WO2020103642A1 - 一种真空氯化焙烧处理重金属危废的装置及方法 - Google Patents

一种真空氯化焙烧处理重金属危废的装置及方法

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Publication number
WO2020103642A1
WO2020103642A1 PCT/CN2019/113144 CN2019113144W WO2020103642A1 WO 2020103642 A1 WO2020103642 A1 WO 2020103642A1 CN 2019113144 W CN2019113144 W CN 2019113144W WO 2020103642 A1 WO2020103642 A1 WO 2020103642A1
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WIPO (PCT)
Prior art keywords
chlorination roasting
heavy metal
vacuum
chamber
chlorination
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PCT/CN2019/113144
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English (en)
French (fr)
Inventor
刘学明
林璋
宿新泰
于垚
周晋
钟祖琪
Original Assignee
华南理工大学
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Application filed by 华南理工大学 filed Critical 华南理工大学
Publication of WO2020103642A1 publication Critical patent/WO2020103642A1/zh

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Classifications

    • 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
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/02—Roasting processes
    • C22B1/08—Chloridising roasting
    • 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
    • C22B34/00—Obtaining refractory metals
    • C22B34/30—Obtaining chromium, molybdenum or tungsten
    • C22B34/32—Obtaining chromium
    • 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

Definitions

  • the invention belongs to the technical field of solid waste treatment, and in particular relates to a device and a method for vacuum chlorination roasting treatment of heavy metal hazardous waste.
  • Chlorination roasting technology is mainly used in the metallurgical industry, the main reasons are divided into three points.
  • elemental chlorine is more likely to react with most metals or their oxides under certain conditions, so that it can obtain metal chlorides that are easily soluble in solvents such as water and ethanol or have low melting points and are easily volatile.
  • solvents such as water and ethanol or have low melting points and are easily volatile.
  • the chlorination roasting method can reduce the roasting temperature to a certain extent and save energy; finally, due to the difference in the nature of different metals, their chlorination
  • the degree of difficulty is different, and the properties of the generated metal chloride are also significantly different.
  • the method of chlorination roasting can effectively separate and enrich different metals to achieve the purpose of comprehensive utilization. It is well known that under vacuum conditions, the saturated vapor pressure of volatile substances can be changed, which is conducive to the volatilization of metal chlorides. However, there is no report on the complete device and application method of chlorinating roasting to deal with heavy metal hazardous solid waste under vacuum conditions.
  • the Chinese patent “A method for selective recovery of mercury from smelting waste residues” takes into account the selective separation of heavy metals by chlorination roasting methods. Under oxygen-rich conditions, low-temperature chlorination roasting is used to make waste residues Mercury sulfide, mercury selenide, etc. are converted into volatile mercury chloride, which is absorbed by lye and then hydrolyzed to recover oxidized mercury.
  • this method requires the introduction of a large amount of oxygen-rich gas with a volume fraction greater than 50% of O 2. Although it can improve the volatilization efficiency of mercury chloride, it also brings unsafe factors to the treatment process.
  • the mainstream technology for the treatment of heavy metal waste residues is the in-situ solidification method, but this technology will not only lead to the slow release and secondary toxicity of heavy metals, but also cannot solve the continuous accumulation of solid waste in the environment.
  • the invention applies the chlorination roasting technology mainly used in the metallurgical industry to the treatment of heavy metal hazardous solid waste. Under different roasting temperature conditions, most metals or metal compounds can be reacted to form corresponding metal chlorides. The physical and chemical properties of these metal chlorides There are differences in properties; at the same time, due to the change of saturated vapor pressure in vacuum, it can improve the volatilization efficiency of volatile metal chlorides.
  • a vacuum chlorination roasting device By reacting with the precipitant in the absorbent, the metal chlorides form solid precipitates or metal chlorides in the low temperature aqueous solution and absorb Precipitants in the liquid such as NaOH, Na 2 CO 3 , and NaHCO 3 generate hydroxide or carbonate precipitates, which are recovered after solid-liquid separation to achieve the purpose of separating heavy metals, and ultimately increase the recovery rate of heavy metals.
  • a vacuum chlorination roasting device has the advantages of simple and convenient operation, and can simultaneously achieve detoxification of waste residues and resource recovery. No three wastes are generated in the entire treatment process, and the economic and social benefits are significant.
  • the primary objective of the present invention is to provide a vacuum chlorination roasting device for processing heavy metal hazardous waste.
  • Another object of the present invention is to provide a vacuum chlorination roasting method for treating heavy metal hazardous waste.
