WO2022141011A1 - Method for cumulative recovery of rhenium, sulfur, and arsenic via vortex furnace self-heated volatilization of rhenium-containing sulfur-arsenic acid sludge - Google Patents

Method for cumulative recovery of rhenium, sulfur, and arsenic via vortex furnace self-heated volatilization of rhenium-containing sulfur-arsenic acid sludge Download PDF

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WO2022141011A1
WO2022141011A1 PCT/CN2020/140551 CN2020140551W WO2022141011A1 WO 2022141011 A1 WO2022141011 A1 WO 2022141011A1 CN 2020140551 W CN2020140551 W CN 2020140551W WO 2022141011 A1 WO2022141011 A1 WO 2022141011A1
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rhenium
arsenic
sulfur
flue gas
furnace
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PCT/CN2020/140551
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French (fr)
Chinese (zh)
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石俊阳
汪琴
梁金凤
石仁章
袁冬华
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耒阳市焱鑫有色金属有限公司
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Priority to PCT/CN2020/140551 priority Critical patent/WO2022141011A1/en
Publication of WO2022141011A1 publication Critical patent/WO2022141011A1/en

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/48—Sulfur dioxide; Sulfurous acid
    • C01B17/50—Preparation of sulfur dioxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G28/00—Compounds of arsenic
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B7/00—Hydraulic cements
    • C04B7/14—Cements containing slag
    • C04B7/147—Metallurgical slag
    • 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
    • C22B61/00—Obtaining metals not elsewhere provided for in this subclass
    • 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
    • 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
    • C22B7/02—Working-up flue dust

Definitions

  • the invention relates to volatilization smelting technology, desulfurization technology and arsenic harmless comprehensive recovery and environmental protection technology, in particular to a process method for comprehensive recovery of rhenium, sulfur and arsenic by self-heating volatilization of rhenium-containing sulfuric arsenic acid sludge in a vortex furnace.
  • the sulfur-containing flue gas acid-making process produces a by-product sulfuric arsenic acid sludge.
  • copper mines in different regions generally contain a very small amount of rhenium, these very small amounts of rhenium are generally volatilized into the flue gas.
  • sulfuric acid production it is enriched in the acid sludge, so that the rhenium content in the sulfuric arsenic acid sludge can reach several hundreds to thousands of grams per ton.
  • Such rich rhenium-containing acid sludge is an important rhenium-containing secondary resource.
  • the traditional comprehensive recovery process is to mix rhenium-containing sulfuric arsenic acid sludge into a large amount of lime and then enter it into a high-temperature furnace, such as rotary kiln, multi-chamber furnace, etc., so that rhenium and calcium are easily dissolved in water.
  • the calcium rhenium oxide is leached with water to separate it from the slag, and then the rhenium is extracted from the aqueous solution.
  • the amount of the leached slag after separation is large, and it contains high residual arsenic, causing serious secondary pollution to the environment. This is the process flow serious shortcomings.
  • the object of the present invention is, in view of the above-mentioned deficiencies of the prior art, to provide a process method for the comprehensive recovery of rhenium, sulfur and arsenic by self-heating volatilization of rhenium-containing sulfuric arsenic acid sludge in a vortex furnace, so as to improve the direct yield of rare element rhenium and achieve no large amount of rhenium. Secondary pollution discharge of toxic waste residues.
  • the technical scheme adopted in the present invention is: a process method for comprehensive recovery of rhenium sulfur arsenic by self-heating volatilization of rhenium sulfur arsenic acid sludge containing rhenium sulfur arsenic in a vortex furnace, please refer to Fig. 1 in conjunction with the method steps as follows:
  • Step 1 Dry the raw material containing rhenium sulfuric arsenic acid in a downstream rotary kiln until the material discharged from the kiln is loose.
  • the above-mentioned rhenium-containing sulfuric arsenic acid sludge is a by-product produced by smelting sulfur-containing flue gas for acid production, and its typical components include: H2O 40%-60%; Re 0.02%-0.5%; As 30%-35%; S 35%-45% %;
  • the water content of rhenium-containing sulfuric arsenic acid mud is about 40% to 60% higher, and sulfur and arsenic are easily volatilized with the increase of drying temperature, so the downstream rotary kiln is generally selected for drying, and the kiln exhaust air
  • the temperature is generally controlled to be less than 80 °C, and the moisture content of the kiln material can be controlled to be 15% to 25%, as long as the kiln material is loose and easy to flow.
  • Step 2 In order to make the vortex furnace run smoothly, 10%-30% of the weight of the kiln discharge material is mixed with slag material as slag auxiliary material, and mixed to form the charging material.
  • the slag material is calcium ferrosilicon slag material, including river sand, iron ore and calcium stone powder that provide SiO2.
  • Step 3 finely smash the incoming charge (loose kiln out-feed and prepared slag charge), and pulverize the incoming charge to a particle size of 1mm to 2mm;
  • Step 4 Vortex furnace volatilization smelting.
  • the equipment adopts a vortex furnace, and the vortex furnace adopts tangential air supply.
  • the wind speed is generally close to the speed of sound.
  • the fuel particles are burned with high intensity in the furnace.
  • First bake the furnace the natural gas burner set at the air inlet on the upper part of the furnace body is first adjusted to a long flame with lower reducing temperature, and fire is sprayed into the furnace until the temperature in the furnace reaches 1200 ° C ⁇ 1300 ° C; then the natural gas burner flame Adjusted to a neutral flame, the size of the flame is related to the air supply volume of the air nozzle, so that the supplied air volume can be heated to 600°C ⁇ 800°C, which is beneficial to the charging material added from the charging port on the top of the furnace can be ignited smoothly, and the furnace wall is violently burned and heated up.
  • the sulfur in it will react with the high-speed air supplied from the air nozzle to have an oxidative exothermic reaction.
  • the temperature in the furnace is as high as 1400°C or more; in order to make the rhenium volatilize into steam smoothly, it is necessary to adjust the oxidative combustion atmosphere in the furnace, so that the combustion air coefficient of sulfur is greater than 1.1, and under the high temperature and oxidative conditions above 1400°C, it is put into the charge. All of the rhenate will be decomposed and volatilized into the flue gas, while the arsenic is oxidized to become As2O3 vapor, and the sulfur is oxidized to become SO2 vapor, which will enter the flue gas together.
  • the temperature of the flue gas from the flue gas outlet at the lower part of the vortex furnace is very high, and it needs to be extracted with water cooling.
