技术领域Technical field
本发明属于环境保护领域，主要针对工业废气汞的去除与回收，涉及到一种通过氯硒汞沉积从含硫含汞烟气中捕集汞的方法与基质材料。The invention belongs to the field of environmental protection, is mainly aimed at the removal and recovery of mercury from industrial waste gas, and relates to a method and matrix material for capturing mercury from sulfur-containing mercury-containing flue gas through chlorine, selenium and mercury deposition.
背景技术Background technique
汞具有长距离迁移、高生物富集和高毒性等特征，是全球重点关注的污染物之一。已经正式生效的《关于汞的水俣公约》旨在全球性的切断汞的排放源，限制含汞产品的区域流通，并且规定了对燃煤电厂、工业锅炉、有色金属冶炼、水泥生产等重点行业进行大气汞排放控制。作为最大的汞排放国，燃煤发电和有色金属冶炼是我国最主要的汞排放源，汞减排压力巨大。随着近年来对大气污染的日益关注，在燃煤发电行业形成了史上最严的超低排放标准，对硫氧化物、氮氧化物以及颗粒物的控制技术进行升级改造的同时，汞也在这些超低排放工艺中同步高效去除。但是，汞在有色冶炼行业的排放特征呈现了完全区别于燃煤发电行业的特征，以金属硫化物为主要成分的矿石在高温焙烧过程中，释放出大量SO2、颗粒物、重金属等污染物，随着烟气向下游迁移的过程中，利用收尘、湿式洗涤等污染控制设备可以把部分颗粒物以及易溶解的污染物(SO3、硒、氯等)去除，净化后含有高浓度SO2(一般>4％)的烟气经过两转两吸工艺用于制硫酸，实现对烟气中SO2以及颗粒物等大宗常规污染物的高效净化以及硫资源的利用。但烟气中的汞，主要是零价汞(Hg0),由于其稳定性高、溶解性低，易于随着烟气进去制酸工艺中，亟需在上游烟气将其拦截捕集，以降低污酸治理难度，提高硫酸产品质量。Mercury has the characteristics of long-distance migration, high bioaccumulation and high toxicity, and is one of the pollutants of global concern. The Minamata Convention on Mercury, which has officially entered into force, aims to cut off the sources of mercury emissions globally, restrict the regional circulation of mercury-containing products, and stipulates regulations on key industries such as coal-fired power plants, industrial boilers, non-ferrous metal smelting, and cement production. Carry out atmospheric mercury emission control. As the largest mercury emitter, coal-fired power generation and non-ferrous metal smelting are the main sources of mercury emissions in my country, and the pressure to reduce mercury emissions is huge. With increasing attention to air pollution in recent years, the most stringent ultra-low emission standards in history have been formed in the coal-fired power generation industry. While the control technologies for sulfur oxides, nitrogen oxides, and particulate matter are being upgraded, mercury is also included in these Simultaneous and efficient removal in ultra-low emission processes. However, the emission characteristics of mercury in the non-ferrous smelting industry are completely different from those in the coal-fired power generation industry. During the high-temperature roasting process of ores with metal sulfides as the main components, large amounts of SO2 , particulate matter, heavy metals and other pollutants are released. As the flue gas migrates downstream, some particulate matter and easily soluble pollutants (SO3 , selenium, chlorine, etc.) can be removed by using pollution control equipment such as dust collection and wet washing. After purification, it contains high concentrations of SO2 ( Generally >4%) flue gas is used to produce sulfuric acid through a two-turn and two-suction process to achieve efficient purification of bulk conventional pollutants such as SO2 and particulate matter in the flue gas and the utilization of sulfur resources. However, the mercury in the flue gas is mainly zero-valent mercury (Hg0 ). Due to its high stability and low solubility, it is easy to enter the acid-making process along with the flue gas. It is urgent to intercept and capture it in the upstream flue gas. In order to reduce the difficulty of treating polluted acid and improve the quality of sulfuric acid products.
