 10～25％ | 3--5 | 17-24 | 26～30％ | 95％ | 79.85％ | Is not safe |
| Inventive example 4 | 96.6％ | 2 | 4.5 | 2.5％ | 1.6～3.7％ Average is 2.7% | 94.1％ | Security |
Claims (2)
1. A decoppering refining agent in the fire refining of low-melting nonferrous metals is characterized in that the decoppering refining agent consists of industrial NaOH and sulfur; wherein, the addition of the industrial NaOH is 1.0-2.0 percent of the total amount of the crude metal, and the addition of the sulfur is 1.25 times of the copper content of the crude metal.
2. A copper removal process in the fire refining of low-melting-point nonferrous metals is characterized by comprising the following steps of adding sulfur alkali at a low temperature, removing copper at a high temperature, cooling and fishing slag, namely: adding industrial NaOH accounting for 1.0-2.0% of the total amount of the crude metal at 280 ℃, wherein the water content of the NaOH is 25-30%, stirring until the NaOH is melted and floats on the surface of the metal to form paste, pressing sulfur with the copper content 1.25 times that of the crude metal, heating to 650-680 ℃, starting a stirrer for stirring for 30 minutes, standing, reducing the temperature to 450-500 ℃, and fishing slag when scum to be refined is crusted and separated from metal melt.
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| CN 200310110830 CN1233857C (en) | 2003-10-28 | 2003-10-28 | Decoppering refining agent in use for fire refining of non-ferrous metal with low melting point and technical procedure |
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| CN 200310110830 CN1233857C (en) | 2003-10-28 | 2003-10-28 | Decoppering refining agent in use for fire refining of non-ferrous metal with low melting point and technical procedure |
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| CN1540007A true CN1540007A (en) | 2004-10-27 |
| CN1233857C CN1233857C (en) | 2005-12-28 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1908853A4 (en) * | 2005-07-26 | 2010-03-17 | Nihon Superior Sha Co Ltd | METHOD OF DEPOSITING COPPER IN LEAD-FREE SOLDER, METHOD OF GRANULATING (CuX)6Sn5 COMPOUND AND METHOD OF SEPARATING THE SAME, AND METHOD OF RECOVERING TIN |
| CN102978416A (en) * | 2012-12-23 | 2013-03-20 | 河南豫光金铅股份有限公司 | Device and method for continuously removing copper from liquid crude lead |
| CN104357682A (en) * | 2014-12-09 | 2015-02-18 | 山东恒邦冶炼股份有限公司 | Method for efficiently removing copper through crude bismuth pot refining |
| CN107574307A (en) * | 2017-09-07 | 2018-01-12 | 昆明鼎邦科技股份有限公司 | A kind of method for recycling stannous sulfide separation signal bronze |
| CN115637368A (en) * | 2017-12-14 | 2023-01-24 | 梅塔洛比利时公司 | Improved pyrometallurgical process |
-
2003
- 2003-10-28 CN CN 200310110830 patent/CN1233857C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1908853A4 (en) * | 2005-07-26 | 2010-03-17 | Nihon Superior Sha Co Ltd | METHOD OF DEPOSITING COPPER IN LEAD-FREE SOLDER, METHOD OF GRANULATING (CuX)6Sn5 COMPOUND AND METHOD OF SEPARATING THE SAME, AND METHOD OF RECOVERING TIN |
| CN102978416A (en) * | 2012-12-23 | 2013-03-20 | 河南豫光金铅股份有限公司 | Device and method for continuously removing copper from liquid crude lead |
| CN102978416B (en) * | 2012-12-23 | 2015-01-07 | 河南豫光金铅股份有限公司 | Device and method for continuously removing copper from liquid crude lead |
| CN104357682A (en) * | 2014-12-09 | 2015-02-18 | 山东恒邦冶炼股份有限公司 | Method for efficiently removing copper through crude bismuth pot refining |
| CN107574307A (en) * | 2017-09-07 | 2018-01-12 | 昆明鼎邦科技股份有限公司 | A kind of method for recycling stannous sulfide separation signal bronze |
| CN107574307B (en) * | 2017-09-07 | 2019-04-23 | 昆明鼎邦科技股份有限公司 | A method of stannous sulfide is recycled and separates copper-tin alloy |
| CN115637368A (en) * | 2017-12-14 | 2023-01-24 | 梅塔洛比利时公司 | Improved pyrometallurgical process |
| CN115637368B (en) * | 2017-12-14 | 2023-08-15 | 梅塔洛比利时公司 | Improved pyrometallurgical process |
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| CN1233857C (en) | 2005-12-28 |
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