  • a small amount of non-volatile substances in the raw materials and an appropriate amount of slag material actively mixed to form slag (such as high-temperature ferrosilicon calcium slag), which falls along the furnace cavity to the bottom hearth, and is regularly released out of the furnace, which can be used as cement
  • slag such as high-temperature ferrosilicon calcium slag
  • Step 5 The high-temperature flue gas is introduced into the flue gas washing tower from the flue gas outlet at the lower part of the furnace through the water-cooled flue gas pipe.
  • the flue gas washing tower is used to collect rhenium arsenic.
  • the flue gas washing tower needs to have a large enough heat dissipation capacity.
  • the air heat exchange cold water tower is equipped to make the circulating water temperature of the flue gas washing tower work below 60 °C, and the high temperature smoke entering the flue gas washing tower
  • the gas is rapidly cooled by the sprayed water droplets (circulating water), and the rhenium oxide vapor in it is easily soluble in water, and is trapped in the circulating water for continuous accumulation and enrichment. into the circulating water and accumulate continuously; SO2 is also cooled, but the solubility in water is small, and most of it enters the subsequent desulfurization tower with the cooling flue gas.
  • the As2O3 crystals are filtered and the pressure filtrate is drawn out, and the rhenium is extracted according to the conventional technology in the field, and at the same time, an equal amount of new water is added to the circulating water.
  • the direct recovery rate of 2 to 4 levels of flue gas water washing towers in series is usually used to ensure the recovery rate.
  • Step 6 The cooling flue gas enters the subsequent desulfurization tower for flue gas desulfurization.
  • Flue gas desulfurization is a conventional technology in the field.
  • the total amount of flue gas in the method of the present invention is generally small, and the water content after washing is relatively high. It is not suitable to choose an acid-making process.
  • traditional mature alkali method or lime method can be selected for disposal. , can meet the requirements of environmental protection.
  • the method of the invention has high thermal efficiency, saves energy by more than 50%, the direct yield of high-value rare elements is about 10%-30% higher, effectively saves valuable resources, and reduces the amount of waste residue by about 75% ⁇ 90%, and the waste slag is non-toxic ferrosilicon calcium slag, which can be recycled by cement plants, completely solving the problem of secondary environmental pollution in traditional methods.
  • FIG. 1 is a flow chart of the method of the present invention.
  • Step 1 Downstream drying and dehydration. Adopt the downstream rotary kiln of ⁇ 1m ⁇ L10m, control the flue gas temperature of the rotary kiln furnace tail to be 60 ⁇ 80°C, the kiln body speed is 6 rpm, the inclination angle is 4.5°, the feed water content is 55%, the feeding speed is 1T/hour, The water content of the kiln material is about 19.5%, and it is in the form of loose blocks and granules. It can process 20-24T/day of raw materials every 24 hours.
  • Step 2 Prepare slag-type material.
  • the total slag-forming components in the raw materials of rhenium-containing thioarsenic acid mud are very small.
  • the raw materials are mixed with 15% slag material.
  • river sand containing SiO2 95%) 4.5%
  • Iron ore containing Fe 55%)
  • calcium stone powder containing CaO 50%
  • Step 3 Finely crush the charge.
  • the mixed incoming charge (the above-mentioned kiln outgoing charge and slag charge) is put into a hammer crusher for fine crushing, and after sieving, the particle size of the charge is 1-2 mm, which is convenient for smelting, feeding, conveying and wind dispersion.
  • the typical composition of the charge sampled and detected is: H2O 19.5%, Re 0.08%, As 25%, S 35%, SiO2 4.4%, Fe 4.5%, Cao 2.4%.
  • Step 4 Vortex furnace volatilization smelting.
  • the equipment adopts a vortex furnace: 1The volume of the top feeding bin is 0.5 ⁇ 1.5m 3 , the inner diameter of the screw feeder is ⁇ 100, with a feeding capacity of 1T/hour, and the feeding flow can be adjusted by stepless speed regulation; 2The top cover of the cold water jacket furnace , there is a feeding through hole on it, and the feeding bin is installed on it; 3. A circular inner cavity furnace body with a forced water-cooling tube is set inside the furnace. The inner diameter of the furnace cavity is ⁇ 500m, and the height is H2000mm.
  • the furnace cavity is made of magnesium with good slag resistance
  • the Luo refractory concrete is rammed, and the upper part is provided with a tangential air inlet, and the lower part is provided with a lower slag convergence port with a reduced diameter of about 60%; 4
  • the diameter of the slag-containing hearth is the same as that of the furnace cavity.
  • a natural gas burner is set in the tangential air inlet on the upper part of the vortex furnace. After ignition, it is adjusted to a long flame with a lower reducing temperature and sprayed into the furnace to dry the moisture on the inner wall of the furnace cavity. , according to the prescribed heating curve, the temperature rises in stages, and after 120 hours, the temperature in the furnace rises to 1300 °C, and the charge is ready to be added.
  • Stage feeding operation adjust the flame of the natural gas burner in the air inlet to a neutral flame, and the amount of fire can make the air entering from the tangential tuyere heated to 600°C ⁇ 800°C, and the feeding from the furnace top can be ignited smoothly
  • the silo feeds the incoming charge that falls into the furnace, so that it burns and heats up tangentially along the inner cavity surface.
  • Most of the charged charge is As2S3 containing rhenium. Under the condition of high temperature oxidation, the exothermic oxidation makes the temperature in the furnace as high as 1400°C or more. Control the appropriate ratio of the charging amount and the amount of air entering the furnace to make the oxidation of sulfur and As.
  • the combustion air coefficient is 1.1 ⁇ 1.25, which maintains the oxidative state in the furnace, which is conducive to the complete and efficient volatilization of rhenate.
  • As is oxidized to As2O3, and at the high temperature of 1400 °C in the furnace, all of it turns into steam and enters the flue gas.
  • S is oxidized to SO2 and enters into the flue gas.
  • the original non-volatile components in the charge and the slag-forming materials that are actively mixed are smelted into calcium ferrosilicon slag (components: SO2 30%, Fe 30%, CaO 18%), along with The inner wall of the furnace flows downward through the convergence port and flows into the hearth.
  • the slag port is regularly opened to discharge to maintain the appropriate height of the molten slag in the hearth. discharge.
  • the residual Re of the slag is less than 0.002%
  • the slag rate is less than 20%
  • the volatilization rate of rhenium in the charge is greater than that.
  • Step 5 The flue gas washing tower captures rhenium arsenic.
