膜催化氧化反应体系的构建及其对烟气中零价汞的转化
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摘要
目前我国因燃煤所造成的汞排放问题十分突出，已成为环保领域亟待解决的问题之一。零价汞（Hg~0）是燃煤烟气中汞的主要存在形式之一，对其治理也最为困难。利用催化氧化的方法将烟气中Hg~0转化为易去除的二价汞（Hg~（2+）），被认为是治理Hg~0的有效途径之一。然而，由于Hg~0在燃煤烟气中为痕量级，采用传统的催化氧化方法（TCO）存在Hg~0转化效率不高、氧化剂或其前体物易流失且用量大、二次污染大等不足。为了克服传统方法的上述问题，本研究针对烟气中痕量级Hg~0的去除，通过研究构建了一种集氧化剂的释放、吸附富集以及Hg~0的催化氧化于一体的反应体系，并以多孔陶瓷膜为主体将二者有机结合起来，形成独特的膜催化-氧化剂输送-汞催化氧化的反应体系（MDCOs）。
论文首先采用过渡金属锰氧化物（MnO_x）为主要活性组分，以多孔陶瓷膜为主体，通过浸渍法形成Mn/Al_2O_3膜催化反应体系，并以氯化氢HCl为氧化剂前体物，研究了Mn/Al_2O_3膜催化体系对模拟烟气中痕量级Hg~0向Hg~（2+）转化的规律，以及烟气中其它组分包括SO_2、NO及O_2等对Hg~0转化的影响，并与TCO模式进行了对比。同时利用该膜催化体系对HCl的活化过程（如HCl在有氧的条件下转化成Cl_2的Deacon反应）也进行了系统研究，探讨了HCl在膜催化体系中传输、转化、吸附与富集的规律。
为增强Mn/Al_2O_3膜催化体系对痕量级Hg~0的催化氧化效率，进一步降低氧化剂用量，研究采用过渡金属Ti对陶瓷管进行改性后再附以过渡金属Ru氧化物，形成了以Ru-Ti/Al_2O_3为主体催化剂的MDCOs体系。研究了不同条件下的Deacon过程，以及Ru-Ti/Al_2O_3膜催化体系在300℃下对Hg~0的转化规律。为适应除尘后低温烟气中Hg~0转化的需求，研究采用过渡金属Mo与Ru对Mn/Al_2O_3膜催化剂进行了掺杂，形成了Mn-Mo-Ru膜催化体系，研究了在低温150℃条件下，Mn-Mo-Ru膜催化体系对HCl的Deacon转化效果，以及对Hg~0的转化规律。论文还对Hg~0转化的动力学方程，以及Hg~0转化的规律进行了讨论，得出了以下主要结论：
（1）在高温300℃下，1ppmv及5ppmv的HCl存在时，Mn/Al_2O_3膜催化体系能分别实现81.8%与93.6%的Hg~0转化率，而Ru-Ti/Al_2O_3膜催化体系能在3ppmv HCl存在的条件下，实现97.4%的Hg~0转化率；在低温150℃和8ppmv的HCl存在的条件下，Mn-Mo-Ru膜催化体系对Hg~0的去除效率能保持在95%以上。与TCO模式相比，三种不同的MDCO_s膜催化体系不但具有较高的Hg~0去除率，而且具有明显的经济优势。与TCO模式相比，三种膜催化体系均表现出了较好的抗硫效果。低浓度SO_2对汞转化的抑制作用几乎可以忽略。然而高浓度如1500ppmv的SO_2对汞的转化仍具有一定的抑制作用。
（2）由于HCl向Cl_2的转化效率对痕量级Hg~0的转化起着非常关键的作用，因此，论文还对HCl在MDCO_s膜催化系统中的活化过程进行了研究。结果显示，在高温300℃下，以Mn/Al_2O_3为膜催化剂的MDCO_s体系，其Deacon反应产率较低，只有32.6%。相比之下，Ru-Ti/Al_2O_3膜催化体系对HCl的Deacon产量与转化率显著提高，HCl的转化率达到了60.3%。与Mn/Al_2O_3膜催化体系在300℃下对HCl的转化率相比，提高了近90%。在低温150℃下，尽管上述两种膜催化体系的Deacon效率较低，然而，Mn-Mo-Ru膜催化体系却能实现23.0%的HCl转化率。另外，在Deacon过程中，HCl的逃逸量非常低，只有0.5mg/m3左右。HCl在MDCO_s膜催化体系中的高Deacon效率有力地验证了MDCO_s膜催化体系对Hg~0的高转化率。
（3） Hg~0在Mn/Al_2O_3膜催化体系中的转化过程，在没有氧化剂前体物的条件下，主要是通过吸附后被催化剂表面上的晶格氧所氧化，并主要以HgO的形式存在；在HCl存在的条件下，则主要以汞与Deacon过程产生的活性氯结合后的HgCl_2形式存在。在Ru-Ti/Al_2O_3及Mn-Mo-Ru膜催化体系对Hg~0的转化产物中，90%以上都是通过Hg~0与活性氯结合生成了HgCl_2，而HgO的形成在MDCO_s体系中并不占主导地位。