  • a vacuum chlorination roasting device for processing heavy metal hazardous waste includes a chlorination roasting chamber, a gas absorption chamber and a high hopper with a sealed cover are provided on the chlorination roasting chamber, the gas absorption chamber and the high hopper with a sealed cover pass through the pipeline and chlorine
  • the interior of the chemical roasting chamber is connected, and the gas absorption chamber is connected to a vacuum pump; the chlorination roasting chamber is provided with a stirring device.
  • a pressure control valve and a vacuum gauge are provided between the gas absorption chamber and the vacuum pump.
  • the stirring device is divided into an upper scraper and a lower material mixer, and the upper scraper is located at the top of the chlorination roasting chamber.
  • the upper scraper is used to scrape off the volatile condensed material on the top of the chlorination roasting chamber, and the lower material stirrer makes the materials fully mixed and heated evenly.
  • a thermal insulation layer and a temperature controller are provided on the surface of the chlorination roasting outdoor. Used to control the temperature in the chlorination roasting chamber.
  • a bracket is provided at the bottom of the chlorination roasting chamber.
  • a vacuum chlorination roasting method for processing heavy metal hazardous waste includes the following steps:
  • the heavy metal hazardous solid waste is dried, ground and sieved, added with chlorinating agent or chlorinating agent and other additives to mix evenly, and then added to the chlorination roasting chamber through a high-level hopper;
  • step (3) The volatile metal chloride generated in step (2) is collected by the gas absorption chamber containing the absorption liquid through the pipeline; the remaining slag obtained in the chlorination roasting chamber is washed with water, filtered and dried to obtain detoxified slag .
  • the heavy metal hazardous solid waste in step (1) refers to chromium slag, electroplating sludge, lead-containing waste slag, arsenic slag or steel slag.
  • the chlorinating agent in step (1) is at least one of hydrochloric acid, magnesium chloride, calcium chloride, ammonium chloride, zinc chloride, copper chloride, ferric chloride, potassium chloride, and chlorine gas.
  • the other auxiliary agent in step (1) is SiO 2 .
  • the mass ratio of the heavy metal hazardous solid waste and the chlorinating agent or the chlorinating agent and other auxiliary agents added in step (1) is 1: (0.5 ⁇ 5).
  • the absorption liquid in step (3) is at least one of pure water, sodium carbonate solution, sodium bicarbonate solution, and sodium hydroxide solution.
  • step (3) the product collected in the gas absorption chamber in step (3) is filtered to recover heavy metals, and the resulting filtrate is evaporated and crystallized to obtain a chlorinating agent for reuse.
  • the solid-liquid mass ratio of the remaining slag and the washing liquid in step (3) is 1: (1.5 ⁇ 10).
  • the filtrate after the pressure filtration in step (3) is evaporated and crystallized to obtain a chlorinating agent for reuse.
  • heavy metals Due to the complex composition of heavy metal hazardous solid wastes, heavy metals exist in various forms.
  • the slow diffusion and dissolution of heavy metals include both free and adsorbed metals on the surface and soluble heavy metals trapped inside the solid particles. Therefore, the vacuum chlorination roasting method is selected. Under different roasting temperature conditions, most metals or metal compounds can be reacted to form corresponding metal chlorides.
  • the physical and chemical properties of these metal chlorides are different; at the same time, due to the change in saturation vapor pressure in vacuum, it can Improve the volatilization efficiency of volatile metal chlorides.
  • the metal chloride forms a solid precipitate in the low-temperature aqueous solution or the metal chloride and the precipitant in the absorbent, such as NaOH, Na 2 CO 3 , NaHCO 3 Generate hydroxide or carbonate precipitates, which are recovered after solid-liquid separation to achieve the purpose of separating heavy metals, and finally increase the recovery rate of heavy metals.
  • the present invention has the following advantages and beneficial effects:
  • the vacuum chlorination roasting device is simple and convenient to operate, and can simultaneously achieve detoxification of waste residues and resource recovery. No three wastes are generated in the entire process route, and the economic and social benefits are significant.
  • the vacuum chlorination roasting technology adopted by the invention has low roasting temperature and low energy consumption. It is suitable for a variety of heavy metal hazardous wastes. The content of heavy metals leached from the treated filter residue is lower than the national standard (HJ / T 301-2007) Limitation of general industrial solid waste.
  • the method of the present invention is simple in process flow, low in cost, and has additional economic benefits, and is suitable for engineering enlargement and large-scale application.
  • the device provides a reference for engineering application equipment.
  • the device and process method of the present invention also have reference significance for the extraction of rare and precious metals in mineral products.
  • FIG. 1 is a schematic structural diagram of a vacuum chlorination roasting device for processing heavy metal hazardous waste according to an embodiment of the present invention.
