WO2023005810A1 - 一种高锑粗锡分离提纯的方法 - Google Patents

一种高锑粗锡分离提纯的方法 Download PDF

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WO2023005810A1
WO2023005810A1 PCT/CN2022/107214 CN2022107214W WO2023005810A1 WO 2023005810 A1 WO2023005810 A1 WO 2023005810A1 CN 2022107214 W CN2022107214 W CN 2022107214W WO 2023005810 A1 WO2023005810 A1 WO 2023005810A1
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antimony
tin
content
crude
gasification
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PCT/CN2022/107214
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English (en)
French (fr)
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李一夫
张环
杨斌
刘大春
徐宝强
田阳
陈秀敏
徐俊杰
周生安
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昆明理工大学
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Priority to JP2023541919A priority Critical patent/JP2024508599A/ja
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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
    • 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
    • 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
    • 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
    • C22B25/00—Obtaining tin
    • 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
    • C22B25/02—Obtaining tin 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
    • 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
    • C22B5/00—General methods of reducing to metals
    • C22B5/02—Dry methods smelting of sulfides or formation of mattes
    • C22B5/16—Dry methods smelting of sulfides or formation of mattes with volatilisation or condensation of the metal being produced
    • 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
    • C22B9/04—Refining by applying a vacuum
    • 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 belongs to the technical field of pyrometallurgy of nonferrous metals, and in particular relates to a method for separating and purifying high-antimony crude tin.
  • tin smelting enterprises at home and abroad adopt pyro-refining process to gradually remove impurities in crude tin.
  • the main processes are condensate removal of iron and arsenic, addition of sulfur to remove copper (sulfur slag), addition of aluminum to remove arsenic and antimony (aluminum slag), crystallization and separation Removal of lead and bismuth and vacuum distillation of solder.
  • aluminum slag generally contains 6% to 12% of aluminum, 10% to 15% of antimony, 1% to 3% of arsenic and 55% to 70% of tin. people die.
  • the cathode produces 99.99% cathode tin, and the antimony ends up in anode slime and electrolytic waste.
  • the composition of anode slime is complex, and it is difficult to comprehensively treat valuable metals such as antimony and tin.
  • the electrolytic waste liquid contains a large amount of arsenic, which is extremely harmful to the environment.
  • High-temperature-low-temperature two-stage continuous vacuum distillation method high-antimony crude tin is subjected to high-temperature vacuum distillation to produce crude tin and tin-lead-antimony alloy I (containing Sn 25-30%, Pb 30% and Sb 25%), tin Lead-antimony alloy I produced tin-antimony alloy (Sb 15.45%) and lead-antimony alloy (Sb 40%) through low-temperature vacuum distillation.
  • the open rate is only 50%.
  • a method for separating antimony from crude tin containing antimony is disclosed.
  • the antimony content in crude tin containing antimony is about 10%.
  • the separation process is carried out in a vacuum furnace, and the temperature of the furnace is controlled at 1200-1300°C , The residual pressure in the furnace is less than 13Pa, and the distillation time is 30-120 minutes. This method effectively separates the impurity antimony, reducing its content in the product to less than 1%.
  • a method for separating the lead-tin-antimony ternary alloy is disclosed.
  • the method of vacuum distillation is used to process the lead-tin-antimony ternary alloy.
  • the distillation temperature is controlled at 900-1200°C, and the distillation time is 40-60min.
  • the vacuum degree is 5-15Pa
  • the three components in the alloy are processed by one-step distillation, so that the high-boiling point tin remains in a liquid state, and the low-boiling point lead and antimony are volatilized from the alloy in gaseous form, thereby separating from the liquid tin.
  • This method is an extension of the aforementioned publication number CN 1156184A, which is used to process tin-lead-antimony alloys, but the resulting residue is crude tin, which still needs to be returned to the tin refining system for purification, and the Sn-Pb-Sb ternary alloy still coexists in the volatile matter. It is not easy to be further processed, resulting in low metal direct recovery rate, failing to achieve the purpose of separate recovery of multi-element alloys.
  • the Chinese patent application number 201510059683.2 discloses a method for removing lead, antimony and arsenic by vacuum distillation of thick tin alloy containing antimony.