（4）催化剂的XPS结果分析显示，新鲜催化剂表面上Mn、Mo、Ru及Ti的存在形态主要为Mn(IV)与Mn(III)、Mo(Ⅵ)与Mo(IV)以及Ru(Ⅳ)与Ti(Ⅳ)。在Hg~0向Hg~（2+）转化的过程中以及在Deacon反应的过程中，上述各过渡金属的形态并没有发生明显变化。其中部分Mn(IV)离子会转化为Mn(III)、Mo(Ⅵ)离子会转化为Mo(Ⅳ)。然后在有氧存在的情况下，这些被转化的金属离子能够完全得到再生，即Mn(III)离子与Mo(Ⅳ)离子会重新还原为Mn (IV)离子与Mo(Ⅵ)离子，从而在保持催化剂稳定性的同时，极大地提高了催化剂的使用寿命与催化活性。
（5）汞的表征分析及动力学方程表明：汞在MDCO_s体系中的转化过程，符合Mars–Maessen机理。膜催化剂体系中产生的Hg~（2+）的量，与烟气中Hg~0的浓度、HCl在体系中的平衡浓度、烟气温度、烟气中氧含量、催化剂BET大小以及过渡金属在膜催化剂表面的形态与含量有关。这些过渡金属离子主要包括Mn(IV)离子、Mo(Ⅵ)离子及不饱和cus-Ru原子。其中影响较大的主要是反应温度以及制备的过渡金属在催化剂表面的形态与含量。影响汞转化率的因素除上述表述外，HCl在陶瓷膜内向外扩散的传质过程也是汞转化的速率限制性因素。
本研究的创新及特色之处主要体现为以下几点：1）针对烟气中痕量级Hg~0的氧化，构建出了以多孔陶瓷管为载体，以过渡金属Mn、Mo、Ru及Ti所形成的不同氧化物为主体的膜催化材料，该膜催化材料将氧化剂的释放、吸附富集以及Hg~0的催化氧化集中于一体形成了MDCO_s膜反应体系，该体系在功能结构上具有明显的创新性。2）论文构造的Mn/Al_2O_3与Mn-Mo-Ru的MDCO_s膜催化体系，能分别在高温300℃与低温150℃下，实现对Hg~0到Hg~（2+）的高效转化，并具有很好的抗硫能力。同时，MDCO_s体系还能显著降低氧化剂的流失，节约氧化剂的用量，有效克服了传统TCO模式在高温下大量灰尘对催化剂的毒害作用，以及低温下催化剂活性不高的问题。3）论文制备的Ru-Ti/Al_2O_3膜催化体系，在300℃下，以HCl与O_2为气体组分，成功实现了HCl的高效活化。
The pollution by atmospheric mercury emitted from coal combustion has beenbecoming more serious, and the development of mercury emission control technology hasbeen paid more and more attention in the environmental field. Elemental mercury (Hg~0) isone of the main forms in coal combustion flue gas, which is difficult to be captured withthe existing air pollution control devices. At present, the favored method for Hg~0removalis to oxidize it to its oxidized form (Hg~（2+）) by means of some proper catalysts. However,the traditional catalytic oxidation mode (TCO) has encountered some obviousdisadvantages on the oxidation of trace level Hg~0in flue gas, including the low removalefficiencies of Hg~0, high operating cost of oxidants and potential secondary pollutionproblems and so on.