专利ZL201310277066.0公开了一种从有色金属冶炼烟气中回收气态零价汞和二氧化硫的方法，以硫酸汞、硫酸铁和硫酸作为主要组分配置成复合吸收液，利用吸收塔对烟气中的零价汞进行高效吸收，将零价汞经转化为亚硫酸汞，利用硫酸铁与二氧化硫的反应生成硫酸。生成的亚硫酸汞通过回收装置分解成单质汞和硫酸汞。与现有技术相比，采用本发明可以提高烟气零价汞的吸收效率，减少吸收剂的使用量，实现零价汞的回收。同时通过对二氧化硫的吸收不仅可以回收硫酸，还能减少二氧化硫对Hg2+的还原作用，提高零价汞的总回收率，因此非常适合应用于二氧化硫浓度较高的烟气汞排放控制。但是，采用该方法需要单独的除汞设备并配置相应的溶液，成本较高且汞去除效率会随着溶液浓度的降低而逐渐丧失，难以适用复杂烟气下的应用。Patent ZL201310277066.0 discloses a method for recovering gaseous zero-valent mercury and sulfur dioxide from non-ferrous metal smelting flue gas. Mercury sulfate, iron sulfate and sulfuric acid are used as the main components to form a composite absorption liquid, and an absorption tower is used to absorb the gas in the flue gas. It efficiently absorbs zero-valent mercury, converts zero-valent mercury into mercury sulfite, and uses the reaction of iron sulfate and sulfur dioxide to generate sulfuric acid. The generated mercury sulfite is decomposed into elemental mercury and mercury sulfate through the recovery device. Compared with the existing technology, the present invention can improve the absorption efficiency of zero-valent mercury in flue gas, reduce the usage of absorbent, and realize the recovery of zero-valent mercury. At the same time, the absorption of sulfur dioxide can not only recover sulfuric acid, but also reduce the reduction effect of sulfur dioxide on Hg2+ and improve the total recovery rate of zero-valent mercury. Therefore, it is very suitable for application in flue gas mercury emission control with high sulfur dioxide concentration. However, this method requires separate mercury removal equipment and the corresponding solution, which is costly and the mercury removal efficiency will gradually lose as the concentration of the solution decreases, making it difficult to apply to applications in complex flue gases.
发明内容Contents of the invention
本发明的目的就是为了克服上述现有技术存在的缺陷而提供一种通过氯硒汞沉积从含硫含汞烟气中捕集汞的方法。The purpose of the present invention is to provide a method for capturing mercury from sulfur-containing mercury-containing flue gas through chloriselenium-mercury deposition to overcome the above-mentioned defects in the prior art.
本发明的目的可以通过以下技术方案来实现：一种通过氯硒汞沉积从含硫含汞烟气中捕集汞的方法，包括以下步骤：The object of the present invention can be achieved by the following technical solution: a method for capturing mercury from sulfur-containing mercury-containing flue gas through chlorine, selenium and mercury deposition, including the following steps:
(1)有色冶炼原烟气经过除尘及余热回收后，向其中喷入一定量的水雾，使其温度降至露点附近，使烟气中的二氧化硒在二氧化硫与水蒸汽的共同作用下被还原为可与烟气中汞快速反应的活性单质硒，并在烟气中HCl的作用下，生成易于沉积的氯硒汞化合物；(1) After dust removal and waste heat recovery, a certain amount of water mist is sprayed into the raw flue gas of non-ferrous smelting to reduce its temperature to near the dew point, so that the selenium dioxide in the flue gas is released under the combined action of sulfur dioxide and water vapor. It is reduced to active elemental selenium that can react quickly with mercury in the flue gas, and under the action of HCl in the flue gas, it generates chlorine, selenium and mercury compounds that are easy to deposit;
(2)然后使烟气与基质材料接触，通过其表面诱导效应，加速氯硒汞的生成及沉积，从而使烟气中的汞被捕集到基质表面。(2) Then the flue gas is brought into contact with the matrix material, and through its surface induction effect, the generation and deposition of chlorine, selenium and mercury are accelerated, so that the mercury in the flue gas is captured on the surface of the matrix.
