CN105688931B - 一种利用菱锰矿制备燃煤烟气脱汞催化剂的新方法 - Google Patents
一种利用菱锰矿制备燃煤烟气脱汞催化剂的新方法 Download PDFInfo
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Abstract
本发明公开了一种利用菱锰矿制备燃煤烟气脱汞催化剂的新方法，包括以下步骤：将菱锰矿粉碎成粉末；在超声波作用下采用盐酸浸取菱锰矿粉末得浸取混合物；将浸取混合物过滤后得到滤清液和浸取不溶物，对滤清液采用碱液调节pH值，将锰与铝、铁、镁、钙等其他金属元素分离，加热浓缩提高锰离子浓度；在超声波作用下采用多孔载体浸渍高浓度含锰浓缩滤液，过滤烘干得到含锰脱汞催化剂；将分离出来的铝、铁、镁、钙及其他金属元素的沉淀物与浸取不溶物相混合，加入胶黏剂和造孔剂，充分混合后经烧结得到含其他活性金属元素（主要为铁、钙、镁和铝）氧化物的脱汞催化剂。
Description
技术领域
本发明涉及环境保护技术领域，具体是一种利用菱锰矿制备燃煤烟气脱汞催化剂的新方法。
背景技术
零价汞（Hg0）是环境中一种生物毒性极强的重金属污染物，而进入大气层中的有害汞污染物的主要来源之一就是煤炭的燃烧。为了降低重金属汞的排放量，在燃煤烟气排放通道中采用脱汞催化剂将零价汞（Hg0）氧化成可溶于水的正二价汞（Hg2+）是有效措施之一。
目前研究最热的燃煤烟气脱汞催化剂是含卤素的金属盐类物质和金属氧化物，主要以含锰、铝、铁、镁和钙的卤素盐类为主，其中尤以金属锰研究最多，乔少华等采用浸渍法，以Mn(NO3)2为前驱体制备的催化剂，该催化剂在300℃左右时催化效率最佳；Ji L等研究了一种MnO/TiO2催化剂，该催化剂由湿法浸渍得到，采用固定床反应器，空速5000h-1时的脱汞效率接近90%，脱除效率主要受床层温度以及Mn的负载量影响。可以看出他们在制备催化剂时几乎都是采用成品金属盐类作为催化活性金属来源。但是采用菱锰矿作为催化活性金属来源的制备方法尚未见到报道。本发明的目的是采用贵州省储量丰富的菱锰矿作为催化剂的制备原料，采取化学浸渍和烧结工艺来制备两种不同的高效燃煤烟气脱汞催化剂。
发明内容
本发明的目的在于提供一种利用菱锰矿制备燃煤烟气脱汞催化剂的新方法，以解决上述背景技术中提出的问题。
为实现上述目的，本发明提供如下技术方案：
一种利用菱锰矿制备燃煤烟气脱汞催化剂的新方法，包括以下步骤：
（1）将菱锰矿粉碎成粉末；
（2）在超声波作用下采用盐酸浸取菱锰矿粉末得浸取混合物；
（3）将步骤（2）中浸取混合物过滤后得到滤清液，对滤清液采用碱液调节pH值，将锰与铝、铁、镁、钙及其他金属元素分离，然后进行加热浓缩提高锰离子浓度；
（4）在超声波作用下采用多孔载体浸渍高浓度含锰滤液，然后进行过滤烘干得到含锰脱汞催化剂；
（5）将步骤（3）中分离出来的铝、铁、镁、钙及其他金属元素与步骤（2）中的浸取不溶物相混合，加入胶黏剂和造孔剂进行充分搅拌后烘干，然后再经过高温热处理得到含铝、铁、镁和钙活性元素的脱汞催化剂
作为本发明进一步的方案：所述步骤（1）中菱锰矿粉碎成粉末的粒度为100—200目。
作为本发明进一步的方案：所述步骤（2）中盐酸的浓度为20%—30%。
作为本发明进一步的方案：所述步骤（3）中的碱液为氨水含氨量为25%—28%。
作为本发明进一步的方案：所述步骤（4）中的多孔载体为活性炭或分子筛，比表面积为500—2000g/m2。
作为本发明进一步的方案：所述步骤（5）中的胶黏剂为氢氧化铝胶体，造孔剂为聚乙烯醇。
