CN108187681A - 一种硼化锆助剂脱硝脱硫催化剂及制备方法 - Google Patents
一种硼化锆助剂脱硝脱硫催化剂及制备方法 Download PDFInfo
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Abstract
本发明涉及一种脱硫脱硝催化剂：采用硅藻土‑石墨烯作为载体，硅藻土与石墨烯的质量比为2:1，将纳米级氧化镍负载到载体上构成复合氧化物活性载基，并在复合氧化物活性载基上负载金属氧化物助剂作为催化助剂，所述的金属氧化物助剂为硼化锆，催化氮氧化物和硫氧化物的脱除率分别为92％、96％以上。
Description
技术领域
本发明属于催化剂的制备技术领域，公开一种硼化锆助剂脱硝脱硫催化剂及制备方法。
背景技术
目前，用于同时脱硫脱硝的技术主要有电子束法，活性炭法，CuO/γ-Al2O3法等，从工业锅炉角度而言，低温脱硝脱硫工艺的技术需求空间巨大，而目前现有进行脱硫脱硝技术中使用的催化剂主要成份为活性炭、Cu/Mg/Al、CuO/Al2O3；活性炭催化剂包括传统活性炭催化剂和专利号为03145680.4公开的蜂窝状活性炭(ACH)催化剂；活性炭、 Cu/Mg/Al、CuO/Al2O3均为中温或高温催化剂，催化温度较高，一般有效催化温度在300℃以上，而在300℃温度以下，催化效率明显下降，无法满足低温脱硫脱硝的技术需求。
发明内容
为解决上述技术问题，本发明的目的是提出一种硼化锆助剂脱硝脱硫催化剂及制备方法。
本发明为完成上述目的采用如下技术方案：
一种硼化锆助剂脱硝脱硫催化剂，采用硅藻土-石墨烯作为载体，其中硅藻土-石墨烯是通过颗粒混合并在150℃下烧结3小时而，将纳米级氧化镍负载到载体上构成复合氧化物活性载基，并在复合氧化物活性载基上负载金属氧化物助剂作为催化助剂，所述催化剂的重量百分比为：硅藻土-石墨烯19.41％～24.45％，纳米级氧化镍57.93％～65.65％，金属氧化物助剂4.09％～5.77％，表面活性剂3.29％～4.16％，交联剂2.24％～3.08％，增强剂 4.28％～4.96％；所述催化剂在300℃以下用于催化SXOY、NOX的同步脱除；在160～250℃反应，以氨蒸汽作为吸收剂时，催化NOX、SO2的脱除率分别为90％、95％以上,，所述的金属氧化物助剂为硼化锆；硅藻土与石墨烯的质量比为2:1。
所述的表面活性剂为硬脂酸、丙三醇中的一种或两种的混合，交联剂为甲基丙烯酸 -2-羧乙酯，增强剂为玻璃纤维。
所述的硅藻土-石墨烯为天然多孔的高比表面积生物成因的硅质沉积岩，其化学成分主要是SiO2，含有少量的Al2O3、Fe2O3、CaO、MgO、K2O、Na2O、P2O5和有机质；其具有细腻、松散、质轻、多孔、吸水性和渗透性强的物性，且储量丰富利于获得。由于硅藻土-石墨烯具有很强的吸附性能，大大增强氧化钴及其他金属助剂的附着力；硅藻土- 石墨烯更进一步的具有大量孔隙和高比表面积，加快催化反应的速率，增加了反应面积。从而为催化效率的提高，提供了有力保证。
所述的纳米级氧化镍为锐钛矿型氧化镍；氧化镍存在两种型态：锐钛矿型氧化镍、金红石型氧化镍，由于锐钛矿型氧化镍具有比金红石型氧化镍更高的催化活性，纳米级氧化镍作为一种重要的加氢脱硫及NO氢化助催化剂，其存在状态对活性组分的催化活性具有较大的影响，因此，选用锐钛矿型氧化镍。
所述的复合氧化物活性载基以硅藻土-石墨烯作为载体，将纳米级氧化镍负载到载体上构成复合氧化物活性载基，大大阻止了锐钛矿型氧化镍向金红石型氧化镍的转变，提高了锐钛矿型氧化镍的机械强度、比表面积、热稳定性和反应活性；此法形成的复合氧化物，为复合活性载基，集成了两者优点于一体，力求获得相互作用后的更高催化性能；将纳米级氧化镍引入硅藻土-石墨烯载体可明显提高纳米级氧化镍晶型的转变温度，提高纳米级氧化镍的热稳定性和反应活性；同时硅藻土-石墨烯具有大量的微孔及大的比表面积，增加了锐钛矿型的氧化镍负载量和反应面积，把锐钛矿型的氧化镍负载在硅藻土- 石墨烯载基上可以增加锐钛矿型的氧化镍稳定性；所形成的复合氧化物活性载基可用于硫氧化物和氮氧化物的同步脱除，具有良好的抗水性、高机械强度、比表面积大、高热稳定性和强反应活性等特点。
