WO2019047468A1 - 一种锡精炼硫渣硫化的方法 - Google Patents

一种锡精炼硫渣硫化的方法 Download PDF

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WO2019047468A1
WO2019047468A1 PCT/CN2018/074464 CN2018074464W WO2019047468A1 WO 2019047468 A1 WO2019047468 A1 WO 2019047468A1 CN 2018074464 W CN2018074464 W CN 2018074464W WO 2019047468 A1 WO2019047468 A1 WO 2019047468A1
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Prior art keywords
tin
sulfur
vulcanizing
vulcanization
copper
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PCT/CN2018/074464
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English (en)
French (fr)
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杨斌
陈巍
戴卫平
韩龙
李红
潘建仁
杨堃
陈浩
速斌
李建国
吕进
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昆明鼎邦科技股份有限公司
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Priority to MYPI2020001159A priority Critical patent/MY194687A/en
Publication of WO2019047468A1 publication Critical patent/WO2019047468A1/zh

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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
    • C22B13/00—Obtaining lead
    • C22B13/02—Obtaining lead by dry processes
    • 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
    • C22B15/00—Obtaining copper
    • 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
    • C22B25/00—Obtaining tin
    • C22B25/06—Obtaining tin from scrap, especially tin scrap
    • 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
    • C22B30/00—Obtaining antimony, arsenic or bismuth
    • C22B30/02—Obtaining antimony
    • 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
    • C22B30/00—Obtaining antimony, arsenic or bismuth
    • C22B30/04—Obtaining arsenic
    • 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
    • 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
    • C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
    • C22B9/02—Refining by liquating, filtering, centrifuging, distilling, or supersonic wave action including acoustic waves
    • 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

Definitions

  • the invention relates to a method for vulcanizing tin refining sulfur slag, belonging to the technical field of non-ferrous metal pyrometallurgy.
  • tin refining slag also called tin slag, copper slag
  • Sulfur is 10% to 20%, and the rest are impurities such as lead, antimony, iron and arsenic.
  • the treatment processes of sulfur slag mainly include: roasting-leaching process, electrolysis process, flotation process. These processes are long in process, difficult to treat wastewater, low in yield of tin and copper, and incompletely separated.
  • the smelting plant uses the sulphurization and volatilization process of the smelting furnace to treat the low-grade tin-containing materials and the low-grade tin ore.
  • the tin in the material or the ore is volatilized in the form of stannous sulfide, and the stannous sulfide is naturally oxidized or After forced oxidation, it is converted into tin dioxide, and more than 50% of tin dioxide dust containing tin is obtained in the dust collection system.
  • the method is suitable for low-grade tin-containing materials and low-grade tin ore; in the process of collecting tin dioxide dust, if the heat of oxidation is improperly recovered, it will explode in the dust collector, causing great safety problems; if using an electric dust collector In the dust collector, a sprinkler system must be installed to increase the humidity of the flue gas. The sprinkler system will produce harmful industrial wastewater, which must be treated before it can be used or discharged, and the cost is high.
  • the patent application No. 201310414183.7 discloses a method for vulcanizing volatile tin-containing materials with high sulfur coal powder.
  • the method comprises the steps of crushing, sieving and mixing the high-sulfur coal powder and the tin-containing material, and vulcanizing and volatilizing the tin element under a weak reducing atmosphere at 880 to 1430 ° C, and the high-temperature dust-containing flue gas produced by the vulcanization and volatilization process is conventional. After cooling and dust collection, the tin resources are recovered in the form of tin dioxide.
  • the method is mainly applicable to materials containing more than 2% tin, such as tin ore, tin-containing slag, flue ash, hard head, and waste slag in the bottom of the furnace.
  • tin-containing material needs to be treated before treatment.
  • the high-sulfur coal powder is separately sieved to a particle size of 100 mesh (about 150 ⁇ m) or less, and is vulcanized in a weak reducing atmosphere.
  • the separation of sulfides from tin, lead, arsenic and antimony was achieved by vacuum distillation in the literature "Recovering copper from copper-arsenic-bismuth multi-alloy by vulcanization-vacuum distillation".