进一步地，有色冶炼原烟气中含有汞、硫氧化物、二氧化硒及氯化氢；Furthermore, the raw flue gas from non-ferrous smelting contains mercury, sulfur oxides, selenium dioxide and hydrogen chloride;
经过上游烟气除尘及余热回收后的烟气的温度降至250℃以下，烟气中的汞主要以零价汞形式存在，其浓度范围在0.1-50mg/m3，SO2范围浓度为0.2％-5％，SeO2浓度在100-2000mg/m3，HCl浓度在20-500mg/m3。After upstream flue gas dust removal and waste heat recovery, the temperature of the flue gas drops below 250°C. The mercury in the flue gas mainly exists in the form of zero-valent mercury, with a concentration range of 0.1-50 mg/m3 and a SO2 concentration range of 0.2 %-5%, SeO2 concentration is 100-2000 mg/m3 , HCl concentration is 20-500 mg/m3 .
进一步地，步骤(1)中向烟气中喷入水雾使用高效雾化喷嘴将水均匀地喷到烟气中，使烟气温度降至比其露点温度高5-10℃的程度；Further, in step (1), spray water mist into the flue gas and use a high-efficiency atomization nozzle to spray water evenly into the flue gas, so that the temperature of the flue gas drops to a level 5-10°C higher than its dew point temperature;
喷入水雾所使用的水为工艺水，或为不含颗粒物的酸性废水，喷水量为使烟气的温度降低至露点附近。The water used to spray water mist is process water or acidic wastewater without particulate matter. The amount of water sprayed is to reduce the temperature of the flue gas to near the dew point.
进一步地，步骤(1)中当烟气温度降至露点附近时，烟气中二氧化硒被二氧化硫快速还原为活性单质硒，二氧化硒还原率达10％以上；通过与烟气中HCl的共同作用，将气相零价汞转化为氯硒汞，汞的气相转化率可达5-20％。Further, when the flue gas temperature drops to near the dew point in step (1), the selenium dioxide in the flue gas is quickly reduced to active elemental selenium by sulfur dioxide, and the selenium dioxide reduction rate reaches more than 10%; through the interaction with HCl in the flue gas Working together, the gas phase zero-valent mercury is converted into chloroselenium mercury, and the gas phase conversion rate of mercury can reach 5-20%.
进一步地，步骤(2)所述基质材料为金属氧化物或多孔材料；Further, the matrix material in step (2) is a metal oxide or porous material;
所述的金属氧化物包括氧化铝、氧化锌、二氧化钛或氧化铁；The metal oxide includes aluminum oxide, zinc oxide, titanium dioxide or iron oxide;
所述的多孔材料为活性炭或二氧化硅。The porous material is activated carbon or silica.
进一步地，步骤(2)中烟气与基质材料接触的接触方式为：Further, the contact method between the flue gas and the matrix material in step (2) is:
基质材料以100-300目的粉状直接喷入烟气中，喷入烟气中的基质材料浓度为5-50g/m3，下游配有袋式除尘器收集。The matrix material is directly sprayed into the flue gas in the form of powder with a mesh size of 100-300. The concentration of the matrix material sprayed into the flue gas is 5-50g/m3 and is collected by a bag dust collector downstream.
或将基质材料制备为直径为2-10mm的球状或柱状颗粒，以固定床或移动床的形式与烟气接触，所使用的空速(即，每立方米吸附剂在1小时内能够处理的气体体积)为2000-20000h-1。Or prepare the matrix material into spherical or columnar particles with a diameter of 2-10mm, and contact the flue gas in the form of a fixed bed or a moving bed, and the space velocity used (that is, the adsorbent per cubic meter can handle it in 1 hour Gas volume) is 2000-20000h-1 .
进一步地，步骤(2)通过基质材料的表面诱导作用，促进烟气汞进一步向氯硒汞转化，总转化效率大于80％。Further, step (2) promotes the further conversion of flue gas mercury into chloroselenium mercury through the surface induction effect of the matrix material, and the total conversion efficiency is greater than 80%.
