WO2014201782A1 - 脱汞剂及其制备方法 - Google Patents

脱汞剂及其制备方法 Download PDF

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WO2014201782A1
WO2014201782A1 PCT/CN2013/084801 CN2013084801W WO2014201782A1 WO 2014201782 A1 WO2014201782 A1 WO 2014201782A1 CN 2013084801 W CN2013084801 W CN 2013084801W WO 2014201782 A1 WO2014201782 A1 WO 2014201782A1
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carrier
mercury
mercury removal
removal agent
oxide
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PCT/CN2013/084801
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English (en)
French (fr)
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肖天存
黄瑜
陈浩逸
张钢
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广州博能能源科技有限公司
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Publication of WO2014201782A1 publication Critical patent/WO2014201782A1/zh

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    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
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    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/64—Heavy metals or compounds thereof, e.g. mercury
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    • B01D2257/602—Mercury or mercury compounds
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Definitions

  • the invention relates to the field of gas chemical adsorption purification, in particular to a mercury removal agent for removing mercury metal in flue gas, syngas and natural gas and liquid substances and a preparation method thereof.
  • mercury is released during the utilization of coal combustion, gasification to syngas and natural gas extraction.
  • the mercury mainly exists in three forms, elemental mercury (Hg D ), oxidized mercury (Hg 2+ ) and particulate state.
  • Mercury (Hg P ) Due to its low melting point, high volatility and poor solubility in water, Hg Q is difficult to be captured by dust removal equipment and discharged into the atmosphere. The form is relatively stable.
  • mercury emissions from coal combustion have become the largest source of anthropogenic mercury pollution. China's energy consumption is dominated by coal, and controlling mercury emissions from coal combustion is an environmental problem that China urgently needs to solve. Therefore, the development of promising mercury control technologies to effectively remove mercury from coal, syngas and natural gas, especially Hg Q, is one of the urgent problems to be solved in environmental pollution control.
  • the mercury removal agent disclosed in the prior art has an unsatisfactory mercury removal performance, because the mercury removal capacity and mercury removal efficiency of the mercury removal agent are small, and many mercury removal agents require vulcanization to function. Therefore, there may be secondary pollution problems not only in the preparation or use of the adsorbent.
  • the single metal mercury removal agent currently used has low oxidation ability, and it is difficult to convert metallic mercury into low-vapor oxidation state. Therefore, there is an urgent need for a multi-metal active mercury removal agent that is high in performance without secondary pollution. Summary of the invention
  • the present invention provides a mercury removal agent and a preparation method thereof.
  • a mercury removal agent comprising 40-90% by weight of a carrier, 1-40% by weight of an active component and 0-30% by weight of a modified urethane ;
  • the modifier is a halogen or a halide
  • the active component is a mixture of at least two oxidizing metal oxides; the modifier enhances the ability to oxidize elemental mercury by a chemical reaction, thereby correspondingly increasing the amount of oxidized and fixed mercury , which is conducive to the efficiency of mercury removal and the improvement of mercury content.
  • the halogen is liquid bromine
  • the halide is a soluble bromine salt.
  • the bromine salt is ammonium bromide, potassium bromide or sodium bromide.
  • the oxidizing metal oxide is manganese dioxide, cobalt oxide, cerium oxide, iron oxide, tungsten oxide, molybdenum oxide, copper oxide or nickel oxide.
  • the carrier is at least one of activated alumina, modified activated alumina, silica, kaolin, diatomaceous earth, activated carbon, aluminum hydroxide or molecular sieve; preferably activated alumina, modified Activated alumina or activated carbon.
  • the modifier is from 0 to 25 wt% by weight; preferably, the modifier has a weight percentage of from 5 to 21 wt%.
  • the active component has a weight percentage of 5 to 35 wt%; the carrier has a weight percentage of 50 to 80 wt%; and the carrier has a specific surface area of 20 to 500 m 2 /g, pore volume It is 0.1-1.0 cm 3 /g; preferably, the active component is 10-35 wt% by weight; the carrier is 55-75 wt% by weight; the carrier can increase the active group in the mercury removal agent The dispersion of the fraction, its contact absorption area with mercury, and the amount of mercury adsorbed, thereby improving the mercury removal efficiency of the mercury removal agent.