  • the flue gas washing tower adopts a multi-nozzle venturi jet to wash the flue gas.
  • the circulating pump adopts the pump parameters of 400m 3 /h flow and 50m head, and the induced air volume can reach 12000 m 3 /h.
  • the flue gas washing tower is equipped with a heat sink
  • the air heat exchange cold water tower with a capacity of 4 million kcal/hour is equipped with cooling circulating water, so that the working temperature of the circulating water is lower than 60 °C.
  • the high-temperature flue gas sent to the flue gas washing tower by the water-cooled flue gas pipe is cooled by high-speed fine-grained water droplets.
  • the As2O3 vapor in the high-temperature flue gas is cooled by high-speed water droplets and becomes fine grains, which are continuously enriched in the circulating water, and SO2 is also cooled, but the solubility in water is small, and most of it enters with the cooling flue gas. Subsequent desulfurization tower.
  • a filter press is used to separate the grains from the circulating water, and then the traditional hot-melt-cold precipitation method is used to purify, separate, dry and package to achieve a purity of more than 99%. , open-circuit disposal for listing and sales.
  • concentration of rhenium in the circulating water of the flue gas washing tower is enriched to 1.5g/L
  • the pressure filtrate separated from the filter press is extracted, and the rhenium is extracted in the form of rhenate by the traditional concentrated chloride salt method.
  • 2 to 4 levels of flue gas washing towers are set up to operate in series.
  • Step 6 Flue gas desulfurization.
  • the washed sulfur-containing flue gas is introduced into the original lime-based desulfurization tower of the smelting enterprise for treatment.
  • the flue gas contains SO2 ⁇ 100mg/m 3 , and after reaching the standard, it is discharged into a 60m-high smoke window for air discharge.
  • this comparative example is made, specifically: the amount of slag added into the charge is reduced from 20% to 5%, and other conditions are the same as those in Example 1. Exactly the same. It is detected that the content of Re in the slag discharged from the hearth is 0.07%, and the direct yield of rhenium volatilization is reduced by 3.9%, which has a significant impact.

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Abstract

A method for cumulative recovery of rhenium, sulfur, and arsenic via vortex furnace self-heated volatilization of rhenium-containing sulfur-arsenic acid sludge, where a rhenium-containing sulfur-arsenic acid sludge raw material is dried until a material output from a kiln is loose, then a molten slag material is added in, fine crushing is performed, and then same enters into a vortex furnace for volatilization smelting, and once an oxidation exothermic reaction of an input furnace material raises the temperature to 1400 °C or more, and in an oxidizing atmosphere, all of a rhenium acid salt in the input furnace material is broken down and volatilized, arsenic oxidizes into As2O3 gas, and sulfur oxidizes into SO2 gas, and all of said gases enter into a flue gas; and a high temperature flue gas undergoes rhenium-arsenic enrichment in a flue gas water washing tower, and SO2 enters into a subsequent desulfurization tower for sulfur separation and recovery. The present method has high thermal efficiency, achieves energy savings of 50% or more, a direct recovery rate for a high value trace element is higher than approximately 10%-30%, precious resources are effectively saved, the quantity of abandoned slag is reduced by approximately 75%-90%, the abandoned slag is usable silicon-iron-calcium slag having no toxic substances, and the problem of secondary environmental pollution in a traditional method is completely solved.

Description

一种旋涡炉自热挥发含铼硫砷酸泥综合回收铼硫砷的工艺方法A process method for comprehensive recovery of rhenium sulphur arsenic by self-heating volatilization of rhenium sulphur arsenic acid sludge in a vortex furnace 技术领域technical field
本发明涉及挥发冶炼技术，脱硫技术及砷无害化综合回收环保技术，具体涉及一种旋涡炉自热挥发含铼硫砷酸泥综合回收铼、硫、砷的工艺方法。The invention relates to volatilization smelting technology, desulfurization technology and arsenic harmless comprehensive recovery and environmental protection technology, in particular to a process method for comprehensive recovery of rhenium, sulfur and arsenic by self-heating volatilization of rhenium-containing sulfuric arsenic acid sludge in a vortex furnace.
背景技术Background technique
在铜冶炼行业，含硫烟气制酸过程，产生副产物硫砷酸泥，因不同地域的铜矿，一般都含极微量的铼，这些极微量的铼，一般都挥发进入烟气，在制硫酸过程中进入酸泥中富集，使得硫砷酸泥中含铼能达到每吨几百克到数千克之间，如此丰富的含铼酸泥，是重要的含铼二次资源。In the copper smelting industry, the sulfur-containing flue gas acid-making process produces a by-product sulfuric arsenic acid sludge. Because copper mines in different regions generally contain a very small amount of rhenium, these very small amounts of rhenium are generally volatilized into the flue gas. In the process of sulfuric acid production, it is enriched in the acid sludge, so that the rhenium content in the sulfuric arsenic acid sludge can reach several hundreds to thousands of grams per ton. Such rich rhenium-containing acid sludge is an important rhenium-containing secondary resource.
对于含铼硫砷酸泥，传统的综合回收工艺是将含铼硫砷酸泥配入大量石灰后进高温炉，例如，转窑、多堂炉等焙烧，使铼与钙生成极易溶于水的铼酸钙，用水浸出，使之与渣分离，而后从水溶液中提取铼，分离后的浸出渣量很大，且含残留较高的砷，对环境造成严重二次污染，是这工艺流程的严重缺点。For rhenium-containing sulfuric arsenic acid sludge, the traditional comprehensive recovery process is to mix rhenium-containing sulfuric arsenic acid sludge into a large amount of lime and then enter it into a high-temperature furnace, such as rotary kiln, multi-chamber furnace, etc., so that rhenium and calcium are easily dissolved in water. The calcium rhenium oxide is leached with water to separate it from the slag, and then the rhenium is extracted from the aqueous solution. The amount of the leached slag after separation is large, and it contains high residual arsenic, causing serious secondary pollution to the environment. This is the process flow serious shortcomings.
发明内容SUMMARY OF THE INVENTION
本发明的目的是，针对现有技术的上述不足，提供一种旋涡炉自热挥发含铼硫砷酸泥综合回收铼硫砷的工艺方法，以提高稀有元素铼的直收率，达到无大量含毒废渣的二次污染排放。The object of the present invention is, in view of the above-mentioned deficiencies of the prior art, to provide a process method for the comprehensive recovery of rhenium, sulfur and arsenic by self-heating volatilization of rhenium-containing sulfuric arsenic acid sludge in a vortex furnace, so as to improve the direct yield of rare element rhenium and achieve no large amount of rhenium. Secondary pollution discharge of toxic waste residues.
