CN112516994B - 一种废弃scr催化剂制备再生粉的方法及再生粉 - Google Patents
一种废弃scr催化剂制备再生粉的方法及再生粉 Download PDFInfo
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及一种废弃SCR催化剂制备再生粉的方法及再生粉,包括对废弃SCR催化剂进行清洗、研磨、制浆,得到催化剂的一次浆液,添加酸性除钒剂并进行搅拌,对搅拌后的一次浆液进行压滤分离获得粉体,添加硅铝除去剂进行洗涤、压滤后制浆,得到催化剂的二次浆液,添加诱导活化剂、分散剂,搅拌、一次研磨、压滤、干燥、焙烧、二次研磨,获得再生粉。本发明有效控制了回收粉中五氧化二钒的含量,降低了无效钒的含量,保留了钨含量,所制得再生粉微观比表面积较高,提高了SCR新催化剂生产过程中再生粉掺加比例,降低了挤出成型工艺、干燥焙烧工艺的破损率和开裂坏品率,经济性和产品性能优良。
Description
技术领域
本发明属于废弃催化剂资源化领域,具体涉及一种废弃SCR催化剂制备再生粉的方法和再生粉。
背景技术
“十二五”期间国内几乎所有电站锅炉都安装了选择性催化还原(SCR)烟气脱硝装置,后续将逐步面临废旧催化剂安全、有效处置和利用的问题。国家环保部《关于加强废烟气脱硝催化剂监管工作的通知》正式将废烟气脱硝催化剂(钒钛系)纳入危险废物进行管理,要求尽快提高废烟气脱硝催化剂(钒钛系)的再生、利用和处置能力。
SCR催化剂的主要成分为二氧化钛、三氧化钨、五氧化二钒等,占总量的95%以上,报废催化剂多为因出现严重物理堵塞、化学失活或者机械破损等问题无法再生恢复脱硝性能。当前对废弃SCR催化剂的再利用大多采用简单清洗研磨后直接加入SCR催化剂制备过程,此类回用粉可能存在粒径过大、微观比表面积低、杂质含量高等问题,增加了新催化剂挤出工艺的难度,降低了脱硝性能。此外,作为主活性成分的钒在SCR催化剂中是以最高价氧化物形式(V2O5)的状态存在,未经钒脱除处理的钒直接加入新催化剂中,因为钒分散性差、还原性钒含量增加、总钒含量高等问题,造成新催化剂表面酸位降低、活性成分添加调节难度增大等,不仅造成催化剂脱硝性能无法正常发挥,而且会导致SO2/SO3转化率提高等,降低了原料适用性。
废弃SCR催化剂原料经钠化焙烧分别提取钒、钨以及二氧化钛的工艺,则存在焙烧温度过高(850℃以上)造成二氧化钛金红石转化的问题,致使废弃SCR催化剂无法有效回用到新催化剂的生产工艺中。而且该工艺焙烧过程废气排放浓度高,存在沉钒、沉钨过程精细化控制难度和废水量大等问题,环境效益不佳。
发明内容
本发明的一个目的是提供一种废弃SCR催化剂制备再生粉的方法,钒含量去除率可达到85%,钨去除率小于8%,对有效控制了钒和钨在再生粉中含量,降低了无效钒含量的同时保留了钨含量。
为达到上述目的,本发明采用的技术方案是:
1. 一种废弃SCR催化剂制备再生粉的方法,其特征在于:依次包括:
1)、对废弃SCR催化剂进行清洗,
2)、对清洗后的催化剂进行研磨、制浆,得到催化剂的一次浆液,向一次浆液中添加酸性除钒剂并进行搅拌,酸性除钒剂的浓度为0.5-9wt%,一次浆液与酸性除钒剂的液固比为3-6:1,对搅拌后的一次浆液进行压滤分离获得粉体,
3)、向粉体内添加硅铝除去剂进行洗涤、压滤后制浆,得到催化剂的二次浆液,向二次浆液中添加诱导活化剂、分散剂,诱导活化剂为二氧化钛前驱体,二氧化钛前驱体的加入量为5~50wt%,分散剂的加入量以二氧化钛干基质量计为0.1-0.7wt%,
4)、调节二次浆液的PH值在6.5-7.5后,进行搅拌、一次研磨、压滤、干燥、焙烧、二次研磨,获得再生粉。