In order to overcome the above disadvantages, a novel MDCO_s technology was putforward for the oxidation of the trace level Hg~0in flue gas. The MDCO_s system employeda porous ceramic membrane as principal body, and the catalytic material of MnO_xwasimpregnated on it. By means of the MDCO_s system, the adjustable delivery of thereagents for Hg~0oxidation (e.g. HCl), adsorption-enrichmen and catalytic oxidation ofHg~0can be well integrated.
Firstly, the Mn/Al_2O_3membrane catalytic system was built with MnO_xas maincatalyst/adsorbent and HCl as oxidant precursor respectively. And then the conversionprocess of Hg~0to Hg~（2+）in the presence/absence of SO_2, NO and O_2were studied.Simultaneously, the Deacon process of HCl (the conversion of HCl to Cl_2)was discussedin detailed by studying its delivery, conversion, adsorption and adsorption-enrichment.Moreover, the above results were compared to that in the TCO mode.
Further, to improve the conversion efficiency of trace level Hg~0in the Mn/Al_2O_3membrane catalytic system, and decrease the consumption of HCl, the Ru-Ti/Al_2O_3membrane catalytic system was built by means of loading RuOxon the ceramic pipe after doping it with TiOx. The Deacon process and conversion of Hg~0were studied under thetemperature of300℃and various flue gasambiences. To obtain higher sufficient activityfor Hg~0conversion under the temperature as low as150℃, the multi-metal oxide catalystswere employed to form the Mn-Mo-Ru membrane catalytic system. And then, theconversion of Hg~0and the Deacon process of HCl were all discussed. Finally, theactivation reactions of HCl by Deacon process were discussed over the catalysts with Ru.The kinetic equations were setup and the key factors that influenced the conversion of Hg~0were also determined. The main conclusions were summarized as follows:
(1) The Hg~0removal efficiency of81.8%and93.6%were achieved with1ppmv and5ppmv of HCl under300℃in the Mn/Al_2O_3membrane catalytic system, respectively. TheHg~0removal efficiency of97.4%was achieved with only3ppmv of HCl in theRu-Ti/Al_2O_3membrane catalytic system. And under low temperature of150℃, over90%of Hg~0removal efficiency could be achieved with only8ppmv of HCl in the Mn-Mo-Rumembrane catalytic system.
Compared with the TCO mode, the MDCO_s system had not only more high removalefficiency of trace level Hg~0, but also significant economic superiority. Moreover, theMDCO_s system exhibited excellent sulfur-tolerance to low concentration SO_2withinsignificant effect for the conversion of Hg~0. However, over1000ppmv of SO_2, forexample,1500ppmv of SO_2, had obvious inhabitation for the conversion of Hg~0.
(2) Because the Deacon process of HCl had a crucial effect on the conversion of Hg~0,the activation of HCl in the MDCO_s system was detailedly studied. The results of theDeacon process of HCl show that low conversion efficiency of HCl of only32.6%wasachieved in the Mn/Al_2O_3membrane catalytic system under300℃. The performance ofRu-Ti/Al_2O_3membrane catalytic system was better than that of Mn/Al_2O_3catalyst, withthe Deacon efficiency of60.3%under300℃. Under low temperature of150℃, the abovetwo membrane catalytic system had lower Deacon efficiency of less than10%. However,the efficiency of23.0%could be reached with the Mn-Mo-Ru membrane catalytic system.Moreover, the amount of escaped HCl was low with only0.5mg/m3. The high Deaconefficiency of HCl effectively validated the high conversion of Hg~0in the MDCO_s system.
(3) The conversion mechanism of Hg~0over the Mn/Al_2O_3membrane catalytic systemshowed that Hg~0was oxidized by the lattice oxygen on the surface of the catalysts, andthen converted to HgO in the absence of oxidants. The speciation of HgCl_2was dominant,which resulted from the combination of Hg~0with activated chlorine under the ambience of HCl. Among the production of Ru-Ti/Al_2O_3and Mn-Mo-Ru membrane catalytic systems,over90%were converted to HgCl_2through the combination of Hg~0with activatedchlorine. However, the speciation of HgO was not dominant in the presence of oxidants.