为达上述目的，本发明所采用的技术方案是：一种旋涡炉自热挥发含铼硫砷酸泥综合回收铼硫砷的工艺方法，请结合参见图1，该方法步骤如下：In order to achieve the above-mentioned purpose, the technical scheme adopted in the present invention is: a process method for comprehensive recovery of rhenium sulfur arsenic by self-heating volatilization of rhenium sulfur arsenic acid sludge containing rhenium sulfur arsenic in a vortex furnace, please refer to Fig. 1 in conjunction with the method steps as follows:
步骤1：将含铼硫砷酸泥原料采用顺流式回转窑烘干至出窑料松散。Step 1: Dry the raw material containing rhenium sulfuric arsenic acid in a downstream rotary kiln until the material discharged from the kiln is loose.
上述含铼硫砷酸泥为冶炼含硫烟气制酸产生的副产物，典型成份包括：H2O 40％～60％；Re 0.02％～0.5％；As 30％～35％；S 35％～45％；一般情况下，含铼硫砷酸泥含水量较高约40％～60％，且硫砷极易随烘干温度上升而挥发，故一般选择顺流式回转窑烘干，窑尾气流温度一般控制小于80℃，出窑料水分含量可控制为15％～25％，只要保证出窑料松散、方便流动即可。The above-mentioned rhenium-containing sulfuric arsenic acid sludge is a by-product produced by smelting sulfur-containing flue gas for acid production, and its typical components include: H2O 40%-60%; Re 0.02%-0.5%; As 30%-35%; S 35%-45% %; Under normal circumstances, the water content of rhenium-containing sulfuric arsenic acid mud is about 40% to 60% higher, and sulfur and arsenic are easily volatilized with the increase of drying temperature, so the downstream rotary kiln is generally selected for drying, and the kiln exhaust air The temperature is generally controlled to be less than 80 ℃, and the moisture content of the kiln material can be controlled to be 15% to 25%, as long as the kiln material is loose and easy to flow.
步骤2：为使旋涡炉能顺利运行，于出窑料中配入为出窑料重量10％～30％的熔渣料作熔渣辅料，混合，形成入炉料。其中，该熔渣料为硅铁钙熔渣料，包括提供SiO2的河沙、铁矿石和钙石粉。Step 2: In order to make the vortex furnace run smoothly, 10%-30% of the weight of the kiln discharge material is mixed with slag material as slag auxiliary material, and mixed to form the charging material. Wherein, the slag material is calcium ferrosilicon slag material, including river sand, iron ore and calcium stone powder that provide SiO2.
步骤3：细碎入炉料(松散的出窑料和配入的熔渣料)，将入炉料粉碎至粒度为1mm～2mm；Step 3: finely smash the incoming charge (loose kiln out-feed and prepared slag charge), and pulverize the incoming charge to a particle size of 1mm to 2mm;
步骤4：旋涡炉挥发熔炼。设备采用旋涡炉，旋涡炉采用切向供风，风速度一般接近音速，燃料颗粒在炉内高强度燃烧，炉温能高达1400℃～1500℃，具有极高的熔炼强度。先烘炉，炉身上部的进风口设置的天然气烧咀先调成还原性较低温度的长火焰，向炉内喷火，至炉内温度达到1200℃～1300℃；再将天然气烧咀火焰调成中性火焰，火焰大小与风咀供风量相关，使供入的风量升温到600℃～800℃，利于从炉顶加料口加入的入炉料能被顺利点燃，沿内炉壁剧烈燃烧升温，由于加入的入炉料大部分是As2S3，其中的硫，将与从风咀供入的高速风发生氧化放热反应，化学反应式是，反应释放出的热量使炉堂内腔快速升温，使炉内温度高达1400℃以上；为了能使铼顺利挥发成蒸气，需调控炉内成氧化性燃烧气氛，使硫的燃烧空气系数大于1.1，在1400℃以上高温、氧化性条件下，入炉料中的所有铼酸盐都会分解挥发进入烟气中，而砷氧化成为As2O3蒸气，硫氧化成为SO2蒸气，一同进入烟气中。在1400℃以上高温、氧化性条件下，从旋涡炉下部的烟气出口出来的烟气温度很高，需用水冷眼观导出。原料中少量的难挥发物与主动配入的适量 的熔渣料形成熔渣(如高温硅铁钙熔渣)，沿炉内腔落向底部炉缸内，定期放出炉外，可用作水泥厂的配铁辅料开路处理。Step 4: Vortex furnace volatilization smelting. The equipment adopts a vortex furnace, and the vortex furnace adopts tangential air supply. The wind speed is generally close to the speed of sound. The fuel particles are burned with high intensity in the furnace. First bake the furnace, the natural gas burner set at the air inlet on the upper part of the furnace body is first adjusted to a long flame with lower reducing temperature, and fire is sprayed into the furnace until the temperature in the furnace reaches 1200 ° C ~ 1300 ° C; then the natural gas burner flame Adjusted to a neutral flame, the size of the flame is related to the air supply volume of the air nozzle, so that the supplied air volume can be heated to 600℃～800℃, which is beneficial to the charging material added from the charging port on the top of the furnace can be ignited smoothly, and the furnace wall is violently burned and heated up. , Since most of the charged charge is As2S3, the sulfur in it will react with the high-speed air supplied from the air nozzle to have an oxidative exothermic reaction. The temperature in the furnace is as high as 1400°C or more; in order to make the rhenium volatilize into steam smoothly, it is necessary to adjust the oxidative combustion atmosphere in the furnace, so that the combustion air coefficient of sulfur is greater than 1.1, and under the high temperature and oxidative conditions above 1400°C, it is put into the charge. All of the rhenate will be decomposed and volatilized into the flue gas, while the arsenic is oxidized to become As2O3 vapor, and the sulfur is oxidized to become SO2 vapor, which will enter the flue gas together. Under high temperature and oxidizing conditions above 1400°C, the temperature of the flue gas from the flue gas outlet at the lower part of the vortex furnace is very high, and it needs to be extracted with water cooling. A small amount of non-volatile substances in the raw materials and an appropriate amount of slag material actively mixed to form slag (such as high-temperature ferrosilicon calcium slag), which falls along the furnace cavity to the bottom hearth, and is regularly released out of the furnace, which can be used as cement The factory's iron distribution accessories are open-circuited.
