CN103127951B - 一种用于柴油车尾气脱硝的低温scr 催化剂及其制备方法 - Google Patents

一种用于柴油车尾气脱硝的低温scr 催化剂及其制备方法 Download PDF

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CN103127951B
CN103127951B CN201310068345.6A CN201310068345A CN103127951B CN 103127951 B CN103127951 B CN 103127951B CN 201310068345 A CN201310068345 A CN 201310068345A CN 103127951 B CN103127951 B CN 103127951B
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molecular sieve
catalyst
scr catalyst
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powder
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CN103127951A (zh
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林涛
刘志昆
陈耀强
李云
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Zhongzi Technology Co ltd
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SICHUAN ZHONGZI EXHAUST PURGE CO Ltd
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Abstract

本发明公开了一种用于柴油车尾气脱硝的低温SCR催化剂及其制备方法。催化剂以分子筛作为载体，以铜、铁金属元素作为活性组分的SCR催化剂；包括分子筛预处理、多次等体积浸渍、浸渍后干燥除水、焙烧，最好制浆涂覆制成。本发明不采用贵金属，而是采用铜、铁贱金属作为活性组分降低了成本，并对人体无害、对环境友好。本发明的催化剂制备方法简便易行，对原料要求不高，采用多次少量的等体积浸渍方法，与现有常规制备方法相比，活性离子分散更加均匀，提高了利用率，从而达到提高低温催化活性及耐久性的目的。

