CN113621820A - Smelting method of precious metal smelting slag - Google Patents

Smelting method of precious metal smelting slag Download PDF

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CN113621820A
CN113621820A CN202110851320.8A CN202110851320A CN113621820A CN 113621820 A CN113621820 A CN 113621820A CN 202110851320 A CN202110851320 A CN 202110851320A CN 113621820 A CN113621820 A CN 113621820A
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smelting
slag
oxide
precious metal
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CN113621820B (en
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李晓波
王立
田飞
刘兴焘
李生民
董春俊
张乃予
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Jinchuan Group Copper Precious Metals Co.,Ltd.
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/04—Working-up slag
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B11/00—Obtaining noble metals
    • C22B11/02—Obtaining noble metals by dry processes
    • C22B11/021—Recovery of noble metals from waste materials
    • C22B11/023—Recovery of noble metals from waste materials from pyrometallurgical residues, e.g. from ashes, dross, flue dust, mud, skim, slag, sludge
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/001—Dry processes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

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Abstract

本发明公开了一种贵金属熔炼渣的熔炼配比方法，包括如下步骤：将贵金属熔炼渣进行烘干、研磨，加入造渣剂得到混合料，控制混合料中的各组分含量及百分比为：二氧化硅30％～40％、氧化钙30％～35％、氧化锌4％～8％、氧化钠7％～10％、氧化硼5％～7％、氧化亚铁＜7％，向混合料中加入质量分数为混合料总量的20％的硫化矿后进行熔炼，经自然冷却后得到含贵金属的锍和还原渣。本发明可达到有效富集贵金属，解决了氧化锌对造渣带来的不利影响，对于含锌物料的火法提取提供了技术支撑。产出的低含贵金属还原渣可直接废弃，贵金属熔炼渣中的贱金属得到了开路。The invention discloses a smelting and proportioning method for precious metal smelting slag. Silica 30%~40%, calcium oxide 30%~35%, zinc oxide 4%~8%, sodium oxide 7%~10%, boron oxide 5%~7%, ferrous oxide <7%, to mix Sulfide ore with a mass fraction of 20% of the total amount of the mixture is added to the material and then smelted, and after natural cooling, the matte and reduced slag containing precious metals are obtained. The invention can achieve effective enrichment of precious metals, solve the adverse effect of zinc oxide on slag formation, and provide technical support for pyrotechnic extraction of zinc-containing materials. The outputted reducing slag with low precious metal content can be directly discarded, and the base metal in the precious metal smelting slag is opened.

