CN101573178B - 用于生产具有高催化活性的活性炭的方法 - Google Patents

用于生产具有高催化活性的活性炭的方法 Download PDF

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CN101573178B
CN101573178B CN2007800370628A CN200780037062A CN101573178B CN 101573178 B CN101573178 B CN 101573178B CN 2007800370628 A CN2007800370628 A CN 2007800370628A CN 200780037062 A CN200780037062 A CN 200780037062A CN 101573178 B CN101573178 B CN 101573178B
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K·-D·亨宁
W·邦加茨
N·达海姆
T·沙夫
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    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
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Abstract

本发明涉及用于生产具有高催化活性的活性炭的方法，其中让含碳的材料与含氮的化合物接触，其中，含碳材料在800℃以上的温度情况下在多级流化床中以本身已知的方式借助由水蒸气、氮气和二氧化碳组成的混合物部分气化，和将含氮化合物计量添加到燃烧室和/或多级流化床的至少一个阶段中。

Description

用于生产具有高催化活性的活性炭的方法
技术领域
本发明涉及一种根据权利要求1前序部分所述的用于生产具有高催化活性的活性炭的方法。
背景技术
由EP 1 200 342 B1已知，通过用含氮化合物处理提高活性炭的催化活性。对此公开过两种基础方法。第一种方法包括用含氮化合物处理活性炭。
第二种方法在于，使含碳材料在碳化或者活化之前与含氮化合物接触。
这两种方法的缺点在于，以含氮化合物的形式计量添加的氮量只有相对较少的部分被嵌入到碳骨架(Kohlenstoffgerüst)中并由此提高催化活性。此外，在任何情况下都需要额外的方法步骤用于生产具有高催化活性的活性炭。
发明内容
本发明的任务在于提供一种简单而经济的用于生产具有高催化活性的活性炭的方法，其中省去了额外的方法步骤。
通过以下方式可以解决该任务，即，含碳材料在800℃以上温度下在多级流化床中以本身已知的方式借助由水蒸气、氮气和二氧化碳组成的混合物部分气化，并且将含氮化合物计量添加到燃烧室和/或多级流化床的至少一个阶段中。
改进方案根据从属权利要求的特征实施。
本发明基于如下基本思想，在常规活性炭生产方法中将含氮化合物计量添加到多级流化床中。多级流化床可以理解为这样的流化床，所述流化床由至少两个至最多八个流化床底板(
Figure G2007800370628D00011
)组成。
通过试验出人意料地发现，可以通过将含氮化合物添加到燃烧室或单个的流化床阶段中以简单的方式产生和有目的地调节这样生产的活性炭的活性。
适合作为含碳材料的是所有制备活性炭的已知材料，如：椰子壳、煤(Steinkohl)、褐煤焦炭、泥煤焦炭或聚合物。
作为含氮化合物首选使用尿素。同样也可以使用六亚甲基四胺、聚丙烯腈或三聚氰胺。
在一种优选实施方式中，以含氮化合物的形式将尿素水溶液计量添加到多级流化床中。尿素溶液的浓度为45％。每100千克的含碳材料使用2至10千克量的尿素。每100千克的含碳材料使用5至6千克尿素量经证实是最佳的。
所生产的活性炭的催化活性可以通过测量NO转化率测定。众所周知，如果活性炭对NO转化具有高的催化活性，那么其同样对二氧化硫氧化、氯胺清除、过氧化物分解、硫化氢氧化以及在很多其它化学反应中都具有提高的催化活性。
NO转化率的测定
在120℃温度下，利用模拟烟道气(400ppm的NO、400ppm的NH3、22体积％的O2与17体积％的H2O，剩余的是N2)测定NO转化率。