Description

一种用于柴油车尾气脱硝的低温SCR 催化剂及其制备方法
技术领域
本发明属于催化剂制备技术领域，尤其属于分子筛SCR催化剂制备技术领域，特别涉及一种用于低温转化NOx气体的柴油车尾气净化的分子筛型SCR催化剂及其制备。
背景技术
柴油机以其低油耗、高功率比的特点得到越来越广泛的应用，但是由于柴油机缸内的高压高温产生的氮氧化物NOx带来了严重的环境问题，加剧了空气质量的恶化，我国对安装柴油发动机的道路车辆提高了排放标准，目前在净化柴油车尾气NOx方面选择性催化还原（SCR）技术是主流技术，而应用最多的是尿素-SCR系统，其原理是通过在SCR催化转化器前端喷射一定比例的尿素溶液，通过尿素水解或热解产生的氨气作为还原剂在催化剂表面来选择性还原NOx，而其核心部件—SCR催化转化器的研制有一个很大的不足，即在车辆怠速或低速工况下尾气温度大多低于200℃，在此种情况下传统钒钛钨型SCR的温度窗口为280℃—400℃，不能满足低温下的NOx净化。同时长期、大量使用贵金属不仅生产成本高，对环境造成污染，对人体也有十分严重的损害。
由此开发更能适应低温高转化率、对环境更友好的SCR催化剂是目前催化剂行业一直在努力探索的方向。
发明内容
本发明根据现有技术的不足公开了一种用于柴油车尾气脱硝的低温SCR催化剂及其制备方法。本发明要解决的第一个问题是提供一种不采用贵金属，而是采用贱金属作为活性组分，对人体无害的催化剂组成；本发明要解决的第二个问题是提供一种新的方法制备分子筛型SCR催化剂，既满足低温高转化的要求又具有较好的耐久性能。
本发明用于柴油车尾气脱硝的低温SCR催化剂由以下技术方案实现：
低温SCR催化剂以分子筛作为载体，以铜、铁金属元素作为活性组分的SCR催化剂。
所述铜以Cu2+计算占分子筛总质量的2～4%，铁以Fe3+计算占分子筛总质量的3～5%。
优选铜以Cu2+计算占分子筛总质量的3%，铁以Fe3+计算占分子筛总质量的4%。
上述载体选自具有空间树枝状孔道结构的分子筛。如选自ZSM-5或Y型分子筛。
本发明低温SCR催化剂制备方法包括以下步骤：
①分子筛预处理：准确称取分子筛并在90℃烘箱中通空气加热4小时，降到室温；
②第一次等体积浸渍：检测①干燥后材料的比孔容，将①分子筛粉料加入反应釜，将可溶解铁盐和可溶解铜盐固体以Cu2+、Fe3+分别计：Cu2+占分子筛总质量的1～2%、Fe3+占分子筛总质量的1.5～2.5%，以Cu2+和Fe3+总量计：Cu2+和Fe3+占分子筛总量2.5～4.5%的比例配成水溶液，溶液的总体积=分子筛的质量×比孔容，溶液以喷雾的形式缓慢加入，不断搅拌，喷完后继续搅拌1小时；然后在60℃搅拌1小时，升温至80℃，持续搅拌至细粉状；
③干燥除水：取出②中的粉末，装入不锈钢盘，在通风烘箱内120℃烘2小时除去表面水分，过40目筛；
④第二次等体积浸渍：将③所得分子筛加入反应釜，重复②③浸渍步骤；
⑤焙烧：将④所得的粉料于550℃煅烧2小时，自然降至室温，得到暗红色粉末；
⑥制浆涂覆：将⑤所得粉末加入粘接剂，制备成浆液，涂覆于载体上，干燥焙烧制得催化剂。
本发明活性组分采用等体积浸渍方法，可以进行一次、两次或多次，优选两次等体积浸渍。实验证明采用多次等体积浸渍使金属铜和金属铁催化剂成分分布更均匀，活性更优，性能更稳定。
本发明可溶解铁盐和可溶解铜盐优选其各自的硝酸盐。
本发明采用沸石分子筛作为原料，将活性成分通过多种负载手段进入分子筛骨架，经过干燥、焙烧等处理制成特殊的催化剂涂层，涂覆在陶瓷或金属基体上形成整体式催化剂，通过特殊的活性组分，可以大幅降低NOx的起燃温度到150℃，且具有一定的耐久性，对城市工况低温运行的柴油车尾气脱硝具有现实意义。
本发明技术的原材料为具有空间树枝状孔道结构的分子筛，选用ZSM-5、Y等类型，将活性组分负载到沸石材料孔道中，再通过干燥、焙烧等步骤使活性组分均匀分散到载体表面孔隙中。从而形成稳定性和选择性更高的催化剂涂层。
涂层材料经过检测，包括XRD、B.E.T.法、粒度、表面酸性、NH3吸附性等的检测，证明材料具有使用温度下高的比表面积和孔径，优良的表面酸性及NH3吸/脱附性，适合NOx催化还原反应的要求。
通过涂层催化活性评价，涂层具有良好的催化活性，经过水热老化及耐硫试验，催化剂仍然保持较高的低温活性，更加适合中国城市工况的柴油车市场需要。
本发明不采用贵金属，而是采用铜、铁贱金属作为活性组分降低了成本，并对人体无害、对环境友好。本发明的催化剂制备方法简便易行，对原料要求不高，采用多次少量的等体积浸渍方法，与现有常规制备方法相比，活性离子分散更加均匀，提高了利用率，从而达到提高低温催化活性及耐久性的目的。
附图说明
图1是本发明中SCR催化剂在高硫环境下的NOx转化性能曲线；
图2是本发明中SCR催化剂在不同空速下的NOx转化性能曲线；
图3是本发明中SCR催化剂在不同水热老化条件下的NOx转化性能曲线；
图4是本发明SCR催化转化器在发动机台架稳态试验前后的NOx排放值（g/kwh）。
具体实施方式
下面通过实施例对本发明进行进一步的描述，本实施例只用于对本发明进行进一步的说明，但不能理解为对本发明保护范围的限制，本领域的技术人员可以根据上述内容作出一些非本质的改进和调整属于本发明保护的范围。
实施例1
低温SCR催化剂制备
①分子筛预处理：准确称取分子筛并在90℃烘箱中通空气加热4小时，除去表面吸附的水分等杂质，降到室温。本例采用BEA或Y型分子筛。