  • the numbers in the figure are explained as follows: 1- chlorination roasting chamber, 2- gas absorption chamber, 3- high hopper with sealed cover, 4- vacuum pump, 5- pressure control valve, 6- vacuum gauge, 7- upper wiper blade, 8 -Lower material mixer, 9-insulation layer, 10-temperature controller, 11-bracket.
  • FIG. 1 A vacuum chlorination roasting device for processing heavy metal hazardous waste in this embodiment is shown in FIG. 1, which includes a chlorination roasting chamber 1.
  • a gas absorption chamber 2 and a high position with a sealing cover are provided on the chlorination roasting chamber 1
  • the hopper 3, the gas absorption chamber 2 and the high-level hopper 3 with a sealed cover communicate with the inside of the chlorination roasting chamber 1 through a pipe.
  • the gas absorption chamber 2 is connected to a vacuum pump 4, and a pressure control valve 5 and a vacuum are provided between the gas absorption chamber 2 and the vacuum pump 4.
  • the chlorination roasting chamber 1 is provided with a stirring device, the stirring device is divided into an upper scraper 7 and a lower material stirrer 8, the upper scraper 7 is located at the top of the chlorination roasting chamber 1 (higher than the gas absorption chamber and with a seal Covered high-level hopper communicates with the inside of the chlorinating roasting chamber); the outer surface of the chlorinating roasting chamber 1 is provided with a thermal insulation layer 9 and a temperature controller 10, and the bottom of the chlorinating roasting chamber 1 is provided with a support 11.
  • the specific operation steps are as follows:
  • the control valve is set to 1Pa
  • the absorption liquid in the gas absorption chamber is pure water
  • the vacuum pump is turned on to perform vacuuming.
  • Turn on the stirring device to make the upper scraper and lower material mixer of the stirring device operate.
  • the temperature controller is set to rise to 550 ° C at a heating rate of 10 ° C / min, and the roasting time is set to 0.5h. After roasting, naturally cool to room temperature slowly;
  • step (3) The filtrate obtained in step (2) and step (3) is heated and evaporated to crystallize to obtain calcium chloride.
  • the lead concentration in the leaching solution of the detoxified residue obtained in this example is 0.005 mg / L, and the purity of the lead chloride obtained is as high as 99% or more.
  • FIG. 1 A vacuum chlorination roasting device for processing heavy metal hazardous waste in this embodiment is shown in FIG. 1, which includes a chlorination roasting chamber 1.
  • a gas absorption chamber 2 and a high position with a sealing cover are provided on the chlorination roasting chamber 1
  • the hopper 3, the gas absorption chamber 2 and the high-level hopper 3 with a sealed cover communicate with the inside of the chlorination roasting chamber 1 through a pipe.
  • the gas absorption chamber 2 is connected to a vacuum pump 4, and a pressure control valve 5 and a vacuum are provided between the gas absorption chamber 2 and the vacuum pump 4.
  • the chlorination roasting chamber 1 is provided with a stirring device, the stirring device is divided into an upper scraper 7 and a lower material stirrer 8, the upper scraper 7 is located at the top of the chlorination roasting chamber 1 (higher than the gas absorption chamber and with a seal Covered high-level hopper communicates with the inside of the chlorinating roasting chamber); the outer surface of the chlorinating roasting chamber 1 is provided with a thermal insulation layer 9 and a temperature controller 10, and the bottom of the chlorinating roasting chamber 1 is provided with a support 11.
  • the specific operation steps are as follows:
  • step (3) The filtrate obtained in step (2) and step (3) is heated and evaporated to crystallize to obtain chloride.
  • the concentration of leached hexavalent chromium in the original chromium slag of this embodiment is 416 mg / L, and the concentration of leached hexavalent chromium in the filter residue after treatment is 0.164 mg / L.
  • FIG. 1 A vacuum chlorination roasting device for processing heavy metal hazardous waste in this embodiment is shown in FIG. 1, which includes a chlorination roasting chamber 1.
  • a gas absorption chamber 2 and a high position with a sealing cover are provided on the chlorination roasting chamber 1
  • the hopper 3, the gas absorption chamber 2 and the high-level hopper 3 with a sealed cover communicate with the inside of the chlorination roasting chamber 1 through a pipe.
  • the gas absorption chamber 2 is connected to a vacuum pump 4, and a pressure control valve 5 and a vacuum are provided between the gas absorption chamber 2 and the vacuum pump Count 6;
  • the chlorination roasting chamber 1 is provided with a stirring device, the stirring device is divided into an upper scraper 7 and a lower material stirrer 8, the upper scraper 7 is located at the top of the chlorination roasting chamber 1 (higher than the gas absorption chamber and with a seal Covered high-level hopper communicates with the inside of the chlorinating roasting chamber);
  • the outer surface of the chlorinating roasting chamber 1 is provided with a thermal insulation layer 9 and a temperature controller 10, and the bottom of the chlorinating roasting chamber 1 is provided with a support 11.
  • step (3) The filtrate obtained in step (2) and step (3) is heated and evaporated to crystallize to obtain chloride.
  • the nickel extraction rate is as high as over 99%, and the chromium extraction rate is around 89%.