  • the copper-arsenide-bismuth multi-alloy vulcanization method is as follows: the multi-alloy alloy is ground into a powder and mixed with sulfur uniformly, and is pressed, and then melted in a vacuum induction furnace, and the sulfur addition rate is 200%. The method needs to mix the material and the vulcanizing agent and compress the film before vulcanization, and the vulcanization agent is used in a large amount. Most of the sulfur is volatilized and burned to form sulfur dioxide, which pollutes the environment, and the vulcanization method has small yield and is not easy to realize industrial production.
  • the present invention provides a method for vulcanizing tin refining sulfur slag, by which more than 97% of the non-sulfided metal in the sulfur residue can be vulcanized into a sulfided substance.
  • the method can firstly vulcanize the non-sulfurized metal element in the sulfur residue into a sulfide, and the product after the vulcanization can be separated from other metals by vacuum distillation.
  • the present invention adopts the following technical solutions to achieve:
  • Step 1 analyzing the mass percentage of the non-sulfided metal in the tin refined sulfur residue
  • Step 2 adding a vulcanizing agent according to a molar fraction of a vulcanizing agent in a non-sulfided metal element in the sulfur residue to be 1.0 to 1.2 times;
  • Step 3 Mix the sulfur residue and the vulcanizing agent uniformly, put them into a closed container and seal them; under the condition of no oxygen and stirring, the heating control temperature is pretreated at 200-320 ° C; after the pretreatment, the oxygen-free and stirring conditions are maintained. The temperature is raised to 320-400 ° C to achieve the spontaneous reaction conditions of the material and the vulcanizing agent, and the heat released by the vulcanization reaction increases the temperature of the system to 600-900 ° C to achieve deep vulcanization of the material.
  • the vulcanized materials include, but are not limited to, tin refining sulfur slag, and may also be non-ferrous metals containing elements such as copper, tin, lead, arsenic, iron, antimony, etc., such as matte, copper-tin multi-alloy.
  • the vulcanizing agent is sulfur.
  • the working mechanism of the invention the vulcanization method is carried out in a closed container, and the reaction in the closed container can ensure that the sulfur does not lose oxidation after being heated, does not generate sulfur dioxide irritating gas, can improve the efficiency of the vulcanization reaction, reduce the dosage of the vulcanizing agent, and avoid the operation site. Dust pollution.
  • Vacuum metallurgy refers to metallurgical processes carried out below 1 atmosphere until ultra-high vacuum conditions, including metal, alloy smelting, purification, refining, forming and processing. It is an advanced clean fine metallurgy technology.
  • the principle of metal vacuum distillation is to separate the difference in saturated vapor pressure of the elements contained in the alloy at different temperatures.
  • the main elements in the sulfur residue are tin and copper, and the rest are impurities such as lead, arsenic and antimony.
  • the boiling points of tin and copper are similar.
  • the saturated vapor pressures of the two are close to each other in the range of 900 ° C to 1300 ° C, and both are less than 4 Pa.
  • the saturated vapor pressure of lead, antimony and arsenic is 10,000 times higher than the saturated vapor pressure of tin and copper. If the sulfur residue is simply treated by vacuum distillation, larger elements such as lead, antimony and arsenic may be volatilized, but tin and copper cannot be separated. Some researches have suggested that the copper and tin in the sulfur residue can be separated by a vulcanization-vacuum distillation method. The volatility of each metal sulfide after vulcanization is superior to that of the corresponding metal element, and the sulfide volatility of tin, lead, antimony and arsenic is better than that of copper.
  • the sulfur slag is vulcanized and separated under vacuum conditions, and the controlled conditions can vulcanize the sulfides of tin, lead, antimony and arsenic, leaving copper sulfide to separate copper from other metals.
  • the degree of metal separation in the vulcanization-vacuum distillation method depends on the degree of vulcanization of the sulfide. The higher the degree of vulcanization of the metal element, the higher the volatilization rate of the volatile sulfide in the vacuum distillation stage, and the more thorough the separation of copper from other metals.
