CN114749020A - 一种常温下湿法联合光催化技术脱硫脱硝一体化工艺 - Google Patents
一种常温下湿法联合光催化技术脱硫脱硝一体化工艺 Download PDFInfo
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Abstract
本发明公开了一种常温下湿法联合光催化技术脱硫脱硝一体化工艺，涉及一种脱硫脱硝工艺。利用湿法脱硫装置将SO2脱除，避免SO2在后续光催化脱硝部分使光催化剂失活。然后脱去烟气中的水分，随后进入光催化脱硝部分，将NO高效催化氧化为NO2，并封存在光催化剂的微孔中。生成的NO2也可从光催化剂中脱附后进一步转化为高附加值的化工产品，实现“变废为宝”的资源化利用。整个脱除工艺在常温下即可高效运行，省去烟气温度升降带来的高额成本，实现了绿色、高效、经济的烟气脱硫脱硝。本案中NO降解率达到了95.02%，且催化剂基本无失活现象。同时，脱硫效率也达到了97.55%。此外，该系统无NO2排放出来。真正意义上达到了高效、绿色脱硫脱硝。
Description
技术领域
本发明涉及一种脱硫脱硝工艺，具体为一种常温下湿法联合光催化技术脱硫脱硝一体化工艺。
背景技术
脱除氮氧化物（NOx）和二氧化硫（SO2）是烟气净化的重要环节。鉴于NO气体占NOx95%左右以及SO2易被碱性溶液吸收脱除，脱硫脱硝工艺中如何高效脱除NO才是核心和关键。现有脱硝方法中选择性催化还原法（SCR）技术成熟，实现了一定规模的商用。但其缺点也很明显，反应温度高，催化剂易中毒失活，常发生氨逃逸，导致运行成本高，易产生二次污染。除此之外，因SCR需在高温下进行，在常规烟气处理系统中SCR需要布置于微细颗粒物脱除装置和脱硫设备前，工艺流程中需增加烟气加热和余热回收等设备，造成脱除流程复杂、缺乏灵活性、占地面积大等问题。为了简化工艺，一些同时脱硫脱硝技术应运而生，如臭氧氧化法，NaClO2氧化法，等离子体法，电子束法，脉冲电晕法，吸附法等。但这些方法成本极高，不适用于实际工业生产。
太阳能来源丰富，且不受地点限制。在常温下通过光激发产生的光生载流子来脱除欲降解物不失为一种绿色、高效、经济的方法。同时，光生活性物质氧化能力强，无选择性，所以光催化技术也可实现SO2和NO的同时脱除。但同时脱除NO和SO2过程中会产生的大量的NO2 -、NO3 -和SO3 -、SO4 -，易覆盖在光催化剂活性位点上，导致催化剂失活。另外，光催化脱除NO过程中易产生毒性更大的NO2，排放到空气中会造成严重的二次污染。因此，仅依赖光催化技术实现高效、绿色的脱硫脱硝不切实际，应该辅以其他脱除方式共同实现。
发明内容
本发明针对以上问题，提出了一种常温下湿法联合光催化技术脱硫脱硝一体化工艺，利用湿法脱硫装置将SO2脱除，避免SO2在后续光催化脱硝部分使光催化剂失活。然后脱去烟气中的水分，随后进入光催化脱硝部分，将NO高效催化氧化为NO2，并封存在光催化剂的微孔中，避免产生的NO2排放造成二次污染。
本发明的技术方案为：按以下步骤进行：
步骤1、将含有一定浓度NO和SO2的烟气以一定流量通入湿法脱硫装置，通过湿法脱硫装置中的吸收剂将SO2除去；避免SO2在后续光催化脱硝部分被氧化成亚硫酸根、硫酸根覆盖在光催化剂表面，使其失活，降低脱硝效率。该部分SO2脱除率大于95%。
步骤2、将经过步骤1脱硫后的气体通入脱水装置进行脱水、干燥，防止水分子在后续的光催化脱硝部分与气体分子在光催化剂表面竞争吸附影响催化反应效率。
步骤3、将经过步骤2脱水后的烟气通入光催化脱硝装置，以光能作为唯一输入能源，将NO高效催化氧化为NO2，并封存在光催化剂的微孔中，避免脱除过程中NO2排放造成二次污染。
