WO2020108188A1 - 低温还原氯化回收危险固废中变价金属的装置及方法 - Google Patents

低温还原氯化回收危险固废中变价金属的装置及方法 Download PDF

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Publication number
WO2020108188A1
WO2020108188A1 PCT/CN2019/113140 CN2019113140W WO2020108188A1 WO 2020108188 A1 WO2020108188 A1 WO 2020108188A1 CN 2019113140 W CN2019113140 W CN 2019113140W WO 2020108188 A1 WO2020108188 A1 WO 2020108188A1
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Prior art keywords
mixing
heating chamber
low
variable
solid waste
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PCT/CN2019/113140
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English (en)
French (fr)
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林璋
刘学明
宿新泰
黄秋云
周晋
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华南理工大学
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Publication of WO2020108188A1 publication Critical patent/WO2020108188A1/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
    • 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
    • C22B7/006—Wet processes
    • C22B7/007—Wet processes by acid leaching
    • 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
    • C22B34/00—Obtaining refractory metals
    • C22B34/30—Obtaining chromium, molybdenum or tungsten
    • C22B34/32—Obtaining chromium
    • 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 the field of clean treatment of hazardous solid waste and recycling of resources, in particular to a detoxification treatment device and application method for low-temperature reduction and chlorination extraction and recovery of variable metals (chromium, arsenic, etc.) in hazardous solid waste.
  • variable-value metals chromium, arsenic, etc.
  • the dangerous solid wastes containing variable-value metals are chromium-containing waste residues and Arsenic waste residues are the main ones.
  • Both the calcium roasting and calcium-free roasting processes used in the production of chromium salts will produce chromium-containing waste residues. Among them, the calcium roasting process will produce 2-3 tons of chromium slag for each ton of product produced.
  • the harmlessness of hazardous solid waste containing variable-value metals is mainly to reduce/fix it in situ to reduce its toxicity and mobility, and the metal is still in solid waste.
  • the trivalent chromium or arsenic in the solid waste after detoxification may still be re-oxidized to hexavalent chromium or pentavalent arsenic under long-term oxidation conditions in the environment or under the action of manganese oxidizing bacteria, with secondary toxicity.
  • the harmless treatment of hazardous solid waste containing variable-value metals is mainly to perform in-situ reduction/fixation to reduce its toxicity and migration, but the metal is still in solid waste.
  • the low-temperature reduction and chlorination device provided by the present invention recovers the price-changing metal in hazardous solid waste by setting a heating rod and a stirring shaft to maintain the temperature in the mixing heating chamber at 300-500°C. Compared with the general chlorination roasting device, the temperature is relatively low Low, low temperature is conducive to product volatilization.
  • the device of the present invention can realize the detoxification treatment of hazardous solid waste containing variable-value metals, and extract variable-value metals from the hazardous solid waste, which solves the problem of difficult separation of variable-value metals and solid particles in the hazardous solid waste, and improves the value of variable-value metals Separation efficiency and recovery efficiency.
  • the low-temperature reduction and chlorination method provided by the present invention recovers the variable-value metals in hazardous solid waste. Through the reduction reaction in the heating process, hexavalent chromium or pentavalent arsenic is reduced to trivalent chromium or trivalent arsenic.
  • the treated solid slag meets National standard (HJ/T301-2007) requirements for general industrial solid waste. At the same time reducing environmental pollution, turning waste into treasure, recycling variable-value metals with high-value industrial products, creating additional economic value, has strong practical and environmental protection significance.
  • the purpose of the present invention is to overcome the shortcomings and deficiencies of the prior art, and to provide a low-temperature reduction and chlorination device for recovering metal of variable value in hazardous solid waste.
  • the device is equipped with a heating rod and a stirring shaft, and the temperature in the mixing heating chamber is maintained Low temperature improves product volatilization efficiency and variable-value metal recovery efficiency.
  • the device has simple structure, convenient operation and strong practicability.
  • Another object of the present invention is to provide a method for low-temperature reduction and chlorination to recover variable-value metals in hazardous solid waste.
  • This method incorporates a catalyst so that the raw materials undergo a reduction reaction during heating to effectively extract variable-value metals.