  • the tin-lead-antimony alloy is subjected to secondary continuous vacuum distillation and graded condensation to obtain tin-lead-antimony alloy and lead-antimony alloy.
  • This method requires a temperature of 1500-1700°C for one continuous vacuum distillation, which not only consumes a lot of energy, but also makes it difficult for conventional vacuum distillation furnaces to achieve such a high temperature environment, requiring special vacuum furnaces, and the universality of the equipment is not high; On the other hand, since the system temperature is higher than the boiling point of tin under vacuum (1521°C), a large amount of metal tin will volatilize, resulting in a low direct yield.
  • the Chinese patent application number 201510060061.1 discloses a method for separating antimony by vacuum distillation of tin-antimony alloy.
  • the process is that the tin-antimony alloy undergoes continuous vacuum distillation to obtain crude tin and tin-antimony mixed metal vapor, and then obtains crude antimony by fractional condensation. and tin-antimony alloys.
  • the disadvantage of this method is also that the continuous vacuum distillation temperature is too high (1000-1700°C), and the process still needs to be repeated many times to obtain the required product, which increases labor intensity and cost.
  • the Chinese patent with the application number 202010547990.6 discloses a method of combining fire and wet processes to open the circuit of antimony in tin smelting.
  • Antimony crude tin and then vacuum distillation to obtain vacuum crude tin and tin-lead-antimony alloy, electrolytic refining of crude tin to obtain refined tin, and tin-lead-antimony alloy to obtain secondary vacuum crude tin and lead-antimony alloy through secondary vacuum distillation.
  • This method recovers tin in an economical way, but the antimony content in the obtained vacuum crude tin is still high (Sb ⁇ 3wt%).
  • a large amount of antimony enters the anode slime, which is difficult for subsequent treatment.
  • the technical problem to be solved by the present invention is to overcome the deficiencies of the prior art and provide a method for separating and purifying high-antimony crude tin.
  • This method solves the problem of the circulation of antimony elements in the tin refining system.
  • the process is short, no "three wastes" are generated, valuable metals are recovered to the maximum extent, the treatment cost is low, the metal recovery rate and direct recovery rate are high, and the working environment is good.
  • the process is safe and controllable.
  • the present invention provides the following technical solutions:
  • a method for separating and purifying high-antimony crude tin comprising the following steps:
  • Step 1 Vacuumize the high-antimony crude tin to maximize the gasification and volatilization of volatile impurity elements in the crude tin to form mixed metal vapor;
  • Step 2 Introduce the mixed metal vapor described in step 1 into the graded condenser connected to the vacuum gasification furnace, and control the temperature of the condensation area in the graded condenser to 550-700°C, 300-450°C and 100-250°C respectively, The crude lead, crude antimony and crude arsenic products and the refined tin product left after gasification and volatilization are obtained respectively.
  • the Sn content of the high-antimony crude tin is 70-95wt%, the Sb content is 5-18wt%, the Pb content is 0.5-10wt%, and the As content is 0.1-5wt%.
  • the temperature of the vacuum gasification treatment in the step 1 is 900-1400° C., the system pressure is 1-100 Pa, and the gasification time is 30-200 min.
  • the above-mentioned graded condenser is made of quartz material, and the graded condenser is provided with a resistance wire heating element and circulating cooling water to control the condensation temperature.
  • This method achieves the purpose of one-step purification and refining of crude tin, and at the same time separately recovers valuable metals such as lead, antimony and arsenic, solves the problem of antimony element circulating in the tin refining system, and greatly reduces the operating cost of the enterprise.
  • metals such as lead, antimony and arsenic
  • Fig. 1 is a process flow diagram of the present invention.
  • the method for the separation and purification of this high-antimony crude tin comprises the following steps:
  • Step 1 Carry out vacuum gasification treatment to 1 kg of high-antimony crude tin (its composition is shown in Table 1), so that the volatile impurity elements in the crude tin are gasified to the greatest extent, and gasified and volatilized to form mixed metal vapor; wherein vacuum During gasification treatment: the temperature is 1400°C, the system pressure is 100Pa, and the gasification time is 200min;
  • Step 2 Introduce the mixed metal vapor described in step 1 into the graded condenser connected to the vacuum gasification furnace, and control the temperature of the condensation area in the graded condenser to 550-700°C, 300-450°C and 100-250°C respectively,
  • the crude lead, crude antimony and crude arsenic products and the refined tin products left by gasification and volatilization are obtained respectively;
  • the graded condenser is made of quartz material, and the graded condenser is equipped with a resistance wire heating element and circulating cooling water to control the condensation temperature.