当烟气中的二氧化硒或HCl不足时，对基质材料表面进行改性处理，增加其表面上的氯或硒元素的含量，避免将这些物质直接喷入烟气而导致的逃逸及二次污染现象。When there is insufficient selenium dioxide or HCl in the flue gas, the surface of the matrix material should be modified to increase the content of chlorine or selenium on the surface to avoid escape and secondary damage caused by directly spraying these substances into the flue gas. pollution phenomenon.
更进一步地，当烟气自身中二氧化硒浓度低于200mg/m3时，用5-20％的亚硒酸钠溶液对基质材料进行浸渍改性，使材料负载1-5％硒，以元素硒质量计，晾干后即可使用；Furthermore, when the selenium dioxide concentration in the flue gas itself is lower than 200mg/m3 , the matrix material is impregnated and modified with 5-20% sodium selenite solution, so that the material is loaded with 1-5% selenium, so as to Elemental selenium mass meter, ready for use after drying;
当烟气自身中HCl浓度低于50mg/m3时，用5-10％的氯化钠溶液对基质材料进行浸渍改性，使材料负载0.5-2％氯，以元素氯质量计，晾干后即可使用。When the HCl concentration in the flue gas itself is lower than 50 mg/m3 , use 5-10% sodium chloride solution to impregnate and modify the matrix material so that the material is loaded with 0.5-2% chlorine, based on the mass of elemental chlorine, and then dry It can be used later.
进一步地，当基质材料表面上的氯硒汞累积到一定量时(当基质材料上氯硒汞的沉积量达到50g/kg以上时，需要将这部分基质材料取出，并进行再生)，再将其从烟气中取出，并利用加热再生的方法，通过冷凝法对再生出的汞及硒进行分别收集和回收，再生后的基质材料经过表面调质改性后，可循环利用。Further, when the chloride, selenium and mercury accumulate on the surface of the matrix material to a certain amount (when the deposition amount of chloride, selenium and mercury on the matrix material reaches more than 50g/kg, this part of the matrix material needs to be taken out and regenerated), then the It is taken out from the flue gas, and the regenerated mercury and selenium are separately collected and recycled through the condensation method through heating and regeneration. The regenerated matrix material can be recycled after surface conditioning and modification.
更进一步地，沉积氯硒汞的基质材料利用加热再生的方法进行处理，在使用氮气保护时将基质加热至300-400℃，得到高浓度零价汞及硒单质气体，经逐级降温冷凝及吸附，可分别回收零价汞及硒单质产品，再生过的基质材料经冷却后及适当调质改性后可循环使用。Furthermore, the matrix material for depositing chloride, selenium and mercury is processed by a heating regeneration method. The matrix is heated to 300-400°C under nitrogen protection to obtain high-concentration zero-valent mercury and selenium elemental gases. After stepwise cooling, condensation and Through adsorption, zero-valent mercury and selenium elemental products can be recovered respectively. The regenerated matrix material can be recycled after cooling and appropriate conditioning and modification.
与现有技术相比，本发明具有以下优点：Compared with the prior art, the present invention has the following advantages:
1)本发明提出了在有色冶炼烟气经过上游除尘后，通过向烟气中适当喷雾加湿，促使烟气中的二氧化硫将二氧化硒还原为对汞有高效捕集能力的活性单质硒，并在烟气中氯的共同作用下形成氯硒汞，随即沉积到所能接触的基质表面，可在烟气半干状态实现汞的高效捕集与回收，避免其过多进入下游洗涤污酸或制酸系统，从而造成回收率下降及跨介质转移等二次污染问题。1) The present invention proposes that after the non-ferrous smelting flue gas undergoes upstream dust removal, appropriate spray humidification is applied to the flue gas to promote the sulfur dioxide in the flue gas to reduce selenium dioxide into active elemental selenium with high efficiency capture ability for mercury, and Chlorine, selenium, and mercury are formed under the combined action of chlorine in the flue gas, and are then deposited on the surface of the substrate that can be contacted. This can achieve efficient capture and recovery of mercury in the semi-dry state of the flue gas, and prevent it from entering the downstream washing acid or wastewater. acid production system, resulting in secondary pollution problems such as reduced recovery rate and cross-media transfer.