Description

Smelting method of precious metal smelting slag
Technical Field
The invention belongs to the field of pyrometallurgical processes, and particularly relates to a method for smelting precious metal smelting slag, which can be used for smelting platinum group metal smelting slag and can also be applied to the pyrometallurgical enrichment of other heavy metals and rare metals.
Background
In the process of noble metal separation and refining, the content of noble metals in the produced wastewater is low, and the noble metals in the waste liquid need to be precipitated and recovered by adopting a zinc powder replacement method. Aiming at the produced precious metal precipitation slag, the precious metal content is generally low and is about 0.1-0.3%, and a wet method or a fire method is selected for further enriching and extracting the precious metal for treatment. The wet method comprises acid leaching and alkaline leaching, and because the activity of the precipitated slag is higher, in order to achieve a better enrichment effect, the precious metals in the leaching solution are dispersed in the solution again and need to be recycled repeatedly, and the base metals cannot be opened, so that the amount of the precipitated slag is increased continuously; in order to improve the treatment capacity and treatment efficiency, a nickel matte trapping method is generally adopted to enrich precious metals.
The zinc in the material is in contact with the air during the placing, and most of the zinc exists in the form of oxide. The zinc oxide is a compound difficult to melt, has great influence on the melting temperature of the slag, and increases the viscosity of the melting slag. In the process of smelting and slagging, the improper selection of the slag type proportion causes the serious dispersion of noble metals in slag, the smelting temperature is higher, the slag and matte are difficult to separate, the energy consumption is high, and the yield of the noble metals is lower.
Disclosure of Invention
In order to solve the adverse effect of zinc oxide in the smelting and slagging process, the invention obtains a smelting method with low smelting temperature, good slag-matte separation effect and low noble metal content in slag through experiments on the basis of researching the zinc-containing slag type and the principle.
The purpose of the invention is realized by the following technical scheme:
a smelting method of precious metal smelting slag comprises the following steps:
drying and grinding the noble metal smelting slag, adding a slagging agent, and mixing to obtain a mixture, wherein the content and percentage of each component in the mixture are controlled as follows: 30-40% of silicon dioxide, 30-35% of calcium oxide, 4-8% of zinc oxide, 7-10% of sodium oxide, 5-7% of boron oxide and less than 7% of ferrous oxide, blending sulphide ore with the mass of 15-25% of the total amount of the mixture into the mixture, smelting according to the mixture ratio, and naturally cooling to obtain the noble metal-containing matte and reducing slag.
Preferably, the slagging agent comprises quartz stone, quicklime, sodium carbonate and borax, wherein the addition of the quartz stone is calculated by silicon dioxide, the addition of the quicklime is calculated by calcium oxide, the addition of the sodium carbonate is calculated by sodium oxide, and the addition of the borax is calculated by boron oxide.
Preferably, the sulphide ore is one of nickel sulphide ore, iron sulphide ore and copper sulphide ore.
Preferably, the particle size of the grinding is-80 to-200 mesh.
Preferably, the smelting temperature is 1300-1400 ℃, and the smelting time is 40-70 min.
Preferably, the reducing slag contains less than 10g/t of precious metals.
The invention has the beneficial effects that: 1. the smelting slag has good fluidity and good smelting index, and provides technical support for the pyrometallurgical extraction of zinc-containing materials; 2. the produced low-content noble metal reducing slag can be directly discarded, and base metals in the noble metal smelting slag are opened.
Detailed Description
The invention is further illustrated by the following specific examples.
A smelting method of precious metal smelting slag comprises the following steps: drying the smelting slag of the platinum group metal, grinding the smelting slag to minus 80 meshes, analyzing the smelting slag of the platinum group metal to obtain the mass percentage content of silicon dioxide, calcium oxide, zinc oxide, sodium oxide, ferrous oxide, noble metals Au, Pd, Pt and the like, adding a slagging agent into the smelting slag of the platinum group metal to obtain a mixture, and controlling the content and percentage of each component in the mixture as follows: 30-40% of silicon dioxide, 30-35% of calcium oxide, 4-8% of zinc oxide, 7-10% of sodium oxide, 5-7% of boron oxide and less than 7% of ferrous oxide, blending sulphide ore with the mass of 15-25% of the total amount of the mixture into the mixture, smelting according to the mixture ratio, and naturally cooling to obtain the noble metal-containing matte and reducing slag.
Specific calculation methods are asThe following: and drying the platinum group metal smelting slag, and grinding to minus 80 meshes. The platinum group metal smelting slag 100g contains SiO232.46％，CaO28.5％，ZnO11.9％，Na2O4.5% and FeO 6.5%. According to the mass components of the mixture of platinum group metal smelting slag and a slagging constituent: 36% of silicon dioxide, 33% of calcium oxide, 5.6% of zinc oxide, 9% of sodium oxide, 5% of boron oxide and 3.0% of ferrous oxide, and calculating the addition amount of the slag former.
Sodium carbonate (Na)2O3) Has a molecular weight of 106, and the molecular weight of 62, 62/106-58%.
Borax Na2B4O7·10H2O may also be written as Na2O·2B2O3·10H2O, molecular weight 382, sodium oxide molecular weight 62, content 62/382 ═ 16%; the boron oxide has a molecular weight of 70 and a boron oxide content of 37%.
Let the SiO content be 85.6%2The addition amount of quartz stone is a/g, the addition amount of quicklime containing 89% of CaO is b/g, and the Na content is 58%2The amount of sodium carbonate O added was c/g, containing 37% of B2O3The adding amount of the borax is d/g,