  • the method for the separation and purification of this high-antimony crude tin comprises the following steps:
  • Step 1 Carry out vacuum gasification treatment to 1 kg of high-antimony crude tin (its composition is shown in Table 3), so that the volatile impurity elements in the crude tin are gasified to the greatest extent, and gasified and volatilized to form mixed metal vapor; wherein vacuum During gasification treatment: the temperature is 900°C, the system pressure is 1Pa, and the gasification time is 30 minutes;
  • Step 2 Introduce the mixed metal vapor described in step 1 into the graded condenser connected to the vacuum gasification furnace, and control the temperature of the condensation area in the graded condenser to 550-700°C, 300-450°C and 100-250°C respectively,
  • the crude lead, crude antimony and crude arsenic products and the refined tin products left by gasification and volatilization are obtained respectively;
  • the graded condenser is made of quartz material, and the graded condenser is equipped with a resistance wire heating element and circulating cooling water to control the condensation temperature.
  • the method for the separation and purification of this high-antimony crude tin comprises the following steps:
  • Step 1 Carry out vacuum gasification treatment to 1kg of high-antimony crude tin (its composition is as shown in Table 5), so that the volatile impurity elements in the crude tin are gasified to the greatest extent, and the gasification volatilizes to form mixed metal vapor; wherein the vacuum During gasification treatment: the temperature is 1200°C, the system pressure is 10Pa, and the gasification time is 30min;
  • Step 2 Introduce the mixed metal vapor described in step 1 into the graded condenser connected to the vacuum gasification furnace, and control the temperature of the condensation area in the graded condenser to 550-700°C, 300-450°C and 100-250°C respectively,
  • the crude lead, crude antimony and crude arsenic products and the refined tin products left by gasification and volatilization are obtained respectively;
  • the graded condenser is made of quartz material, and the graded condenser is equipped with a resistance wire heating element and circulating cooling water to control the condensation temperature.
  • the method for the separation and purification of this high-antimony crude tin comprises the following steps:
  • Step 1 Carry out vacuum gasification treatment to 1 kg of high-antimony crude tin (its composition is shown in Table 7), so that the volatile impurity elements in the crude tin are gasified to the greatest extent, and the gasification volatilizes to form mixed metal vapor; wherein the vacuum During gasification treatment: the temperature is 1200°C, the system pressure is 10Pa, and the gasification time is 100min;
  • Step 2 Introduce the mixed metal vapor described in step 1 into the graded condenser connected to the vacuum gasification furnace, and control the temperature of the condensation area in the graded condenser to 550-700°C, 300-450°C and 100-250°C respectively,
  • the crude lead, crude antimony and crude arsenic products and the refined tin products left by gasification and volatilization are obtained respectively;
  • the graded condenser is made of quartz material, and the graded condenser is equipped with a resistance wire heating element and circulating cooling water to control the condensation temperature.
  • the components of the crude lead, crude antimony and crude arsenic products obtained after the treatment by this method are shown in Table 8.
  • the metal recoveries of tin, lead, antimony and arsenic are 98.6%, 98.9%, 99.2% and 99.1% respectively.