2)本发明的捕汞方法，可在烟气半干状态实现汞的高效捕集，避免其过多进入下游洗涤污酸或制酸系统，从而造成回收率下降及跨介质转移等二次污染问题；2) The mercury capture method of the present invention can achieve high-efficiency capture of mercury in the semi-dry state of flue gas, preventing excessive mercury from entering the downstream washing acid or acid making system, thereby causing secondary pollution such as reduced recovery rate and cross-medium transfer. question;
3)本发明的基质材料调质方法简单，能耗低，能够实验大规模生产；3) The matrix material conditioning method of the present invention is simple, has low energy consumption, and is capable of experimental large-scale production;
4)本发明的基质材料使用后，可通过加热再生回收硒、汞资源，且基质材料可循环使用。4) After the matrix material of the present invention is used, selenium and mercury resources can be recovered through heating and regeneration, and the matrix material can be recycled.
附图说明Description of the drawings
图1为本发明通过氯硒汞沉积从含硫含汞烟气中捕集汞的方法的工艺流程图。Figure 1 is a process flow diagram of the method of capturing mercury from sulfur-containing mercury-containing flue gas through chloriselenium-mercury deposition according to the present invention.
具体实施方式Detailed ways
为了使本发明的目的、技术方案及优点更加清楚明白，一下结合具体实施案例，对本发明进行进一步的说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。此外，下面所描述的本发明各个实施方式中所涉及的技术特征只要彼此未构成冲突就可以互相组合。In order to make the purpose, technical solutions and advantages of the present invention more clear, the present invention will be further described with reference to specific implementation examples. It should be understood that the specific embodiments described here are only used to explain the present invention and are not intended to limit the present invention. In addition, the technical features involved in the various embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other.
如图1所示，一种通过氯硒汞沉积从含硫含汞烟气中捕集汞的方法与基质材料，主要包括以下步骤：As shown in Figure 1, a method and matrix material for capturing mercury from sulfur-containing mercury-containing flue gas through chlorine, selenium and mercury deposition mainly include the following steps:
第一步：有色冶炼原烟气I101经过除尘器1除尘及余热回收后，向其中喷入一定量的水雾I102，使其温度降至露点附近(可以为使烟气的温度降至250℃以下，或者使烟气温度降至比其露点温度高5-10℃的程度)，从而使烟气中的二氧化硒在二氧化硫与水蒸汽的共同作用下被还原为可与烟气中汞快速反应的活性单质硒，二氧化硒还原率可达10％以上；活性单质硒在烟气中HCl的作用下，生成易于沉积的氯硒汞化合物；将气相零价汞转化为氯硒汞，汞的转化率可达5-20％；The first step: After the non-ferrous smelting raw flue gas I101 is dusted and recovered by the dust collector 1, a certain amount of water mist I102 is sprayed into it to reduce the temperature to near the dew point (can be to reduce the temperature of the flue gas to 250°C below, or lower the flue gas temperature to 5-10°C higher than its dew point temperature), so that the selenium dioxide in the flue gas is reduced to a state that can quickly react with the mercury in the flue gas under the combined action of sulfur dioxide and water vapor. The reaction's active elemental selenium and selenium dioxide reduction rate can reach more than 10%; under the action of HCl in the flue gas, the active elemental selenium generates chlorine-selenium-mercury compounds that are easy to deposit; the gas phase zero-valent mercury is converted into chlorine-selenium-mercury, mercury The conversion rate can reach 5-20%;
有色冶炼原烟气I101为有色金属冶炼行业所产生的含汞及硫氧化物废气，同时还含有一定量的二氧化硒及氯化氢。经过上游烟气除尘及余热回收，使烟气的温度降至露点附近。烟气中的汞主要以零价汞形式存在，其浓度范围在0.1-50mg/m3；SO2范围浓度为0.2％-5％。SeO2浓度在100-2000mg/m3，HCl浓度在20-500mg/m3。Non-ferrous smelting raw flue gas I101 is waste gas containing mercury and sulfur oxides produced by the non-ferrous metal smelting industry. It also contains a certain amount of selenium dioxide and hydrogen chloride. After upstream flue gas dust removal and waste heat recovery, the temperature of the flue gas is reduced to near the dew point. Mercury in flue gas mainly exists in the form of zero-valent mercury, and its concentration range is 0.1-50mg/m3 ; the SO2 concentration range is 0.2%-5%. The concentration of SeO2 is 100-2000mg/m3 and the concentration of HCl is 20-500mg/m3 .