  • the carrier has a specific surface area of 50-450 m 2 /g and a pore volume of 0.2-0.7 cm 3 /g; the specific surface area and pore volume of the carrier further contribute to the improvement of the mercury removal agent. Mercury capacity and mercury removal efficiency.
  • the preparation method of the above mercury removal agent comprises the following steps:
  • the carrier is placed in a solution of a soluble metal salt, and immersed for l-24 hours to obtain a supported salt carrier;
  • the supported salt carrier obtained in the step (1) is dried or calcined, it is placed in one or two or more kinds of soluble metal salt solutions other than the soluble metal salt described in the step (1), and immersed for l-24h. After drying, calcination at 350-600 ° C for 2-10 h under aerobic conditions (with oxygen as a carrier, without oxygen), to obtain a supported metal oxide support after calcination;
  • the calcined supported metal oxide support obtained in the step (2) is placed in a modifier solution, immersed for l-24 hours, dried, and then calcined at 100-300 ° C for l-6 h.
  • the above supported metal oxide carrier may be further immersed, dried, and calcined in a modifier solution.
  • the soluble metal salt is a nitrate, a sulfate, an organic acid salt or a halogenated salt of an oxidizing metal oxide;
  • the oxidizing metal oxide is a soluble oxidized metal salt prepared by calcination Into
  • the above organic acid salts include: formate, acetate, citrate, oxalate, and the like. Of course, it is not limited to the above salts, and various organic acid salts which can stably form a solution with the solvent used are included.
  • the drying in step (2) and step (3) is carried out at a temperature of from 50 to 200 ° C for a period of from 1 to 8 hours; preferably at a temperature of from 100 to 120 ° C.
  • the mercury removal agent of the present invention contains no sulfur, and has an oxidizing metal oxide as an active component, a halogen or a halide as a modifier, and the mercury removal agent obtained has a mercury content of more than 10% by weight. And the mercury removal efficiency is over 99.9%.
  • the mercury removal agent of the present invention can be widely applied to the removal process of mercury metal in a mercury-containing gas source in flue gas, syngas and natural gas, and liquid substances.
  • the preparation method of the present invention is preferably an aqueous solution impregnation method, and the active component is an oxidized metal oxide.
  • the preparation process does not need to be vulcanized as many existing mercury removal agents to function, and is flexible in carrier selection. According to the needs, it is possible to flexibly prepare a mercury removal agent suitable for different performances in different occasions. detailed description
  • the invention adopts the active component to be supported on the carrier, and can be modified by using a modifier to achieve the removal of mercury; wherein the carrier comprises activated alumina, modified activated alumina, kaolin, diatomaceous earth, Activated carbon, aluminum hydroxide, molecular sieve, etc., the active component is a compound of a transition metal element such as manganese dioxide, cobalt oxide, cerium oxide, iron oxide, tungsten oxide, molybdenum oxide, copper oxide and nickel oxide, and the modifier is halogen and A halide that converts mercury vapor into an oxidizing oxidant by an oxidation mechanism.
  • the carrier comprises activated alumina, modified activated alumina, kaolin, diatomaceous earth, Activated carbon, aluminum hydroxide, molecular sieve, etc.
  • the active component is a compound of a transition metal element such as manganese dioxide, cobalt oxide, cerium oxide, iron oxide, tungsten oxide, molybdenum oxide, copper oxide
  • the halide of the present invention means a chloride, a bromide or an iodide
  • the halogen means fluorine, chlorine, bromine or iodine
  • the halogenated salt refers to ammonium chloride, potassium chloride, ammonium bromide, sodium bromide or potassium bromide;
  • the molecular sieve refers to a molecular sieve of series A, X series, Y. series, ZSM, etc.;
  • activated alumina was purchased from Qingdao Lianxin Chemical Co., Ltd. and Chinalco's Zibo Aluminum Plant;
  • the modified activated alumina is modified with activated carbon such as titanium oxide, alkali metal such as potassium or sodium, alkaline earth metal such as calcium, magnesium or barium.
  • activated carbon such as titanium oxide, alkali metal such as potassium or sodium, alkaline earth metal such as calcium, magnesium or barium.
