CN101935761A - A method for separating copper and selenium tellurium from lead copper matte - Google Patents

A method for separating copper and selenium tellurium from lead copper matte Download PDF

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CN101935761A
CN101935761A CN2010102435118A CN201010243511A CN101935761A CN 101935761 A CN101935761 A CN 101935761A CN 2010102435118 A CN2010102435118 A CN 2010102435118A CN 201010243511 A CN201010243511 A CN 201010243511A CN 101935761 A CN101935761 A CN 101935761A
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copper
lead
tellurium
sulfuric acid
leaching
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杨天足
文剑锋
蔡练兵
王安
肖峰
刘伟锋
窦爱春
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Central South University
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Abstract

一种从铅铜锍中分离铜和硒碲的方法,本发明是将破碎后的铅铜锍粉末、氢氧化钠、碳酸钠、水按一定的配比混合投入高压釜,往高压釜中通入氧气并控制釜内氧气的压力进行氧化反应,硒被氧化进入碱性浸出液,铜、铅和碲被氧化进入碱性浸出渣,碱性浸出渣再用硫酸溶液浸出铜和碲,铅富集在酸性浸出渣中。本发明铜的浸出率达到98%以上,碲的浸出率达到90%以上。本发明对材质要求低,碱性介质对设备的腐蚀小、操作安全,有价金属综合回收效益好,同时劳动强度低、处理时间短、操作环境好。

Figure 201010243511

A method for separating copper, selenium and tellurium from lead-copper matte. The invention is to mix crushed lead-copper matte powder, sodium hydroxide, sodium carbonate, and water into an autoclave according to a certain ratio, and pass through the autoclave. Introduce oxygen and control the pressure of oxygen in the kettle to carry out oxidation reaction, selenium is oxidized into alkaline leaching solution, copper, lead and tellurium are oxidized into alkaline leaching residue, alkaline leaching residue is then leached copper and tellurium with sulfuric acid solution, and lead is enriched in the acidic leach residue. The copper leaching rate of the invention reaches over 98%, and the tellurium leaching rate reaches over 90%. The invention has low requirements on materials, less corrosion of equipment by alkaline medium, safe operation, good comprehensive recovery benefits of valuable metals, low labor intensity, short processing time and good operating environment.

Figure 201010243511

Description

一种从铅铜锍中分离铜和硒碲的方法 A method for separating copper and selenium tellurium from lead copper matte

技术领域  本发明涉及冶金领域中湿法冶金过程,特别是从铅冶炼过程中的副产物铅铜锍中有效地分离铜和硒碲的湿法冶金方法。Technical Field The present invention relates to the hydrometallurgical process in the field of metallurgy, especially the hydrometallurgical method for effectively separating copper, selenium and tellurium from the by-product lead-copper matte in the lead smelting process.