  • Low-temperature reduction and chlorination device for recovering variable-value metals in hazardous solid waste, including raw material pulverizer, feeder, material mixing heating device and product collection device, the raw material pulverizer is connected to the feeder, and the feeder Connected with the material mixing heating device, the material mixing heating device is connected with the product collection device;
  • the material mixing heating device includes a mixing heating chamber, a stirring shaft and a heating rod;
  • the shell of the mixing heating chamber is provided There are a feed port, a catalyst inlet, a hydrochloric acid inlet, a first exhaust port and a second exhaust port, the stirring shaft extends from the center of the top of the mixing heating chamber into the mixing heating chamber and is heated with the mixing
  • the sealing cover at the bottom of the chamber is connected; the heating rod is attached to the inner wall of the mixing heating chamber;
  • the product collection device includes a first recovery area and a second recovery area, the first recovery area and the second row respectively The gas port and the second recovery area are connected, and the second recovery area is filled with
  • a plurality of fan blades are provided on the stirring shaft, and the diameter of the fan blades is greater than or equal to 300 mm.
  • the stirring shaft feeds from the center upwards, so that the raw materials are stirred more evenly.
  • a scraper connected to the stirring shaft is provided at the top of the interior of the mixing heating chamber.
  • the wiper blade can clearly coagulate the catalyst crystals on the top of the mixing heating chamber.
  • the inner wall of the shell of the mixing heating chamber is provided with a corrosion-resistant coating, and a heat insulation layer is provided between the inner and outer walls of the shell.
  • the heat preservation layer can effectively improve the heat preservation performance of the mixed heating chamber.
  • the low-temperature reduction and chlorination method for recovering metal of variable value in hazardous solid waste includes the following steps:
  • Dangerous solid waste is fed into the raw material crusher by continuous feeding, and then fed by the feeder to the material mixing and heating device, keeping the amount of raw materials in the material mixing and heating device at 50 ⁇ 1000kg;
  • the gas generated during the roasting process is discharged from the second exhaust port of the mixing heating chamber, control the temperature in the first recovery zone to condense and recover the catalyst, and then pass the lye in the second recovery zone for washing And drying variable-value metal recycling products.
  • the catalyst is magnesium chloride or ammonium chloride.
  • the mass ratio of the hazardous solid waste to the catalyst is 1:0.5 ⁇ 1:1.5.
  • the reducing atmosphere gas is nitrogen or argon.
  • the alkaline solution is sodium hydroxide solution or ammonia water, and the pH of the alkaline solution is >14.
  • variable-value metal recovery product is chromium hydroxide or arsenic.
  • the present invention has the following advantages and beneficial effects:
  • the low-temperature reduction and chlorination device provided by the present invention is a device for recovering variable-value metals in hazardous solid waste.
  • the device is equipped with a heating rod and a stirring shaft to maintain the temperature in the mixing heating chamber at 300-500°C, compared with the general chlorination
  • the roasting device has a lower temperature, and the low temperature is conducive to product volatilization.
  • the low-temperature reduction and chlorination device recovers the metal of variable value in hazardous solid waste, which is simple and convenient to operate and has strong practicability.
  • the device can realize the detoxification treatment of hazardous solid wastes containing variable-value metals, and extract variable-value metals from the hazardous solid wastes, which solves the problem of difficult separation of variable-value metals and solid particles in hazardous solid wastes, and improves the separation efficiency of variable-value metals With recycling efficiency.
  • the method of low-temperature reduction and chlorination provided by the present invention for recovering variable-value metals in hazardous solid waste, through the reduction reaction in the heating process, reduces hexavalent chromium or pentavalent arsenic to trivalent chromium or trivalent arsenic, and the treated solid
  • the slag meets the national standard (HJ/T301-2007) requirements for general industrial solid waste.
  • the present invention reduces environmental pollution while turning waste into treasure, recycling variable-value metals with high-value industrial products, creating additional economic value, and has strong practical and environmental protection significance.
  • FIG. 1 is a schematic structural diagram of a device for recovering variable-value metals in hazardous solid waste according to an embodiment of the present invention
  • 1 raw material pulverizer
  • 2 feeder
  • 3 material mixing heating device
  • 31 mixing heating chamber
  • 311 insulation layer
  • 312 corrosion-resistant coating
  • 313 hydrochloric acid inlet
  • 314 catalyst inlet
  • 315 Scraper
  • 316 sealing cap
  • 317 first exhaust port
  • 318 second exhaust port
  • 32 stirring shaft
  • 321 fan blade
  • 322 motor
  • 33 heating rod
  • 4 product collection device
  • 42 first recycling area
  • 41 second recycling area
  • an embodiment of the present invention provides a device for low-temperature reduction and chlorination to recover variable metals in hazardous solid waste.