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Abstract

本发明属于有色金属火法冶炼技术领域，具体涉及一种高锑粗锡分离提纯的方法。本发明通过对高锑粗锡进行真空气化处理，使粗锡中的易挥发杂质元素最大限度地气化，气化挥发形成混合金属蒸气；将所述混合金属蒸气导入与真空气化炉相连的分级冷凝器，分别控制分级冷凝器冷凝区域温度为550～700℃、300～450℃和100～250℃，分别得到粗铅、粗锑和粗砷产品以及气化挥发留下的精锡产品。本方法解决了锑元素在锡精炼系统中循环的问题，流程短，无"三废"产生，最大限度地回收了有价金属，处理成本低廉，金属回收率和直收率高，作业环境好，过程安全可控。

Description

一种高锑粗锡分离提纯的方法
本申请要求于2021年07月28日提交中国专利局、申请号为202110854401.3、发明名称为“一种高锑粗锡分离提纯的方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明属于有色金属火法冶炼技术领域，具体涉及一种高锑粗锡分离提纯的方法。
背景技术
国内外炼锡企业大多采用火法精炼工艺逐步除去粗锡中杂质，其主要流程为凝析除铁砷、加硫除铜(硫渣)、加铝除砷和锑(铝渣)、结晶分离除铅和铋以及真空蒸馏处理焊锡。其中，铝渣一般含有铝6％～12％、锑10％～15％、砷1％～3％和锡55％～70％，属于危废，处置不当会产生剧毒的砷化氢，致人死亡。
铝渣大多采用电炉熔炼产出锡锑砷烟尘(含锡30～35％、砷0.5～1％和锑2～4％)、电炉渣和高锑粗锡(含锡80～85％、锑3～12％和砷1～2％)。含砷锑烟尘经脱砷处理后返回还原熔炼，锑重新进入锡冶炼系统造成累积，影响锡冶炼流程的正常运行。
高锑粗锡主要处理方法有以下三种：(1)将铜渣与铝渣混合熔炼产出高铜锑铅铋的粗锡，再采用真空蒸馏分离铅和铋的方法，制备巴氏合金，但是巴氏合金的市场需要小，一般以销定产，销售价格偏低。(2)电解法：首先将高锑粗锡合金铸成阳极板，在电解液浓度为70g/L、Sn 2+浓度为60g/L以及电流密度为120A/m 2的条件下进行常温电解，阴极产出99.99％阴极锡，锑最终进入阳极泥和电解废液中。阳极泥的成分复杂，不易对锑和锡等有价金属进行综合处理，同时电解废液中含有大量砷元素，对环境危害极大。(3)高温-低温两段连续真空蒸馏法：高锑粗锡经一次高温真空蒸馏产出粗锡和锡铅锑合金Ⅰ(含Sn 25～30％、Pb 30％和Sb 25％)，锡铅锑合金Ⅰ经低温真空蒸馏产出锡锑合金(Sb 15.45％)和铅锑合金(Sb 40％)，此方法实现锡锑和铅锑的分别回收，实现了部分锑的 开路，但锑的开路率仅为50％。
在公开号为CN 1156184A的专利中公开了一种含锑粗锡分离锑的方法，含锑粗锡中锑含量为10％左右，分离过程在真空炉内进行，控制炉温在1200-1300℃，炉内残压小于13Pa，蒸馏时间30-120分钟。此方法有效地分离了杂质锑，使其在产品中的含量降低到了1％以下，但经粗锡真空蒸馏生产实践发现，当蒸馏温度高于1200℃时，锡会大量挥发，同时从Sn-Sb二元合金相图中得知，锡与锑间存在Sb 2Sn 3金属间化合物，因此在锑的挥发过程中同样会将部分锡带出熔体，所产生的锡铅锑合金仍需进一步处理，最终导致了金属锡的直收率严重降低。
在公开号CN 101696475B的专利中公开了一种分离铅锡锑三元合金的方法，采用真空蒸馏的方法处理铅锡锑三元合金，控制蒸馏温度为900～1200℃，蒸馏时间为40～60min，真空度为5～15Pa，合金中三组元成分通过一步蒸馏处理，使高沸点的锡保持液态而低沸点的铅锑则以气态形式从合金中挥发出来，从而与液态锡分离。此法是前述公开号为CN 1156184A的延伸，用以处理锡铅锑合金，但是所得残余物为粗锡，仍需返回锡精炼系统提纯，挥发物中Sn-Pb-Sb三元合金依然共存，不易进一步处理，造成金属直收率不高，未能达到多元合金单独回收的目的。
申请号为201510059683.2的中国专利中公开了一种含锑粗锡合金真空蒸馏脱除铅锑砷的方法，主要过程是含锑粗锡合金经连续真空蒸馏得到精锡和锡铅锑合金，再将锡铅锑合金进行二次连续真空蒸馏经分级冷凝，得到锡铅锑合金和铅锑合金。此法在进行一次连续真空蒸馏时所需温度为1500～1700℃，不仅能耗高，而且常规的真空蒸馏炉较难实现如此高温的环境，需要特质真空炉，设备的普适性不高；另一方面，由于系统温度高于真空下锡的沸点(1521℃)，金属锡会大量挥发，导致其直收率不高。