背景技术  铅铜锍(俗称铅冰铜)是铅精矿在鼓风炉熔炼和氧气底吹熔炼过程中产出的一种主要含有铜和铅硫化物的副产物,其中富集了铅精矿中的铜、硒、碲,并含有一部分的铅和银,是回收铜、硒、碲的重要原料。目前,铅铜锍的处理是作为炼铜的原料进入铜熔炼系统,即含铜较高的铅铜锍直接进行铜的转炉吹炼,铅和硫进入气相挥发,产出粗铜进行电解精炼,铅以烟尘的形式回收;含铜较低的铅铜锍进行氧化焙烧脱硫,铜转化成氧化铜或硫酸铜,用硫酸浸出法将铜与铅分离,产出的硫酸铜溶液进入铜冶炼系统,浸出渣返回铅系统。近年来,研究了采用硫酸加压氧化浸出法进行铜和铅的分离,产出的硫酸铜溶液通过电积回收铜,浸出渣返回铅冶炼系统。如许并社,李明照等著的《铜冶炼工艺》.化学工业出版社.2007.1;中国专利申请200810058113.1“从铅冰铜中回收铜的工艺”。Background technology Lead-copper matte (commonly known as lead matte) is a by-product mainly containing copper and lead sulfide produced during blast furnace smelting and oxygen bottom blowing smelting of lead concentrate, which is enriched in lead concentrate Copper, selenium, tellurium, and contains a part of lead and silver, is an important raw material for recycling copper, selenium, tellurium. At present, the treatment of lead-copper matte is to enter the copper smelting system as the raw material for copper smelting, that is, the lead-copper matte with high copper content is directly smelted in the converter of copper, and the lead and sulfur enter the gas phase to volatilize, and the crude copper is produced for electrolytic refining. Lead is recovered in the form of soot; lead copper matte with low copper content is oxidized and roasted for desulfurization, copper is converted into copper oxide or copper sulfate, copper and lead are separated by sulfuric acid leaching, and the copper sulfate solution produced enters the copper smelting system. The leach residue is returned to the lead system. In recent years, the sulfuric acid pressure oxidation leaching method has been studied for the separation of copper and lead. The produced copper sulfate solution is used to recover copper through electrowinning, and the leached slag is returned to the lead smelting system. "Copper Smelting Technology" by Xu Bingshe, Li Mingzhao et al. Chemical Industry Press. 2007.1; Chinese Patent Application 200810058113.1 "Copper Recovery Process from Lead Matte".

上述铅铜锍(铅冰铜)的处理方法存在如下缺点:There is following shortcoming in the processing method of above-mentioned lead copper matte (lead matte):

(1)铜含量高的铅铜锍进入铜的转炉吹炼系统得到粗铜,将铅氧化挥发进入气相分离,工艺流程长,金属的回收率低,成本高,产出的粗铜质量低。铅冶炼厂产出的铅铜锍只能作为铜原料出售给铜冶炼厂,铅铜锍中的铅、银、硒、碲等均不计价,经济效益低。(1) The lead-copper matte with high copper content enters the copper converter blowing system to obtain blister copper, and the lead is oxidized and volatilized into the gas phase separation. The process is long, the metal recovery rate is low, the cost is high, and the quality of the produced blister copper is low. The lead copper matte produced by lead smelters can only be sold to copper smelters as copper raw materials. The lead, silver, selenium, tellurium, etc. in the lead copper matte are not priced, and the economic benefits are low.

(2)铜含量较低的铅铜锍用氧化焙烧法处理后,再用硫酸浸出法分离铜,由于焙烧过程容易烧结,硫化铜的氧化不彻底,导致铜回收率低;铅铜锍中其他有价金属如硒、碲等分散,难以回收;过程产生低浓度二氧化硫烟气污染。(2) Lead copper matte with low copper content is treated by oxidation roasting method, and then copper is separated by sulfuric acid leaching method. Since the roasting process is easy to sinter, the oxidation of copper sulfide is not complete, resulting in low copper recovery rate; Valuable metals such as selenium and tellurium are dispersed and difficult to recover; the process produces low-concentration sulfur dioxide flue gas pollution.

(3)硫酸加压氧化浸出法虽可以实现铜与铅的分离,但铅铜锍中的硒碲分散不利于回收,同时酸性浸出体系不可避免地存在的设备腐蚀问题,设备腐蚀速度快,维修频率高,使酸性加压设备不能长时间地正常应用于工业生产。(3) Although the sulfuric acid pressurized oxidation leaching method can realize the separation of copper and lead, the dispersion of selenium and tellurium in the lead-copper matte is not conducive to recovery. At the same time, the equipment corrosion problem inevitably exists in the acid leaching system, and the corrosion speed of the equipment is fast. The high frequency prevents acid pressurization equipment from being normally used in industrial production for a long time.

发明内容  本发明的目的是提供一种在碱性介质中进行铅铜锍的氧化,能有效地实现铜与铅的分离,并富集回收铅铜锍中的硒碲,且过程基本无污染的湿法冶金方法。SUMMARY OF THE INVENTION The purpose of the present invention is to provide a method for oxidizing lead-copper matte in an alkaline medium, which can effectively separate copper from lead, enrich and recover selenium and tellurium in lead-copper matte, and the process is basically pollution-free. Hydrometallurgical method.