步骤5：高温烟气从炉下部的烟气出口，经水冷烟气管后导入烟气水洗塔。烟气水洗塔辅收铼砷，烟气水洗塔需有足够大的散热容量，通常配置空气换热冷水塔，使烟气水洗塔循环水温低于60℃工作，进入烟气水洗塔的高温烟气，被喷雾细水滴(循环水)迅速降温，其中的氧化铼蒸气，极易溶于水，被捕集入循坏水中，不断累积富集；As2O3蒸气被水滴冷却析出细小晶粒，捕集入循环水中，不断累积；SO2亦被冷却，但在水中溶解度较小，大部分随冷却烟气进入后续的脱硫塔。Step 5: The high-temperature flue gas is introduced into the flue gas washing tower from the flue gas outlet at the lower part of the furnace through the water-cooled flue gas pipe. The flue gas washing tower is used to collect rhenium arsenic. The flue gas washing tower needs to have a large enough heat dissipation capacity. Usually, the air heat exchange cold water tower is equipped to make the circulating water temperature of the flue gas washing tower work below 60 °C, and the high temperature smoke entering the flue gas washing tower The gas is rapidly cooled by the sprayed water droplets (circulating water), and the rhenium oxide vapor in it is easily soluble in water, and is trapped in the circulating water for continuous accumulation and enrichment. into the circulating water and accumulate continuously; SO2 is also cooled, but the solubility in water is small, and most of it enters the subsequent desulfurization tower with the cooling flue gas.
当烟气水洗塔循环水中As2O3晶体浓度过高，固相达到20％时，用压滤机分离出去，压滤液返回循环水中，分离出的高砷晶体，可按传统的热水溶，冷冻析晶法进一步提纯后，按As2O3产品市售开路处置。When the concentration of As2O3 crystals in the circulating water of the flue gas washing tower is too high and the solid phase reaches 20%, it is separated by a filter press, and the pressure filtrate is returned to the circulating water. After further purification by the method, it is disposed of as a commercially available As2O3 product.
当循环水中含铼浓度富集到Re≥1.5g/L时，As2O3晶体压滤后抽出压滤液，按本领域常规技术提取铼，同时向循环水中补充等量的新水，为了确保铼和砷的直收率，通常要采用串联2～4级的烟气水洗塔来保证回收率。When the concentration of rhenium in the circulating water is enriched to Re ≥ 1.5g/L, the As2O3 crystals are filtered and the pressure filtrate is drawn out, and the rhenium is extracted according to the conventional technology in the field, and at the same time, an equal amount of new water is added to the circulating water. The direct recovery rate of 2 to 4 levels of flue gas water washing towers in series is usually used to ensure the recovery rate.
步骤6：冷却烟气进入后续的脱硫塔后进行烟气脱硫。烟气脱硫为本领域的常规技术，本发明方法的烟气总量规模一般都较小，且水洗后水分含量较高，不宜选择制酸流程，一般可选择传统成熟的碱法或者石灰法处置，都能达到环保要求。Step 6: The cooling flue gas enters the subsequent desulfurization tower for flue gas desulfurization. Flue gas desulfurization is a conventional technology in the field. The total amount of flue gas in the method of the present invention is generally small, and the water content after washing is relatively high. It is not suitable to choose an acid-making process. Generally, traditional mature alkali method or lime method can be selected for disposal. , can meet the requirements of environmental protection.
本发明方法与传统的方法相比，热效率高，节能50％以上，高价值的稀有元素，直收率高出约10％～30％，有效的节约宝贵资源，弃渣量减少了约75％～90％，且弃渣为无毒害物的硅铁钙渣，可被水泥厂资源化利用，彻底的解决了传统方法中二次环境污染问题。Compared with the traditional method, the method of the invention has high thermal efficiency, saves energy by more than 50%, the direct yield of high-value rare elements is about 10%-30% higher, effectively saves valuable resources, and reduces the amount of waste residue by about 75% ～90%, and the waste slag is non-toxic ferrosilicon calcium slag, which can be recycled by cement plants, completely solving the problem of secondary environmental pollution in traditional methods.
附图说明Description of drawings
图1是本发明的方法流程图。FIG. 1 is a flow chart of the method of the present invention.
具体实施方式Detailed ways
实施例1Example 1
在湖南耒阳的某冶炼企业，按本发明的方法，作了如下具体的实施。In a certain smelting enterprise in Leiyang, Hunan, according to the method of the present invention, the following concrete implementation is made.
步骤1：顺流烘干脱水。采用Φ1m×L10m的顺流式回转窑，控制转窑炉尾烟气温度为60～80℃，窑身转速6转每分钟，倾角4.5°，进料水份55％，加料速度1T/小时，出窑料含水份约19.5％，呈松散块粒状，每24小时可处理原料20～24T/天。Step 1: Downstream drying and dehydration. Adopt the downstream rotary kiln of Φ1m×L10m, control the flue gas temperature of the rotary kiln furnace tail to be 60～80℃, the kiln body speed is 6 rpm, the inclination angle is 4.5°, the feed water content is 55%, the feeding speed is 1T/hour, The water content of the kiln material is about 19.5%, and it is in the form of loose blocks and granules. It can process 20-24T/day of raw materials every 24 hours.
步骤2：配渣型料。含铼硫砷酸泥原料中总造渣成份很少，为使旋涡炉能顺利操作，将原料配入15％的熔渣料，熔渣料中：河沙(含SiO2 95％)4.5％、铁矿石(含Fe 55％)8％及钙石粉(含CaO50％)4.8％。Step 2: Prepare slag-type material. The total slag-forming components in the raw materials of rhenium-containing thioarsenic acid mud are very small. In order to make the vortex furnace operate smoothly, the raw materials are mixed with 15% slag material. In the slag material: river sand (containing SiO2 95%) 4.5%, Iron ore (containing Fe 55%) 8% and calcium stone powder (containing CaO 50%) 4.8%.
步骤3：细碎炉料。将混合后的入炉料(上述出窑料与熔渣料)进锤式破碎机细碎，过筛后，使炉料粒径1～2mm，便于熔炼加料输送及风力分散。Step 3: Finely crush the charge. The mixed incoming charge (the above-mentioned kiln outgoing charge and slag charge) is put into a hammer crusher for fine crushing, and after sieving, the particle size of the charge is 1-2 mm, which is convenient for smelting, feeding, conveying and wind dispersion.