水雾I102通过高效雾化喷嘴均匀地喷到烟气中，使烟气温度降至比其露点温度高5-10℃的程度。所使用的水可以为工艺水，或为不含颗粒物的酸性废水。Water mist I102 is evenly sprayed into the flue gas through a high-efficiency atomization nozzle, causing the flue gas temperature to drop to 5-10°C higher than its dew point temperature. The water used can be process water or acidic wastewater without particulate matter.
第二步：在其下游烟气中使用有利于单质硒或硒化汞沉积的基质材料2，通过其表面诱导效应，加速氯硒汞的生成及沉积，从而使烟气中的汞被捕集到基质表面；Step 2: Use a matrix material 2 that is conducive to the deposition of elemental selenium or mercury selenide in the downstream flue gas. Through its surface induction effect, it accelerates the generation and deposition of chlorine, selenium and mercury, thereby capturing the mercury in the flue gas. to the substrate surface;
所述的基质材料为氧化铝、氧化锌、二氧化钛及氧化铁等金属氧化物，或活性炭、二氧化硅等多孔材料。可以100-300目的粉状直接喷入烟气中，或制备为直径为2-10mm的球状或柱状颗粒，以固定床或移动床的形式与烟气接触；The matrix material is metal oxides such as aluminum oxide, zinc oxide, titanium dioxide and iron oxide, or porous materials such as activated carbon and silica. It can be directly sprayed into the flue gas in the form of 100-300 mesh powder, or prepared into spherical or columnar particles with a diameter of 2-10mm, and contacted with the flue gas in the form of a fixed bed or a moving bed;
所述的基质材料为粉末或颗粒。当基质为粉状时，喷入烟气中的基质浓度为5-50g/m3，下游配有袋式除尘器收集；当基质为颗粒时，采用固定床或移动床方式对烟气进行处理，所使用的空速(即，每立方米吸附剂在1小时内能够处理的气体体积)为2000-20000h-1，当基质材料上氯硒汞的沉积量达到50g/kg以上时，需要将这部分基质材料取出，并进行再生。The matrix material is powder or granules. When the substrate is powdery, the concentration of the substrate sprayed into the flue gas is 5-50g/m3 , and a bag dust collector is installed downstream for collection; when the substrate is granular, the flue gas is treated using a fixed bed or moving bed method. , the space velocity used (that is, the gas volume that each cubic meter of adsorbent can handle in 1 hour) is 2000-20000h-1 . When the deposition amount of chlorine, selenium and mercury on the matrix material reaches more than 50g/kg, it is necessary to This part of the matrix material is removed and regenerated.
第三步：当烟气中的二氧化硒或HCl不足时，可对上述基质表面继续改性处理，增加其表面上的氯或硒元素的含量，避免将这些物质直接喷入烟气而导致的逃逸及二次污染现象；Step 3: When there is insufficient selenium dioxide or HCl in the flue gas, the surface of the above substrate can be continued to be modified to increase the content of chlorine or selenium on the surface to avoid spraying these substances directly into the flue gas and causing Escape and secondary pollution phenomena;
所述的二氧化硒不足指当烟气自身中二氧化硒浓度低于200mg/m3时，需要对基质材料表面进行增硒调质改性，用5-20％的亚硒酸钠溶液对基质材料进行浸渍改性，使材料负载1-5％硒(以元素硒质量计)，晾干后即可使用。The lack of selenium dioxide means that when the concentration of selenium dioxide in the flue gas itself is lower than 200 mg/m3 , the surface of the matrix material needs to be modified by increasing selenium and using 5-20% sodium selenite solution. The matrix material is impregnated and modified so that the material is loaded with 1-5% selenium (based on the mass of elemental selenium), and can be used after drying.