为达到上述目的本发明采用的技术方案是将破碎后的铅铜锍粉末、氢氧化钠、碳酸钠、水按一定的配比混合投入高压釜,在一定温度下,往高压釜中通入氧气并控制釜内氧气的压力进行氧化反应,硒被氧化进入碱性浸出液,铜、铅和碲被氧化进入碱性浸出渣,碱性浸出渣再用硫酸溶液浸出铜和碲,铅富集在酸性浸出渣中。In order to achieve the above-mentioned purpose, the technical solution adopted by the present invention is to mix the crushed lead-copper matte powder, sodium hydroxide, sodium carbonate, and water into the autoclave according to a certain proportion, and feed oxygen into the autoclave at a certain temperature. And control the pressure of oxygen in the kettle to carry out the oxidation reaction, selenium is oxidized into the alkaline leaching solution, copper, lead and tellurium are oxidized into the alkaline leaching slag, the alkaline leaching slag is then leached copper and tellurium with sulfuric acid solution, and the lead is enriched in the acidic leaching solution. leached into the slag.

具体的处理方法如下:The specific processing method is as follows:

1 氧化浸出1 Oxidation leaching

将铅铜锍先破碎并磨成粒径为0.25~0.074mm的粉末,用一定浓度的氢氧化钠和碳酸钠溶液浆化并加入高压反应釜中,升温后通入氧气进行氧化反应。氧化反应的温度为150~250℃,氢氧化钠浓度为1.0~3.0mol/L,碳酸钠浓度为0~2mol/L,浸出的重量液固比(溶液重量与铅铜锍重量之比)为3~10∶1,氧气的分压控制在0.3~1.5MPa,体系的总压力维持在1.5~3.5MPa,反应时间为2~6h。反应完毕后,冷却至20~60℃,过滤。氧化浸出过程发生的主要化学反应为:The lead-copper matte is first crushed and ground into a powder with a particle size of 0.25-0.074 mm, slurried with a certain concentration of sodium hydroxide and sodium carbonate solution and added to a high-pressure reactor, and then oxygen is introduced to carry out oxidation reaction after heating up. The temperature of the oxidation reaction is 150-250°C, the concentration of sodium hydroxide is 1.0-3.0mol/L, the concentration of sodium carbonate is 0-2mol/L, and the weight-liquid-solid ratio of leaching (the ratio of solution weight to lead-copper matte weight) is 3-10:1, the partial pressure of oxygen is controlled at 0.3-1.5 MPa, the total pressure of the system is maintained at 1.5-3.5 MPa, and the reaction time is 2-6 hours. After the reaction is complete, cool to 20-60°C and filter. The main chemical reactions that occur in the oxidation leaching process are:

Cu2S+2.5O2+2NaOH+H2O=2Cu(OH)2↓+Na2SO4          (1)Cu 2 S+2.5O 2 +2NaOH+H 2 O=2Cu(OH) 2 ↓+Na 2 SO 4 (1)

Cu2S+2.5O2+2Na2CO3+H2O=2CuCO3↓+Na2SO4+2NaOH    (2)Cu 2 S+2.5O 2 +2Na 2 CO 3 +H 2 O=2CuCO 3 ↓+Na 2 SO 4 +2NaOH (2)

PbS+2O2=PbSO4↓                                 (3)PbS+2O 2 =PbSO 4 ↓ (3)

PbS+2O2+2NaOH=Pb(OH)2↓+Na2SO4                  (4)PbS+2O 2 +2NaOH=Pb(OH) 2 ↓+Na 2 SO 4 (4)

PbS+2O2+Na2CO3=PbCO3↓+Na2SO4                   (5)PbS+2O 2 +Na 2 CO 3 =PbCO 3 ↓+Na 2 SO 4 (5)