后续，步骤3生成的NO2也可从光催化剂中脱附后进一步转化为高附加值的化工产品，实现“变废为宝”的资源化利用。该部分NO的脱除率大于90%。
进一步的，步骤1中湿法脱硫装置的吸收剂为海水，饱和石灰水，亚硫酸铵溶液中的一种。
进一步的，步骤2中脱水装置中的除水剂为变色硅胶，CaCl2，MgCl2中的一种。
进一步的，步骤3中所用光催化剂为UiO-66-NH2。
另外，
本发明涉及的光催化剂UiO-66-NH2通过溶剂热法合成：
1）将氯化锆溶于N,N-二甲基甲酰胺（DMF）溶液中，超声溶解2min后磁力搅拌20min得到无色透明的氯化锆溶液；然后加入2-氨基对苯二甲酸，再搅拌10min，然后超声处理10min，加入20mL冰醋酸后搅拌20min得到前驱体。
2）将前驱体倒入聚四氟乙烯反应釜中120 oC反应24小时。
3）待自然冷却后，分别用DMF和甲醇离心洗涤3次，然后用甲醇浸泡一天，中间12h时更换一次甲醇，最后真空干燥得到光催化剂UiO-66-NH2。
本发明湿法脱硫部分使用的饱和石灰水配置方法为：
1）称取0.6g氧化钙分散到400mL超纯水中。
2）搅拌10min后静置30min，上清液即为饱和石灰水。
本发明的有益之处：
（1）本发明的常温下湿法联合光催化技术脱硫脱硝一体化工艺仅通过简单脱水装置将湿法脱硫和基于UiO-66-NH2的光催化脱硝串联起来，结构简单，方便易行。
（2）本发明的常温下湿法联合光催化技术脱硫脱硝一体化工艺在常温下即可高效脱硫脱硝，几乎实现零排放。
（3）整个工艺只需提供烟气前进的动力，光催化脱硝部分的光能可用太阳能代替。且光催化剂可通过简单的洗涤实现再生，重复利用。运行成本低，经济适用。
（4）该工艺湿法脱硫部分吸收的SO2可进一步转化为硫酸盐，光催化剂UiO-66-NH2将NO高效转化为NO2，并吸附在微孔中，NO2脱附后可进一步转化为高附加值的化工产品，实现“变废为宝”的资源化利用。
（5）湿法脱硫和光催化脱硝无有毒副产物排放，绿色环保。具体来说，本案中NO降解率达到了95.02 %，且催化剂基本无失活现象。同时，脱硫效率也达到了97.55 %。此外，该系统无NO2排放出来。真正意义上达到了高效、绿色脱硫脱硝。
附图说明
图1为常温下湿法联合光催化技术脱硫脱硝一体化工艺的实验系统示意图；
图2a为烟气先进入光催化脱硝部分然后直接进入湿法脱硫部分工艺的气体浓度降解曲线（图中横坐标为时间，纵坐标为气体浓度）；
图2b为烟气先进入光催化脱硝部分然后直接进入湿法脱硫部分工艺的气体去除率变化曲线（图中横坐标为时间，纵坐标为去除率）；
图3a为烟气先进入湿法脱硫部分后直接进入光催化脱硝部分工艺的气体浓度降解曲线（图中横坐标为时间，纵坐标为气体浓度）；
图3b为烟气先进入湿法脱硫部分后直接进入光催化脱硝部分工艺的气体去除率变化曲线（图中横坐标为时间，纵坐标为去除率）；
图4a为先进行湿法脱硫，经脱水后进入光催化脱硝部分工艺的气体浓度降解曲线（图中横坐标为时间，纵坐标为气体浓度）；
图4b为先进行湿法脱硫，经脱水后进入光催化脱硝部分工艺的气体去除率变化曲线（图中横坐标为时间，纵坐标为去除率）。
具体实施方式
为能清楚说明本专利的技术特点，下面通过具体实施方式，并结合其附图，对本专利进行详细阐述。
图1为常温下湿法联合光催化技术脱硫脱硝一体化工艺的实验系统示意图，其中湿法脱硫装置，除湿装置，光催化脱硝反应器可自行拆卸、调换工艺顺序。通过质量流量控制器调节不同气体的流速形成一定浓度NO、SO2的烟气，烟气总流量为300±2mL/min，然后进行实验。
其中所用平板式光催化反应器根据国际标准（ISO 22197-1:2007）进行构建，通过连续傅里叶变换红外分析仪(美国，MKS MultiGas 2060)对气体浓度进行监测，每15秒记录一个数据。