取样检测入炉料的典型成份是：H2O 19.5％、Re 0.08％、As 25％、S 35％、SiO2 4.4％、Fe 4.5％、Cao 2.4％。The typical composition of the charge sampled and detected is: H2O 19.5%, Re 0.08%, As 25%, S 35%, SiO2 4.4%, Fe 4.5%, Cao 2.4%.
步骤4：旋涡炉挥发熔炼。Step 4: Vortex furnace volatilization smelting.
A.设备采用旋涡炉：①炉顶加料仓容积0.5～1.5m 3的，螺旋加料机内径为Φ100，具备1T/小时的加料能力，无级调速调节加料流量；②冷水套式炉顶盖，其上开有加料通孔，加料仓安装在其上；③炉内部设 置强制水冷管的圆形内腔炉身，炉腔内径选择Φ500m，高度选择H2000mm，炉腔用抗渣性好的镁洛耐火混泥土料捣筑，在其上部开设有切向进风口，下部设有缩径约60％的下渣收敛通口；④盛渣炉缸直径与炉腔相同等。 A. The equipment adopts a vortex furnace: ①The volume of the top feeding bin is 0.5～1.5m 3 , the inner diameter of the screw feeder is Φ100, with a feeding capacity of 1T/hour, and the feeding flow can be adjusted by stepless speed regulation; ②The top cover of the cold water jacket furnace , there is a feeding through hole on it, and the feeding bin is installed on it; 3. A circular inner cavity furnace body with a forced water-cooling tube is set inside the furnace. The inner diameter of the furnace cavity is Φ500m, and the height is H2000mm. The furnace cavity is made of magnesium with good slag resistance The Luo refractory concrete is rammed, and the upper part is provided with a tangential air inlet, and the lower part is provided with a lower slag convergence port with a reduced diameter of about 60%; ④ The diameter of the slag-containing hearth is the same as that of the furnace cavity.
B.烘炉开炉准备：旋涡炉上部的切向进风口内设置天燃气烧咀，点火后调成还原性较低温度的长火焰，向炉内喷入，烘干炉腔内壁的水份，按规定升温曲线，分阶段升温，120小时后，炉内温度上升到1300℃，准备加入炉料。B. Preparation for opening the oven: A natural gas burner is set in the tangential air inlet on the upper part of the vortex furnace. After ignition, it is adjusted to a long flame with a lower reducing temperature and sprayed into the furnace to dry the moisture on the inner wall of the furnace cavity. , according to the prescribed heating curve, the temperature rises in stages, and after 120 hours, the temperature in the furnace rises to 1300 ℃, and the charge is ready to be added.
C.阶段加料运行：将进风口内的天燃气烧咀火焰调节成中性火焰，火量大小能使从切向风口进入的风加热升温到600℃～800℃，可顺利点燃从炉顶加料仓加料落入炉内的入炉料，使其切向沿内腔面剧烈燃烧升温。加入的入炉料大部分是含铼的As2S3，在高温氧化条件下，氧化放热使炉内温度高达1400℃以上，控制加料量与进入炉内的空气量的适当比例，使硫和As的氧化燃烧空气系数为1.1～1.25，保持炉内的氧化性状态，有利于铼酸盐的完全高效挥发，同时As氧化成As2O3，在炉内高温1400℃条件下，全部变成蒸气进入烟气中，S氧化成SO2，进入烟气中，炉料中原有的难挥发成份与主动配入的造渣物熔炼成硅铁钙熔渣(成份为：SO2 30％、Fe 30％、CaO 18％)，沿炉内壁向下经收敛口，流入炉缸中，根据炉况，定期捅开放渣口排出，维持熔渣在炉缸中的适当高度，高温烟气从炉缸上部的出口，经水冷烟气管排出。经多次取排渣样检测，排出渣的残留Re＜0.002％，渣率＜20％，炉料中铼的挥发直收率＞。C. Stage feeding operation: adjust the flame of the natural gas burner in the air inlet to a neutral flame, and the amount of fire can make the air entering from the tangential tuyere heated to 600℃～800℃, and the feeding from the furnace top can be ignited smoothly The silo feeds the incoming charge that falls into the furnace, so that it burns and heats up tangentially along the inner cavity surface. Most of the charged charge is As2S3 containing rhenium. Under the condition of high temperature oxidation, the exothermic oxidation makes the temperature in the furnace as high as 1400℃ or more. Control the appropriate ratio of the charging amount and the amount of air entering the furnace to make the oxidation of sulfur and As. The combustion air coefficient is 1.1~1.25, which maintains the oxidative state in the furnace, which is conducive to the complete and efficient volatilization of rhenate. At the same time, As is oxidized to As2O3, and at the high temperature of 1400 °C in the furnace, all of it turns into steam and enters the flue gas. S is oxidized to SO2 and enters into the flue gas. The original non-volatile components in the charge and the slag-forming materials that are actively mixed are smelted into calcium ferrosilicon slag (components: SO2 30%, Fe 30%, CaO 18%), along with The inner wall of the furnace flows downward through the convergence port and flows into the hearth. According to the furnace conditions, the slag port is regularly opened to discharge to maintain the appropriate height of the molten slag in the hearth. discharge. After taking slag samples for many times and testing, the residual Re of the slag is less than 0.002%, the slag rate is less than 20%, and the volatilization rate of rhenium in the charge is greater than that.
步骤5：烟气水洗塔捕收铼砷。烟气水洗塔采用多喷咀文氏射流器，洗涤烟气，循环泵选用400m 3/h流量，50m扬程的泵参数，引风量能达到12000m 3/h，烟气水洗塔配置了一台散热量达400万大卡/小时的空气换热冷水塔配套冷却循环水，使循环水工作温度低于60℃。工作运行时，由水冷烟气管送进烟气水洗塔的高温烟气，被高速细粒的水滴冷却降温，烟气中的氧化铼降温后，极易溶于水，在循环喷射中不断地被富集，高温烟气中的As2O3蒸气，被高速水滴冷却后，变成细小晶粒，在循环水中不断富集，SO2亦被冷却，但在水中溶解度较小，大部分随冷却烟气进入后续的脱硫塔。 Step 5: The flue gas washing tower captures rhenium arsenic. The flue gas washing tower adopts a multi-nozzle venturi jet to wash the flue gas. The circulating pump adopts the pump parameters of 400m 3 /h flow and 50m head, and the induced air volume can reach 12000 m 3 /h. The flue gas washing tower is equipped with a heat sink The air heat exchange cold water tower with a capacity of 4 million kcal/hour is equipped with cooling circulating water, so that the working temperature of the circulating water is lower than 60 °C. When working, the high-temperature flue gas sent to the flue gas washing tower by the water-cooled flue gas pipe is cooled by high-speed fine-grained water droplets. After being enriched, the As2O3 vapor in the high-temperature flue gas is cooled by high-speed water droplets and becomes fine grains, which are continuously enriched in the circulating water, and SO2 is also cooled, but the solubility in water is small, and most of it enters with the cooling flue gas. Subsequent desulfurization tower.