Cu2Se+2O2+2NaOH+H2O=2Cu(OH)2+Na2SeO3            (6)Cu 2 Se+2O 2 +2NaOH+H 2 O=2Cu(OH) 2 +Na 2 SeO 3 (6)

Cu2Te+2.5O2+2NaOH+H2O=2Cu(OH)2+Na2TeO4↓        (7)Cu 2 Te+2.5O 2 +2NaOH+H 2 O=2Cu(OH) 2 +Na 2 TeO 4 ↓ (7)

2 碱浸渣的硫酸浸出2 Sulfuric acid leaching of alkali leaching residue

氧化浸出反应后得到的浸出渣,在温度为70~85℃下,用浓度为0.5~2.5mol/L的硫酸溶液以重量液固比为2~8∶1,浸出2~3h,硫酸浸出反应完毕后,过滤,得到的硫酸酸性浸出渣返铅冶炼系统。硫酸浸出发生的主要化学反应为:The leaching residue obtained after the oxidation leaching reaction is leached for 2 to 3 hours with a sulfuric acid solution with a concentration of 0.5 to 2.5 mol/L at a temperature of 70 to 85 ° C and a weight-liquid-solid ratio of 2 to 8:1, and the sulfuric acid leaching reaction After completion, it is filtered, and the obtained sulfuric acid acidic leaching residue is returned to the lead smelting system. The main chemical reactions that occur in sulfuric acid leaching are:

Cu(OH)2+H2SO4=CuSO4+2H2O             (8)Cu(OH) 2 +H 2 SO 4 =CuSO 4 +2H 2 O (8)

CuCO3+H2SO4=CuSO4+CO2+H2O            (9)CuCO 3 +H 2 SO 4 =CuSO 4 +CO 2 +H 2 O (9)

Pb(OH)2+H2SO4=PbSO4+2H2O             (10)Pb(OH) 2 +H 2 SO 4 =PbSO 4 +2H 2 O (10)

PbCO3+H2SO4=PbSO4+CO2+H2O            (11)PbCO 3 +H 2 SO 4 =PbSO 4 +CO 2 +H 2 O (11)

Na2TeO4+H2SO4=Na2SO4+H2TeO4          (12)Na 2 TeO 4 +H 2 SO 4 =Na 2 SO 4 +H 2 TeO 4 (12)

3 硫酸铜溶液中碲的置换3 Displacement of tellurium in copper sulfate solution

硫酸浸出得到的浸出液,在温度为70~80℃下,加入重量为浸出液中碲含量2.5~3.0倍的铜粉,还原2~5h。还原过程发生的主要化学反应为:Add copper powder whose weight is 2.5 to 3.0 times the tellurium content in the leaching solution to the leaching solution obtained by sulfuric acid leaching at a temperature of 70 to 80° C., and reduce for 2 to 5 hours. The main chemical reactions that occur during the reduction process are:

H2TeO4+5Cu+6H+=Cu2Te↓+3Cu2++4H2O    (13)H 2 TeO 4 +5Cu+6H + =Cu 2 Te↓+3Cu 2+ +4H 2 O (13)

所述的氢氧化钠、碳酸钠、硫酸、铜粉、氧气均为工业级试剂。Described sodium hydroxide, sodium carbonate, sulfuric acid, copper powder, oxygen are all industrial grade reagents.

本发明适合于处理含铜铅精矿熔炼产出的铅铜锍(铅冰铜),其成份范围为(%):Cu 10~50,Pb 7.5~45,S8~29,Ni 0~10,Se 0.2~4,Te 0.1~3,Au 0.07~3.5,Ag 0.02~0.20,As 0.5~5,Fe 0.5~15;也适合于处理复杂的含铜铅硫化矿精矿。The present invention is suitable for processing lead-copper matte (lead matte) produced by smelting copper-containing lead concentrate, and its composition range is (%): Cu 10-50, Pb 7.5-45, S8-29, Ni 0-10, Se 0.2~4, Te 0.1~3, Au 0.07~3.5, Ag 0.02~0.20, As 0.5~5, Fe 0.5~15; also suitable for processing complex copper-lead-containing sulfide ore concentrates.