  • titanium-containing activated alumina is purchased from Qingdao Lianxin Chemical Company. The invention will be further described below in conjunction with specific embodiments.
  • Example 1 A mercury removal agent comprising 90 wt% of an activated alumina carrier, 5 wt% of manganese dioxide and 5 % of a cobalt oxide active component; and a preparation method of the mercury removal agent comprising the following steps:
  • a mercury removal agent comprising 56% of activated carbon carrier, 14% by weight of copper oxide and 18% of manganese dioxide active component, 12wt%/H 4 Cl modifier; preparation method of the mercury removal agent, Including the following steps:
  • the carrier obtained in the step (1) is dried at 100 ° C for 5 hours to remove water in the carrier, and the dried copper nitrate-loaded activated carbon carrier is placed in 12 ml containing 29.1 g of MnCl 2 ⁇ 4 ⁇ 2 0
  • the solution was immersed for 12 hours, and the carrier was taken out, dried at 120 ° C for 6 hours, and calcined and activated at 450 ° C for 3 hours under anaerobic conditions to decompose the chloride salt and further obtain copper oxide supported thereon.
  • an activated carbon carrier of the active component of manganese dioxide is an activated carbon carrier of the active component of manganese dioxide;
  • a mercury removal agent comprising 60% by weight of a titanium-containing activated alumina carrier, 22% by weight of copper oxide and 12% by weight of a manganese dioxide active component, and 6% by weight of a 3 ⁇ 4B r modifier; a method for preparing the mercury removal agent, Including the following steps: (1) 40g of titanium-containing activated alumina having a specific surface of 240-60 mesh, a specific surface area of 240 m 2 /g, and a pore volume of 0.4 cm 3 /g is placed in 20 ml of 36.2 g (CH 3 COO) 2 Cu ⁇ ⁇ 2 0 In the solution, immersed for 10 hours, after the above immersion liquid is completely immersed in the carrier, the carrier is taken out;
  • a mercury removal agent comprising 70% by weight of a titanium-containing activated alumina carrier, 21% by weight of copper oxide and 9% by weight of a manganese dioxide active component; and a method for preparing the mercury removal agent, comprising the steps of:
  • Example 5 (2) drying at 110 ° C for 6 hours, removing the water in the carrier, and then placing the dried copper-containing activated alumina carrier loaded with copper acetate in 18 ml of a solution containing 12.4 g of MnCl 2 ⁇ 4 ⁇ 2 0 After immersing for 10 hours, the carrier was taken out, dried at 110 ° C for 5 hours, and then calcined and activated at 350 ° C for 3 hours under aerobic conditions to decompose the acetate and the chloride salt, and further obtained a load.
  • Example 5 The titanium-containing activated alumina support of the active component of copper oxide and manganese dioxide, i.e., a mercury removal agent
  • a mercury removal agent comprising 75 wt% of an activated alumina carrier, 14 wt% of cobalt oxide and 11% of a molybdenum oxide active component; and a method for preparing the mercury removal agent, comprising the steps of: (1) 40 g of activated alumina having a 40-60 mesh, specific surface area of 200 m 2 /g and a pore volume of 0.8 cm 3 /g is placed in 25 ml of a solution containing 38.6 g of Co(N0 3 ) 2 .6H 2 0. After immersing for 12 hours, after the above immersion liquid is completely immersed in the carrier, the carrier is taken out;
  • Example 6 (2) drying at 100 ° C for 5 hours, removing the water in the carrier, and then adding the dried cobalt oxide-loaded activated alumina carrier to 15 ml containing 7.2 g ( ⁇ 4 ) 6 ⁇ ⁇ 7 0 24 ⁇ 4 ⁇ 20 was, for 12 hours, the carrier removed, dried at 120 ° C 6 hours, and then under aerobic conditions, activated for 4 hours at 400 ° C firing, so that the decomposition of cobalt nitrate and ammonium molybdate, and Further, an activated alumina carrier carrying an active component of cobalt oxide and molybdenum oxide is obtained, that is, a mercury removal agent is obtained, which is designated as E.