实验过程中，通入烟气的NO浓度为50±1ppm，SO2浓度为250±10ppm，通入烟气的总流量为300±2mL/min。
光催化脱硝装置中所用光源为300W氙灯，发射出的光为波长大于380nm的可见光，光强为90±10 mW/cm2，并且0.075g光催化剂UiO-66-NH2被均匀的涂覆在5×10cm2的玻璃片上，放入平板式光催化反应器进行光催化脱硝。
如图2所示，若先进行光催化脱硝，其NO催化降解效率只有68.55%，且失活现象严重。但湿法脱硫部分不受影响，吸收脱硫率高达 95%以上。之所以光催化部分效率差、失活现象严重，是因为SO2在光催化的作用下易生产硫酸盐，覆盖到催化剂的活性位点上，导致催化效率下降、失活。所以应当将脱硫部分提前，来避免光催化剂中毒现象的发生。
如图3所示，将湿法脱硫部分挪到光催化脱硝前不但没有促进脱硝反应，反而更差，但湿法脱除SO2的效率仍不受影响。经分析，这种现象应该是由湿法脱硫后烟气中水分含量过高，大量水分子在催化剂表面与NO分子竞争吸附，并与生成的NO2发生反应生成硝酸盐，覆盖催化活性位点所致。因此，湿法脱硫后烟气除湿是必不可少的一环。
如图4所示，用除湿脱水装置将湿法脱硫和光催化脱硝部分串联后，该系统 NO降解率达到了95.02 %，且催化剂基本无失活现象。同时，脱硫效率也达到了97.55 %。此外，该系统无NO2排放出来。真正意义上达到了高效、绿色脱硫脱硝。
本发明具体实施途径很多，以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以作出若干改进，这些改进也应视为本发明的保护范围。
Claims (6)
1.一种常温下湿法联合光催化技术脱硫脱硝一体化工艺，其特征在于，按以下步骤进行：
步骤1、将含有NO和SO2的烟气通入湿法脱硫装置，通过湿法脱硫装置中的吸收剂将SO2除去；
步骤2、将经过步骤1脱硫后的气体通入脱水装置进行脱水、干燥，防止水分子在后续的光催化脱硝部分与气体分子在光催化剂表面竞争吸附影响催化反应效率；
步骤3、将经过步骤2脱水后的烟气通入光催化脱硝装置，以光能作为唯一输入能源，将NO高效催化氧化为NO2，并封存在光催化剂的微孔中。
2.根据权利要求1所述的一种常温下湿法联合光催化技术脱硫脱硝一体化工艺，其特征在于，步骤1中湿法脱硫装置的吸收剂为海水，饱和石灰水，亚硫酸铵溶液中的一种。
3.根据权利要求1所述的一种常温下湿法联合光催化技术脱硫脱硝一体化工艺，其特征在于，所述饱和石灰水配置方法为：
1）称取0.6g氧化钙分散到400mL超纯水中。
2）搅拌10min后静置30min，上清液即为饱和石灰水。
4.根据权利要求1所述的一种常温下湿法联合光催化技术脱硫脱硝一体化工艺，其特征在于，步骤2中脱水装置中的除水剂为变色硅胶，CaCl2，MgCl2中的一种。
5.根据权利要求1所述的一种常温下湿法联合光催化技术脱硫脱硝一体化工艺，其特征在于，步骤3中所用光催化剂为UiO-66-NH2。
6.根据权利要求5所述的一种常温下湿法联合光催化技术脱硫脱硝一体化工艺，其特征在于，所述光催化剂UiO-66-NH2通过溶剂热法合成：
1）将氯化锆溶于N,N-二甲基甲酰胺（DMF）溶液中，超声溶解2min后磁力搅拌20min得到无色透明的氯化锆溶液；然后加入2-氨基对苯二甲酸，再搅拌10min，然后超声处理10min，加入20mL冰醋酸后搅拌20min得到前驱体；
2）将前驱体倒入聚四氟乙烯反应釜中120 oC反应24小时；
3）待自然冷却后，分别用DMF和甲醇离心洗涤3次，然后用甲醇浸泡一天，中间12h时更换一次甲醇，最后真空干燥得到光催化剂UiO-66-NH2。
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