  • the device includes a raw material grinder 1, a feeder 2, a material mixing and heating device 3, and a product collection ⁇ 4 ⁇ 4 devices.
  • the raw material crusher 1 is connected to the feeder 2, and the raw material crusher 1 can crush the raw materials.
  • the feeder 2 is connected to the feed port of the material mixing and heating device 3, and the feeder 2 transports the crushed raw materials to the material mixing and heating device 3 through the conveying pipeline.
  • the material mixing and heating device 3 is connected to the product collection device 4. The raw materials are mixed, heated and undergo a reduction reaction in the material mixing and heating device 3, and then the variable-value metal is recovered in the product collection device 4.
  • the material mixing and heating device 3 includes a mixing and heating chamber 31, a stirring shaft 32 and a heating rod 33.
  • the housing of the mixing heating chamber 31 is provided with a feed port, a catalyst inlet 314, a hydrochloric acid inlet 313, a first exhaust port 317, and a second exhaust port 318.
  • the feed port is used to transport raw materials
  • the catalyst inlet 314 is used to transport the catalyst
  • the hydrochloric acid inlet 313 is used to transport hydrochloric acid.
  • the second exhaust port 318 is connected to the product collection device 4. During mixing of the raw materials in the mixing heating chamber 31, the second exhaust port 318 is closed, and the first exhaust port 317 is used to discharge carbon dioxide generated during the mixing of the raw materials.
  • both the first exhaust port 317 and the second exhaust port 318 are opened, and the first exhaust port 317 serves as an intake port to pass the reducing atmosphere gas.
  • the first exhaust port 317 is closed.
  • the outer wall of the housing of the mixing heating chamber 31 is made of 304 stainless steel, and the inner wall is made of 316L stainless steel.
  • a corrosion-resistant coating 312 is provided on the inner wall of the casing, and a heat insulation layer 311 is provided between the inner and outer walls of the casing.
  • the heat preservation layer 311 can improve the heat preservation performance of the mixed heating chamber 31.
  • a scraper 315 connected to the stirring shaft 32 is provided at the top inside the mixing heating chamber 31. During heating in the mixing heating chamber 31, part of the catalyst will volatilize. When the catalyst condenses and condenses on the inner top of the mixing heating chamber, the wiper blade 315 rotates with the stirring shaft, which can remove the crystals of the condensed catalyst and improve the use efficiency of the catalyst.
  • the stirring shaft 32 extends into the mixing heating chamber 31 from the center of the top of the mixing heating chamber 31 and is connected to the sealing cover 316 at the bottom of the mixing heating chamber.
  • the stirring shaft 32 is provided with a plurality of fan blades 321, and the diameter of the fan blade is 300 mm or more.
  • the mixing shaft is fed upward from the center to make the raw materials uniformly mixed.
  • the mixing shaft 32 is connected to the motor 322.
  • the raw material is stirred in the mixing heating chamber 31 and the motor 322 rotates forward during the heating process.
  • the mixing shaft 32 mixes the raw materials.
  • the stirring shaft 32 serves as a feeding mechanism to discharge the processed powder.
  • the heating rod 33 is attached to the inner wall of the mixing heating chamber 31 to heat the mixing heating chamber 31.
  • the heating temperature of the heating rod 33 ranges from 300 degrees to 500 degrees.
  • the product collection device 4 includes a first recovery zone 42 and a second recovery zone 41.
  • the first recovery zone 42 is connected to the second exhaust port 318 and the second recovery zone 41, respectively.
  • the second recovery zone 41 is filled with alkaline liquid. Both the first recovery area 42 and the second recovery area 41 are provided with thermal insulation blankets, and the first recovery area 42 is kept at a temperature of 250 degrees to 300 degrees.