  • Example 6 Example 6
  • a mercury removal agent comprising 60% by weight of a titanium-containing activated alumina carrier, 10% by weight of molybdenum oxide and 10% by weight of manganese dioxide active component, and 20% by weight of Br 2 modifier; a method for preparing the mercury removal agent, Including the following steps:
  • the carrier was taken out, dried at 120 ° C for 6 h, and then calcined and activated at 450 ° C for 5 hours under aerobic conditions to decompose manganese chloride and further obtain activity of supporting molybdenum oxide and manganese dioxide.
  • a titanium-containing activated alumina carrier of the component a titanium-containing activated alumina carrier of the component;
  • the mercury removal agent particles prepared in the above Examples 1 to 6 were filled in a 1.5 ml mercury removal purification bed having an inner diameter of 6 mm. Under the conditions of normal temperature, normal pressure and volumetric space velocity of ⁇ 1 , the mercury removal effect of the mercury removal agent is carried out by using methane containing 70 ppm of hydrogen sulfide and 10500 ⁇ g of ⁇ / ⁇ 3 ( ⁇ 2%). The evaluation was carried out, and the results obtained are shown in Table 1.
  • the mercury removal agent prepared by the present invention has a remarkable mercury removal effect, and the mercury content can be up to 10% by weight, and the mercury removal rate can be up to 99.999%.
  • the mercury removal rate refers to the percentage of mercury removed and the amount of mercury in the raw gas source. It can be seen that the mercury removal agent used in the present invention has high mercury removal activity, that is, high mercury capacity and high mercury removal efficiency.

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Abstract