复合氧化物活性载基可以负载其他活性组分进一步调变催化剂的活性和选择性催化性；在复合氧化物活性载基上负载金属氧化物助剂作为催化助剂，可以进一步提高催化反应活性。
所述的金属氧化物助剂为两性氧化物，目的在于两性氧化物，在高的活性载基中被活化，表现出两性氧化物独有的高催化氧化型或者高催化还原性，大大提高催化剂的整体催化性能；而且，被活化的两性氧化物还可以进一步提高活性载基本身的活性，从而再次提高催化剂的整体催化活性；所述的两性氧化物为Mn氧化物、V氧化物、Cr氧化物、Ce氧化物、W氧化物、Mo氧化物中的一种或几种Cr氧化物、Mn氧化物、Ce氧化物分别由相应的硝酸盐溶液热解制备；W氧化物和Mo氧化物分别由钨酸铵和钥酸铵热解制备，V氧化物由正钒酸铵、偏钒酸铵或多钒酸铵或硫酸氧钒热解制备。
所述的瓦砾纸状，是一种新型设计的催化剂形状，该形状能有效提高催化剂比表面积，同时其机械强度高，耐空气动力学磨损，能有效提高催化剂使用寿命。
一种硼化锆助剂脱硝脱硫催化剂及制备方法的制备方法，采用硅藻土-石墨烯、纳米级氧化镍以及金属氧化物助剂，经过混料工艺制备出氧化镍固定在硅藻土-石墨烯上的粉末状复合催化剂初料，再经过成型工艺，即经过二次混料、成型及锻烧，最终形成一种瓦砾纸状低温烟气同步脱硝脱硫催化剂，其具体步骤如下：
1)制备硅藻土-石墨烯、纳米级氧化镍、金属氧化物助剂：纳米级氧化镍、硅藻土-石墨烯、金属氧化物助剂的制备均采用现有技术中的成熟工艺制备，也可以市购；其中硅藻土-石墨烯是通过颗粒混合并在150℃下烧结3小时而。
2)混料工艺：采用溶胶凝胶法，取85～125重量份钛酸四丁酯溶于无水乙醇中，每重量份钛酸四丁酯对应无水乙醇量为4ml；搅拌后加10～12重量份的二乙醇胺做抑制剂，延缓钛酸四丁酯的强烈水解，继续搅拌并逐滴加入蒸馏水，直至得无色透明溶胶；取30～40重量份的硅藻土-石墨烯加入到上述溶胶中，搅拌使由钛酸四丁酯水解产生的氧化镍负载到硅藻土-石墨烯上，并加入6～7重量份的金属氧化物助剂，进行搅拌之后抽滤干燥，最后将得到的固体粉末，置于马福炉中煅烧之后冷却并再次粉碎即得到氧化镍固定在硅藻土-石墨烯上的粉末状复合催化剂初料；
3)成型工艺：称取混料工艺所得的粉末状复合催化剂初料，并加入表面活性剂、交联剂、增强剂，并加入纯氨水和去离子水；粉末状复合催化剂初料、表面活性剂、交联剂、增强剂的配比分别为：88.49～89.28％、3.53～3.57％、2.65～3.54％、4.45～5.31％、每克粉末状复合催化剂初料对应的纯氨水和去离子水量各为0.5ml～1ml，再经过炼泥、真空炼泥、在恒温恒湿条件下陈腐、成型、干燥、在隧道窑中烧结，直至充分干燥，成为瓦砾纸状脱硝脱硫催化剂。
所述的表面活性剂为硬脂酸、丙三醇中的一种或两种的混合。
所述的交联剂为甲基丙烯酸-2-羧乙酯。
所述的增强剂为玻璃纤维，对催化剂起到物理增强作用。
步骤3)中加入纯氨水的目的是利用其碱性及强的挥发性，在催化剂成型后，加热过程中强烈挥发，为催化剂提供更多的孔道，且本身作为碱可进一步提高NOX的催化剂吸收效率。
步骤3)中加入去离子水的目的在于调节催化剂炼泥的硬度，便于成型，此处必须要用去离子水，以防止普通水中还有的其它离子，造成催化剂中有效成份的团聚，造成催化效率降低。
本发明提出的一种生物基瓦砾纸状低温同步脱硫脱硝催化剂及制备方法，采用硅藻土-石墨烯作为载体，将纳米级氧化镍负载到载体上构成复合氧化物活性载基，并在复合氧化物活性载基上添加两性氧化物作为金属氧化物助剂，可在300℃以下用于催化硫氧化物和氮氧化物的同步脱除，具有良好的抗水性、机械强度高、比表面积大、热稳定性高和反应活性强的特点。在160～250℃反应，以氨蒸汽作为吸收剂时，催化NOX、SO2的脱除率分别为92％、96％以上并具有良好的寿命和机械强度。