  • the first stage pretreatment temperature is 200-320 ° C
  • the melting point of sulfur is 119 ° C
  • the boiling point is 444.6 ° C.
  • the tin refining slag, matte and copper-tin multi-alloys do not melt at the first pretreatment temperature, and the sulphur begins to melt into a liquid.
  • the liquid sulfur and the sulfide are contacted with the metal under stirring to carry out a preliminary reaction. Liquid sulfur is sufficiently encapsulated outside the sulfide and metal particles to facilitate subsequent reactions.
  • the anaerobic and agitation conditions are maintained, and the temperature is raised to 320-400 ° C to bring the materials and the vulcanizing agent to spontaneous reaction conditions.
  • the sulfur-coated sulfides and metal particles begin to melt and release a small amount of liquid.
  • the alloy, the reaction mass and the vulcanizing agent are both liquid, and the liquid-liquid phase reaction rate is increased.
  • the vulcanization reaction is an exothermic reaction.
  • the temperature of the system increases.
  • the high temperature promotes the melting of the reaction material, and accelerates the contact of the vulcanizing agent with the non-sulfided metal under stirring, so that the reaction rate increases sharply and the temperature of the reaction system increases rapidly.
  • the material is deep vulcanized. After the end of the reaction process, the sulfurized product is taken out after the material is cooled.
  • the vulcanization reaction temperatures for different compositions of metal materials are different.
  • the metal vulcanization rate is 99.5% or more by the method of the present invention.
  • Vulcanization method is used to vulcanize non-sulfurized metals in sulfur slag, such as copper, tin, lead, antimony, arsenic and other impurity elements into sulfides, which increases the volatility of metals such as tin, lead, antimony and arsenic.
  • Slag vacuum separation provides an effective pretreatment method.
  • the vulcanization method is simple in operation, and only needs to crush the material to a particle size of less than 1 cm or less, and it is not necessary to sieve the material to 100 mesh, and the material and the vulcanizing agent need not be subjected to tableting treatment.
  • Deep vulcanization is carried out by two-stage treatment, the utilization rate of the vulcanizing agent is high, the vulcanization efficiency of the metal element is high, and the metal vulcanization rate in the sulfur residue is above 99.5%.
  • the obtained sulfurized product can be separated by more than 99% by vacuum separation of elements such as tin, lead, antimony and arsenic.
  • Sulfur is added to 1.0 times the mole fraction of the vulcanizing agent required for tin, copper, lead, antimony, arsenic, and iron.
  • the sulfur residue and the sulfur are uniformly mixed, placed in a closed container and sealed, and subjected to a stepwise vulcanization treatment under the condition of no oxygen and stirring.
  • the first stage of the vulcanization pretreatment is controlled at a temperature of 200 to 250 ° C for 30 minutes. After the first stage of pretreatment, the oxygen-free and agitation conditions were maintained, and the temperature was raised to 320-350 ° C to bring the materials and the vulcanizing agent to spontaneous reaction conditions. The temperature of the system increased to 600 ° C as the sulfurization exothermic reaction proceeded. After the reaction is completed, the heating is stopped, and after the material is cooled, the sulfurized product is taken out.
  • the sulfided material is X-ray diffraction analysis (XRD).
  • the copper in the sulfide product exists in the form of cuprous sulfide.
  • the tin exists in the form of stannous sulfide.
  • the lead exists in the form of lead sulfide.
  • the antimony exists in the form of disulfide trisulfide.
  • the form of arsenic exists. After the vulcanization, the material was found to contain S 22.93%, Sn 48.42%, Cu 17.61%, Pb 2.42%, Sb 1.43%, As 1.40%, Fe 5.85%, and the calculated vulcanization rate of the metal was 99.85. %.
  • the method has simple operation, small dosage of vulcanizing agent and high metal vulcanization efficiency. After vulcanization, the separation of copper and tin, lead, antimony, arsenic and other impurities can be achieved by vacuum distillation.
  • the sulfur residue and the sulfur are uniformly mixed, placed in a closed container and sealed, and subjected to a stepwise vulcanization treatment under the conditions of no oxygen and stirring.