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  • Chemical & Material Sciences (AREA)
  • Metallurgy (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Organic Chemistry (AREA)
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Abstract

一种真空氯化焙烧处理重金属危废的装置及方法。将重金属危险固体废弃物经干燥研磨过筛，加入氯化剂或氯化剂与其他助剂混合均匀，然后通过高位料斗（3）加入到氯化焙烧室（1）中；设置压力为1～10 5Pa，进行抽真空处理，然后设置加热温度为200～600℃，对氯化焙烧室（1）中的物料进行搅拌加热焙烧处理0.5～2h；所产生的挥发性金属氯化物，经管道被盛有吸收液的气体吸收室（2）收集；氯化焙烧室（1）中所得剩余烧渣经水洗后压滤、干燥，得到脱毒渣。该装置及方法操作简单方便，能够同时实现废渣解毒与资源回收，整个工艺路线无三废产生，经济效益和社会效益显著。

Description

一种真空氯化焙烧处理重金属危废的装置及方法 技术领域
本发明属于固废处理技术领域，具体涉及一种真空氯化焙烧处理重金属危废的装置及方法。
 背景技术
近年来，电镀、精细化工等行业产生的重金属危险固体废物产生量巨大，是一种普遍存在的典型污染物。目前重金属废渣的处理主流技术是原位固化法，但该技术不仅会导致重金属的缓释和二次毒性，而且无法解决固废在环境中的持续性累积。重金属在环境中的大量存在，无可避免的会进入人类食物链，长期危害人类健康。因此，发展一种彻底的提取技术，从根本上减少有毒有害物质，是重金属固体废物处置领域的迫切需求。
氯化焙烧技术主要用于冶金行业，主要原因分为三点。其一，氯元素在一定条件下较易与大多金属或其氧化物发生反应，从而可以得到易溶于水、乙醇等溶剂或是熔点低、易于挥发的金属氯化物，根据金属氯化物上述特性，能够使目的金属分离；其二，与其他火法冶金方法相比，氯化焙烧法在一定程度上能降低焙烧温度，节约能源；最后，由于不同金属其本身的性质差异，导致其氯化的难易程度有别，所生成的金属氯化物的性质也存在明显差异，故对于组分复杂的矿物，采用氯化焙烧的方法能够有效分离富集不同金属，达到综合利用的目的。而众所周知，真空条件下能够改变物质挥发饱和蒸气压，有利于金属氯化物的挥发。但目前尚未有真空条件下采用氯化焙烧处理重金属危险固体废弃物的完整装置及应用方法的报道。
中国专利“一种从冶炼废渣中选择性回收汞的方法”（CN 108034808 A）考虑到了氯化焙烧方法对重金属的选择性分离作用，在富氧条件下，采用中低温氯化焙烧使废渣中硫化汞、硒化汞等转化为易挥发的氯化汞，通过碱液吸收，再水解，回收氧化汞。但是这种方法需要通入大量体积分数大于50%的O 2的富氧气体，虽然能够提高氯化汞的挥发效率，但同时也为处理过程带来不安全因素。
技术问题
目前重金属废渣的处理主流技术是原位固化法，但该技术不仅会导致重金属的缓释和二次毒性，而且无法解决固废在环境中的持续性累积。本发明将主要用于冶金行业的氯化焙烧技术应用于处理重金属危险固体废弃物，在不同焙烧温度条件下能使大部分金属或金属化合物反应生成对应的金属氯化物，这些金属氯化物的物化性质具有差异；同时由于真空中饱和蒸气压改变，能够提高挥发性金属氯化物的挥发效率，通过与吸收剂中的沉淀剂进行反应，金属氯化物在低温水溶液形成固体沉淀或金属氯化物与吸收液中的沉淀剂如NaOH、Na 2CO 3、NaHCO 3生成氢氧化物或碳酸盐沉淀，经固液分离后回收，达到重金属分离的目的，最终增加重金属的再回收率。相应的配套一种真空氯化焙烧装置，具有操作简单方便的优点，能够同时实现废渣解毒与资源回收，整个处理过程无三废产生，经济效益和社会效益显著。
技术解决方案
针对以上现有技术存在的缺点和不足之处，本发明的首要目的在于提供一种真空氯化焙烧处理重金属危废的装置。
本发明的另一目的在于提供一种真空氯化焙烧处理重金属危废的方法。
本发明目的通过以下技术方案实现：
一种真空氯化焙烧处理重金属危废的装置，包括氯化焙烧室，氯化焙烧室上设置气体吸收室和带密封盖的高位料斗，气体吸收室和带密封盖的高位料斗通过管道与氯化焙烧室内部连通，气体吸收室连接真空泵；所述氯化焙烧室内设置搅拌装置。