申请号为201510060061.1的中国专利公开了一种锡锑合金真空蒸馏分离锑的方法，其流程为锡锑合金经连续真空蒸馏，得到粗锡和锡锑混合金属蒸气，再经分级冷凝分别获得粗锑和锡锑合金。此方法的缺点同样是连续真空蒸馏温度过高(1000～1700℃)，同时仍需多次重复该流程才能获得符合要求的产品，增加了劳动强度和成本。
申请号为202010547990.6的中国专利公开了一种联合火法与湿法工 艺使锑在锡冶炼中开路的方法，是将粗锡精炼过程中加铝除砷锑产出的铝渣用电炉熔炼得到高锑粗锡，再经真空蒸馏得到真空粗锡和锡铅锑合金，粗锡进行电解精炼得到精锡，而锡铅锑合金经二次真空蒸馏分别得到二次真空粗锡和铅锑合金。此法较经济的方式回收了锡，但所得真空粗锡中锑含量依然较高(Sb<3wt％)，再进行电解精炼的过程中，大量的锑进入阳极泥，不易后续处理。
发明内容
本发明要解决的技术问题在于克服现有技术的不足，提供一种高锑粗锡分离提纯的方法。本方法解决了锑元素在锡精炼系统中循环的问题，流程短，无“三废”产生，最大限度地回收了有价金属，处理成本低廉，金属回收率和直收率高，作业环境好，过程安全可控。
为了实现上述目的，本发明提供以下技术方案：
一种高锑粗锡分离提纯的方法，包括以下步骤：
步骤1：对高锑粗锡进行真空气化处理，使粗锡中的易挥发杂质元素最大限度地气化挥发，形成混合金属蒸气；
步骤2：将步骤1所述混合金属蒸气导入与真空气化炉相连的分级冷凝器中，分别控制分级冷凝器中冷凝区域的温度为550～700℃、300～450℃和100～250℃，分别得到粗铅、粗锑和粗砷产品以及气化挥发结束后留下的精锡产品。
所述步骤1中高锑粗锡的Sn含量为70～95wt％，Sb含量为5～18wt％，Pb含量为0.5～10wt％，As含量为0.1～5wt％。
所述步骤1中真空气化处理的温度为900～1400℃，系统压强为1～100Pa，气化时间为30～200min。
上述分级冷凝器由石英材料制成，分级冷凝器上设有电阻丝发热体和循环冷却水控制冷凝温度。
经本发明处理精锡产品中Sn>99.9％；粗铅中Pb含量为90～95％，Sn含量为4～10％，Sb含量为0.3～3％，As含量<1％；粗锑中Sb含量为90～98％，Pb含量为0.7～10％，As含量<1％；粗砷中As含量为98～99％。
本发明锡、铅、锑和砷的金属回收率均在97％以上。
本发明的有益效果是：
本方法实现了粗锡一步提纯精炼的目的，同时又分别单独回收了铅、锑和砷等有价金属，解决了锑元素在锡精炼系统中循环的问题，极大地减轻了企业的运行成本，处理过程无“三废”产生，整个过程安全可靠，操作方便，所需设备简单，成本低廉，金属回收效率高，作业环境友好。
附图说明
为了更清楚地说明本发明具体实施方式或现有技术中的技术方案，下面将对具体实施方式或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图是本发明的一些实施方式，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1是本发明工艺流程图。
具体实施方式
为了进一步说明本发明，下面结合附图和具体实施例，对本发明的方案作进一步详细地说明，但不能将它们理解为对本发明保护范围的限定。
实施例1
如图1所示，该高锑粗锡分离提纯的方法，包括以下步骤：
步骤1：对1kg高锑粗锡(其成分组成如表1所示)进行真空气化处理，使粗锡中的易挥发杂质元素最大限度地气化，气化挥发形成混合金属蒸气；其中真空气化处理中：温度为1400℃、系统压强为100Pa、气化时间为200min；
表1实施例1中高锑粗锡的成分组成
Figure PCTCN2022107214-appb-000001
步骤2：将步骤1所述混合金属蒸气导入与真空气化炉相连的分级冷凝器中，分别控制分级冷凝器中冷凝区域的温度为550～700℃、300～450℃和100～250℃，分别得到粗铅、粗锑和粗砷产品以及气化挥发留下的精锡产品；其中分级冷凝器由石英材料制成，分级冷凝器上设有电阻丝发热体和循环冷却水控制冷凝温度。