当循环水中As2O3晶粒固相达20％时采用压滤机，将晶粒从循环水中分离出去，再利用传统的热溶冷析法，将其提纯分离烘干包装，达到99％以上的纯度，上市销售开路处置。当烟气水洗塔循环水中的含铼浓度富集到1.5g/L时，将从压滤机分离的压滤液抽取出来，采用传统的浓缩氯化盐法，将铼以铼酸盐形式提取出来，达到回收目的，而传统方法提取铼的直收率一般小于98％，为提高烟气水洗塔对烟气中铼及砷的回收效率，一般设2～4级烟气水洗塔串联运行。When the solid phase of the As2O3 grains in the circulating water reaches 20%, a filter press is used to separate the grains from the circulating water, and then the traditional hot-melt-cold precipitation method is used to purify, separate, dry and package to achieve a purity of more than 99%. , open-circuit disposal for listing and sales. When the concentration of rhenium in the circulating water of the flue gas washing tower is enriched to 1.5g/L, the pressure filtrate separated from the filter press is extracted, and the rhenium is extracted in the form of rhenate by the traditional concentrated chloride salt method. In order to improve the recovery efficiency of rhenium and arsenic in the flue gas by the flue gas washing tower, generally 2 to 4 levels of flue gas washing towers are set up to operate in series.
步骤6：烟气脱硫。将水洗后的含硫烟气，引入冶炼企业原有的石灰法脱硫塔处理，烟气中含SO2＜100mg/m 3，达标后排入60m高的烟窗中对空排放。 Step 6: Flue gas desulfurization. The washed sulfur-containing flue gas is introduced into the original lime-based desulfurization tower of the smelting enterprise for treatment. The flue gas contains SO2<100mg/m 3 , and after reaching the standard, it is discharged into a 60m-high smoke window for air discharge.
对比实施例Comparative Example
为测出入炉料中配入熔渣料对炉况的影响，做了本对比实施例，具体是：把配入入炉料中的熔渣量从20％减少到5％，其它条件与实施例1完全相同。检测从炉缸中排出的炉渣中含Re为0.07％，铼的挥发直收率，直收率降低3.9％，有明显影响。In order to measure the effect of adding slag into the charge on furnace conditions, this comparative example is made, specifically: the amount of slag added into the charge is reduced from 20% to 5%, and other conditions are the same as those in Example 1. Exactly the same. It is detected that the content of Re in the slag discharged from the hearth is 0.07%, and the direct yield of rhenium volatilization is reduced by 3.9%, which has a significant impact.

Claims (10)

  1. 一种旋涡炉自热挥发含铼硫砷酸泥综合回收铼硫砷的工艺方法，其特征在于，该方法步骤如下：A process method for comprehensive recovery of rhenium sulfur arsenic by self-heating volatilization of rhenium sulfur arsenic acid sludge in a vortex furnace, characterized in that the method steps are as follows:
    步骤1：将含铼硫砷酸泥原料采用顺流式回转窑烘干至出窑料松散；Step 1: Dry the raw material containing rhenium sulfuric arsenic acid in a downstream rotary kiln until the material discharged from the kiln is loose;
    步骤2：于出窑料中配入为出窑料重量10％～30％的熔渣料，形成入炉料；Step 2: adding slag material with a weight of 10% to 30% of the weight of the kiln material into the kiln discharge material to form the charging material;
    步骤3：将入炉料粉碎至粒度为1mm～2mm；Step 3: pulverize the incoming charge to a particle size of 1mm to 2mm;
    步骤4：旋涡炉挥发熔炼：先烘炉至旋涡炉炉内温度达到1200℃～1300℃；再将进风口中的天然气烧咀火焰调成中性火焰，使切向供入的风量升温到600℃～800℃，以使加入的入炉料能被顺利点燃，沿内炉壁剧烈燃烧升温，发生氧化放热反应，化学反应式是，释放的热量使炉内快速升温达1400℃以上；同时控制炉内成氧化性燃烧气氛，使硫的燃烧空气系数大于1.1，在温度1400℃以上、氧化性条件下，入炉料中的铼酸盐分解挥发进入高温烟气中，As氧化成As2O3蒸气，S氧化成SO2蒸气，一并进入高温烟气中；Step 4: Vortex furnace volatilization smelting: first bake the furnace until the temperature in the vortex furnace reaches 1200 ℃ ~ 1300 ℃; then adjust the flame of the natural gas burner in the air inlet to a neutral flame, so that the tangentially supplied air volume rises to 600 ℃～800℃, so that the added charge can be ignited smoothly, and the temperature rises violently along the inner furnace wall, and an oxidation exothermic reaction occurs. An oxidative combustion atmosphere is formed in the furnace, so that the combustion air coefficient of sulfur is greater than 1.1. At a temperature above 1400 ° C and oxidative conditions, the rhenate in the charge is decomposed and volatilized into the high-temperature flue gas, As is oxidized into As2O3 vapor, S It is oxidized into SO2 vapor and enters into the high temperature flue gas together;
    步骤5：将高温烟气导入烟气水洗塔，塔内循环水工作温度低于60℃，进入塔内的高温烟气在循环水作用下迅速降温，其中，氧化铼蒸气被捕集入循坏水中，不断累积；As2O3蒸气被冷却析出晶粒，捕集入循环水中，不断累积；SO2被冷却后大部分随冷却烟气出塔；当循环水中As2O3晶体固相达到20％时，将循环水压滤分离，分离出的晶体按常规技术提纯后得As2O3产品，压滤液则返回循环水中，当循环水中含Re≥1.5g/L，则将压滤液按常规技术提取铼酸盐，得铼产品；Step 5: Introduce the high-temperature flue gas into the flue gas washing tower. The working temperature of the circulating water in the tower is lower than 60 °C. The high-temperature flue gas entering the tower is rapidly cooled by the circulating water. Among them, the rhenium oxide vapor is trapped into the circulating water. In water, it accumulates continuously; As2O3 vapor is cooled to separate out crystal grains, captured in circulating water, and accumulated continuously; after SO2 is cooled, most of it exits the tower with the cooling flue gas; when the solid phase of As2O3 crystal in circulating water reaches 20%, the circulating water Press filtration for separation, the separated crystals are purified by conventional techniques to obtain As2O3 products, and the press filtrate is returned to the circulating water. When the circulating water contains Re ≥ 1.5g/L, the press filtrate is extracted by conventional techniques to obtain rhenium salts to obtain rhenium products. ;
    步骤6：冷却烟气进入后续的脱硫塔进行烟气脱硫。Step 6: The cooled flue gas enters the subsequent desulfurization tower for flue gas desulfurization.