与现有技术相比，本发明采用化学浸渍菱锰矿结合pH值调节的工艺来分离具有脱汞催化活性的金属锰与其他金属元素（铁、钙、镁和铝），再通过浸渍多孔载体和加入胶黏剂烧结的工艺来制备两种不同的脱汞催化剂，两种脱汞催化剂的脱汞效率都可达到80%以上。
具体实施方式
下面结合具体实施方式对本专利的技术方案作进一步详细地说明。
一种利用菱锰矿制备燃煤烟气脱汞催化剂的新方法，包括以下步骤：
（1）将菱锰矿粉碎成粉末；菱锰矿粉碎成粉末的粒度为100—200目，含锰量为8—25（wt）%；
（2）在超声波作用下采用盐酸浸取菱锰矿粉末得浸取混合物；盐酸的浓度为20%—30%；浸取矿粉时，采用超声波辅助，超声波功率为100—500W，浸取温度80—90℃，浸取时间2—4小时，搅拌速率100—300r/min，酸矿比1—2.5；
（3）将步骤（2）中浸取混合物过滤后得到滤清液，对滤清液采用碱液调节pH值，将锰与铝、铁、镁、钙及其他金属元素分离，然后进行加热浓缩提高锰离子浓度；碱液为氨水含氨量为25%—28%；
（4）在超声波作用下采用多孔载体浸渍高浓度含锰滤液，然后进行过滤烘干得到含锰脱汞催化剂；多孔载体为活性炭或分子筛，比表面积为500—2000g/m2，采用超声波辅助，超声波功率为100—500W，浸渍时间为5—10h，过滤后烘干温度为80—120℃，催化剂中含锰量为5—20%；
（5）将步骤（3）中分离出来的铝、铁、镁、钙及其他金属元素与步骤（2）中的浸取不溶物相混合，加入胶黏剂和造孔剂进行充分搅拌后烘干，然后再经过高温热处理得到含铝、铁、镁和钙活性元素的脱汞催化剂；胶黏剂为氢氧化铝胶体，加入比例为3—7（wt）%；造孔剂为聚乙烯醇，平均分子量为16000—20000，加入比例为5—15（wt）%，搅拌时间为1—5h，搅拌速率为100—300r/min。在制备含铁、钙、镁和铝活性元素的催化剂时，高温烧结温度为300—600℃，升温速率为5—10℃/min，烧结时间为4—10h。
实施例
本发明提供了一种制备高效燃煤烟气脱汞催化剂的方法，以粒度为100目含锰量为20（wt）%的菱锰矿粉和浓度为25%的盐酸作为原料，第一步进行浸取实验，浸取时超声波功率为250W，浸取温度为85℃，搅拌速率为200r/min，浸取时间为3h，酸矿比为2.0；第二步浸取结束进行过滤，滤清液采用浓度为25%的氨水调节pH值，过滤分离其他金属元素的碱性沉淀物，所得滤清液在90℃加热浓缩1h得到高浓度含锰滤清液；第三步采用比表面积为1000g/㎡的三氧化二铝分子筛浸渍第二步中得到的高浓度含锰滤清液，浸渍时超声波功率为300W，浸渍时间为6h，过滤后再90℃烘干，得到含锰量为8%的催化剂样品一；第四步将浸取过滤和调节pH值时所产生的沉淀物混合，加入5（wt）%的胶黏剂和8（wt）%的造孔剂，200r/min条件下搅拌2h，然后空气气氛条件下在500℃烧结6h，得到脱汞催化剂样品二。
上面对本专利的较佳实施方式作了详细说明，但是本专利并不限于上述实施方式，在本领域的普通技术人员所具备的知识范围内，还可以在不脱离本专利宗旨的前提下做出各种变化。
Claims (6)
1.一种利用菱锰矿制备燃煤烟气脱汞催化剂的新方法，其特征在于，包括以下步骤：
（1）将菱锰矿粉碎成粉末；
（2）在超声波作用下采用盐酸浸取菱锰矿粉末得浸取混合物；
（3）将步骤（2）中浸取混合物过滤后得到滤清液，对滤清液采用碱液调节pH值，将锰与铝、铁、镁、钙及其他金属元素分离，然后进行加热浓缩提高锰离子浓度；
（4）在超声波作用下采用多孔载体浸渍高浓度含锰滤液，然后进行过滤烘干得到含锰脱汞催化剂；