经过本方法处理后得到的粗铅、粗锑和粗砷产品化验产品成分见表2，其中锡、铅、锑和砷的金属回收率分别为98.7％、99.1％、98.8％和99.4％。
表2实施例1得到的产品成分表(wt％)
Figure PCTCN2022107214-appb-000002
实施例2
如图1所示，该高锑粗锡分离提纯的方法，包括以下步骤：
步骤1：对1kg高锑粗锡(其成分组成如表3所示)进行真空气化处理，使粗锡中的易挥发杂质元素最大限度地气化，气化挥发形成混合金属蒸气；其中真空气化处理中：温度为900℃、系统压强为1Pa、气化时间为30min；
表3实施例2中高锑粗锡的成分组成
Figure PCTCN2022107214-appb-000003
步骤2：将步骤1所述混合金属蒸气导入与真空气化炉相连的分级冷凝器中，分别控制分级冷凝器中冷凝区域的温度为550～700℃、300～450℃和100～250℃，分别得到粗铅、粗锑和粗砷产品以及气化挥发留下的精锡产品；其中分级冷凝器由石英材料制成，分级冷凝器上设有电阻丝发热体和循环冷却水控制冷凝温度。
经过本方法处理后得到的粗铅、粗锑和粗砷产品化验产品成分见表4，锡、铅、锑和砷的金属回收率分别为99.0％、97.3％、98.2％和99.6％。
表4实施例2得到的产品成分表(wt％)
Figure PCTCN2022107214-appb-000004
Figure PCTCN2022107214-appb-000005
实施例3
如图1所示，该高锑粗锡分离提纯的方法，包括以下步骤：
步骤1：对1kg高锑粗锡(其成分组成如表5所示)进行真空气化处理，使粗锡中的易挥发杂质元素最大限度地气化，气化挥发形成混合金属蒸气；其中真空气化处理中：温度为1200℃、系统压强为10Pa、气化时间为30min；
表5实施例3中高锑粗锡的成分组成
Figure PCTCN2022107214-appb-000006
步骤2：将步骤1所述混合金属蒸气导入与真空气化炉相连的分级冷凝器中，分别控制分级冷凝器中冷凝区域的温度为550～700℃、300～450℃和100～250℃，分别得到粗铅、粗锑和粗砷产品以及气化挥发留下的精锡产品；其中分级冷凝器由石英材料制成，分级冷凝器上设有电阻丝发热体和循环冷却水控制冷凝温度。
经过本方法处理后得到的粗铅、粗锑和粗砷产品化验产品成分见表6，锡、铅、锑和砷的金属回收率分别为99.0％、97.3％、98.2％和99.6％。
表6实施例3得到的产品成分表(wt％)
Figure PCTCN2022107214-appb-000007
实施例4
如图1所示，该高锑粗锡分离提纯的方法，包括以下步骤：
步骤1：对1kg高锑粗锡(其成分组成如表7所示)进行真空气化处理，使粗锡中的易挥发杂质元素最大限度地气化，气化挥发形成混合金属蒸气；其中真空气化处理中：温度为1200℃、系统压强为10Pa、气化时 间为100min；
表7实施例4中高锑粗锡的成分组成
Figure PCTCN2022107214-appb-000008
步骤2：将步骤1所述混合金属蒸气导入与真空气化炉相连的分级冷凝器中，分别控制分级冷凝器中冷凝区域的温度为550～700℃、300～450℃和100～250℃，分别得到粗铅、粗锑和粗砷产品以及气化挥发留下的精锡产品；其中分级冷凝器由石英材料制成，分级冷凝器上设有电阻丝发热体和循环冷却水控制冷凝温度。
经过本方法处理后得到的粗铅、粗锑和粗砷产品化验产品成分见表8，锡、铅、锑和砷的金属回收率分别为98.6％、98.9％、99.2％和99.1％。
表8实施例4得到的产品成分表(wt％)
Figure PCTCN2022107214-appb-000009
以上结合附图对本发明的具体实施方式作了详细说明，但是本发明并不限于上述实施方式，它仅仅是本发明一部分实施例，而不是全部实施例，在本领域普通技术人员所具备的知识范围内，还可以在不脱离本发明宗旨的前提下作出各种变化，这些都属于本发明保护范围。

Claims (16)

  1. 一种高锑粗锡分离提纯的方法，其特征在于，包括以下步骤：
    步骤1：对高锑粗锡进行真空气化处理，气化挥发，形成混合金属蒸气；
    步骤2：将步骤1所述混合金属蒸气导入与真空气化炉相连的分级冷凝器中，分别控制分级冷凝器中冷凝区域的温度为550～700℃、300～450℃和100～250℃，分别得到粗铅、粗锑和粗砷产品以及气化挥发结束后留下的精锡产品。