②第一次等体积浸渍：检测①干燥后材料的比孔容，将①分子筛粉料加入反应釜，将可溶解铁盐和可溶解铜盐固体以Cu2+、Fe3+分别计：Cu2+占分子筛总质量的1～2%、Fe3+占分子筛总质量的1.5～2.5%，以Cu2+和Fe3+总量计：Cu2+和Fe3+占分子筛总量2.5～4.5%的比例配成水溶液，溶液的总体积=分子筛的质量×比孔容，溶液以喷雾的形式缓慢加入，不断搅拌，喷完后继续搅拌1小时；然后在60℃搅拌1小时，升温至80℃，持续搅拌至细粉状；
③干燥除水：取出②中的粉末，装入不锈钢盘，在通风烘箱内120℃烘2小时除去表面水分，过40目筛；
④第二次等体积浸渍：将③所得分子筛加入反应釜，重复②③浸渍步骤；
⑤焙烧：将④所得的粉料于550℃煅烧2小时，自然降至室温，得到暗红色粉末；
⑥制浆涂覆：将粉料制成固含量为40%～42%的浆料。将浆料涂覆在堇青石陶瓷载体上，放入电热鼓风干燥箱干燥后，再放入箱式电阻炉内，按照从室温→300℃（1hr）→550℃（2hr）焙烧后即制得低温SCR催化剂。
实施例2
Cu2+和Fe3+质量比为2:5的低温SCR催化剂制备
准确称取200g分子筛并在90℃烘箱中通空气加热4小时，除去表面吸附的水分等杂质，降到室温。检测其比孔容，并将其加入反应釜。将硝酸铜[Cu(NO3)2.3H2O]7.56g，硝酸铁[Fe(NO3)3.9H2O]36.07g溶于103.85ml去离子水中，搅拌至溶解。将溶液缓慢加入分子筛中，不断搅拌，溶液加完后继续搅拌1小时。取出粉末，装入不锈钢盘，在通风烘箱内120℃烘2小时除去表面水分，过40目筛。将所得粉末加入反应釜，再次加入等量的溶液进行喷雾并干燥。将所得的粉料于550℃煅烧2小时，得到暗红色粉末；暗红色粉末中加入粘接剂，制备成浆液，涂覆在孔目数400cell/in2，体积38.4ml堇青石陶瓷蜂窝载体上，干燥焙烧，即得低温SCR催化剂。
实施例3
Cu2+和Fe3+质量比为3:4的低温SCR催化剂制备
准确称取200g分子筛并在90℃烘箱中通空气加热4小时，除去表面吸附的水分等杂质，降到室温。检测其比孔容，并将其加入反应釜。将硝酸铜[Cu(NO3)2.3H2O]11.34g，硝酸铁[Fe(NO3)3.9H2O]28.86g溶于105.89ml去离子水中，搅拌至溶解。其他与实施例2同样操作。
实施例4
Cu2+和Fe3+质量比为4:3的低温SCR催化剂制备
准确称取200g分子筛并在90℃烘箱中通空气加热4小时，除去表面吸附的水分等杂质，降到室温。检测其比孔容，并将其加入反应釜。将硝酸铜[Cu(NO3)2.3H2O]15.13g，硝酸铁[Fe(NO3)3.9H2O]21.64g溶于107.93ml去离子水中，搅拌至溶解。其他与实施例2同样操作。
比较例1
将市场上在售的传统V-Ti-W型SCR催化剂进行解剖，取载体规格与实施例1中载体规格相同的催化剂。
检测结果
将以上实施例与比较例中的催化剂进行活性评价试验。试验条件如下所示：
气体体积组成：一氧化氮：500ppm，氨气：500ppm，二氧化碳：5％，水蒸气：4.5％，氧气：14%，氮气：平衡气；空速：40000h-1。
活性评价结果如下表1
从上表1可以得知：
（1）制备的3种催化剂具有很好的NOx转化温度，适用目前柴油车尾气净化需要。
（2）与比较例对比，实施例2，实施例3，实施例4均具有对NOx更低的起燃温度和更大的转化温度窗口。说明本发明的低温SCR催化剂比传统V-Ti-W型SCR催化剂具有更好的催化性能。
（3）在实施例2，实施例3，实施例4中，实施例3对NOx的起燃温度较低和转化温度窗口最大，说明实施例3催化剂的催化性能最高。
实施例5
催化剂性能检测实验
用实施例3制备的催化剂进行相关检测实验。通过耐硫性实验、不同空速实验、水热老化实验以及台架试验的结果，可看出本发明制备的催化剂对NOx具有优良的低温起燃活性以及高硫、高空速、高温度下的稳定性。
图1是本发明中SCR催化剂在高硫环境下的NOx转化性能曲线。图中可以看出，本催化剂经过200ppmSO2，200℃29hr老化（相当于在含硫量670ppm的燃油中运行15000公里）后，性能基本没有下降；在经过600ppmSO2，200℃29hr老化（相当于在含硫量2000ppm的燃油中运行15000公里）后，仍具有非常有效的性能。而柴油车国IV标准中，硫含量为350ppm，所以说，本催化剂具有很好的耐硫性能。结果如下表2
图2是本发明中SCR催化剂在不同空速下的NOx转化性能曲线。图中可以看出，本催化剂的NOx转化性能随空速的升高而有所降低，但降低的并不明显，在110,000h-1空速条件下，仍具有非常有效的性能。所以说，本催化剂具有很好的空速性能。结果如下表3
图3是本发明中SCR催化剂在不同水热老化条件下的NOx转化性能曲线。图中可以看出，本催化剂按照传统V-Ti-W型SCR催化剂的老化条件550℃75hr和600℃50hr进行老化后，性能下降的并不明显；而按照更加恶劣的670℃64hr高温老化后，仍具有非常有效的性能。所以说，本催化剂具有很好的抗水热老化性能。结果如下表4
图4是本发明SCR催化剂在发动机台架稳态试验前后的NOx排放值。图中可以看出，加装本发明SCR催化转化器后，NOx的平均排放值为2.8g/kwh，达到国Ⅳ标准。（发动机型号：WP7，4.2L，国Ⅳ标准为3.5g/kwh。采用中国标准国Ⅳ规定的测试规程，进行台架试验。）
从以上结果可以看出，本催化剂相比传统V-Ti-W型SCR催化剂而言，具有更好的催化性能。