  • the first stage of the vulcanization pretreatment is controlled at a temperature of 230 to 280 ° C for 30 minutes. After the first stage of pretreatment, the mixture was kept under no oxygen and stirring conditions, and the temperature was raised to 350-400 ° C to make the materials and the vulcanizing agent reach the spontaneous reaction condition. The temperature of the system increased to 800 ° C as the sulfurization exothermic reaction proceeded. After the reaction is completed, the heating is stopped, and after the material is cooled, the sulfurized product is taken out.
  • the sulfided material was analyzed by XRD.
  • the copper in the sulfided product was in the form of cuprous sulfide.
  • the tin was in the form of stannous sulfide.
  • the lead was in the form of lead sulfide.
  • the antimony exists in the form of antimony trisulfide.
  • the arsenic exists in the form of arsenic trisulfide. After the vulcanization, the material was found to contain S 21.98%, Sn 26.23%, Cu 40.13%, Pb 3.05%, Sb3.85%, As 0.71%, Fe 4.33%, and the calculated vulcanization rate of the metal was 99.72. %.
  • the material was vacuum distilled at a temperature of 1200 ° C and a vacuum of 1 to 10 Pa for 60 minutes to obtain a volatile stannous sulfide containing 0.08% of Cu; the residual cuprous sulfide containing Sn 0.46%.
  • tin refined sulfur residue (mass percentage: Sn60.86%, Cu20.44%, Pb3.28%, Sb1.40%, As3.26%, S 7.06%, Fe3.70%) in the non-sulfided state
  • Sulfur is added to tin, copper, lead, antimony, arsenic, and iron to 1.2 times the mole fraction of the vulcanizing agent required for the sulfide state.
  • the tin refined sulfur slag and sulfur are uniformly mixed, placed in a closed container and sealed, and subjected to a stepwise vulcanization treatment under the condition of no oxygen and stirring.
  • the first stage of the vulcanization pretreatment control temperature is 280-320 ° C, and the reaction is carried out for 50 minutes.
  • the conditions of oxygen-free and agitation were maintained, and the temperature was raised to 360-400 ° C to bring the materials and the vulcanizing agent to spontaneous reaction conditions.
  • the temperature of the system increased to 900 ° C as the sulfurization exothermic reaction proceeded. After the reaction is completed, the heating is stopped, and after the material is cooled, the sulfurized product is taken out.
  • the sulfided material was analyzed by XRD.
  • the copper in the sulfided product was in the form of cuprous sulfide.
  • the tin was in the form of stannous sulfide.
  • the lead was in the form of lead sulfide.
  • the antimony exists in the form of antimony trisulfide.
  • the arsenic exists in the form of arsenic trisulfide. After the vulcanization, the material was found to contain S 22.33%, Sn50.83%, Cu17.07%, Pb2.74%, Sb1.17%, As2.72%, Fe3.09%, and the calculated vulcanization rate of the metal was 99.56. %.