  2. 根据权利要求1所述的方法，其特征在于，所述步骤1中高锑粗锡的Sn含量为70～95wt％，Sb含量为5～18wt％，Pb含量为0.5～10wt％，As含量为0.1～5wt％。
  3. 根据权利要求1所述的方法，其特征在于，所述步骤1中真空气化处理中：温度为900～1400℃，系统压强为1～100Pa，气化时间为30～200min。
  4. 根据权利要求1或3所述的方法，其特征在于，所述步骤1中真空气化处理的温度为1400℃、1200℃或900℃。
  5. 根据权利要求1或3所述的方法，其特征在于，所述步骤1中真空气化处理的气化时间为200min、100min或30min。
  6. 根据权利要求1或3所述的方法，其特征在于，所述步骤1中真空气化处理的系统压强为100Pa、10Pa或1Pa。
  7. 根据权利要求1或3所述的方法，其特征在于，所述步骤1中真空气化处理的温度为1400℃，系统压强为100Pa，气化时间为200min。
  8. 根据权利要求1或3所述的方法，其特征在于，所述步骤1中真空气化处理中温度为900℃，系统压强为1Pa，气化时间为30min。
  9. 根据权利要求1或3所述的方法，其特征在于，所述步骤1中真空气化处理中温度为1200℃，系统压强为10Pa，气化时间为30min。
  10. 根据权利要求1或3所述的方法，其特征在于，所述步骤1中真空气化处理中温度为1200℃，系统压强为10Pa，气化时间为100min。
  11. 根据权利要求1或2所述的方法，其特征在于，所述步骤1中高锑粗锡的Sn含量为71.65wt％，Sb含量为16.72wt％，Pb含量为8.46wt％， As含量为3.17wt％。
  12. 根据权利要求1或2所述的方法，其特征在于，所述步骤1中高锑粗锡的Sn含量为88.48wt％，Sb含量为6.39wt％，Pb含量为3.87wt％，As含量为1.26wt％。
  13. 根据权利要求1或2所述的方法，其特征在于，所述步骤1中高锑粗锡的Sn含量为94.29wt％，Sb含量为3.49wt％，Pb含量为1.27wt％，As含量为0.95wt％。
  14. 根据权利要求1或2所述的方法，其特征在于，所述步骤1中高锑粗锡的Sn含量为90.76wt％，Sb含量为8.25wt％，Pb含量为0.82wt％，As含量为0.17wt％。
  15. 根据权利要求1所述的方法，其特征在于，所述步骤2中分级冷凝器上设有电阻丝发热体和循环冷却水控制冷凝温度。
  16. 根据权利要求1所述的方法，其特征在于，所述步骤2中分级冷凝器由石英材料制成。
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116411175A (zh) * 2023-06-12 2023-07-11 昆明理工大学 一种复杂粗铅火法精炼方法

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113737007B (zh) * 2021-07-28 2023-03-17 昆明理工大学 一种高锑粗锡分离提纯的方法
CN114774704B (zh) * 2022-04-20 2023-09-15 柳州华锡有色设计研究院有限责任公司 一种利用锡精炼渣生产低铅锡基巴氏合金的方法
CN114807620B (zh) * 2022-04-21 2024-04-26 昆明理工大学 一种铅锑砷三元合金真空气化-定向冷凝分离的设备及其方法
CN115259220A (zh) * 2022-07-25 2022-11-01 云南锡业锡化工材料有限责任公司 一种三锡酸二锑的制备方法
CN116426766B (zh) * 2023-06-12 2023-08-29 昆明理工大学 一种复杂粗铅提银的方法

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101781711A (zh) * 2010-03-29 2010-07-21 广西华锡集团股份有限公司 多元合金馏分分步冷凝和底流或馏分再蒸馏的真空蒸馏炉
CN102492861A (zh) * 2011-12-29 2012-06-13 昆明理工大学 一种粗锡火法精炼的方法