本发明公开了一种脱汞剂及其制备方法，所述脱汞剂包括40-90wt%的载体、1-40wt%的活性组分和0-30wt%的改性剂；所述改性剂为卤素或卤化物；所述活性组分为至少两种的氧化性金属氧化物的混合物；所述制备方法为：将载体置于一种或多种可溶的氧化性金属盐溶液中，浸渍干燥，煅烧，再置于除上述可溶性金属盐外的一种或两种以上的可溶性金属盐溶液中，浸渍、干燥、煅烧，即可。本发明所述脱汞剂不需要硫化，其以氧化性金属氧化物作为活性组分，卤素或卤化物作为改性剂，具有大于10wt%的汞容，且脱汞效率达99.9%以上的有益效果，还可广泛应用于烟气、合成气和天然气以及液态物质中含汞气源中汞金属的脱除工艺中。

Description

脱汞剂及其制备方法 技术领域
本发明涉及气体化学吸附净化领域， 特别是涉及一种用于烟气、 合成气和天然气以及液 态物质中汞金属脱除的脱汞剂及其制备方法。 背景技术
目前， 由于煤炭燃烧、 气化制合成气和天然气开采等利用过程中释放汞， 其中， 该汞主 要以三种形态存在， 元素汞 (HgD)、 氧化态汞 (Hg2+ )和颗粒态汞 (HgP)。 HgQ由于其熔点低、 挥 发性高和难溶于水等特点， 很难被除尘设备捕获， 排放到大气中， 形态相对比较稳定， 目前 燃煤汞排放已经成为最大的人为汞污染排放源， 中国的能源消耗以煤为主， 控制燃煤汞排放 是我国急需解决的环境问题。 因此， 开发有发展前景的汞控制技术来有效脱除煤气、 合成气 和天然气中的汞， 特别是 HgQ是环境污染治理急需解决的问题之一。
而目前现有技术中公开的脱汞剂， 其脱汞性能不理想， 由于该种脱汞剂的汞容和脱汞效 率都较小， 且很多的脱汞剂都需要硫化才能起作用， 这使得不仅在吸附剂的制备还是使用中 都可能存在二次污染问题. 另外,目前所采用的单金属脱汞剂的氧化能力低， 难于把金属态的 汞转化为蒸汽压低的氧化态的汞， 所以迫切需要一种高性能而又不产生二次污染的多金属活 性 脱汞剂。 发明内容
基于此， 本发明提供一种脱汞剂及其制备方法。
解决上述技术问题的具体技术方案如下：
一种脱汞剂， 所述脱汞剂包括 40-90 ^%的载体、 l-40wt%的活性组分和 0-30 wt%的改性 齐 U; 所述改性剂为卤素或卤化物； 所述活性组分为至少两种的氧化性金属氧化物的混合物； 所述改性剂可通过化学反应加强了氧化单质汞的能力， 也就相应增大了被氧化并固定的汞的 量， 有利于脱汞效率和汞容的提高。
在其中一些实施例中， 所述卤素为液溴， 所述卤化物为可溶的溴盐。 在其中一些实施例中， 所述溴盐为溴化铵、 溴化钾或溴化钠。
在其中一些实施例中， 所述氧化性金属氧化物为二氧化锰、 氧化钴、 氧化铈、 氧化铁、 氧化钨、 氧化钼、 氧化铜或氧化镍。
在其中一些实施例中， 所述载体为活性氧化铝、 改性活性氧化铝、 氧化硅、 高岭土、 硅 藻土、 活性炭、 氢氧化铝或分子筛中的至少一种； 优选活性氧化铝、 改性活性氧化铝或活性 炭。
在其中一些实施例中， 所述改性剂的重量百分比为 0-25wt%; 优选的， 改性剂的重量百 分比为 5-21 wt%。
在其中一些实施例中， 所述活性组分的重量百分比为 5-35 wt%; 所述载体的重量百分比 为 50-80wt%; 所述载体的比表面积为 20-500m2/g， 孔容为 0.1-1.0cm3/g; 优选的， 所述活性组 分的重量百分比为 10-35 wt%；所述载体的重量百分比为 55-75wt%；所述载体可提高脱汞剂中 活性组分的分散度， 及其与汞的接触吸收面积， 以及汞的吸附量， 从而提高了脱汞剂的脱汞 效率。
在其中一些实施例中， 所述载体的比表面积为 50-450m2/g， 孔容为 0.2-0.7cm3/g; 所述载 体的比表面积和孔容更有助于提高脱汞剂的汞容和脱汞效率。
上述脱汞剂的制备方法， 包括如下步骤：
( 1 ) 将载体置于一种可溶性金属盐的溶液中， 浸渍 l-24h， 得负载盐载体；
(2)将步骤（1 )所得的负载盐载体干燥或焙烧后， 置于除步骤（1 )所述的可溶性金属 盐外的一种或两种以上的可溶性金属盐溶液中， 浸渍 l-24h后干燥， 在有氧（在用活性炭作为 载体时， 无氧） 条件下， 于 350-600°C下煅烧 2-10h， 得煅烧后的负载金属氧化物载体；