(4) The XPS results show that the speciation of Mn, Mo, Ru and Ti on the freshcatalysts were mainly Mn(IV) and Mn(III), Mo(Ⅵ) and Mo(IV), Ru(Ⅳ) and Ti(Ⅳ),respectively. The above speciation had no obvious change during the process of theconversion of Hg~0to Hg~（2+）and the process of the Deacon reaction. During the processabove, part of Mn(IV) and Mo(Ⅵ) could be regenerated by the oxidation of Mn(III) toMn(IV) and the oxidation of Mo(Ⅳ) to Mo(Ⅵ) under the ambience of oxygen,respectively. And the regeneration process of Mn(IV) and Mo(Ⅵ) kept the stability of thecatalysts, and meanwhile, improved the life and catalytic activity of the catalysts.
(5) The characterizations and kinetic analysis showed that the conversion of Hg~0mainly occurred via a Mars-Maessen mechanism. The produced amount of Hg~（2+）in theMDCO_s system would be affected by the concentration of Hg~0, balance concentration ofHCl in the flue gas, content of oxygen, BET of the catalysts, especially reactiontemperature and the speciation and content of transition metals. In addition, the masstransfer process of HCl in the MDCO_s system was also determined to be the rate limitingstep for the conversion of Hg~0.
In a word, the innovations and characteristics of the article included mainly:1) toimprove the removal efficiency of trace level Hg~0in flue gas, a MDCO_s technology wasput forward, which employed ceramic membrane as catalytic carrier, and the transitionmetals of Mn, Mo, Ru and Ti as catalytic materials. The MDCO_s system had obviousinnovation over the system structure by integrating the release and adsorption-enrichmentof oxidants, and catalytic oxidation for Hg~0.2) The MDCO_s not only could achieved theexcellent conversion of Hg~0, but also had better resistance ability against SO_2under thetemperature of300℃and150℃. Moreover, compared with the TCO mode, the MDCO_ssystem could significantly decrease the dosage and escaped amount of oxidants, inhibit thepoison for catalysts resulted from the lots of dusts in the flue gas, and improve theactivation of catalysts under the low temperature.3) The high Deacon efficiencies wereachieved with the Mn-Mo-Ru membrane catalytic system under the ambience of HCl andO_2and the temperature of300℃.
论文首先采用过渡金属锰氧化物（MnO_x）为主要活性组分，以多孔陶瓷膜为主体，通过浸渍法形成Mn/Al_2O_3膜催化反应体系，并以氯化氢HCl为氧化剂前体物，研究了Mn/Al_2O_3膜催化体系对模拟烟气中痕量级Hg~0向Hg~（2+）转化的规律，以及烟气中其它组分包括SO_2、NO及O_2等对Hg~0转化的影响，并与TCO模式进行了对比。同时利用该膜催化体系对HCl的活化过程（如HCl在有氧的条件下转化成Cl_2的Deacon反应）也进行了系统研究，探讨了HCl在膜催化体系中传输、转化、吸附与富集的规律。