Figure BDA0003182610430000021
Figure BDA0003182610430000031
Figure BDA0003182610430000032
Figure BDA0003182610430000033
(1) division of (2) yields 0.58c +0.16d ═ 0.214a +3.615 (5)
(1) Division of (3) yields 0.37d ═ 0.214a +3.615 (6)
(1) Div (4) yields 0.89b ═ 0.7847a +1.255 (7)
Substituting (5), (6) and (7) into the formula (1) to obtain:
0.1455a＝6.916，a＝47.531g，
b is 43.318g obtained according to the formula (7),
d is 27.45g obtained according to the formula (6),
c is obtained 16.195g according to equation (5),
and (3) substituting the values of a, b, c and d into the values (8) and (9) to calculate the content of zinc oxide and ferrous oxide, and increasing or decreasing the addition of the slag former when the content of the zinc oxide and the ferrous oxide exceeds or is lower than the proportioning value in the mixture.
Figure BDA0003182610430000034
Figure BDA0003182610430000035
In the invention, the used quartz stone, quicklime, sodium carbonate and borax are fluxing agents commonly used in fire metallurgy in the nonferrous metallurgy industry.
Example 1
And drying the platinum group metal smelting slag, and grinding to minus 80 meshes. 100g of platinum group metal smelting slag is sent to a sample for analysis to obtain 32.46 percent of silicon dioxide, 28.5 percent of calcium oxide, 11.9 percent of zinc oxide, 4.5 percent of sodium oxide, 6.5 percent of ferrous oxide, noble metals Au, Pd, Pt and the like, and according to the mass components of the mixture of the platinum group metal smelting slag and the slag former: 36% of silicon dioxide, 33% of calcium oxide, 5.6% of zinc oxide, 9% of sodium oxide, 5% of boron oxide and 3.0% of ferrous oxide, and calculating the addition amount of the slag former. The content of silicon dioxide in the quartz stone is 85.6 percent, the adding amount of the quartz stone is calculated to be 47.531g, the content of calcium oxide in the quicklime is 89 percent, the adding amount of the quicklime is calculated to be 43.318g, the content of sodium oxide in the sodium carbonate is 58 percent, the adding amount of the sodium carbonate is calculated to be 16.195g, the content of boron oxide in the borax is 37 percent, the content of sodium oxide is 16 percent, and the adding amount of the borax is calculated to be 27.459 g. Adding nickel sulfide ore with the mass fraction of 15% of the total amount of the mixture into the mixture, uniformly mixing, smelting at 1350 ℃, keeping the temperature for 40min, naturally cooling, separating matte and reducing slag, enriching and linking precious metals in the matte, and performing subsequent treatment to obtain reducing slag with low content of precious metals, wherein the reducing slag can be discarded when the content of the precious metals is below 10g/t as shown in Table 1.
Noble Metal content (g/t) in the reducing slag produced in Table 1
Figure BDA0003182610430000041
Example 2
And drying the platinum group metal smelting slag, and grinding to minus 80 meshes. After 100g of platinum group metal smelting slag is fed for analysis, 17.6 percent of silicon dioxide, 19.5 percent of calcium oxide, 11.9 percent of zinc oxide, 9.5 percent of ferrous oxide, noble metals Au, Pd, Pt and the like are obtained, and according to the mass components of the mixture of the platinum group metal smelting slag and the slag former: 30% of silicon dioxide, 32% of calcium oxide, 8% of zinc oxide, 9% of sodium oxide, 5% of boron oxide and 6.85% of ferrous oxide, and calculating the addition amount of the slag former. The content of silicon dioxide in the quartz stone is 85.6 percent, the adding amount of the quartz stone is 29.6g, the content of calcium oxide in the quicklime is 89 percent, the adding amount of the quicklime is 26.92g, the content of sodium oxide in the sodium carbonate is 58 percent, the adding amount of the sodium carbonate is 9.32g, the content of boron oxide in the borax is 37 percent, the content of sodium oxide is 16 percent, and the adding amount of the borax is 19.51 g. And then adding copper sulfide ore with the mass fraction of 20% of the total amount of the mixture into the mixture, uniformly mixing, smelting at 1350 ℃, keeping the temperature for 40min, naturally cooling, separating matte and reducing slag, enriching and linking precious metal in the matte, and performing subsequent treatment to obtain reducing slag with low content of precious metal, wherein the reducing slag can be discarded after being below 10g/t as shown in Table 2.
Table 2 shows the content (g/t) of noble metals in the reducing slag
Figure BDA0003182610430000042
Example 3
And drying the platinum group metal smelting slag, and grinding to minus 80 meshes. 100g of platinum group metal smelting slag is fed for analysis to obtain 21.6 percent of silicon dioxide, 19.5 percent of calcium oxide, 5.9 percent of zinc oxide, 9.5 percent of ferrous oxide, noble metals Au, Pd, Pt and the like, and according to the mass components of the mixture of the platinum group metal smelting slag and the slag former: 35% of silicon dioxide, 32% of calcium oxide, 4% of zinc oxide, 9% of sodium oxide, 5% of boron oxide and 7% of ferrous oxide, and calculating the addition amount of the slag former. The content of silicon dioxide in the quartz stone is 85.6 percent, the adding amount of the quartz stone is 29.6g, the content of calcium oxide in the quicklime is 89 percent, the adding amount of the quicklime is 26.9g, the content of sodium oxide in the sodium carbonate is 58 percent, the adding amount of the sodium carbonate is 8.8g, the content of boron oxide in the borax is 37 percent, the content of sodium oxide is 16 percent, and the adding amount of the borax is 19.51 g. Adding nickel sulfide ore with the mass fraction of 25% of the total amount of the mixture into the mixture, uniformly mixing, smelting at 1350 ℃, keeping the temperature for 40min, naturally cooling, separating matte and reducing slag, enriching and linking precious metal in the matte, and performing subsequent treatment to obtain reducing slag with low content of precious metal, wherein the reducing slag can be discarded after being below 10g/t as shown in Table 3.
Table 3 shows the content (g/t) of noble metals in the reducing slag
Figure BDA0003182610430000051