Claims (4)

1.一种用于柴油车尾气脱硝的低温SCR催化剂的制备方法，所述催化剂以分子筛作为载体，以铜、铁金属元素作为活性组分，所述铜以Cu2+计算占分子筛总质量的2～4％，铁以Fe3+计算占分子筛总质量的3～5％；所述载体选自具有空间树枝状孔道结构的ZSM-5或Y型分子筛，其特征是包括以下步骤：
①分子筛预处理：准确称取分子筛，在90℃烘箱中通空气加热4小时，降到室温；
②第一次等体积浸渍：检测①干燥后材料的比孔容，将①分子筛粉料加入反应釜，将可溶解铁盐和可溶解铜盐固体以Cu2+、Fe3+分别计：Cu2+占分子筛总质量的1～2％、Fe3+占分子筛总质量的1.5～2.5％，以Cu2+和Fe3+总量计：Cu2+和Fe3+占分子筛总量2.5～4.5％的比例配成水溶液，溶液的总体积＝分子筛的质量×比孔容，溶液以喷雾的形式缓慢加入，不断搅拌，喷完后继续搅拌1小时；然后在60℃搅拌1小时，升温至80℃，持续搅拌至细粉状；
③干燥除水：取出②中的粉末，装入不锈钢盘，在通风烘箱内120℃烘2小时除去表面水分，过40目筛；
④第二次等体积浸渍：将③所得分子筛加入反应釜，重复②③浸渍步骤；
⑤焙烧：将④所得的粉料于550℃煅烧2小时，自然降至室温，得到暗红色粉末；
⑥制浆涂覆：将⑤所得粉末加入粘接剂，制备成浆液，涂覆于载体上，干燥焙烧制得催化剂。
2.根据权利要求1所述的用于柴油车尾气脱硝的低温SCR催化剂的制备方法，其特征是：所述等体积浸渍进行两次或多次。
3.根据权利要求1所述的用于柴油车尾气脱硝的低温SCR催化剂的制备方法，其特征是：所述可溶解铁盐和可溶解铜盐均为其各自的硝酸盐。
4.根据权利要求1所述的用于柴油车尾气脱硝的低温SCR催化剂的制备方法，其特征是：所述催化剂中铜以Cu2+计算占分子筛总质量的3％，铁以Fe3+计算占分子筛总质量的4％。
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