( 3 ) 将步骤 （2) 所得的煅烧后的负载金属氧化物载体置于改性剂溶液中， 浸渍 l-24h 后干燥， 再于 100-300°C下焙烧 l-6h， 即可。 有时为了增加汞容， 可以把以上负载金属氧化物 载体再置于改性剂溶液中浸渍、 干燥、 焙烧。
在其中一些实施例中， 所述可溶性金属盐为氧化性金属氧化物的硝酸盐、 硫酸盐、 有机 酸盐或卤化盐； 所述氧化性金属氧化物是可溶的氧化金属盐经煅烧制备而成的；
以上所述有机酸盐包括： 甲酸盐、 乙酸盐、 柠檬酸盐、 草酸盐等。 当然并不局限于以上 几种盐类， 各种能和所用溶剂稳定形成溶液的有机酸盐都包括在内。 在其中一些实施例中， 步骤（2)和步骤（3 )中所述干燥的温度为 50-200°C， 时间为 l-8h; 优选温度为 100- 120 °C。
本发明一种脱汞剂及其制备方法具有以下优点和有益效果：
( 1 ) 本发明所述的脱汞剂不含硫， 其以氧化性金属氧化物作为活性组分， 卤素或卤化物 作为改性剂， 制得的脱汞剂具有大于 10^%的汞容， 且脱汞效率达 99.9%以上。
(2) 本发明所述脱汞剂可广泛应用于烟气、 合成气和天然气以及液态物质中含汞气源中 汞金属的脱除工艺中。
( 3 ) 本发明所述制备方法优选水溶液浸渍法， 活性组分为氧化态的金属氧化物， 制备过 程不需要像很多现有脱汞剂一样需要进行硫化才能起作用， 在载体选择方面较为灵活， 根据 需要， 可灵活制备出适用于不同场合具备不同性能的脱汞剂。 具体实施方式
本发明采用将活性组分负载于载体之上， 并可选用改性剂进行改性以便实现其对汞的脱 除； 其中载体包括活性氧化铝、 改性活性氧化铝、 高岭土、 硅藻土、 活性炭、 氢氧化铝、 分 子筛等， 活性组分选用二氧化锰、 氧化钴、 氧化铈、 氧化铁、 氧化钨、 氧化钼， 氧化铜和氧 化镍等过渡金属元素的化合物， 改性剂为卤素和卤化物， 通过氧化机理把汞蒸气转化为氧化 隶。
本发明所述卤化物是指氯化物、 溴化物或碘化物；
所述卤素是指氟、 氯、 溴或碘；
所述卤化盐是指氯化铵、 氯化钾、 溴化铵、 溴化钠或溴化钾等；
所述分子筛是指 A系列、 X系列、 Y.系列、 ZSM等系列的分子筛；
下述实施例中活性氧化铝购自青岛联信化学公司以及中国铝业淄博铝厂；
改性活性氧化铝为用氧化钛， 碱金属如钾或钠， 碱土金属如钙、 镁或钡等对活性氧化铝 进行改性， 如： 含钛活性氧化铝购自青岛联信化学公司。 以下将结合具体实施例对本发明做进一步说明。
实施例 1 一种脱汞剂， 包括 90wt%的活性氧化铝载体、 5wt%的二氧化锰和 5^%的氧化钴活性组 分； 该种脱汞剂的制备方法， 包括如下步骤：
( 1 ) 选取 40-60 目， 比表面为 80m2/g、 孔容为 0.1 cm3/g的活性氧化铝载体 40g， 放入 20ml含有 7.0g CoCl2 ·6Η20的溶液中， 浸渍 1小时， 待上述浸渍液完全浸入载体后， 将载体 取出；
(2) 于 110°C下将步骤 （1 ) 所得的载体干燥 8小时， 除去载体中水分， 再将经过干燥 后的负载有氯化钴的活性氧化铝载体放入含有 5.1g MnCl2*4H20的溶液中， 浸渍 24小时， 将 载体取出， 于 120°C干燥 1小时， 在有氧条件下， 于 400°C下焙烧活化 2小时， 使得氯化盐分 解， 并进而得到负载有二氧化锰和氧化钴活性组分的活性氧化铝载体， 即得到脱汞剂， 记为 A。 实施例 2
一种脱汞剂， 包括 56^%的活性炭载体、 14wt%的氧化铜和 18^%的二氧化锰活性组分、 12wt°/ H4Cl改性剂； 该种脱汞剂的制备方法， 包括如下步骤：
( 1 )取 40-60目、 比表面为 400m2/g、孔容为 1.0cm3/g的活性炭载体 40g放入 15ml含有
30.5g Cu(NO3)2*3H2O的溶液中， 浸渍 12小时， 待上述浸渍液完全浸入载体后， 将载体取出；
(2) 于 100°C下将步骤 （1 ) 所得的载体干燥 5小时， 除去载体中水分， 再将经过干燥 后的负载有硝酸铜的活性炭载体放入 12ml含有 29.1g MnCl2 ·4Η20的溶液中， 浸渍 12小时， 将此载体取出， 于 120°C干燥 6小时， 在无氧条件下， 于 450°C下焙烧活化 3小时， 使得氯化 盐分解， 并进而得到负载有氧化铜和二氧化锰活性组分的活性炭载体；