所述的HCl不足指当烟气自身中HCl浓度低于50mg/m3时，需要对基质材料表面进行增氯调质改性，用5-10％的氯化钠溶液对基质材料进行浸渍改性，使材料负载0.5-2％氯(以元素氯质量计)，晾干后即可使用。The lack of HCl means that when the HCl concentration in the flue gas itself is lower than 50mg/m3 , the surface of the matrix material needs to be modified by adding chlorine and immersed in 5-10% sodium chloride solution. properties, so that the material is loaded with 0.5-2% chlorine (based on the mass of elemental chlorine), and it can be used after drying.
第四步：当基质材料表面上的氯硒汞累积到一定量时，再将其从烟气中取出，并利用加热再生的方法，通过冷凝法对再生出的汞及硒进行分别收集和回收。再生后的基质材料经过表面调质改性后。可循环利用。通过上述方法，可将烟气中汞及硒充分资源化回收，防止汞的二次污染等问题。剩余烟气进入洗涤系统4制酸。Step 4: When the chlorine, selenium and mercury on the surface of the matrix material accumulate to a certain amount, take it out from the flue gas, and use the method of heating and regeneration to collect and recycle the regenerated mercury and selenium respectively through condensation. . The regenerated matrix material has been surface tempered and modified. Can be recycled. Through the above method, mercury and selenium in flue gas can be fully recovered as resources, preventing secondary pollution of mercury and other problems. The remaining flue gas enters the washing system 4 to produce acid.
所述的加热再生方法指在使用氮气保护时将沉积氯硒汞3后的基质材料加热至300-400℃，得到高浓度零价汞及硒单质气体，经逐级降温冷凝及吸附，可分别回收零价汞及硒单质产品。再生过的基质材料2经冷却后及适当调质改性后可循环使用。The heating regeneration method refers to heating the matrix material after depositing chlorine, selenium and mercury 3 to 300-400°C while using nitrogen protection to obtain high-concentration zero-valent mercury and selenium elemental gases. After step-by-step cooling, condensation and adsorption, they can be produced respectively. Recover zero-price mercury and selenium elemental products. The regenerated matrix material 2 can be recycled after being cooled and appropriately tempered and modified.
实施例1Example 1
一种增硒调质的基质材料的制备方法及捕汞实验，包括以下步骤：A method for preparing a selenium-enhanced and tempered matrix material and a mercury capture experiment, including the following steps:
1)配置0,0.1,0.25,0.5,1mol/L的Na2SeO3溶液；1) Configure 0, 0.1, 0.25, 0.5, 1mol/L Na2 SeO3 solution;
2)称取100g 1-2mm的Al2O3小球，分别加入75mL上述溶液，超声1h后，80℃干燥12h，得到增硒材料；2) Weigh 100g of 1-2mm Al2 O3 pellets, add 75 mL of the above solution respectively, ultrasonic for 1 hour, and dry at 80°C for 12 hours to obtain the selenium-enhancing material;
3)称取0.5g材料于10mm石英反应管中，控制进口Hg0浓度为1.2mg/m3,SO2浓度为5％，H2O含量为4％，O2含量10％，总流量为300mL/min，反应温度80℃；3) Weigh 0.5g of material into a 10mm quartz reaction tube, control the inlet Hg0 concentration to 1.2 mg/m3 , SO2 concentration to 5%, H2 O content to 4%, O2 content to 10%, and the total flow rate is 300mL/min, reaction temperature 80℃;
4)当不添加HCl时，随着NaSeO3负载比例的增加，Hg0的3h的去除效率分别为5％，23％，36％，48％，67％；4) When no HCl is added, as the loading ratio of NaSeO3 increases, the removal efficiency of Hg0 in 3 h is 5%, 23%, 36%, 48%, and 67% respectively;
5)当添加100ppm HCl时，随着NaSeO3负载比例的增加，Hg0的3h的去除效率分别为12％，55％，78％，83％，96％。5) When 100ppm HCl is added, as the NaSeO3 loading ratio increases, the removal efficiency of Hg0 in 3h is 12%, 55%, 78%, 83%, 96% respectively.