进一步地，所述气体吸收室与真空泵之间设置压力控制阀和真空计。
进一步地，所述搅拌装置分为上部刮片与下部物料搅拌器，上部刮片位于氯化焙烧室顶部。上部刮片用于刮去挥发凝结在氯化焙烧室顶部的物质，下部物料搅拌器使物料充分混合，并且受热均匀。
进一步地，所述氯化焙烧室外表面设置保温层和温度控制器。用于控制氯化焙烧室内的温度。氯化焙烧室底部设置支架。
一种真空氯化焙烧处理重金属危废的方法，包括如下步骤：
（1）将重金属危险固体废弃物经干燥研磨过筛，加入氯化剂或氯化剂与其他助剂混合均匀，然后通过高位料斗加入到氯化焙烧室中；
（2）设置压力为1~10 5Pa，进行抽真空处理，然后设置加热温度为200~600℃，对氯化焙烧室中的物料进行搅拌加热焙烧处理0.5~2h；
（3）步骤（2）所产生的挥发性金属氯化物，经管道被盛有吸收液的气体吸收室收集；氯化焙烧室中所得剩余烧渣经水洗后压滤、干燥，得到脱毒渣。
进一步地，步骤（1）中所述重金属危险固体废弃物是指铬渣、电镀污泥、含铅废渣、砷渣或钢渣。
优选地，步骤（1）中所述氯化剂为盐酸、氯化镁、氯化钙、氯化铵、氯化锌、氯化铜、氯化铁、氯化钾、氯气中的至少一种。
优选地，步骤（1）中所述其他助剂为SiO 2。
优选地，步骤（1）中所述重金属危险固体废弃物与氯化剂或氯化剂与其他助剂加入的质量比为1:（0.5~5）。
优选地，步骤（3）中所述的吸收液为纯水、碳酸钠溶液、碳酸氢钠溶液、氢氧化钠溶液中的至少一种。
进一步地，步骤（3）中所述气体吸收室收集得到的产物经过滤回收重金属，所得滤液经蒸发、结晶得到氯化剂重复使用。
进一步地，步骤（3）中所述剩余烧渣与水洗液的固液质量比为1:（1.5~10）。
进一步地，步骤（3）中所述压滤后的滤液经蒸发、结晶得到氯化剂重复使用。
本发明的原理如下：
由于重金属危险固体废弃物成分复杂，重金属在其中的存在形式多种多样，重金属缓慢扩散和溶出既包括表面游离态和吸附态的金属，也包括固体颗粒内部包夹的可溶性重金属。因此选择真空氯化焙烧法，在不同焙烧温度条件下能使大部分金属或金属化合物反应生成对应的金属氯化物，这些金属氯化物的物化性质具有差异；同时由于真空中饱和蒸气压改变，能够提高挥发性金属氯化物的挥发效率，通过与吸收剂中的沉淀剂进行反应，金属氯化物在低温水溶液形成固体沉淀或金属氯化物与吸收液中的沉淀剂如NaOH、Na 2CO 3、NaHCO 3生成氢氧化物或碳酸盐沉淀，经固液分离后回收，达到重金属分离的目的，最终增加重金属的再回收率。
有益效果
相对于现有技术，本发明具有如下优点及有益效果：
（1）本发明涉及的真空氯化焙烧装置操作简单方便，能够同时实现废渣解毒与资源回收，整个工艺路线无三废产生，经济效益和社会效益显著。
（2）本发明采用的真空氯化焙烧技术，焙烧温度低，能源消耗小，适用于多种重金属危险废弃物，处理后的滤渣浸出重金属的含量低于国家标准（HJ/T 301-2007）一般工业固体废渣的限制。
（3）本发明方法工艺流程简单，成本低廉，同时具有额外的经济效益，适于工程放大及规模化应用，所述的装置为工程化应用设备提供了参考。
（4）本发明所述装置及工艺方法对矿产中稀贵重金属的提取同样具有借鉴意义。
 附图说明
图1为本发明实施例中一种真空氯化焙烧处理重金属危废的装置的结构示意图。图中编号说明如下：1-氯化焙烧室，2-气体吸收室，3-带密封盖的高位料斗，4-真空泵，5-压力控制阀，6-真空计，7-上部刮片，8-下部物料搅拌器，9-保温层，10-温度控制器，11-支架。
 本发明的实施方式
下面结合实施例及附图对本发明作进一步详细的描述，但本发明的实施方式不限于此。
实施例1
本实施例的一种真空氯化焙烧处理重金属危废的装置，其结构示意图如图1所示，包括氯化焙烧室1，氯化焙烧室1上设置气体吸收室2和带密封盖的高位料斗3，气体吸收室2和带密封盖的高位料斗3通过管道与氯化焙烧室1内部连通，气体吸收室2连接真空泵4，气体吸收室2与真空泵4之间设置压力控制阀5和真空计6；所述氯化焙烧室1内设置搅拌装置，搅拌装置分为上部刮片7与下部物料搅拌器8，上部刮片7位于氯化焙烧室1顶部（高于气体吸收室和带密封盖的高位料斗与氯化焙烧室内部连通的管道口）；氯化焙烧室1外表面设置保温层9和温度控制器10，氯化焙烧室1底部设置支架11。利用该装置通过真空氯化焙烧处理重金属危废的方法，具体操作步骤如下：