Abstract

一种锡精炼硫渣硫化的方法，将硫渣与硫化剂混合均匀后放入密封容器中，在无氧、搅拌条件下进行硫化反应，使硫渣中易硫化的非硫化态金属元素变为硫化态，增加了金属的挥发性。硫渣中金属硫化率在99.5%以上，硫化后产物可采用真空蒸馏进一步分离。

Description

一种锡精炼硫渣硫化的方法 技术领域
本发明涉及一种锡精炼硫渣硫化的方法，属于有色金属火法冶金技术领域。
背景技术
在粗锡火法精炼加硫除铜作业过程中产生的浮渣称为锡精炼硫渣(也称锡铜渣、除铜渣)，主要含锡30％～70％、铜10％～50％，硫10％～20％，其余为铅、锑、铁、砷等杂质。
硫渣中积压了大量的锡、铜及其他有价金属，如何处理硫渣一直是各炼锡厂生产中急需解决的问题。目前，硫渣的处理工艺主要有：焙烧—浸出工艺、电解工艺、浮选工艺。这些工艺处理流程长，废水难处理，锡和铜收率低，且分离不彻底。
冶炼厂采用烟化炉硫化挥发工艺处理低品位含锡物料及低品位锡中矿，在硫化剂的作用下使物料或矿中的锡以硫化亚锡的形式挥发，硫化亚锡经自然氧化或强制氧化后转化为二氧化锡，在收尘系统中得到含锡50％以上的二氧化锡烟尘。该方法适用于低品位含锡物料及低品位锡中矿；二氧化锡烟尘收集过程中，如果氧化热量回收不当会在收尘器中产生爆炸，造成很大安全问题；如果使用电收尘器，在收尘器前必须设置喷淋系统增加烟气湿度，喷淋系统会产生有害的工业废水，必须进行处理才能利用或排放，成本较高。
申请号为201310414183.7的专利公开了一种高硫煤粉硫化挥发含锡物料的方法。该方法将高硫煤粉、含锡物料经破碎、筛分、混匀后，在880～1430℃下弱还原气氛下进行锡元素硫化挥发，硫化挥发过程产出的高温含尘烟气经常规冷却、收尘处理后以二氧化锡形态回收其中锡资源。该方法主要适用于含锡在2％以上的物料，如锡中矿、含锡炉渣、烟道灰、硬头、废炉底选洗渣中一种或几种，处理前需将含锡物料、高硫煤粉分别筛分至粒度100目(约150微米)以下占70％，且要在弱还原气氛中进行硫化。
文献《采用硫化-真空蒸馏法从铜砷锑多元合金中回收铜》中采用真空蒸馏的方法实现了硫化亚铜与锡、铅、砷、锑的硫化物的分离。文献中铜砷锑多元合金硫化方法为：将多元合金磨成粉末与硫磺混合均匀，并压片，然后在真空感应炉中熔化，加硫过量率为200％。该方法硫化前需将物料和硫化剂混合并压片，硫化步骤多，硫化剂用量大，大部分硫磺受热后挥发燃烧形成二氧化硫，污染环境，硫化方法产量小，不易于实现工业化生产。
发明内容
基于上述方法存在的不足，本发明提供一种锡精炼硫渣硫化的方法，通过本方法可将硫渣中的97％以上非硫化态金属硫化为硫化态物质。本方法先可将硫渣中非硫化状态的金属元素深度硫化为硫化物，硫化后产物可采用真空蒸馏方法实现铜与其它金属的分离。
为实现上述目的，本发明采取以下技术方案来实现：
步骤一、分析锡精炼硫渣中非硫化态的金属的质量百分比；
步骤二、按硫渣中非硫化态的金属元素变为硫化态所需硫化剂摩尔分数的1.0～1.2倍添加硫化剂；
步骤三、将硫渣与硫化剂混合均匀后放入密闭容器中并密封；在无氧、搅拌条件下，加热控制温度在200～320℃进行预处理；预处理结束后保持无氧及搅拌条件，升温至320～400℃使物料及硫化剂达到自发反应条件，通过硫化反应放出的热量使体系温度增加至600～900℃使物料达到深度硫化。
硫化的物料包括但不局限于锡精炼硫渣，还可以是冰铜、铜锡多元合金等含有铜、锡、铅、砷、铁、锑等元素的有色金属。
所述硫化剂为硫磺。
本发明工作机理：硫化方法在密闭容器中进行，在密闭容器中反应可保证硫磺受热后不会氧化损失，不会产生二氧化硫刺激性气体，可提高硫化反应效率，降低硫化剂用量，避免操作现场出现粉尘污染。