  • the method of low-temperature reduction and chlorination to recover variable-value metals in hazardous solid waste includes the following steps:
  • the chromium slag is fed into the raw material pulverizer in a continuous feeding mode, and then fed by the feeder to the material mixing and heating device, keeping the amount of raw materials in the material mixing and heating device at 100 kg;
  • the gas generated during the roasting process is discharged from the second exhaust port of the mixing heating chamber, control the temperature in the first recovery zone, condense and recover the magnesium chloride, and then pass the lye in the second recovery zone to obtain Chromium hydroxide is precipitated, washed and dried to obtain chromium recovery products.
  • the concentration of leached hexavalent chromium in the original chromium slag of this embodiment is 496 mg/L, and the concentration of leached hexavalent chromium in the detoxified slag after treatment is 0.85 mg/L.
  • the method of low-temperature reduction and chlorination to recover variable-value metals in hazardous solid waste includes the following steps:
  • the chromium slag is fed into the raw material pulverizer by continuous feeding, and then fed by the feeder to the material mixing and heating device to keep the amount of raw materials in the material mixing and heating device at 500 kg;
  • the gas generated during the roasting process is discharged from the second exhaust port of the mixing heating chamber, control the temperature in the first recovery zone, condense and recover the magnesium chloride, and then pass the lye in the second recovery zone to obtain Chromium hydroxide is precipitated, washed and dried to obtain chromium recovery products.
  • the concentration of leached hexavalent chromium in the original chromium slag of this embodiment is 715 mg/L, and the concentration of leached hexavalent chromium in the detoxified slag after treatment is 0.92 mg/L.
  • the method of low-temperature reduction and chlorination to recover variable-value metals in hazardous solid waste includes the following steps:
  • the arsenic slag is fed into the raw material pulverizer in a continuous feeding mode, and then fed by the feeder to the material mixing and heating device, keeping the amount of raw materials in the material mixing and heating device at 500 kg;
  • the gas generated during the roasting process is discharged from the second exhaust port of the mixing heating chamber, control the temperature in the first recovery zone, make ammonium chloride condensate and recover, and then pass the lye in the second recovery zone , To obtain elemental arsenic precipitation, washing and drying to obtain arsenic recovery products.
  • the concentration of leached pentavalent arsenic in the original chromium slag of this embodiment is 328 mg/L, and the concentration of leached pentavalent arsenic in the detoxified slag after treatment is 0.56 mg/L.

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Abstract

一种低温还原氯化回收危险固废中变价金属的装置及方法，装置包括原料粉碎机(1)、进料机(2)、物料混合加热装置(3)以及产品收集装置(4)，原料粉碎机(1)与进料机(2)连接，进料机(2)与物料混合加热装置(3)连接，物料混合加热装置(3)与产品收集装置(4)连接；物料混合加热装置(3)包括混合加热室(31)、搅拌轴(32)以及加热棒(33)；混合加热室(31)的壳体上设有进料口、催化剂入口(314)、盐酸入口(313)、第一排气口(317)以及第二排气口(318)，搅拌轴(32)从混合加热室(31)的顶部中心位置伸入混合加热室(31)内并与混合加热室(31)底部的密封盖(316)连接；加热棒(33)贴于混合加热室(31)的内壁；产品收集装置(4)包括第一回收区(42)和第二回收区(41)，第一回收区(42)分别与第二排气口(318)以及第二回收区(41)连接，第二回收区(41)内装有碱液。该装置结构简单、操作方便、实用性强。

Description

低温还原氯化回收危险固废中变价金属的装置及方法 技术领域
本发明涉及危险固废的清洁处理及资源的循环再利用领域，特别涉及一种低温还原氯化提取回收危险固废中变价金属（铬、砷等）的脱毒处理装置和应用方法。
 背景技术
变价金属（铬、砷等）污染主要来源于化学原料及化学制品制造业、有色金属冶炼及压延加工业、非金属矿采选业等行业，含变价金属的危险固废以含铬废渣和含砷废渣为主。铬盐生产过程中所使用的有钙焙烧和无钙焙烧工艺均会产生含铬废渣。其中有钙焙烧工艺每生成1吨产品就将产生2-3吨的铬渣，无钙焙烧虽然显著降低了铬渣排放量及其中的六价铬含量，但风险依然存在。鉴于此，为了摆脱铬渣污染的困扰，一些发达国家不断压缩铬盐生产能力，改为从发展中国家进口铬盐产品。目前中国已经成为铬盐的生产和使用大国，产量及消费量居世界第一，也是铬渣产生量及堆储量最多的国家。最主要的含砷废渣包括两种，一种是被砷污染的土壤，另一种是冶金过程中产生的含砷尾矿。除此之外，还有一些沉积物和生物垃圾中也含有浓度较高的砷，会对环境造成极大危害。因此，既能将含变价金属的危险固废解毒又能回收变价金属资源的处理思路，已经成为了处理含变价金属危险固废的重要思路。
含变价金属危险固废的无害化主要是对其进行原位还原/固定以降低其毒性和迁移性，金属仍在固废中。我们知道，即使是低毒的三价铬或砷，在环境中的大量存在，也会带来土壤中铬、砷富集以及进入人类食物链，长期将危害人类健康。况且脱毒后的固废中的三价铬或砷仍有可能在环境中长期氧化条件下或者锰氧化菌的作用下被重新氧化成六价铬或五价砷，具有二次毒性。因此，更理想的解决方式是将含变价金属危险固废中的铬或砷提取并回用到工业中——从根本上减少有毒有害物质，同时回收再利用稀有的战略金属资源。从这个意义上来说，将变价金属危险固废的无害化与资源化相结合，是含变价金属危险固废治理研究的重要发展方向。因此，如何经济高效将含变价金属危险固废脱毒处理，同时实现变价金属资源的回收处理，开发新型处理装置是当下急需解决的问题。