本发明与现有的铅铜锍的处理流程比较,有以下优点:采用碱性加压氧化处理铅铜锍,使铜、铅、碲等的硫化物被氧化,便于后续过程的分离回收,消除了在火法处理铅铜锍过程中产出的二氧化硫烟气和含铅烟尘产生的污染问题;加压碱性氧化浸出渣用硫酸溶液浸出时,铜、碲与铅的分离效果好,铜的的浸出率达到98%以上,碲的浸出率达到90%以上;硫酸铜溶液中用铜粉置换碲,碲脱除效果好且回收率,利于碲的集中处理;采用碱性体系加压氧化浸出,设备的材质要求低,碱性介质对设备的腐蚀小、操作安全,有价金属综合回收效益好;本发明的劳动强度低、处理时间短、操作环境好。Compared with the existing lead-copper matte treatment process, the present invention has the following advantages: the lead-copper matte is treated with alkaline pressurized oxidation to oxidize the sulfides of copper, lead, tellurium, etc., which facilitates the separation and recovery of subsequent processes, eliminates The pollution problems caused by sulfur dioxide fume and lead-containing fume produced in the process of pyroprocessing lead-copper matte were solved; when the pressurized alkaline oxidation leaching residue was leached with sulfuric acid solution, the separation effect of copper, tellurium and lead was good, and the copper The leaching rate of tellurium can reach more than 98%, and the leaching rate of tellurium can reach more than 90%. In the copper sulfate solution, copper powder is used to replace tellurium, and the removal effect of tellurium is good and the recovery rate is good for the concentrated treatment of tellurium; the alkaline system is used for pressurized oxidation leaching , the material requirements of the equipment are low, the corrosion of the equipment by the alkaline medium is small, the operation is safe, and the comprehensive recovery of valuable metals is good; the labor intensity of the present invention is low, the processing time is short, and the operating environment is good.

附图说明Description of drawings

图1:本发明工艺流程示意图。Figure 1: Schematic diagram of the process flow of the present invention.

具体实施方式Detailed ways

实施例1:Example 1:

铅精矿经氧气底吹工艺产出的铅铜锍磨至粒度100%小于0.149mm,其主要成分以重量百分比计为(%):Cu 44.32,Pb 18.21,S 16.50,Se 0.74,Te 0.21,Ag 0.14,As 0.61,Fe 0.75;工业烧碱,其中氢氧化钠的含量≥96%;工业硫酸,其中H2SO4含量≥98%;工业氧气,其中O2含量≥99%;工业铜粉,其中铜含量≥99%。The lead concentrate produced by the oxygen bottom blowing process is ground to a particle size of 100% less than 0.149mm, and its main components are (%) by weight: Cu 44.32, Pb 18.21, S 16.50, Se 0.74, Te 0.21, Ag 0.14, As 0.61, Fe 0.75; industrial caustic soda , in which the content of sodium hydroxide is ≥96%; industrial sulfuric acid, in which the content of H2SO4 is ≥98%; industrial oxygen, in which the content of O2 is ≥99%; industrial copper powder, Among them, the copper content is ≥99%.