（1）取0.5t经干燥研磨过筛后的废铅膏与0.2t氯化钙及0.3t二氧化硅混合置于高位料斗，从而进入氯化焙烧室中，盖上高位料斗密封盖，压力控制阀设置为1Pa，气体吸收室吸收液为纯水，打开真空泵，进行抽真空。打开搅拌装置，使搅拌装置的上部刮片与下部物料搅拌器运行。温度控制器设置以10℃/min的升温速率升至550℃，焙烧时间设定为0.5h，焙烧后，自然缓慢冷却至室温；
（2）将压力调回正常气压，关闭真空泵，将气体吸收室其中的固液混合物进行过滤，得到PbCl3沉淀及滤液，将固体物质烘干；
（3）从氯化焙烧室底部的出料口取出剩余烧渣，加入自来水进行洗涤，然后通过板框压滤机压滤得到脱毒渣及滤液；
（4）将步骤（2）和步骤（3）得到的滤液加热蒸发结晶，得到氯化钙。
本实施例所得脱毒渣的浸出液中铅浓度为0.005 mg/L，得到氯化铅的纯度高达99 %以上。
实施例2
本实施例的一种真空氯化焙烧处理重金属危废的装置，其结构示意图如图1所示，包括氯化焙烧室1，氯化焙烧室1上设置气体吸收室2和带密封盖的高位料斗3，气体吸收室2和带密封盖的高位料斗3通过管道与氯化焙烧室1内部连通，气体吸收室2连接真空泵4，气体吸收室2与真空泵4之间设置压力控制阀5和真空计6；所述氯化焙烧室1内设置搅拌装置，搅拌装置分为上部刮片7与下部物料搅拌器8，上部刮片7位于氯化焙烧室1顶部（高于气体吸收室和带密封盖的高位料斗与氯化焙烧室内部连通的管道口）；氯化焙烧室1外表面设置保温层9和温度控制器10，氯化焙烧室1底部设置支架11。利用该装置通过真空氯化焙烧处理重金属危废的方法，具体操作步骤如下：
（1）取1.0t经干燥研磨过筛后的铬渣与0.5t氯化铵混合置于高位料斗，从而进入氯化焙烧室中，盖上高位料斗密封盖，压力控制阀设置为常压，气体吸收室吸收液为1mol/L NaOH溶液，打开真空泵，进行抽真空。打开搅拌装置，使搅拌装置的上部刮片与下部物料搅拌器运行。温度控制器设置以10℃/min的升温速率升至300℃，焙烧时间设定为2.0h，焙烧后，自然缓慢冷却至室温；
（2）关闭真空泵，将气体吸收室其中的固液混合物进行过滤，得到Cr( OH )3沉淀及滤液，将固体物质烘干回收；
（3）从氯化焙烧室底部的出料口取出剩余烧渣，加入自来水进行洗涤，然后通过板框压滤机压滤得到脱毒渣及滤液；
（4）将步骤（2）和步骤（3）得到的滤液加热蒸发结晶，得到氯化物。
本实施例的原始铬渣浸出六价铬浓度为416mg/L，处理后滤渣浸出六价铬浓度为0.164mg/L。
实施例3
本实施例的一种真空氯化焙烧处理重金属危废的装置，其结构示意图如图1所示，包括氯化焙烧室1，氯化焙烧室1上设置气体吸收室2和带密封盖的高位料斗3，气体吸收室2和带密封盖的高位料斗3通过管道与氯化焙烧室1内部连通，气体吸收室2连接真空泵4，气体吸收室2与真空泵4之间设置压力控制阀5和真空计6；所述氯化焙烧室1内设置搅拌装置，搅拌装置分为上部刮片7与下部物料搅拌器8，上部刮片7位于氯化焙烧室1顶部（高于气体吸收室和带密封盖的高位料斗与氯化焙烧室内部连通的管道口）；氯化焙烧室1外表面设置保温层9和温度控制器10，氯化焙烧室1底部设置支架11。利用该装置通过真空氯化焙烧处理重金属危废的方法，具体操作步骤如下：
（1）取1.0t经干燥研磨过筛后的含铬电镀镍泥与0.5t浓盐酸混合置于高位料斗，从而进入氯化焙烧室中，盖上高位料斗密封盖，压力控制阀设置为常压，气体吸收室吸收液为0.5mol/L NaOH溶液，打开真空泵，进行抽真空。打开搅拌装置，使搅拌装置的上部刮片与下部物料搅拌器运行。温度控制器设置以10℃/min的升温速率升至200℃，焙烧时间设定为2.0h，焙烧后，自然缓慢冷却至室温；
（2）关闭真空泵，将气体吸收室其中的固液混合物进行过滤，得到Cr( OH )3及Ni( OH )2沉淀及滤液，将固体物质烘干回收；
（3）从氯化焙烧室底部的出料口取出剩余烧渣，加入自来水进行洗涤，然后通过板框压滤机压滤得到脱毒渣及滤液；
（4）将步骤（2）和步骤（3）得到的滤液加热蒸发结晶，得到氯化物。
本实施例处理后镍的提取率高达99%以上，铬提取率在89%左右。
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其它的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。