具体实施方式
下面结合具体的实施例对本发明进行进一步的详细描述。
(1)混料工艺：
称取850g钛酸四丁酯溶于3.4L无水乙醇中，搅拌30min，加二乙醇胺100g做抑制剂，延缓钛酸四丁酯的强烈水解，继续搅拌1h，然后逐滴加入蒸馏水搅拌，直至得无色透明溶胶。取300g硅藻土-石墨烯加入到上述溶胶中，搅拌使由钛酸四丁酯水解产生的氧化镍负载到硅藻土-石墨烯上，其中硅藻土-石墨烯是通过颗粒混合并在150℃下烧结3小时而，并加入金属氧化物助剂60g，搅拌后抽滤在于70℃鼓风干燥2h，最后将得到的固体粉末置于马福炉中于500℃煅烧2h，冷却后再次粉碎成为粉末状复合催化剂初料；
(2)成型工艺：
称取混料工艺所得的粉末状复合催化剂初料200g、加入硬脂酸8g、加入甲基丙烯酸 -2-羧乙酯6g、加入玻璃纤维l0g、加入纯氨水和去离子水，每克粉末状复合催化剂初料对应的纯氨水和去离子水量各为0.5ml，经过炼泥、真空炼泥、在恒温恒湿条件下陈腐 24h、用特殊磨具成型为瓦砾纸状并在60℃的条件下干燥60～90h、在隧道窑中以
180～450℃烧结2h成为瓦砾纸状脱硝脱硫催化剂。
实施例2：
(1)混料工艺：
(2)称取1000g钛酸四丁酯溶于4.0L无水乙醇中，搅拌30min，加二乙醇胺110g 做抑制剂，延缓钛酸四丁酯的强烈水解，继续搅拌1h，然后逐滴加入蒸馏水搅拌，直至得无色透明溶胶。取350g硅藻土-石墨烯加入到上述溶胶中，搅拌使氧化镍负载到硅藻土-石墨烯上，其中硅藻土-石墨烯是通过颗粒混合并在150℃下烧结3小时而，并加入提供金属氧化物助剂65g，搅拌后抽滤在于70℃鼓风干燥2h，最后将得到的固体粉末置于马福炉中于500℃煅烧2h，冷却后再粉碎成为粉末状复合催化剂初料；成型工艺：
称取混料工艺所得的粉末状复合催化剂初料200g、加入硬脂酸8g、加入甲基丙烯酸 -2-羧乙酯8g、加入玻璃纤维l0g、加入纯氨水和去离子水，每克粉末状复合催化剂初料对应的纯氨水和去离子水量各为1ml，经过炼泥、真空炼泥、在恒温恒湿条件下陈腐24h、用特殊磨具成型为瓦砾纸状并在60℃的条件下干燥60～90h、在隧道窑中以180～450℃烧结2h成为瓦砾纸状脱硝脱硫催化剂。
实施例3：
(1)混料工艺：
称取1250g钛酸四丁酯溶于4.96L无水乙醇中，搅拌30min，加二乙醇胺120g做抑制剂，延缓钛酸四丁酯的强烈水解，继续搅拌1h，然后逐滴加入蒸馏水搅拌，直至得无色透明溶胶。取400g硅藻土-石墨烯加入到上述溶胶中，搅拌使氧化镍负载到硅藻土-石墨烯上，其中硅藻土-石墨烯是通过颗粒混合并在150℃下烧结3小时而，并加入提供金属氧化物助剂70g，搅拌后抽滤在于70℃鼓风干燥2h，最后将得到的固体粉末置于马福炉中于500℃煅烧2h，冷却后粉碎成为粉末状复合催化剂初料；
(2)成型工艺：
称取混料工艺所得的粉末状复合催化剂初料200g、加入硬脂酸8g、加入甲基丙烯酸 -2-羧乙酯6g、加入玻璃纤维l2g、加入纯氨水和去离子水，每克粉末状复合催化剂初料对应的纯氨水和去离子水量各为1ml，经过炼泥、真空炼泥、在恒温恒湿条件下陈腐24h、用特殊磨具成型为瓦砾纸状并在60℃的条件下干燥60～90h、在隧道窑中以180～450℃烧结2h成为瓦砾纸状脱硝脱硫催化剂。
以上的具体实施方式仅为本创作的较佳实施例，并不用以限制本创作，凡在本创作的精神及原则之内所做的任何修改、等同替换、改进等，均应包含在本创作的保护范围之内。
Claims (6)