将上述成分的工业烧碱85.0g,用1200ml水配成溶液并加入上述成分的铅铜锍200g,浆化后加入到容积为2000ml的反应釜中,密闭好反应釜,调节搅拌速度为700~800r.min-1,通入工业氧气5min驱赶反应釜中残存的空气。然后,将反应釜逐渐升温至160℃时,通入工业氧气并维持氧分压为0.7MPa,反应温度在20min后快速升至218℃,随后下降,将温度维持在200℃反应1.5h。达到反应时间后,往反应釜中通入冷却水,温度降至50℃以下时,从反应釜中放出浆料并过滤,滤渣用200ml水洗涤。浸出渣烘干后重176.2g,其要成分以重量百分比计为(%):Cu 50.98,Pb 19.52,S 0.9,Se 0.015,Te 0.22,Ag 0.16,As 0.49,Fe 0.85,硒的浸出率为98.20%;浸出液1070ml,其成份(g/L)为:Na2SO4 116.16,Pb 0.53,As 0.31,Se 1.19,NaOH 2.50。Make a solution of 85.0g of the above-mentioned industrial caustic soda with 1200ml of water and add 200g of the above-mentioned lead-copper matte. After slurrying, add it into a reaction kettle with a volume of 2000ml, seal the reaction kettle well, and adjust the stirring speed to 700-800r .min -1 , inject industrial oxygen for 5 minutes to drive away the remaining air in the reactor. Then, when the temperature of the reactor was gradually raised to 160°C, industrial oxygen was introduced to maintain the oxygen partial pressure at 0.7 MPa. The reaction temperature rose rapidly to 218°C after 20 minutes, then dropped, and the temperature was maintained at 200°C for 1.5 hours. After reaching the reaction time, feed cooling water into the reactor, and when the temperature drops below 50°C, discharge the slurry from the reactor and filter, and the filter residue is washed with 200ml of water. The weight of the leached slag is 176.2g after drying, and its main components are calculated in weight percent (%): Cu 50.98, Pb 19.52, S 0.9, Se 0.015, Te 0.22, Ag 0.16, As 0.49, Fe 0.85, the leaching rate of selenium 98.20%; 1070ml of leach solution, its composition (g/L) is: Na 2 SO 4 116.16, Pb 0.53, As 0.31, Se 1.19, NaOH 2.50.

将上述碱性浸出渣176g,用1.5mol/L硫酸溶液1500ml调浆,在搅拌速度为400r.min-1、温度为70℃下浸出2h,浸出结束后过滤,浸出渣用150ml水洗涤后烘干,酸性浸出渣62.48g,其主要成份以重量百分比计为(%):Cu 0.43,Pb 54.52,S 8.37,Se 0.032,Te 0.053,Ag 0.422,As 0.96,Fe 1.01,铜和碲的浸出率分别为99.7%和90.65%;得到硫酸浸出的含铜溶液1490ml,其成份为(g/L):Cu 59.21,Fe 0.55,As 0.15,Te 0.23。Slurry 176g of the above-mentioned alkaline leaching residue with 1500ml of 1.5mol/L sulfuric acid solution, leaching for 2 hours at a stirring speed of 400r.min -1 and a temperature of 70°C, filter after leaching, wash the leaching residue with 150ml of water, and then dry Dry, acidic leaching slag 62.48g, its main components are in weight percent (%): Cu 0.43, Pb 54.52, S 8.37, Se 0.032, Te 0.053, Ag 0.422, As 0.96, Fe 1.01, leaching rate of copper and tellurium 99.7% and 90.65% respectively; Obtain 1490ml of copper-containing solution leached by sulfuric acid, its composition is (g/L): Cu 59.21, Fe 0.55, As 0.15, Te 0.23.

将上述硫酸铜溶液400ml,在搅拌速度为400r.min-1、温度为85℃下,加入铜粉6g,反应2h,达到反应时间后过滤,得到铜碲渣0.93g,得到除碲后的硫酸铜溶液390ml,其成份为(g/L):Cu 62.57,Fe 0.53,As 0.14,Te 0.001,碲的置换沉淀率为99.57%。Add 400ml of the above copper sulfate solution, at a stirring speed of 400r.min -1 and a temperature of 85°C, add 6g of copper powder, react for 2h, and filter after reaching the reaction time to obtain 0.93g of copper tellurium slag, and obtain sulfuric acid after tellurium removal Copper solution 390ml, its composition is (g/L): Cu 62.57, Fe 0.53, As 0.14, Te 0.001, the replacement precipitation rate of tellurium is 99.57%.