优选地,在2)中,酸性除钒剂采用草酸,添加草酸后在30-60℃下,搅拌1-7h,并调节PH值在3.0-1.0。
优选地,在3)中,硅铝除去剂包括硫酸、氢氟酸、氟化铵。
优选地,在3)中,分散剂包括阴离子聚羧酸盐类、六偏磷酸钠、磷酸二氢钠。
优选地,在2)中,一次浆液的浓度为25~35wt%,催化剂颗粒的粒径要求在75μm -150μm;在3)中,二次浆液的浓度为10~25wt%,催化剂颗粒的粒径要求在75μm -150μm。
优选地,在4)中,通过向二次浆液中添加硫酸、氨水调节PH值。
优选地,在4)中,干燥温度为90-115℃。
优选地,在4)中,焙烧温度为250-500℃。
优选地,在4)中,二次研磨后,再生粉D50≤3.0μm,D90≤10.0μm,微观比表面积50-90m2/g。
本发明的一个目的是提供一种再生粉。
为达到上述目的,本发明采用的技术方案是:
一种再生粉,该再生粉由所述的一种废弃SCR催化剂制备再生粉的方法制备而成。
优选地,该再生粉为钛钨粉或钛钨钒粉,其中二氧化钛的含量大于90%,二氧化钛晶钛为锐钛型。
由于上述技术方案运用,本发明与现有技术相比具有下列优点:
本发明有效控制了回收粉中五氧化二钒的含量,钒含量去除率可达到85%,降低了无效钒的含量,钨去除率小于8%,保留了钨含量;所制得再生粉微观比表面积较高,达到50-90m2/g,粒径在2.5-6.27μm之间,提高了SCR新催化剂生产过程中再生粉掺加比例,降低了挤出成型工艺、干燥焙烧工艺的破损率和开裂坏品率,经济性和产品性能优良。
附图说明
附图1为本实施例方法的流程框图。
具体实施方式
下面将结合附图对本发明的技术方案进行清楚、完整地描述,显然,所描述的实施例是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
在本发明的描述中,需要说明的是,术语“中心”、“上”、“下”、“左”、“右”、“竖直”、“水平”、“内”、“外”等指示的方位或位置关系为基于附图所示的方位或位置关系,仅是为了便于描述本发明和简化描述,而不是指示或暗示所指的装置或元件必须具有特定的方位、以特定的方位构造和操作,因此不能理解为对本发明的限制。此外,术语“第一”、“第二”、“第三”仅用于描述目的,而不能理解为指示或暗示相对重要性。
在本发明的描述中,需要说明的是,除非另有明确的规定和限定,术语“安装”、“相连”、“连接”应做广义理解,例如,可以是固定连接,也可以是可拆卸连接,或一体地连接;可以是机械连接,也可以是电连接;可以是直接相连,也可以通过中间媒介间接相连,可以是两个元件内部的连通。对于本领域的普通技术人员而言,可以具体情况理解上述术语在本发明中的具体含义。
如图1所示:一种废弃SCR催化剂制备再生粉的方法,包括:
对废弃SCR催化剂进行清洗,清洗包括机械除灰、喷淋冲洗、药剂清洗、鼓泡或超声波清洗、清水漂洗,使得催化剂恢复微观特性,具体可以采用公开号为CN105032504A所公开的药剂、清洗方法进行清洗。
对清洗后的催化剂进行研磨、制浆,得到催化剂的一次浆液,一次浆液的浓度为30wt%,催化剂颗粒的粒径在75μm -150μm之间,向一次浆液中添加草酸进行除钒处理,并在反应釜内采用机械搅拌,调节PH值在2.0,对搅拌后的一次浆液进行压滤分离获得粉体。其中,草酸的加入量、搅拌条件如下表所示:
向粉体内添加硅铝除去剂,去除粉体中的硅、铝,硅铝除去剂采用如硫酸、氢氟酸、氟化铵等,进行洗涤、压滤后制浆,得到催化剂的二次浆液,二次浆液的浓度为17wt%,催化剂颗粒的粒径在75μm -150μm之间,二次浆液中铝的含量小于0.05%。