(3 ) 将上述负载有活性组分的载体放入 10ml含 8.7g H4C1的溶液中， 浸渍 10小时， 将载体取出， 于 100°C干燥 3小时， 之后在无氧条件下， 于 200°C下焙烧活化 3小时， 即得到 脱汞剂， 记为 B。 实施例 3
一种脱汞剂， 包括 60wt%的含钛活性氧化铝载体、 22wt%的氧化铜和 12wt%的二氧化锰 活性组分、 6wt% ¾Br改性剂； 该种脱汞剂的制备方法， 包括如下步骤： ( 1 )取 40-60目、 比表面为 240m2/g、 孔容为 0.4cm3/g的含钛活性氧化铝 40g放入 20ml 含有 36.2g (CH3COO)2Cu ·Η20的溶液中， 浸渍 10小时， 待上述浸渍液完全浸入载体后， 将 载体取出；
(2) 于 110°C下干燥 6小时， 除去载体中水分， 再将经过干燥后的负载有醋酸铜的含钛 活性氧化铝载体放入 15ml含有 19.1g MnCl2 ·4Η20的溶液中， 浸渍 10小时， 将载体取出， 于 120°C干燥 6小时， 之后在有氧条件下， 于 400°C下焙烧活化 4小时， 使得醋酸盐和氯化盐分 解， 并进而得到负载有氧化铜和二氧化锰活性组分的含钛活性氧化铝载体；
(3 ) 将上述负载有活性组分的载体放入 12ml含 3.9g H4Br的溶液中， 浸渍 10小时， 将载体取出， 于 120°C干燥 3小时， 之后在有氧条件下， 于 250°C下焙烧活化 1小时， 即得到 脱汞剂， 记为 C。 实施例 4
一种脱汞剂， 包括 70wt%的含钛活性氧化铝载体、 21wt%的氧化铜和 9wt%的二氧化锰活 性组分； 该种脱汞剂的制备方法， 包括如下步骤：
( 1 ) 取 40-60目、 比表面为 280m2/g、 孔容为 0.6cm3/g的含钛活性氧化铝 40g放入 25ml 含有 26.5g CuCl2 ·2Η20的溶液中， 浸渍 12小时， 待上述浸渍液完全浸入载体后， 将载体取 出；
(2) 于 110°C下干燥 6小时， 除去载体中水分， 之后再将经过干燥后的负载有醋酸铜的 含钛活性氧化铝载体放入 18ml含有 12.4g MnCl2 ·4Η20的溶液中，浸渍 10小时，将此载体取 出， 于 110°C干燥 5小时， 之后在有氧条件下， 于 350°C下焙烧活化 3小时， 使得醋酸盐和氯 化盐分解， 并进而得到负载有氧化铜和二氧化锰活性组分的含钛活性氧化铝载体， 即得到脱 汞剂， 记为 D。 实施例 5
—种脱汞剂， 包括 75wt%的活性氧化铝载体、 14wt%的氧化钴和 11^%的氧化钼活性组 分； 该种脱汞剂的制备方法， 包括如下步骤： ( 1 ) 取 40-60目、 比表面为 200m2/g、 孔容为 0.8cm3/g的活性氧化铝 40g放入 25ml含有 38.6g Co(N03)2.6H20的溶液中， 浸渍 12小时， 待上述浸渍液完全浸入载体后， 将载体取出；
(2) 于 100°C下干燥 5小时， 除去载体中水分， 之后再将经过干燥后的负载有硝酸钴的 活性氧化铝载体放入 15ml含有 7.2g (ΝΗ4)6Μο7024·4Η20的溶液中， 浸渍 12小时， 将此载体 取出， 于 120°C干燥 6小时， 之后在有氧条件下， 于 400°C下焙烧活化 4小时， 使得硝酸钴和 钼酸铵分解， 并进而得到负载有氧化钴和氧化钼活性组分的活性氧化铝载体， 即得到脱汞剂， 记为 E。 实施例 6
一种脱汞剂， 包括 60wt%的含钛活性氧化铝载体、 10wt%的氧化钼和 10wt%二氧化锰活 性组分， 及 20wt%Br2改性剂； 该种脱汞剂的制备方法， 包括如下步骤：
( 1 )取 40-60目、 比表面为 80m2/g、孔容为 0.75cm3/g的含钛活性氧化铝 6.5g放入 25ml 含有 (ΝΗ4)6Μο7024·4Η20的溶液中， 浸渍 24小时， 待上述浸渍液完全浸入载体后， 将此载体 取出， 于 110°C干燥 6小时， 再于空气中 400°C焙烧 3小时， 得到负载氧化钼的载体；