实施例2:Example 2:

铅精矿经氧气底吹工艺产出的铅铜锍磨至粒度100%小于0.149mm,其主要成分以重量百分比计为(%):Cu 26.21,Pb 8.04,S 10.50,Se 0.40,Ag 0.07,As 0.82,Fe 15.7;工业碳酸钠,其含量≥96%;工业硫酸,其中H2SO4含量≥98%;工业氧气,其中O2含量≥99%。The lead concentrate produced by the oxygen bottom blowing process is ground to a particle size of 100% less than 0.149mm, and its main components are (%) by weight: Cu 26.21, Pb 8.04, S 10.50, Se 0.40, Ag 0.07, As 0.82, Fe 15.7; industrial sodium carbonate, its content ≥96%; industrial sulfuric acid, its H2SO4 content ≥98%; industrial oxygen, its O2 content ≥99%.

将上述成分的工业碳酸钠80.0g,用1200ml水配成溶液后加入上述成分的铅铜锍200g,浆化后加入到容积为2000ml的压力反应釜中。密闭好反应釜,开启搅拌,调节搅拌速度为700~800r.min-1,通入工业氧气1min驱赶反应釜中残存的空气。然后,将反应釜逐渐升温,当温度升至160℃时,通入工业氧气,维持氧气分压为0.7MPa,反应温度在20min后快速升至215℃,随后下降,将温度维持在200℃反应1.5h。达到反应时间后,往反应釜中通入冷却水,温度降至50℃以下时,从反应釜中放出浆料并过滤,滤渣用200ml水洗涤。浸出渣烘干后重164.7g,其主要成分以重量百分比计为(%):Cu 32.51,Pb 9.18,S 0.73,Se 0.03,Ag 0.09,As 0.69,Fe 18.91,硒的浸出率为93.93%;浸出液1030ml,其成份(g/L)为:Na2SO4 87.6,Pb 0.42,As 0.423,Se 0.67,pH 8.81。80.0 g of industrial sodium carbonate of the above-mentioned components was made into a solution with 1200 ml of water, and then 200 g of lead-copper matte of the above-mentioned components were added, and after slurrying, it was added into a pressure reaction kettle with a volume of 2000 ml. Seal the reactor well, turn on the stirring, adjust the stirring speed to 700-800r.min -1 , and inject industrial oxygen for 1 minute to drive out the remaining air in the reactor. Then, the reaction kettle was gradually heated up. When the temperature rose to 160°C, industrial oxygen was introduced to maintain the partial pressure of oxygen at 0.7MPa. The reaction temperature rose rapidly to 215°C after 20 minutes, and then dropped, and the temperature was maintained at 200°C for the reaction. 1.5h. After reaching the reaction time, feed cooling water into the reactor, and when the temperature drops below 50°C, discharge the slurry from the reactor and filter, and the filter residue is washed with 200ml of water. The leached slag weighs 164.7g after drying, and its main components are (%) by weight percentage: Cu 32.51, Pb 9.18, S 0.73, Se 0.03, Ag 0.09, As 0.69, Fe 18.91, and the leaching rate of selenium is 93.93%; The leach solution is 1030ml, and its composition (g/L) is: Na 2 SO 4 87.6, Pb 0.42, As 0.423, Se 0.67, pH 8.81.