Claims (10)

  1. 一种真空氯化焙烧处理重金属危废的装置，其特征在于：所述装置包括氯化焙烧室，氯化焙烧室上设置气体吸收室和带密封盖的高位料斗，气体吸收室和带密封盖的高位料斗通过管道与氯化焙烧室内部连通，气体吸收室连接真空泵；所述氯化焙烧室内设置搅拌装置。
  2. 根据权利要求1所述的一种真空氯化焙烧处理重金属危废的装置，其特征在于：所述搅拌装置分为上部刮片与下部物料搅拌器，上部刮片位于氯化焙烧室顶部。
  3. 根据权利要求1所述的一种真空氯化焙烧处理重金属危废的装置，其特征在于：所述气体吸收室与真空泵之间设置压力控制阀和真空计；所述氯化焙烧室外表面设置保温层和温度控制器，氯化焙烧室底部设置支架。
  4. 一种真空氯化焙烧处理重金属危废的方法，其特征在于包括如下步骤：
    （1）将重金属危险固体废弃物经干燥研磨过筛，加入氯化剂或氯化剂与其他助剂混合均匀，然后通过高位料斗加入到氯化焙烧室中；
    （2）设置压力为1~10 5Pa，进行抽真空处理，然后设置加热温度为200~600℃，对氯化焙烧室中的物料进行搅拌加热焙烧处理0.5~2h；
    （3）步骤（2）所产生的挥发性金属氯化物，经管道被盛有吸收液的气体吸收室收集；氯化焙烧室中所得剩余烧渣经水洗后压滤、干燥，得到脱毒渣。
  5. 根据权利要求4所述的一种真空氯化焙烧处理重金属危废的方法，其特征在于：步骤（1）中所述重金属危险固体废弃物是指铬渣、电镀污泥、含铅废渣、砷渣或钢渣；所述氯化剂为盐酸、氯化镁、氯化钙、氯化铵、氯化锌、氯化铜、氯化铁、氯化钾、氯气中的至少一种；所述其他助剂为SiO 2。
  6. 根据权利要求4所述的一种真空氯化焙烧处理重金属危废的方法，其特征在于：步骤（1）中所述重金属危险固体废弃物与氯化剂或氯化剂与其他助剂加入的质量比为1:（0.5~5）。
  7. 根据权利要求4所述的一种真空氯化焙烧处理重金属危废的方法，其特征在于：步骤（3）中所述的吸收液为纯水、碳酸钠溶液、碳酸氢钠溶液、氢氧化钠溶液中的至少一种。
  8. 根据权利要求4所述的一种真空氯化焙烧处理重金属危废的方法，其特征在于：步骤（3）中所述气体吸收室收集得到的产物经过滤回收重金属，所得滤液经蒸发、结晶得到氯化剂重复使用。
  9. 根据权利要求4所述的一种真空氯化焙烧处理重金属危废的方法，其特征在于：步骤（3）中所述剩余烧渣与水洗液的固液质量比为1:（1.5~10）。
  10. 根据权利要求4所述的一种真空氯化焙烧处理重金属危废的方法，其特征在于：步骤（3）中所述压滤后的滤液经蒸发、结晶得到氯化剂重复使用。
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114622106A (zh) * 2022-03-15 2022-06-14 崇义章源钨业股份有限公司 一种利用氯化焙烧法回收含钨废料中钨的方法

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109554536A (zh) * 2018-11-23 2019-04-02 华南理工大学 一种真空氯化焙烧处理重金属危废的装置及方法
CN110980794A (zh) * 2019-11-28 2020-04-10 华南理工大学 一种利用SiO2调控含铜污泥制备高纯二水合氯化铜的方法
CN111484252A (zh) * 2020-04-26 2020-08-04 烟台泰新环保科技有限公司 一种危废焚烧残余物熔融氯化焙烧资源化利用的方法
CN112501436A (zh) * 2020-10-16 2021-03-16 华南理工大学 氯化结合水浸回收电镀污泥中重金属的装置及方法
CN112853112A (zh) * 2021-01-09 2021-05-28 中新国际联合研究院 一种实现全回收铬渣中铬的方法
CN113337717B (zh) * 2021-06-11 2022-07-19 南昌航空大学 一种采用组合氯化剂分离回收电镀污泥中有价金属的方法
CN113620318B (zh) * 2021-07-31 2022-10-25 华南理工大学 一种氯化法处理含铬芒硝废盐的方法
CN115386723A (zh) * 2022-08-16 2022-11-25 中南大学 一种铜熔炼渣真空负压焙烧回收有价金属的方法
CN117127023A (zh) * 2023-08-31 2023-11-28 常熟理工学院 从净化钴渣中回收钴的方法