真空冶金是指低于1个大气压直至超高真空条件下进行的冶金过程，包括金属及合金的冶炼、提纯、精炼、成型和处理，是一种先进的清洁精细冶金技术。金属真空蒸馏的原理是利用合金中所含元素在不同温度下饱和蒸气压的差异进行分离。硫渣中的主要元素为锡和铜，其余为铅、砷、锑等杂质，锡和铜的沸点相近，在 900℃至1300℃范围内两者的饱和蒸气压相近，且都小于4Pa，同一温度下铅、锑、砷的饱和蒸气压是锡、铜饱和蒸气压的一万倍以上。如果单纯采用真空蒸馏法处理硫渣，饱和蒸气压较大元素如铅、锑、砷可以挥发出来，但锡和铜无法分离。有研究分析认为可以采用硫化—真空蒸馏方法将硫渣中的铜和锡分离。硫渣硫化后各金属硫化物的挥发性都不同程度的优于对应的金属单质，并且锡、铅、锑、砷的硫化物挥发性优于铜的硫化物。所以，硫渣硫化后在真空条件下分离，控制条件可使锡、铅、锑、砷的硫化物挥发，留下铜的硫化物，使铜和其它金属分离。在硫化—真空蒸馏法中金属分离程度取决于硫化物的硫化程度，金属元素硫化程度越高，真空蒸馏阶段易挥发硫化物挥发率就越高，铜与其它金属分离越彻底。
第一段预处理温度为200～320℃，硫磺的熔点为119℃，沸点为444.6℃。第一段预处理温度下锡精炼硫渣、冰铜及铜锡多元合金不会熔化，而硫磺开始熔化为液体。在搅拌条件下液体硫磺和硫化物和金属接触，进行初步反应。液体硫磺充分包裹在硫化物和金属颗粒外，有利于后续反应。
第一段预处理结束后继续保持无氧及搅拌条件，升温至320～400℃使物料及硫化剂达到自发反应条件，在此温度条件下被硫磺包裹的硫化物和金属颗粒开始熔化放出少量液态合金，反应物料和硫化剂均为液体，液相-液相反应速率增加。硫化反应为放热反应，随着反应速率的增加体系温度不断升高，高温促进反应物料熔化，在搅拌作用下加速硫化剂与非硫化态金属接触，使反应速率急 剧增加，反应体系温度快速增加至600～900℃，使物料达到深度硫化。反应过程结束后，待物料冷却后取出硫化产物。
在本发明方法中针对不同组成的金属物料硫化反应温度不同。
采用本发明方法金属硫化率在99.5％以上。
本发明的有益效果是：
1.采用硫化法将硫渣中非硫化状态的金属，如铜、锡、铅、锑、砷等杂质元素硫化为硫化物，增加了锡、铅、锑、砷等金属的挥发性，为硫渣真空分离提供了一种有效的预处理方法。
2.硫化方法操作简单，只需将物料破碎至粒度小于1厘米以下或不破碎，无需将物料筛分至100目，不需对物料和硫化剂进行压片处理。
3.通过两段处理进行深度硫化，硫化剂利用率高，金属元素的硫化效率高，硫渣中金属硫化率在99.5％以上。得到的硫化产物通过真空分离锡、铅、锑、砷等元素脱除率可达99％以上。
具体实施方式
下面结合实施例，对本发明作进一步说明。
实施例1
按锡精炼硫渣(质量百分含量：Sn56.36％、Cu20.50％、Pb2.82％、Sb1.67％、As1.63％、S 10.09％、Fe6.93％)中非硫化态的 锡、铜、铅、锑、砷、铁变为硫化态所需硫化剂摩尔分数的1.0倍添加硫磺。
将硫渣与硫磺混合均匀后放入密闭容器中并密封，在无氧、搅拌的条件下，升温进行分段硫化处理。第一段硫化预处理控制温度在200～250℃，反应30分钟。第一段预处理结束后保持无氧、搅拌条件，升温至320～350℃，使物料及硫化剂达到自发反应条件，随着硫化放热反应的进行，体系温度增加至600℃。反应结束后，停止加热，待物料冷却后取出硫化产物。
硫化后物料经X射线衍射分析(XRD)硫化产物中铜以硫化亚铜形式存在，锡以硫化亚锡形态存在，铅以硫化铅形态存在，锑以三硫化二锑形式存在，砷以三硫化二砷形式存在。硫化后物料经化验检测知含S 22.93％、Sn48.42％、Cu17.61％、Pb2.42％、Sb1.43％、As1.40％、Fe5.85％，计算得金属的硫化率为99.85％。