向二次浆液中添加诱导活化剂,辅助添加分散剂,诱导活化剂为二氧化钛前驱体,二氧化钛前驱体的加入量为30wt%,分散剂采用阴离子聚羧酸盐类(DA型)、六偏磷酸钠、磷酸二氢钠等,分散剂的加入量以二氧化钛干基质量计为0.4wt%,并采用如硫酸、氨水等调节二次浆液的PH值在7.0,进行搅拌2h后加入湿式研磨机,充分研磨后压滤、干燥,干燥温度100℃,干燥后的粉体在350℃条件下进行焙烧,再进行二次研磨,控制粉体D50≤3.0μm,D90≤10.0μm,微观比表面积50-90m2/g。
最终获得再生粉为钛钨粉、钛钨钒粉,其中二氧化钛的含量95%,二氧化钛晶钛为锐钛型。
对比例:
公开号为CN105481007A所公开的当前对废弃SCR催化剂的回收利用,采用碱液将钒和钨分别浸出,利用调节PH值分部沉淀的方法或者钒盐和钨盐,回收产物中TiO2的含量为78~82%。该方法工艺流程长,钒钨性质相近,两种物质的分离操作复杂,经济性相对较差;回收TiO2粉作为SCR催化剂生产原料需要二次加工,成本增加。
上述实施例只为说明本发明的技术构思及特点,其目的在于让熟悉此项技术的人士能够了解本发明的内容并据以实施,并不能以此限制本发明的保护范围。凡根据本发明精神实质所作的等效变化或修饰,都应涵盖在本发明的保护范围之内。
Claims (9)
1.一种废弃SCR催化剂制备再生粉的方法,其特征在于:依次包括:
1)、对废弃SCR催化剂进行清洗,
2)、对清洗后的催化剂进行研磨、制浆,得到催化剂的一次浆液,向一次浆液中添加酸性除钒剂并进行搅拌,酸性除钒剂采用草酸,酸性除钒剂的浓度为3-9wt%,一次浆液与酸性除钒剂的液固比为6:1,添加草酸后在60℃下,搅拌4-7h,并调节pH值在3.0-1.0,对搅拌后的一次浆液进行压滤分离获得粉体,
3)、向粉体内添加硅铝除去剂进行洗涤、压滤后制浆,得到催化剂的二次浆液,向二次浆液中添加诱导活化剂、分散剂,诱导活化剂为二氧化钛前驱体,二氧化钛前驱体的加入量为5~50wt%,分散剂的加入量以二氧化钛干基质量计为0.1-0.7wt%,
4)、调节二次浆液的pH值在6.5-7.5后,进行搅拌、一次研磨、压滤、干燥、焙烧、二次研磨,获得再生粉。
2.根据权利要求1所述的废弃SCR催化剂制备再生粉的方法,其特征在于:在3)中,硅铝除去剂包括硫酸、氢氟酸、氟化铵。
3.根据权利要求1所述的废弃SCR催化剂制备再生粉的方法,其特征在于:在3)中,分散剂包括阴离子聚羧酸盐类、六偏磷酸钠、磷酸二氢钠。
4. 根据权利要求1所述的废弃SCR催化剂制备再生粉的方法,其特征在于:在2)中,一次浆液的浓度为25%~35wt%,催化剂颗粒的粒径要求在75μm -150μm;在3)中,二次浆液的浓度为10%~25wt%,催化剂颗粒的粒径要求在75μm -150μm。
5.根据权利要求1所述的废弃SCR催化剂制备再生粉的方法,其特征在于:在4)中,通过向二次浆液中添加硫酸、氨水调节pH值。
6.根据权利要求1所述的废弃SCR催化剂制备再生粉的方法,其特征在于:在4)中,干燥温度为90-115℃;焙烧温度为250-500℃。
7.根据权利要求1所述的废弃SCR催化剂制备再生粉的方法,其特征在于:在4)中,二次研磨后,再生粉D50≤3.0μm,D90≤10.0μm,微观比表面积50-90m2/g。
8.一种再生粉,其特征在于:该再生粉由权利要求1至7中任意一项权利要求所述的方法制备而成。
9.根据权利要求8所述的再生粉,其特征在于:该再生粉为钛钨粉或钛钨钒粉,其中二氧化钛的含量大于90%,二氧化钛晶钛为锐钛型,钒含量小于等于0.2%,钨保留相对含量大于原废催化剂钨含量的90%。
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