 技术问题
目前针对含变价金属危险固废的无害化主要是对其进行原位还原/固定以降低其毒性和迁移性，但金属仍在固废中。本发明提供的低温还原氯化回收危险固废中变价金属的装置通过设置加热棒及搅拌轴，使混合加热室内的温度维持在300-500℃，相比于一般的氯化焙烧装置，温度较低，低温有利于产物挥发。本发明的装置能实现含变价金属危险固废的脱毒处理，并将变价金属从危险固废中提取出来，解决了危险固废中变价金属与固体颗粒难分离的难题，提高了变价金属的分离效率与回收效率。本发明提供的低温还原氯化回收危险固废中变价金属的方法，通过加热过程中的还原反应，将六价铬或者五价砷还原为三价铬或三价砷，处理后的固体渣满足国家标准（HJ/T301-2007）一般工业固体废渣的要求。减少环境污染的同时变废为宝，将变价金属以高值工业产品回收，创造了额外的经济价值，具有很强的现实与环保意义。
 技术解决方案
本发明的目的在于克服现有技术的缺陷和不足，提供了一种低温还原氯化回收危险固废中变价金属的装置，该装置设置有加热棒及搅拌轴，混合加热室内的温度维持在较低的温度，提高产物挥发效率及变价金属回收效率。该装置结构简单、操作方便、实用性强。
本发明的另一个目的在于提供一种低温还原氯化回收危险固废中变价金属的方法，该方法加入催化剂，使原料在加热过程中发生还原反应，有效提取变价金属。
本发明的目的可以通过如下技术方案实现：
低温还原氯化回收危险固废中变价金属的装置，包括原料粉碎机、进料机、物料混合加热装置以及产品收集装置，所述原料粉碎机与所述进料机连接，所述进料机与所述物料混合加热装置连接，所述物料混合加热装置与所述产品收集装置连接；所述物料混合加热装置包括混合加热室、搅拌轴以及加热棒；所述混合加热室的壳体上设有进料口、催化剂入口、盐酸入口、第一排气口以及第二排气口，所述搅拌轴从所述混合加热室的顶部中心位置伸入所述混合加热室内并与所述混合加热室底部的密封盖连接；所述加热棒贴于所述混合加热室的内壁；所述产品收集装置包括第一回收区和第二回收区，所述第一回收区分别与所述第二排气口以及第二回收区连接，所述第二回收区内装有碱液。
作为优选的技术方案，所述搅拌轴上设置有多片扇叶，所述扇叶的直径为大于等于300mm。搅拌轴由中心向上送料，使原料搅拌更均匀。
作为优选的技术方案，所述混合加热室内部顶部处设置有与所述搅拌轴连接的刮片。刮片可清楚凝结在混合加热室顶部的催化剂结晶。
作为优选的技术方案，所述混合加热室的壳体内壁上设置有耐腐蚀涂层，在壳体内外壁之间设置有保温层。保温层可有效提高混合加热室的保温性能。
本发明的另一个目的可以通过如下技术方案实现：
低温还原氯化回收危险固废中变价金属的方法，包括如下步骤：
将危险固废以连续进料的方式送入原料粉碎机粉碎，然后由进料机输送至物料混合加热装置中，保持物料混合加热装置内的原料量为50~1000kg；
将催化剂与盐酸分别通过催化剂入口和盐酸入口加入混合加热室内，启动搅拌轴，使催化剂和盐酸与进料机送入的原料混合均匀；
关闭催化剂入口、盐酸入口和进料机入口，从第一排气口通入还原气氛气体，同时以10~60℃/min的加热速率升温至300~500℃，在还原气氛中进行低温焙烧处理2~12h；
关闭第一排气口，焙烧过程中产生的气体从混合加热室的第二排气口排出，在第一回收区控制温度，使催化剂冷凝回收，然后在第二回收区通入碱液，洗涤并干燥变价金属回收产品。
作为优选的技术方案，所述催化剂为氯化镁或氯化铵。
作为优选的技术方案，所述危险固废与催化剂加入的质量比为1：0.5~1：1.5。
作为优选的技术方案，所述还原气氛气体为氮气或氩气。
作为优选的技术方案，所述碱液为氢氧化钠溶液或氨水，所述碱液的pH＞14。
作为优选的技术方案，所述变价金属回收产品为氢氧化铬或砷单质。
 有益效果
本发明与现有技术相比，具有如下优点和有益效果：
1、本发明提供的低温还原氯化回收危险固废中变价金属的装置，该装置通过设置加热棒及搅拌轴，使混合加热室内的温度维持在300-500℃，相比于一般的氯化焙烧装置，温度较低，低温有利于产物挥发。
2、本发明提供的低温还原氯化回收危险固废中变价金属的装置，操作简单方便，实用性强。该装置能实现含变价金属危险固废的脱毒处理，并将变价金属从危险固废中提取出来，解决了危险固废中变价金属与固体颗粒难分离的难题，提高了变价金属的分离效率与回收效率。
3、本发明提供的低温还原氯化回收危险固废中变价金属的方法，通过加热过程中的还原反应，将六价铬或者五价砷还原为三价铬或三价砷，处理后的固体渣满足国家标准（HJ/T301-2007）一般工业固体废渣的要求。