将上述碱性浸出渣150g,用1.5mol/L硫酸溶液900ml调浆,在搅拌速度为400r.min-1、温度为70℃下浸出2h,浸出结束后过滤,浸出渣用100ml水洗涤后烘干,酸性浸出渣61.2g,其主要成份以重量百分比计为(%):Cu 0.49,Pb 22.37,S 5.08,Se 0.068,Ag 0.207,As 1.41,Fe 23.17,铜的浸出率为99.39%;得到硫酸浸出的含铜溶液892ml,其成份为(g/L):Cu 52.73,Fe 17.12,As 0.17。Slurry 150g of the above-mentioned alkaline leaching residue with 900ml of 1.5mol/L sulfuric acid solution, leaching for 2 hours at a stirring speed of 400r.min -1 and a temperature of 70°C, filter after leaching, wash the leaching residue with 100ml of water, and then dry Dry, acid leaching slag 61.2g, its main component is (%) by weight percent: Cu 0.49, Pb 22.37, S 5.08, Se 0.068, Ag 0.207, As 1.41, Fe 23.17, the leaching rate of copper is 99.39%; Obtain 892ml of copper-containing solution leached by sulfuric acid, its composition is (g/L): Cu 52.73, Fe 17.12, As 0.17.

Claims (2)

1. the method for separating copper and selen-tellurjum from a lead copper matte is characterized in that being made up of following steps:
(1) oxidation is leached
Lead copper matte is earlier broken and wear into the powder that particle diameter is 0.25~0.074mm, with sodium hydroxide and sodium carbonate solution pulp and add in the autoclave, the back aerating oxygen that heats up carries out oxidizing reaction, the temperature of oxidizing reaction is 150~250 ℃, naoh concentration is 1.0~3.0mol/L, concentration of sodium carbonate is 0~2mol/L, the weight liquid-solid ratio that leaches is 3~10: 1, the dividing potential drop of oxygen is controlled at 0.3~1.5MPa, the total pressure of system maintains 1.5~3.5MPa, and the reaction times is 2~6h, after reaction finishes, be cooled to 20~60 ℃, filter;
(2) alkali soaks the sulfuric acid leaching of slag
The leached mud that obtains after the reaction is leached in oxidation, is under 70~85 ℃ in temperature, is that the sulphuric acid soln of 0.5~2.5mol/L is 2~8: 1 with the weight liquid-solid ratio with concentration, leach 2~3h, after sulfuric acid leaching reaction finishes, filter, the sulfuric acid leached mud that obtains returns plumbous smelting system;
(3) displacement of tellurium in the copper-bath
Sulfuric acid leaches the leach liquor obtain, is under 70~80 ℃ in temperature, adds weight and be the copper powder of 2.5~3.0 times of tellurium content in the leach liquor, reductase 12~5h.
2. according to claim 1 from lead copper matte the method for separating copper and selen-tellurjum, it is characterized in that: described sodium hydroxide, yellow soda ash, sulfuric acid, copper powder and oxygen are technical grade reagent.
CN2010102435118A 2010-08-03 2010-08-03 A method for separating copper and selenium tellurium from lead copper matte Pending CN101935761A (en)

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CN105886785A (en) * 2015-01-25 2016-08-24 昆明冶金高等专科学校 Method for preparing high-purity silver powder from silver-rich residue containing high selenium and tellurium
CN104947145A (en) * 2015-06-10 2015-09-30 云南驰宏锌锗股份有限公司 Method of balancing acid in high-lead copper sulphate oxygen pressure leaching-electrodepositing process
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CN105219958B (en) * 2015-11-16 2018-08-24 湖南城市学院 A kind of method of alkali oxide leaching separation selen-tellurjum enriching noble metals
CN105219958A (en) * 2015-11-16 2016-01-06 湖南城市学院 A kind of alkali oxide leaching is separated the method for selen-tellurjum enriching noble metals
CN106477533A (en) * 2016-10-19 2017-03-08 中南大学 A kind of method that copper anode mud separates and recovers selenium and tellurium
CN107190143A (en) * 2017-05-12 2017-09-22 江西铜业集团公司 The technique that a kind of Whote-wet method reclaims valuable element in complicated low-grade sulphide ore
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CN109052339A (en) * 2018-08-31 2018-12-21 昆明鼎邦科技股份有限公司 A method of extracting tellurium from copper telluride or copper tellurium slag
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CN111172390B (en) * 2020-02-06 2022-07-26 中国恩菲工程技术有限公司 Method for treating valuable metal sulfide concentrate by using oxygen pressure

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