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001011542A (ja) * 1999-07-02 2001-01-16 Ct Umwelttechnik Ag 残留物質からの金属の除去方法
US20120114539A1 (en) * 2009-01-16 2012-05-10 Minex Technologies Limited Metal Recovery Process
CN104611542A (zh) * 2015-02-09 2015-05-13 池州冠华黄金冶炼有限公司 一种中温氯化法处理金银铜阳极泥的方法
CN205599155U (zh) * 2016-04-29 2016-09-28 湖北武洲新材料科技有限公司 带尾气处理装置的密封反应釜
CN106676257A (zh) * 2016-12-23 2017-05-17 江西理工大学 一种含砷废渣的脱砷方法
CN107151738A (zh) * 2016-10-21 2017-09-12 河北信谷环保科技有限公司 一种提锌尾矿的资源化利用方法
CN207632860U (zh) * 2017-11-24 2018-07-20 姚俊 一种降低生活垃圾焚烧炉渣中金属溶出的装置
CN108330274A (zh) * 2018-01-30 2018-07-27 华南理工大学 一种氯化焙烧联合水热矿化处理铬渣的方法
CN109554536A (zh) * 2018-11-23 2019-04-02 华南理工大学 一种真空氯化焙烧处理重金属危废的装置及方法
CN209276586U (zh) * 2018-11-23 2019-08-20 华南理工大学 一种真空氯化焙烧处理重金属危废的装置

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN2483839Y (zh) * 2001-05-31 2002-03-27 吴显积 废电池处理装置
JP2005137982A (ja) * 2003-11-05 2005-06-02 Sintokogio Ltd 固体廃棄物中に含まれる重金属の分離方法及びその分離回収システム。
CN205860705U (zh) * 2016-06-30 2017-01-04 浙江金立源药业有限公司 高效沸腾干燥机
CN206244594U (zh) * 2016-11-11 2017-06-13 周梁源 一种环保型化工生产污水处理设备
CN206570317U (zh) * 2017-02-16 2017-10-20 潍坊昆腾农业发展股份有限公司 生物菌肥菌种发酵罐
CN206911345U (zh) * 2017-06-07 2018-01-23 张家界贵友环保材料科技有限公司 一种生产聚氯化铝的反应釜搅拌装置
CN107827112A (zh) * 2017-12-25 2018-03-23 郑州恒生科技有限公司 一种碳化硅微粉提纯装置

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001011542A (ja) * 1999-07-02 2001-01-16 Ct Umwelttechnik Ag 残留物質からの金属の除去方法
US20120114539A1 (en) * 2009-01-16 2012-05-10 Minex Technologies Limited Metal Recovery Process
CN104611542A (zh) * 2015-02-09 2015-05-13 池州冠华黄金冶炼有限公司 一种中温氯化法处理金银铜阳极泥的方法
CN205599155U (zh) * 2016-04-29 2016-09-28 湖北武洲新材料科技有限公司 带尾气处理装置的密封反应釜
CN107151738A (zh) * 2016-10-21 2017-09-12 河北信谷环保科技有限公司 一种提锌尾矿的资源化利用方法
CN106676257A (zh) * 2016-12-23 2017-05-17 江西理工大学 一种含砷废渣的脱砷方法
CN207632860U (zh) * 2017-11-24 2018-07-20 姚俊 一种降低生活垃圾焚烧炉渣中金属溶出的装置
CN108330274A (zh) * 2018-01-30 2018-07-27 华南理工大学 一种氯化焙烧联合水热矿化处理铬渣的方法
CN109554536A (zh) * 2018-11-23 2019-04-02 华南理工大学 一种真空氯化焙烧处理重金属危废的装置及方法
CN209276586U (zh) * 2018-11-23 2019-08-20 华南理工大学 一种真空氯化焙烧处理重金属危废的装置

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
SUN, QING ET AL.: "The Disposal of Waste Dry Batteries with Vacum Chloridizing Roasting", JOURNAL OF HEBEI UNIVERSITY OF SCIENCE AND TECHNOLOGY, vol. 24, no. 4, 31 December 2003 (2003-12-31), ISSN: 1008-1542, DOI: 20200110101527 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114622106A (zh) * 2022-03-15 2022-06-14 崇义章源钨业股份有限公司 一种利用氯化焙烧法回收含钨废料中钨的方法
CN114622106B (zh) * 2022-03-15 2023-09-05 崇义章源钨业股份有限公司 一种利用氯化焙烧法回收含钨废料中钨的方法

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