4、本发明减少环境污染的同时变废为宝，将变价金属以高值工业产品回收，创造了额外的经济价值，具有很强的现实与环保意义。
 附图说明
图1是本发明实施例中回收危险固废中变价金属装置的结构示意图
其中：1：原料粉碎机，2：进料机，3：物料混合加热装置，31：混合加热室，311：保温层，312：耐腐蚀涂层，313：盐酸入口，314：催化剂入口，315：刮片，316：密封盖，317：第一排气口，318：第二排气口，32：搅拌轴，321：扇叶，322：电机，33：加热棒，4：产品收集装置，42：第一回收区，41：第二回收区
 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。
如图1所示，本发明实施例中提供了一种低温还原氯化回收危险固废中变价金属的装置，该装置包括原料粉碎机1、进料机2、物料混合加热装置3以及产品收集装置4。原料粉碎机1与进料机2连接，原料粉碎机1可将原料进行粉碎。进料机2与物料混合加热装置3的进料口连接，进料机2将粉碎后的原料通过输送管道输送到物料混合加热装置3内。物料混合加热装置3与产品收集装置4连接，原料在物料混合加热装置3内混合、加热并发生还原反应，之后在产品收集装置4内完成变价金属的回收。
物料混合加热装置3包括混合加热室31、搅拌轴32以及加热棒33。混合加热室31的壳体上设有进料口、催化剂入口314、盐酸入口313、第一排气口317以及第二排气口318。进料口用于输送原料，催化剂入口314用于输送催化剂，盐酸入口313用于输送盐酸。第二排气口318与产品收集装置4连接。混合加热室31内原料搅拌过程中，第二排气口318关闭，第一排气口317用于排出原料搅拌过程中产生的二氧化碳。混合加热室31内原料加热过程中，第一排气口317和第二排气口318都打开，第一排气口317作为进气口通入还原气氛气体。混合加热室31内原料加热完毕后，第一排气口317关闭。
混合加热室31的壳体外壁由304不锈钢材质制成，内壁由316L不锈钢材质制成。壳体内壁上设置有耐腐蚀涂层312，壳体内外壁之间设置有保温层311。保温层311可以提高混合加热室31的保温性能。混合加热室31内部顶部处设置有与搅拌轴32连接的刮片315。混合加热室31内加热时会有部分催化剂挥发，催化剂遇冷凝结在混合加热室的内部顶部，刮片315随着搅拌轴转动，可以将凝结的催化剂结晶清除，提高催化剂的使用效率。
搅拌轴32从混合加热室31的顶部中心位置伸入混合加热室31内并与混合加热室底部的密封盖316连接。搅拌轴32上设置有多片扇叶321，扇叶的直径为大于等于300mm。搅拌时，搅拌轴由中心往上送料使原料能做到搅拌均匀，搅拌轴32外接电机322，原料在混合加热室31内搅拌及加热过程中电机322正转，搅拌轴32搅拌原料；原料在混合加热室31内停止加热后电机322反转时，搅拌轴32作为送料机构排出处理后的粉末。
加热棒33贴于混合加热室31的内壁，用于给混合加热室31加热。加热棒33的加热温度范围为300度至500度。
产品收集装置4包括第一回收区42和第二回收区41，第一回收区42分别与第二排气口318以及第二回收区41连接，第二回收区41内装有碱液。第一回收区42和第二回收区41外部都设有保温毯，第一回收区42保温在250度至300度。
实施例一
本实施例中，低温还原氯化回收危险固废中变价金属的方法，包括如下步骤如下：
将铬渣以连续进料的方式进入原料粉碎机粉碎，然后由进料机输送至物料混合加热装置中，保持物料混合加热装置内原料量为100kg；
将60kg氯化镁与60kg盐酸分别通过催化剂入口和盐酸入口加入混合加热室内，启动搅拌轴，使氯化镁和盐酸与进料机送入的原料混合均匀；
关闭催化剂入口、盐酸入口和进料机入口，从第一排气口通入氮气，同时以20℃/min的加热速率升温至300℃，在还原气氛中进行低温焙烧处理3h；
关闭第一排气口，焙烧过程中产生的气体从混合加热室的第二排气口排出，在第一回收区控制温度，使氯化镁冷凝回收，然后在第二回收区通入碱液，得到氢氧化铬沉淀，洗涤并干燥，得到铬回收产品。
本实施例的原始铬渣浸出六价铬浓度为496mg/L，处理后脱毒渣浸出六价铬浓度为0.85mg/L。
实施例二
本实施例中，低温还原氯化回收危险固废中变价金属的方法，包括如下步骤如下：
将铬渣以连续进料的方式进入原料粉碎机粉碎，然后由进料机输送至物料混合加热装置中，保持物料混合加热装置内原料量为500kg；
将250kg氯化镁与250kg盐酸分别通过催化剂入口和盐酸入口加入混合加热室，启动搅拌轴，使氯化镁和盐酸与进料机送入的原料混合均匀；
关闭催化剂入口、盐酸入口和进料机入口，从第一排气口通入氮气，同时以40℃/min的加热速率升温至500℃，在还原气氛中进行低温焙烧处理4h；
关闭第一排气口，焙烧过程中产生的气体从混合加热室的第二排气口排出，在第一回收区控制温度，使氯化镁冷凝回收，然后在第二回收区通入碱液，得到氢氧化铬沉淀，洗涤并干燥，得到铬回收产品。