1.一种脱硫脱硝催化剂，其特征在于：采用硅藻土-石墨烯作为载体，硅藻土-石墨烯是通过颗粒混合并在150℃下烧结3小时而，将纳米级氧化镍负载到载体上构成复合氧化物活性载基，并在复合氧化物活性载基上负载金属氧化物助剂作为催化助剂，所述催化剂的重量百分比为：硅藻土-石墨烯19.41％～24.45％，纳米级氧化镍57.93％～65.65％，金属氧化物助剂4.09％～5.77％，表面活性剂3.29％～4.16％，交联剂2.24％～3.08％，增强剂4.28％～4.96％。所述催化剂在300℃以下用于催化氮氧化物和硫氧化物的同步脱除；在160～250℃反应，以氨蒸汽作为吸收剂时，催化氮氧化物和硫氧化物的脱除率分别为92％、96％以上，所述的金属氧化物助剂为硼化锆；硅藻土与石墨烯的质量比为2:1。
2.如权利要求1所述的催化剂，其特征在于：所述的表面活性剂为硬脂酸、丙三醇中的一种或两种的混合；交联剂为甲基丙烯酸-2-羧乙酯；增强剂为玻璃纤维。
3.如权利要求1所述的催化剂，其特征在于：所述的纳米级氧化镍为锐钛矿型氧化镍。
4.如权利要求1所述的催化剂，其特征在于：金属氧化物助剂中的Cr氧化物、Mn氧化物、Ce氧化物分别由相应的硝酸盐溶液热解制备；金属氧化物助剂中的W氧化物和Mo氧化物分别由钨酸铵和钥酸铵热解制备，V氧化物由正钒酸铵、偏钒酸铵或多钒酸铵或硫酸氧钒热解制备。
5.如权利要求1所述的催化剂，其特征在于：所制得的催化剂为瓦砾纸状，较蜂窝煤状催化剂，其比表面积更大，机械强度更高，催化效果更好。
6.权利要求1所述的催化剂的制备方法，其特征在于：采用硅藻土-石墨烯、纳米级氧化镍以及金属氧化物助剂，经过混料工艺制备出氧化镍固定在硅藻土-石墨烯上的粉末状复合催化剂初料，再经过成型工艺，即经过二次混料、成型及锻烧，最终形成一种瓦砾纸状低温烟气同步脱硝脱硫催化剂，其具体步骤如下：
1)制备硅藻土-石墨烯、纳米级氧化镍、金属氧化物助剂：纳米级氧化镍、硅藻土-石墨烯、金属氧化物助剂的制备均采用现有技术中的成熟工艺制备，也可以市购；
2)混料工艺：采用溶胶凝胶法，取85～125重量份钛酸四丁酯溶于无水乙醇中，每重量份钛酸四丁酯对应无水乙醇量为4ml；搅拌后加10～12重量份的二乙醇胺做抑制剂，延缓钛酸四丁酯的强烈水解，继续搅拌并逐滴加入蒸馏水，直至得无色透明溶胶；取30～40重量份的硅藻土-石墨烯加入到上述溶胶中，搅拌使由钛酸四丁酯水解产生的氧化镍负载到硅藻土-石墨烯上，并加入6～7重量份的金属氧化物助剂，进行搅拌之后抽滤干燥，最后将得到的固体粉末，置于马福炉中煅烧之后冷却并再次粉碎即得到氧化镍固定在硅藻土-石墨烯上的粉末状复合催化剂初料；
3)成型工艺：称取混料工艺所得的粉末状复合催化剂初料，并加入表面活性剂、交联剂、增强剂，并加入纯氨水和去离子水；粉末状复合催化剂初料、表面活性剂、交联剂、增强剂的配比分别为：88.49～89.28％、3.53～3.57％、2.65～3.54％、4.45～5.31％、每克粉末状复合催化剂初料对应的纯氨水和去离子水量各为0.5mll～1ml，再经过炼泥、真空炼泥、在恒温恒湿条件下陈腐、成型、干燥、在隧道窑中烧结，直至充分干燥，成为瓦砾纸状脱硝脱硫催化剂。
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| CN114797895A (zh) * | 2019-03-25 | 2022-07-29 | 河北地质大学 | 一种复合催化剂及其制备方法和应用 |
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| CN114797895A (zh) * | 2019-03-25 | 2022-07-29 | 河北地质大学 | 一种复合催化剂及其制备方法和应用 |
| CN111841614A (zh) * | 2020-08-18 | 2020-10-30 | 福州大学 | 氮硼共掺杂石墨烯复合脱硝抗硫催化剂及其制备方法 |
| CN111841614B (zh) * | 2020-08-18 | 2021-10-29 | 福州大学 | 氮硼共掺杂石墨烯复合脱硝抗硫催化剂及其制备方法 |
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