Claims (6)

1.一种贵金属熔炼渣的熔炼方法，其特征在于，包括以下步骤：1. a smelting method of precious metal smelting slag, is characterized in that, comprises the following steps: 将贵金属熔炼渣进行烘干、研磨后加入造渣剂进行混合，得到混合料，控制混合料中的各组分含量及百分比为：二氧化硅30％～40％、氧化钙30％～35％、氧化锌4％～8％、氧化钠7％～10％、氧化硼5％～7％、氧化亚铁＜7％，向混合料中再配入质量为混合料总量的15-25％的硫化矿，按上述配比进行熔炼经自然冷却，得到含贵金属的锍和还原渣。The precious metal smelting slag is dried, ground, and then mixed with a slag-forming agent to obtain a mixture, and the content and percentage of each component in the mixture are controlled as follows: silicon dioxide 30%-40%, calcium oxide 30%-35% , Zinc oxide 4%~8%, sodium oxide 7%~10%, boron oxide 5%~7%, ferrous oxide <7%, and then add into the mixture with a mass of 15-25% of the total amount of the mixture The sulfide ore is smelted according to the above ratio and naturally cooled to obtain matte and reduced slag containing precious metals. 2.根据权利要求1所述的贵金属熔炼渣的熔炼方法，其特征在于，所述造渣剂包括石英石、生石灰、碳酸钠、硼砂，所述石英石的加入量是以二氧化硅计，所述生石灰的加入量是以氧化钙计，所述碳酸钠的加入量是以氧化钠计，所述硼砂的加入量是以氧化硼计。2. the smelting method of precious metal smelting slag according to claim 1, is characterized in that, described slagging agent comprises quartzite, quicklime, sodium carbonate, borax, and the addition of described quartzite is in silicon dioxide, The addition amount of the quicklime is calculated as calcium oxide, the addition amount of the sodium carbonate is calculated as sodium oxide, and the addition amount of the borax is calculated as boron oxide. 3.根据权利要求1所述的贵金属熔炼渣的熔炼方法，其特征在于，所述硫化矿为硫化镍矿、硫化铁矿、硫化铜矿的一种。3 . The method for smelting precious metal smelting slag according to claim 1 , wherein the sulfide ore is one of nickel sulfide ore, iron sulfide ore, and copper sulfide ore. 4 . 4.根据权利要求1所述的贵金属熔炼渣的熔炼方法，其特征在于，所述研磨的粒度为-80～-200目。4 . The method for smelting precious metal smelting slag according to claim 1 , wherein the grinding particle size is -80 to -200 mesh. 5 . 5.根据权利要求1所述的贵金属熔炼渣的熔炼方法，其特征在于，所述熔炼温度为1300℃-1400℃，熔炼时间为40min-70min。5 . The method for smelting precious metal smelting slag according to claim 1 , wherein the smelting temperature is 1300°C-1400°C, and the smelting time is 40min-70min. 6 . 6.根据权利要求1所述的贵金属熔炼渣的熔炼方法，其特征在于，所述还原渣含贵金属小于10g/t。6 . The method for smelting precious metal smelting slag according to claim 1 , wherein the reduction slag contains less than 10 g/t of precious metal. 7 .
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103334010A (en) * 2013-07-15 2013-10-02 贵研资源（易门）有限公司 Method for fusing enriched precious metal from spent automotive catalyst
CN105400962A (en) * 2015-11-18 2016-03-16 金川集团股份有限公司 Method for recycling platinum group metal from waste catalysts
CN110777259A (en) * 2019-10-23 2020-02-11 金川集团股份有限公司 Method for pre-treating platinum group metal refining tailings to enrich precious metals by fire method
CN111549225A (en) * 2020-04-17 2020-08-18 金川集团股份有限公司 Method for recovering and enriching precious metals in low-grade precious metal complex material

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103334010A (en) * 2013-07-15 2013-10-02 贵研资源（易门）有限公司 Method for fusing enriched precious metal from spent automotive catalyst
CN105400962A (en) * 2015-11-18 2016-03-16 金川集团股份有限公司 Method for recycling platinum group metal from waste catalysts
CN110777259A (en) * 2019-10-23 2020-02-11 金川集团股份有限公司 Method for pre-treating platinum group metal refining tailings to enrich precious metals by fire method
CN111549225A (en) * 2020-04-17 2020-08-18 金川集团股份有限公司 Method for recovering and enriching precious metals in low-grade precious metal complex material

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Patentee after: Jinchuan Group Copper Precious Metals Co.,Ltd.

Country or region after: China

Address before: No.2 Jianshe Road, Jinchuan District, Jinchang City, Gansu Province (east of Beijing Road, west of Heya Road, south of Guiyang Road)

Patentee before: Jinchuan Group Copper Gui Co.,Ltd.

Country or region before: China

CP03 Change of name, title or address