（5）将步骤（3）中分离出来的铝、铁、镁、钙及其他金属元素与步骤（2）中的浸取不溶物相混合，加入胶黏剂和造孔剂进行充分搅拌后烘干，然后再经过高温热处理得到含铝、铁、镁和钙活性元素氧化物的脱汞催化剂。
2.根据权利要求1所述的利用菱锰矿制备燃煤烟气脱汞催化剂的新方法，其特征在于，所述步骤（1）中菱锰矿粉碎成粉末的粒度为100—200目。
3.根据权利要求1所述的利用菱锰矿制备燃煤烟气脱汞催化剂的新方法，其特征在于，所述步骤（2）中盐酸的浓度为20%—30%。
4.根据权利要求1所述的利用菱锰矿制备燃煤烟气脱汞催化剂的新方法，其特征在于，所述步骤（3）中的碱液为氨水含氨量为25%—28%。
5.根据权利要求1所述的利用菱锰矿制备燃煤烟气脱汞催化剂的新方法，其特征在于，所述步骤（4）中的多孔载体为活性炭或分子筛，比表面积为500—2000㎡/g。
6.根据权利要求1所述的利用菱锰矿制备燃煤烟气脱汞催化剂的新方法，其特征在于，所述步骤（5）中的胶黏剂为氢氧化铝胶体，造孔剂为聚乙烯醇。
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| US4149997A (en) * | 1977-01-20 | 1979-04-17 | Kureha Kagaku Kogyo Kabushiki Kaisha | Method for manufacture of catalyst used for reduction of nitrogen oxides and the catalyst produced by the method |
| CN102266769A (zh) * | 2011-06-14 | 2011-12-07 | 张丽莉 | 一种用于同步脱硝脱汞的催化剂及其制备方法 |
| CN102698771A (zh) * | 2012-06-01 | 2012-10-03 | 江苏和亿昌环保工程科技有限公司 | 一种烟气脱汞催化剂及其制备方法 |
| CN103084165A (zh) * | 2013-01-23 | 2013-05-08 | 广东电网公司电力科学研究院 | 一种用于氧化燃煤烟气中零价汞的脱汞催化剂及其制备方法 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4149997A (en) * | 1977-01-20 | 1979-04-17 | Kureha Kagaku Kogyo Kabushiki Kaisha | Method for manufacture of catalyst used for reduction of nitrogen oxides and the catalyst produced by the method |
| CN102266769A (zh) * | 2011-06-14 | 2011-12-07 | 张丽莉 | 一种用于同步脱硝脱汞的催化剂及其制备方法 |
| CN102698771A (zh) * | 2012-06-01 | 2012-10-03 | 江苏和亿昌环保工程科技有限公司 | 一种烟气脱汞催化剂及其制备方法 |
| CN103084165A (zh) * | 2013-01-23 | 2013-05-08 | 广东电网公司电力科学研究院 | 一种用于氧化燃煤烟气中零价汞的脱汞催化剂及其制备方法 |
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