CN104651625A (zh) * 2015-02-05 2015-05-27 昆明理工大学 一种含锑粗锡合金真空蒸馏脱除锑铅砷的方法
CN104651626A (zh) * 2015-02-05 2015-05-27 昆明鼎邦科技有限公司 一种锡铅锑砷合金真空蒸馏分离锡的方法
CN206232790U (zh) * 2016-12-09 2017-06-09 郴州万墨环保科技有限公司 一种铜阳极泥真空还原脱铅锑铋硒碲砷的环保生产系统
CN107217145A (zh) * 2016-12-09 2017-09-29 郴州万墨环保科技有限公司 一种铜阳极泥真空还原脱铅锑铋硒碲砷的方法
CN111607708A (zh) * 2020-07-14 2020-09-01 湖南金马冶金技术开发有限公司 一种高砷合金连续真空蒸馏脱砷工艺及系统
CN113737007A (zh) * 2021-07-28 2021-12-03 昆明理工大学 一种高锑粗锡分离提纯的方法

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1189579C (zh) * 1996-10-18 2005-02-16 昆明理工大学 含锑粗锡分离锑的方法
JP2005002984A (ja) * 2003-01-09 2005-01-06 Hiroyasu Tanigawa 各種竪型全動翼蒸気ガスタービン合体機関
CN101696475B (zh) 2009-10-29 2012-08-01 昆明理工大学 一种分离铅锡锑三元合金的方法
CN104561595A (zh) * 2014-12-08 2015-04-29 广西泰星电子焊接材料有限公司 粗锡真空精炼除锑的方法
CN104651627A (zh) * 2015-02-05 2015-05-27 昆明鼎邦科技有限公司 一种锡锑合金真空蒸馏分离锑的方法
TW202035716A (zh) * 2019-01-30 2020-10-01 比利時商梅泰洛比利時公司 經改良之錫產物
CN112176196B (zh) * 2020-10-12 2022-05-27 昆明理工大学 一种金银铜合金分离提纯的方法

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101781711A (zh) * 2010-03-29 2010-07-21 广西华锡集团股份有限公司 多元合金馏分分步冷凝和底流或馏分再蒸馏的真空蒸馏炉
CN102492861A (zh) * 2011-12-29 2012-06-13 昆明理工大学 一种粗锡火法精炼的方法
CN104651625A (zh) * 2015-02-05 2015-05-27 昆明理工大学 一种含锑粗锡合金真空蒸馏脱除锑铅砷的方法
CN104651626A (zh) * 2015-02-05 2015-05-27 昆明鼎邦科技有限公司 一种锡铅锑砷合金真空蒸馏分离锡的方法
CN206232790U (zh) * 2016-12-09 2017-06-09 郴州万墨环保科技有限公司 一种铜阳极泥真空还原脱铅锑铋硒碲砷的环保生产系统
CN107217145A (zh) * 2016-12-09 2017-09-29 郴州万墨环保科技有限公司 一种铜阳极泥真空还原脱铅锑铋硒碲砷的方法
CN111607708A (zh) * 2020-07-14 2020-09-01 湖南金马冶金技术开发有限公司 一种高砷合金连续真空蒸馏脱砷工艺及系统
CN113737007A (zh) * 2021-07-28 2021-12-03 昆明理工大学 一种高锑粗锡分离提纯的方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116411175A (zh) * 2023-06-12 2023-07-11 昆明理工大学 一种复杂粗铅火法精炼方法
CN116411175B (zh) * 2023-06-12 2023-08-25 昆明理工大学 一种复杂粗铅火法精炼方法

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