在反应器中，填入1.06升的干燥活性炭，并且在120℃反应温度下用模拟烟道气流经该干燥活性炭。接触时间为10秒钟。在测量期间，记录NO的突破浓度(Durchbruchskonzentration)，并且在20小时后，相对于NO-初始浓度，由纯气体中的NO浓度计算转化率。
下面将根据实施例对本发明进行详细说明。
实施例1(比较实施例)：
活性炭的生产是在八级流化床反应器中进行的。燃烧室温度为800℃至940℃。流化气体(Wirbelgas)可以通过燃烧天然气产生。另外添加300千克/小时的蒸汽。
在八级流化床反应器中，以600千克/小时计量添加入含碳材料。最终产物的排放速度为400千克/小时。未计量添加尿素溶液。所生产活性炭的活性可以通过测量NO转化率测定。所生产的活性炭具有0.4重量％的含氮量。根据以上所述试验测得催化活性为45％的NO转化率。
实施例2：
在八级流化床反应器中，在燃烧室中以50升每小时计量加入45％的尿素溶液。活性炭生产的其它条件没有改变。尿素与含碳材料的比例为：每100千克含碳材料4.2千克的尿素。
这样生产的活性炭的含氮量为1.0重量％。在NO测试中，测得的NO转化率为87％。
实施例3：
在八级流化床反应器中，除了将50升45％的尿素溶液计量加入到燃烧室中之外，还将10升尿素溶液计量加入到第三个流化床底板中。这样生产的活性炭的含氮量为1.26重量％，所测得的NO转化率为89％。比例为每100千克含碳材料5.0千克尿素。
实施例4：
在八级流化床反应器中，除了将50升/小时的尿素溶液计量添加到燃烧室中外，还将30升/小时的尿素溶液计量添加到第三个流化床底板中。
这样生产的活性炭的含氮量为1.41重量％。在测试装置中测得91％的NO转化率。比例为每100千克含碳材料5.9千克尿素。
实施例5：
在八级流化床反应器中，除了将60升/小时的尿素溶液计量添加到燃烧室中外，还将20升尿素溶液计量添加到第二个流化床底板中，以及将另外20升尿素计量添加到第三个流化床底板中。这样生产的活性炭的含氮量为1.5重量％。测得92％的NO转化率。尿素对含碳材料的比例为8.3千克尿素比100千克含碳材料。
这些实施例证明，通过将含氮化合物添加到燃烧室中或多级流化床的单个流化层中，生产活性炭的方法可以以简单的方式得以改进，从而制备在NO-转化方面具有高催化活性的活性炭。
在这些实施例中，选择尿素作为含氮化合物。尿素的浓度可以在每100千克含碳材料4.2千克尿素至每100千克含碳材料8.3千克尿素间变化。试验结果表明，从技术与经济的角度来讲，每100千克含尿素材料5-6千克尿素是最佳量。把每100千克5.9千克进一步提高至8.3千克仅导致略微提高的催化活性。

Claims (5)

1.用于生产具有高催化活性的活性炭的方法，其中让含碳材料与含氮化合物接触，其特征在于，含碳材料在800℃以上的温度情况下在多级流化床中以本身已知的方式借助由水蒸气、氮气和二氧化碳组成的混合物部分气化，并且将含氮化合物进料到燃烧室和/或多级流化床的至少一个阶段中。
2.根据权利要求1所述的方法，其特征在于，所述含碳材料为椰子壳、煤、褐煤焦炭、泥煤焦炭或聚合物。
3.根据权利要求1或2所述的方法，其特征在于，所述含氮化合物以尿素水溶液的形式添加。
4.根据权利要求3所述的方法，其特征在于，尿素以每100千克含碳材料2至10千克尿素的量添加。
5.根据权利要求4所述的方法，其特征在于，尿素以每100千克含碳材料5至6千克尿素的量添加。
CN2007800370628A 2006-10-04 2007-09-13 用于生产具有高催化活性的活性炭的方法 Expired - Fee Related CN101573178B (zh)

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CN104056829B (zh) * 2014-05-30 2018-09-21 浙江大学 一种热等离子体反应器的连续清焦方法
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PL1981634T3 (pl) 2010-01-29
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