  2. 如权利要求1所述的一种旋涡炉自热挥发含铼硫砷酸泥综合回收铼硫砷的工艺方法，其特征在于，所述步骤1中含铼硫砷酸泥为冶炼含硫烟气制酸产生的副产物。A process method for comprehensively recovering rhenium, sulfur and arsenic by self-heating volatilization of rhenium-containing sulfuric arsenic acid sludge in a vortex furnace as claimed in claim 1, characterized in that, in the step 1, the rhenium-containing sulfuric arsenic acid sludge is used for smelting sulfur-containing flue gas By-products of acid production.
  3. 如权利要求1所述的一种旋涡炉自热挥发含铼硫砷酸泥综合回收铼硫砷的工艺方法，其特征在于，所述步骤1中烘干时控制窑尾气流温度＜80℃、出窑料水分含量为15％～25％。The process method for comprehensively recovering rhenium, sulfur and arsenic by self-heating volatilization of rhenium sulfuric arsenic acid sludge in a vortex furnace as claimed in claim 1, characterized in that, in the step 1, the temperature of the kiln tail gas flow is controlled to be less than 80° C., The moisture content of the kiln material is 15% to 25%.
  4. 如权利要求1所述的一种旋涡炉自热挥发含铼硫砷酸泥综合回收铼硫砷的工艺方法，其特征在于，所述步骤2中的熔渣料为硅铁钙熔渣料，该硅铁钙熔渣料包括提供SiO2的河沙、铁矿石和钙石粉。The process method for comprehensively recovering rhenium, sulfur and arsenic by self-heating volatilization of rhenium-sulfur-arsenic acid sludge in a vortex furnace as claimed in claim 1, wherein the slag material in the step 2 is calcium ferrosilicon slag material, The calcium ferrosilicon slag material includes river sand, iron ore and limestone powder that provide SiO2.
  5. 如权利要求4所述的一种旋涡炉自热挥发含铼硫砷酸泥综合回收铼硫砷的工艺方法，其特征在于，所述步骤4中原料中的难挥发物与配入的熔渣料形成硅铁钙熔渣，落入旋涡炉底部的炉缸内。A process method for comprehensive recovery of rhenium sulphur arsenic by self-heating volatilization of rhenium sulphur arsenic acid sludge in a vortex furnace as claimed in claim 4, characterized in that in the step 4, the hardly volatile matter in the raw material and the mixed slag The material forms calcium ferrosilicon slag, which falls into the hearth at the bottom of the vortex furnace.
  6. 如权利要求1所述的一种旋涡炉自热挥发含铼硫砷酸泥综合回收铼硫砷的工艺方法，其特征在于，所述步骤5中高温烟气从旋涡炉出来后经水冷烟气管导入烟气水洗塔中。A process method for comprehensive recovery of rhenium, sulfur and arsenic by self-heating volatilization of rhenium sulfur-arsenic acid sludge in a vortex furnace as claimed in claim 1, characterized in that, in the step 5, the high-temperature flue gas comes out of the vortex furnace and passes through the water-cooled flue gas. The pipe is introduced into the flue gas washing tower.
  7. 如权利要求1所述的一种旋涡炉自热挥发含铼硫砷酸泥综合回收铼硫砷的工艺方法，其特征在于，所述步骤5中烟气水洗塔搭配空气换热冷水塔使用，以使烟气水洗塔内循环水的工作温度低于60℃。A process method for comprehensive recovery of rhenium sulfur arsenic by vortex furnace self-heating volatilization of rhenium sulfur arsenic acid sludge as claimed in claim 1, it is characterized in that, in described step 5, flue gas water washing tower is used with air heat exchange cold water tower, So that the working temperature of the circulating water in the flue gas washing tower is lower than 60 ℃.
  8. 如权利要求1所述的一种旋涡炉自热挥发含铼硫砷酸泥综合回收铼硫砷的工艺方法，其特征在于，所述烟气水洗塔串联2～4级，以提高铼、砷的回收率。A process method for comprehensive recovery of rhenium, sulfur and arsenic by self-heating volatilization of rhenium-containing sulfuric arsenic acid sludge in a vortex furnace as claimed in claim 1, wherein the flue gas washing towers are connected in series with 2 to 4 stages, so as to increase rhenium, arsenic recovery rate.
  9. 如权利要求1所述的一种旋涡炉自热挥发含铼硫砷酸泥综合回收铼硫砷的工艺方法，其特征在于，所述步骤5中As2O3产品是将As2O3晶体以热水溶解后冷冻析晶得到；铼产品则是以传统氯盐法提取得到。A process method for comprehensive recovery of rhenium, sulfur and arsenic by self-heating volatilization of rhenium sulfuric arsenic acid sludge in a vortex furnace as claimed in claim 1, characterized in that, in the step 5, the As2O3 product is to dissolve the As2O3 crystal with hot water and then freeze it Crystallization is obtained; rhenium products are obtained by traditional chloride extraction.
  10. 如权利要求1所述的一种旋涡炉自热挥发含铼硫砷酸泥综合回收铼硫砷的工艺方法，其特征在于，所述步骤6中烟气脱硫采用碱法或石灰法烟气脱硫。A process method for comprehensive recovery of rhenium, sulfur and arsenic by self-heating volatilization of rhenium-sulfur-arsenic acid sludge in a vortex furnace as claimed in claim 1, characterized in that, in the step 6, the flue gas desulfurization adopts an alkali method or a lime method for flue gas desulfurization .
PCT/CN2020/140551 2020-12-29 2020-12-29 Method for cumulative recovery of rhenium, sulfur, and arsenic via vortex furnace self-heated volatilization of rhenium-containing sulfur-arsenic acid sludge WO2022141011A1 (en)

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