(2) 将上述得到的负载氧化钼的载体放入 15ml含有 12.2gMnCl2*4H20的溶液中， 浸渍
12小时， 将此载体取出， 于 120°C干燥 6h， 之后在有氧条件下， 于 450°C下焙烧活化 5小时， 使得氯化锰分解， 并进而得到负载有氧化钼和二氧化锰活性组分的含钛活性氧化铝载体；
( 3 ) 将上述负载有活性组分的载体放入 12ml含 13.3g Br2的溶液中， 浸渍 10小时， 将 载体取出， 于 120°C干燥 3小时， 之后在有氧条件下， 于 250°C下焙烧活化 1小时， 即得到脱 汞剂， 记为 F。 实施例 7 活性评价
一、 评价方法
将上述实施例 1~6制备得到的脱汞剂颗粒填充至内径为 6mm的 1.5ml脱汞净化床内。在 常温、常压、体积空速为 δΟΟΟΐΤ1的条件下，以含有硫化氢 70ppm和汞浓度为 10500μ§/ιη3(±2%) 的甲烷经过该净化床， 对脱汞剂的脱汞效果进行评价， 所得到的结果如表 1。
二、 评价结果 表 1 净化前后脱汞效果对比结果
Figure imgf000008_0001
从表 1可知， 本发明制备得到的脱汞剂脱汞效果很显著， 汞容最高可达到 10wt%以上， 脱汞率最高可到 99.999%。 所述脱汞率是指脱除的汞的量与原气源中汞的量的百分比。 可见， 使用本发明所述的脱汞剂具有较高的脱汞活性， 即汞容高和脱汞效率高。 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

权利 要 求
1、 一种脱汞剂， 其特征在于， 所述脱汞剂包括 40-90 ^%的载体、 l-40wt%的活性组分 和 0-30wt%的改性剂； 所述改性剂为卤素或卤化物； 所述活性组分为至少两种的氧化性金属 氧化物的混合物。
2、 根据权利要求 1所述的脱汞剂， 其特征在于， 所述卤素为液溴， 所述卤化物为可溶的 溴盐。
3、 根据权利要求 2所述的脱汞剂， 其特征在于， 所述溴盐为溴化铵、 溴化钾或溴化钠。
4、 根据权利要求 1所述的脱汞剂， 其特征在于， 所述氧化性金属氧化物为氧化锰、 氧化 钴、 氧化铁、 氧化钨、 氧化铈、 氧化钼、 氧化铜或氧化镍； 所述载体为活性氧化铝、 改性活 性氧化铝、 二氧化硅、 高岭土、 硅藻土、 活性炭、 氢氧化铝或分子筛中的至少一种。
5、 根据权利要求 1所述的脱汞剂， 其特征在于， 所述活性组分的重量百分比为 5-35wt%； 所述载体的重量百分比为 50-80wt%； 改性剂的重量百分比为 0-25wt%。
6、 根据权利要求 5所述的脱汞剂， 其特征在于， 所述载体的比表面积为 20-500m2/g， 孔 容为 0.1-1.0cm3/g。
7、 根据权利要求 6所述的脱汞剂， 其特征在于， 所述载体的比表面积为 50-450m2/g， 孔 容为 0.2-0.7cm3/g。
8、 根据权利要求 1-7任一项所述脱汞剂的制备方法， 其特征在于， 包括如下步骤： ( 1 ) 将载体置于一种或多种可溶性金属盐的溶液中， 浸渍 l-24h， 得负载盐载体； (2)将步骤（1 )所得的负载盐载体干燥或焙烧后， 置于除步骤（1 )所述的可溶性金属 盐外的一种或两种以上的可溶性金属盐溶液中， 浸渍 l-24h后干燥， 于 350-600°C煅烧 2-10h， 得煅烧后的负载氧化性金属氧化物的载体；
(3 ) 将步骤 （2) 所得的煅烧后的负载氧化性金属氧化物的载体置于改性剂溶液中， 浸 渍 l-24h后干燥， 再于 100-300°C下焙烧 l-6h， 即可。
9、 根据权利要求 8所述的脱汞剂的制备方法， 其特征在于， 所述可溶性金属盐为氧化性 金属氧化物的硝酸盐、 硫酸盐、 有机酸盐或 ¾化盐。
10、 根据权利要求 9所述脱汞剂的制备方法， 其特征在于， 步骤 （2)和步骤 （3 ) 中所述 干燥的温度为 50-200 °C， 时间为 l-8h。
PCT/CN2013/084801 2013-06-18 2013-09-30 脱汞剂及其制备方法 WO2014201782A1 (zh)

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