本方法操作简单，硫化剂用量小，金属硫化效率高。硫化后物料通过真空蒸馏可实现铜与锡、铅、锑、砷等杂质的分离。
实施例2
按硫渣(质量百分含量：Sn31.58％、Cu48.32％、Pb3.67％、Sb4.63％、As0.85％、S 5.74％、Fe5.21％)中非硫化态的锡、铜、铅、锑、砷、铁变为硫化态所需硫化剂摩尔分数的1.15倍添加硫磺。
将硫渣与硫磺混合均匀后放入密闭容器中并密封，在无 氧、搅拌的条件下，升温进行分段硫化处理。第一段硫化预处理控制温度在230～280℃，反应30分钟。第一段预处理结束后保持无氧、搅拌条件，升温至350～400℃，使物料及硫化剂达到自发反应条件，随着硫化放热反应的进行，体系温度增加至800℃。反应结束后，停止加热，待物料冷却后取出硫化产物。
硫化后物料经XRD分析硫化产物中铜以硫化亚铜形式存在，锡以硫化亚锡形态存在，铅以硫化铅形态存在，锑以三硫化二锑形式存在，砷以三硫化二砷形式存在。硫化后物料经化验检测知含S 21.98％、Sn26.23％、Cu40.13％、Pb3.05％、Sb3.85％、As0.71％、Fe4.33％，计算得金属的硫化率为99.72％。
硫化后物料在温度1200℃，真空度1～10Pa下真空蒸馏60分钟，得到挥发物硫化亚锡，含Cu 0.08％；残留物硫化亚铜含Sn0.46％。
实施例3
按锡精炼硫渣(质量百分含量：Sn60.86％、Cu20.44％、Pb3.28％、Sb1.40％、As3.26％、S 7.06％、Fe3.70％)中非硫化态的锡、铜、铅、锑、砷、铁变为硫化态所需硫化剂摩尔分数的1.2倍添加硫磺。
将锡精炼硫渣与硫磺混合均匀后放入密闭容器中并密封，在无氧、搅拌的条件下，升温进行分段硫化处理。第一段硫化预处理控制温度在280～320℃，反应50分钟。第一段预处理结束后保 持无氧、搅拌条件，升温至360～400℃，使物料及硫化剂达到自发反应条件，随着硫化放热反应的进行，体系温度增加至900℃。反应结束后，停止加热，待物料冷却后取出硫化产物。
硫化后物料经XRD分析硫化产物中铜以硫化亚铜形式存在，锡以硫化亚锡形态存在，铅以硫化铅形态存在，锑以三硫化二锑形式存在，砷以三硫化二砷形式存在。硫化后物料经化验检测知含S 22.33％、Sn50.83％、Cu17.07％、Pb2.74％、Sb1.17％、As2.72％、Fe3.09％，计算得金属的硫化率为99.56％。

Claims (5)

  1. 一种锡精炼硫渣硫化的方法，其特征在于具体步骤如下：
    步骤一、分析锡精炼硫渣中非硫化态的金属的质量百分比；
    步骤二、按硫渣中非硫化态的金属元素变为硫化态所需硫化剂摩尔分数的1.0～1.2倍添加硫化剂；
    步骤三、将硫渣与硫化剂混合均匀后放入密闭容器中并密封；在无氧、搅拌条件下，加热控制温度在200～320℃进行预处理；预处理结束后保持无氧及搅拌条件，升温至320～400℃使物料及硫化剂达到自发反应条件，通过硫化反应放出的热量使体系温度增加至600～900℃使物料达到深度硫化。
  2. 根据权利要求1所述一种锡精炼硫渣硫化的方法，其特征在于：所述非硫化态的金属包括锡、铜、铅、锑、砷、铁。
  3. 根据权利要求1所述一种锡精炼硫渣硫化的方法，其特征在于：所述硫化剂为硫磺。
  4. 根据权利要求1所述一种锡精炼硫渣硫化的方法，其特征在于：金属总的硫化率在99.5％以上。
  5. 根据权利要求1所述一种锡精炼硫渣硫化的方法，其特征在于：硫化的物料包括但不局限于锡精炼硫渣，还可以是冰铜、铜锡多元合金等含有铜、锡、铅、砷、铁、锑元素的有色金属。
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