本实施例的原始铬渣浸出六价铬浓度为715mg/L，处理后脱毒渣浸出六价铬浓度为0.92mg/L。
实施例三
本实施例中，低温还原氯化回收危险固废中变价金属的方法，包括如下步骤如下：
将砷渣以连续进料的方式进入原料粉碎机粉碎，然后由进料机输送至物料混合加热装置中，保持物料混合加热装置内原料量为500kg；
将300kg氯化铵与300kg盐酸分别通过催化剂入口和盐酸入口加入混合加热室内，启动搅拌轴，使氯化铵和盐酸与进料机送入的原料混合均匀；
关闭催化剂入口、盐酸入口和进料机入口，从第一排气口通入氮气，同时以40℃/min的加热速率升温至500℃，在还原气氛中进行低温焙烧处理4h；
关闭第一排气口，焙烧过程中产生的气体从混合加热室的第二排气口排出，在第一回收区控制温度，使氯化铵冷凝回收，然后在第二回收区通入碱液，得到单质砷沉淀，洗涤并干燥，得到砷回收产品。
本实施例的原始铬渣浸出五价砷浓度为328mg/L，处理后脱毒渣浸出五价砷浓度为0.56mg/L。
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对本发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。

Claims (10)

  1. 低温还原氯化回收危险固废中变价金属的装置，其特征在于，包括原料粉碎机、进料机、物料混合加热装置以及产品收集装置，所述原料粉碎机与所述进料机连接，所述进料机与所述物料混合加热装置连接，所述物料混合加热装置与所述产品收集装置连接；
    所述物料混合加热装置包括混合加热室、搅拌轴以及加热棒；所述混合加热室的壳体上设有进料口、催化剂入口、盐酸入口、第一排气口以及第二排气口，所述搅拌轴从所述混合加热室的顶部中心位置伸入所述混合加热室内并与所述混合加热室底部的密封盖连接；所述加热棒贴于所述混合加热室的内壁；
    所述产品收集装置包括第一回收区和第二回收区，所述第一回收区分别与所述第二排气口以及第二回收区连接，所述第二回收区内装有碱液。
  2. 根据权利要求1所述的低温还原氯化回收危险固废中变价金属的装置，其特征在于，所述搅拌轴上设置有多片扇叶，所述扇叶的直径为大于等于300mm。
  3. 根据权利要求1所述的低温还原氯化回收危险固废中变价金属的装置，其特征在于，所述混合加热室内部顶部处设置有与所述搅拌轴连接的刮片。
  4. 根据权利要求1所述的低温还原氯化回收危险固废中变价金属的装置，其特征在于，所述混合加热室的壳体内壁上设置有耐腐蚀涂层，在壳体内外壁之间设置有保温层。
  5. 低温还原氯化回收危险固废中变价金属的方法，其特征在于，包括如下步骤：
    将危险固废以连续进料的方式送入原料粉碎机粉碎，然后由进料机输送至物料混合加热装置中，保持物料混合加热装置内的原料量为50~1000kg；
    将催化剂与盐酸分别通过催化剂入口和盐酸入口加入混合加热室内，启动搅拌轴，使催化剂和盐酸与进料机送入的原料混合均匀；
    关闭催化剂入口、盐酸入口和进料机入口，从第一排气口通入还原气氛气体，同时以10~60℃/min的加热速率升温至300~500℃，在还原气氛中进行低温焙烧处理2~12h；
    关闭第一排气口，焙烧过程中产生的气体从混合加热室的第二排气口排出，在第一回收区控制温度，使催化剂冷凝回收，然后在第二回收区通入碱液，洗涤并干燥变价金属回收产品。
  6. 根据权利要求5所述的低温还原氯化回收危险固废中变价金属的方法，其特征在于，所述催化剂为氯化镁或氯化铵。
  7. 根据权利要求5所述的低温还原氯化回收危险固废中变价金属的方法，其特征在于，所述危险固废与催化剂加入的质量比为1：0.5~1：1.5。
  8. 根据权利要求5所述的低温还原氯化回收危险固废中变价金属的方法，其特征在于，所述还原气氛气体为氮气或氩气。
  9. 根据权利要求5所述的低温还原氯化回收危险固废中变价金属的方法，其特征在于，所述碱液为氢氧化钠溶液或氨水，所述碱液的pH＞14。
  10. 根据权利要求5所述的低温还原氯化回收危险固废中变价金属的方法，其特征在于，所述变价金属回收产品为氢氧化铬或砷单质。
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CN107904405A (zh) * 2017-11-24 2018-04-13 台州学院 一种降低生活垃圾焚烧炉渣中金属溶出的方法与装置
CN109593964A (zh) * 2018-11-29 2019-04-09 华南理工大学 低温还原氯化回收危险固废中变价金属的装置及方法
CN209276594U (zh) * 2018-11-29 2019-08-20 华南理工大学 低温还原氯化回收危险固废中变价金属的装置

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