为增强Mn/Al_2O_3膜催化体系对痕量级Hg~0的催化氧化效率，进一步降低氧化剂用量，研究采用过渡金属Ti对陶瓷管进行改性后再附以过渡金属Ru氧化物，形成了以Ru-Ti/Al_2O_3为主体催化剂的MDCOs体系。研究了不同条件下的Deacon过程，以及Ru-Ti/Al_2O_3膜催化体系在300℃下对Hg~0的转化规律。为适应除尘后低温烟气中Hg~0转化的需求，研究采用过渡金属Mo与Ru对Mn/Al_2O_3膜催化剂进行了掺杂，形成了Mn-Mo-Ru膜催化体系，研究了在低温150℃条件下，Mn-Mo-Ru膜催化体系对HCl的Deacon转化效果，以及对Hg~0的转化规律。论文还对Hg~0转化的动力学方程，以及Hg~0转化的规律进行了讨论，得出了以下主要结论：
（1）在高温300℃下，1ppmv及5ppmv的HCl存在时，Mn/Al_2O_3膜催化体系能分别实现81.8%与93.6%的Hg~0转化率，而Ru-Ti/Al_2O_3膜催化体系能在3ppmv HCl存在的条件下，实现97.4%的Hg~0转化率；在低温150℃和8ppmv的HCl存在的条件下，Mn-Mo-Ru膜催化体系对Hg~0的去除效率能保持在95%以上。与TCO模式相比，三种不同的MDCO_s膜催化体系不但具有较高的Hg~0去除率，而且具有明显的经济优势。与TCO模式相比，三种膜催化体系均表现出了较好的抗硫效果。低浓度SO_2对汞转化的抑制作用几乎可以忽略。然而高浓度如1500ppmv的SO_2对汞的转化仍具有一定的抑制作用。
（2）由于HCl向Cl_2的转化效率对痕量级Hg~0的转化起着非常关键的作用，因此，论文还对HCl在MDCO_s膜催化系统中的活化过程进行了研究。结果显示，在高温300℃下，以Mn/Al_2O_3为膜催化剂的MDCO_s体系，其Deacon反应产率较低，只有32.6%。相比之下，Ru-Ti/Al_2O_3膜催化体系对HCl的Deacon产量与转化率显著提高，HCl的转化率达到了60.3%。与Mn/Al_2O_3膜催化体系在300℃下对HCl的转化率相比，提高了近90%。在低温150℃下，尽管上述两种膜催化体系的Deacon效率较低，然而，Mn-Mo-Ru膜催化体系却能实现23.0%的HCl转化率。另外，在Deacon过程中，HCl的逃逸量非常低，只有0.5mg/m3左右。HCl在MDCO_s膜催化体系中的高Deacon效率有力地验证了MDCO_s膜催化体系对Hg~0的高转化率。
（3） Hg~0在Mn/Al_2O_3膜催化体系中的转化过程，在没有氧化剂前体物的条件下，主要是通过吸附后被催化剂表面上的晶格氧所氧化，并主要以HgO的形式存在；在HCl存在的条件下，则主要以汞与Deacon过程产生的活性氯结合后的HgCl_2形式存在。在Ru-Ti/Al_2O_3及Mn-Mo-Ru膜催化体系对Hg~0的转化产物中，90%以上都是通过Hg~0与活性氯结合生成了HgCl_2，而HgO的形成在MDCO_s体系中并不占主导地位。
（4）催化剂的XPS结果分析显示，新鲜催化剂表面上Mn、Mo、Ru及Ti的存在形态主要为Mn(IV)与Mn(III)、Mo(Ⅵ)与Mo(IV)以及Ru(Ⅳ)与Ti(Ⅳ)。在Hg~0向Hg~（2+）转化的过程中以及在Deacon反应的过程中，上述各过渡金属的形态并没有发生明显变化。其中部分Mn(IV)离子会转化为Mn(III)、Mo(Ⅵ)离子会转化为Mo(Ⅳ)。然后在有氧存在的情况下，这些被转化的金属离子能够完全得到再生，即Mn(III)离子与Mo(Ⅳ)离子会重新还原为Mn (IV)离子与Mo(Ⅵ)离子，从而在保持催化剂稳定性的同时，极大地提高了催化剂的使用寿命与催化活性。
（5）汞的表征分析及动力学方程表明：汞在MDCO_s体系中的转化过程，符合Mars–Maessen机理。膜催化剂体系中产生的Hg~（2+）的量，与烟气中Hg~0的浓度、HCl在体系中的平衡浓度、烟气温度、烟气中氧含量、催化剂BET大小以及过渡金属在膜催化剂表面的形态与含量有关。这些过渡金属离子主要包括Mn(IV)离子、Mo(Ⅵ)离子及不饱和cus-Ru原子。其中影响较大的主要是反应温度以及制备的过渡金属在催化剂表面的形态与含量。影响汞转化率的因素除上述表述外，HCl在陶瓷膜内向外扩散的传质过程也是汞转化的速率限制性因素。
本研究的创新及特色之处主要体现为以下几点：1）针对烟气中痕量级Hg~0的氧化，构建出了以多孔陶瓷管为载体，以过渡金属Mn、Mo、Ru及Ti所形成的不同氧化物为主体的膜催化材料，该膜催化材料将氧化剂的释放、吸附富集以及Hg~0的催化氧化集中于一体形成了MDCO_s膜反应体系，该体系在功能结构上具有明显的创新性。2）论文构造的Mn/Al_2O_3与Mn-Mo-Ru的MDCO_s膜催化体系，能分别在高温300℃与低温150℃下，实现对Hg~0到Hg~（2+）的高效转化，并具有很好的抗硫能力。同时，MDCO_s体系还能显著降低氧化剂的流失，节约氧化剂的用量，有效克服了传统TCO模式在高温下大量灰尘对催化剂的毒害作用，以及低温下催化剂活性不高的问题。3）论文制备的Ru-Ti/Al_2O_3膜催化体系，在300℃下，以HCl与O_2为气体组分，成功实现了HCl的高效活化。
The pollution by atmospheric mercury emitted from coal combustion has beenbecoming more serious, and the development of mercury emission control technology hasbeen paid more and more attention in the environmental field. Elemental mercury (Hg~0) isone of the main forms in coal combustion flue gas, which is difficult to be captured withthe existing air pollution control devices. At present, the favored method for Hg~0removalis to oxidize it to its oxidized form (Hg~（2+）) by means of some proper catalysts. However,the traditional catalytic oxidation mode (TCO) has encountered some obviousdisadvantages on the oxidation of trace level Hg~0in flue gas, including the low removalefficiencies of Hg~0, high operating cost of oxidants and potential secondary pollutionproblems and so on.