实施例2Example 2
一种增氯调质的基质材料的制备方法及捕汞实验，包括以下步骤：A preparation method of chlorine-added and tempered matrix material and a mercury capture experiment, including the following steps:
1)配置0,0.1,0.25,0.5,1mol/L的NaCl溶液；1) Configure 0, 0.1, 0.25, 0.5, 1 mol/L NaCl solution;
2)称取100g 1-2mm的Al2O3小球，分别加入75mL上述溶液，超声1h后，80℃干燥12h，得到增氯材料；2) Weigh 100g of 1-2mm Al2 O3 pellets, add 75 mL of the above solution respectively, and after ultrasonic for 1 hour, dry at 80°C for 12 hours to obtain the chlorine-increasing material;
3)称取0.5g材料于10mm石英反应管中，控制进口Hg0浓度为1.2mg/m3,SO2浓度为5％，H2O含量为4％，O2含量10％，总流量为300mL/min，反应温度80℃；3) Weigh 0.5g of material into a 10mm quartz reaction tube, control the inlet Hg0 concentration to 1.2 mg/m3 , SO2 concentration to 5%, H2 O content to 4%, O2 content to 10%, and the total flow rate is 300mL/min, reaction temperature 80℃;
4)当不添加SeO2时，Hg0的3h的去除效率均低于10％4) WhenSeO2 is not added, the removal efficiency ofHg0 for 3h is less than 10%
5)当添加300mg/m3 SeO2时，随着NaCl负载比例的增加，Hg0的3h的去除效率分别为46％，68％，79％，88％，97％。5) When 300 mg/m3 SeO2 is added, as the NaCl loading ratio increases, the removal efficiency of Hg0 in 3 h is 46%, 68%, 79%, 88%, and 97% respectively.
实施例3Example 3
一种同时增硒增氯调质的基质材料的制备方法及捕汞实验，包括以下步骤：A preparation method and mercury capture experiment of a matrix material that is tempered by adding selenium and chlorine at the same time, including the following steps:
1)分别称取0.01mol NaSeO3,0.0075mol NaSeO3+0.0025mol NaCl，0.005molNaSeO3+0.005mol NaCl，0.0025mol NaSeO3+0.0075mol NaCl，0.01mol NaCl，加入15mL去离子水，超声溶解；1) Weigh 0.01mol NaSeO3 , 0.0075mol NaSeO3 +0.0025mol NaCl, 0.005molNaSeO3 +0.005mol NaCl, 0.0025mol NaSeO3 +0.0075mol NaCl, 0.01mol NaCl respectively, add 15mL deionized water, and dissolve with ultrasound;
2)分别称取2 0g 1-2mm的Al2O3小球，加入上述溶液中，超声1h后，80℃干燥12h，得到增硒增氯材料；2) Weigh 20g of 1-2mm Al2 O3 pellets respectively, add them to the above solution, ultrasonic for 1 hour, and dry at 80°C for 12 hours to obtain the selenium-enhancing and chlorine-enhancing material;
3)称取0.5g材料于10mm石英反应管中，控制进口Hg0浓度为1.2mg/m3,H2O含量为4％，O2含量10％，总流量为300mL/min，反应温度80℃；3) Weigh 0.5g of material into a 10mm quartz reaction tube, control the inlet Hg0 concentration to 1.2mg/m3 , H2 O content to 4%, O2 content to 10%, the total flow rate to 300mL/min, and the reaction temperature to 80 ℃;
4)当不添加SO2时，Hg0的去除效率均低于5％4) When noSO2 is added, the removal efficiency ofHg0 is less than 5%
5)当添加5000ppm SO2时，随着Se/Cl比值的增加，Hg0的3h的去除效率分别为53％，68％，85％，99％，30％。5) When 5000ppmSO2 is added, as the Se/Cl ratio increases, the removal efficiency ofHg0 in 3h is 53%, 68%, 85%, 99%, and 30% respectively.
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