In order to overcome the above disadvantages, a novel MDCO_s technology was putforward for the oxidation of the trace level Hg~0in flue gas. The MDCO_s system employeda porous ceramic membrane as principal body, and the catalytic material of MnO_xwasimpregnated on it. By means of the MDCO_s system, the adjustable delivery of thereagents for Hg~0oxidation (e.g. HCl), adsorption-enrichmen and catalytic oxidation ofHg~0can be well integrated.
Firstly, the Mn/Al_2O_3membrane catalytic system was built with MnO_xas maincatalyst/adsorbent and HCl as oxidant precursor respectively. And then the conversionprocess of Hg~0to Hg~（2+）in the presence/absence of SO_2, NO and O_2were studied.Simultaneously, the Deacon process of HCl (the conversion of HCl to Cl_2)was discussedin detailed by studying its delivery, conversion, adsorption and adsorption-enrichment.Moreover, the above results were compared to that in the TCO mode.
Further, to improve the conversion efficiency of trace level Hg~0in the Mn/Al_2O_3membrane catalytic system, and decrease the consumption of HCl, the Ru-Ti/Al_2O_3membrane catalytic system was built by means of loading RuOxon the ceramic pipe after doping it with TiOx. The Deacon process and conversion of Hg~0were studied under thetemperature of300℃and various flue gasambiences. To obtain higher sufficient activityfor Hg~0conversion under the temperature as low as150℃, the multi-metal oxide catalystswere employed to form the Mn-Mo-Ru membrane catalytic system. And then, theconversion of Hg~0and the Deacon process of HCl were all discussed. Finally, theactivation reactions of HCl by Deacon process were discussed over the catalysts with Ru.The kinetic equations were setup and the key factors that influenced the conversion of Hg~0were also determined. The main conclusions were summarized as follows:
(1) The Hg~0removal efficiency of81.8%and93.6%were achieved with1ppmv and5ppmv of HCl under300℃in the Mn/Al_2O_3membrane catalytic system, respectively. TheHg~0removal efficiency of97.4%was achieved with only3ppmv of HCl in theRu-Ti/Al_2O_3membrane catalytic system. And under low temperature of150℃, over90%of Hg~0removal efficiency could be achieved with only8ppmv of HCl in the Mn-Mo-Rumembrane catalytic system.
Compared with the TCO mode, the MDCO_s system had not only more high removalefficiency of trace level Hg~0, but also significant economic superiority. Moreover, theMDCO_s system exhibited excellent sulfur-tolerance to low concentration SO_2withinsignificant effect for the conversion of Hg~0. However, over1000ppmv of SO_2, forexample,1500ppmv of SO_2, had obvious inhabitation for the conversion of Hg~0.
(2) Because the Deacon process of HCl had a crucial effect on the conversion of Hg~0,the activation of HCl in the MDCO_s system was detailedly studied. The results of theDeacon process of HCl show that low conversion efficiency of HCl of only32.6%wasachieved in the Mn/Al_2O_3membrane catalytic system under300℃. The performance ofRu-Ti/Al_2O_3membrane catalytic system was better than that of Mn/Al_2O_3catalyst, withthe Deacon efficiency of60.3%under300℃. Under low temperature of150℃, the abovetwo membrane catalytic system had lower Deacon efficiency of less than10%. However,the efficiency of23.0%could be reached with the Mn-Mo-Ru membrane catalytic system.Moreover, the amount of escaped HCl was low with only0.5mg/m3. The high Deaconefficiency of HCl effectively validated the high conversion of Hg~0in the MDCO_s system.
(3) The conversion mechanism of Hg~0over the Mn/Al_2O_3membrane catalytic systemshowed that Hg~0was oxidized by the lattice oxygen on the surface of the catalysts, andthen converted to HgO in the absence of oxidants. The speciation of HgCl_2was dominant,which resulted from the combination of Hg~0with activated chlorine under the ambience of HCl. Among the production of Ru-Ti/Al_2O_3and Mn-Mo-Ru membrane catalytic systems,over90%were converted to HgCl_2through the combination of Hg~0with activatedchlorine. However, the speciation of HgO was not dominant in the presence of oxidants.
(4) The XPS results show that the speciation of Mn, Mo, Ru and Ti on the freshcatalysts were mainly Mn(IV) and Mn(III), Mo(Ⅵ) and Mo(IV), Ru(Ⅳ) and Ti(Ⅳ),respectively. The above speciation had no obvious change during the process of theconversion of Hg~0to Hg~（2+）and the process of the Deacon reaction. During the processabove, part of Mn(IV) and Mo(Ⅵ) could be regenerated by the oxidation of Mn(III) toMn(IV) and the oxidation of Mo(Ⅳ) to Mo(Ⅵ) under the ambience of oxygen,respectively. And the regeneration process of Mn(IV) and Mo(Ⅵ) kept the stability of thecatalysts, and meanwhile, improved the life and catalytic activity of the catalysts.
(5) The characterizations and kinetic analysis showed that the conversion of Hg~0mainly occurred via a Mars-Maessen mechanism. The produced amount of Hg~（2+）in theMDCO_s system would be affected by the concentration of Hg~0, balance concentration ofHCl in the flue gas, content of oxygen, BET of the catalysts, especially reactiontemperature and the speciation and content of transition metals. In addition, the masstransfer process of HCl in the MDCO_s system was also determined to be the rate limitingstep for the conversion of Hg~0.
In a word, the innovations and characteristics of the article included mainly:1) toimprove the removal efficiency of trace level Hg~0in flue gas, a MDCO_s technology wasput forward, which employed ceramic membrane as catalytic carrier, and the transitionmetals of Mn, Mo, Ru and Ti as catalytic materials. The MDCO_s system had obviousinnovation over the system structure by integrating the release and adsorption-enrichmentof oxidants, and catalytic oxidation for Hg~0.2) The MDCO_s not only could achieved theexcellent conversion of Hg~0, but also had better resistance ability against SO_2under thetemperature of300℃and150℃. Moreover, compared with the TCO mode, the MDCO_ssystem could significantly decrease the dosage and escaped amount of oxidants, inhibit thepoison for catalysts resulted from the lots of dusts in the flue gas, and improve theactivation of catalysts under the low temperature.3) The high Deacon efficiencies wereachieved with the Mn-Mo-Ru membrane catalytic system under the ambience of HCl andO_2and the temperature of300℃.
引文
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