CN111495386A - 一种磁性稀土掺杂低温脱硝催化剂的制备方法及应用 - Google Patents
一种磁性稀土掺杂低温脱硝催化剂的制备方法及应用 Download PDFInfo
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- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 3
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- MEYVLGVRTYSQHI-UHFFFAOYSA-L cobalt(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Co+2].[O-]S([O-])(=O)=O MEYVLGVRTYSQHI-UHFFFAOYSA-L 0.000 description 2
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- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
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- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
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- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
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- GFNGCDBZVSLSFT-UHFFFAOYSA-N titanium vanadium Chemical compound [Ti].[V] GFNGCDBZVSLSFT-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及一种磁性稀土掺杂低温脱硝催化剂的制备方法及应用,实现催化剂良好的低温脱硝活性和抗失活性能,并在催化剂失活后可以有效分离循环,提高利用率。将各前驱体前驱体溶于水中搅拌形成均相溶液;加入碱性沉淀试剂,调节pH值到碱性,使前驱体在溶液中发生共沉淀反应;在搅拌条件下加入氧化剂,使溶液中沉淀发生价态转化,形成具有磁性的金属氧化物浆料;对纳米浆料进行连续磁分离、洗涤、烘干得到磁性稀土低温脱硝催化剂。催化剂失活后,更换出失活催化剂,通过湿法研磨、连续磁力分离;将分离出来的催化剂磁性部分重新造粒,得到新鲜催化剂样品;将分离出来的催化剂失效部分溶解于水中,浓缩后,重复催化剂的制备过程。
Description
技术领域
本发明属于烟气脱硝技术领域,具体涉及一种磁性稀土掺杂低温脱硝催化剂的制备方法及应用。
背景技术
随着国家对各种燃烧烟气污染物排放控制标准的严格,电力行业、钢铁焦化等领域逐步实施了NH3-SCR脱硝技术,为我国良好的大气环境做出了贡献。现阶段应用的脱硝催化剂主要为钒钛系催化剂,应用温度窗口在200-400℃,主要应用于燃煤电厂高尘烟气环境。采用规整的蜂窝状或板式催化剂进行脱硝。
然而,中国有大量工业燃烧烟气,包括烟气脱硫之后,温度低于200℃,处于100-200℃,无法采用传统的钒钛系催化剂进行脱硝。研究者均在研究在该温度下具有优良脱硝活性的催化剂配方与制备工艺,锰系催化剂具有良好的低温活性成为主要的研究和报道对象。如专利CN201610231704报道了一种基于天然锰铁矿石的SCR脱硝催化剂及其制备方法,在150-240℃具有良好的脱硝活性。CN201710600936报道了一种锰铁钴整体式SCR低温催化剂制备与应用方法,通过在整体堇青石表面浸渍锰铁钴硝酸盐前驱体的方式进行制备,在125-200℃达到80%的脱硝效率。CN201110142238提出了一种同时脱硝脱汞的锰铁复合氧化物催化剂及制备方法,该催化剂活性组分为MnO2和Fe2O3,并添加有CuO、CeO2、V2O5等氧化物,采用浸渍或共沉淀发制备,具有同时催化氧化脱汞的效果。CN201610021790提出了铁锰钛复合金属氧化物脱硝催化剂制备方法,通过氨水沉淀制备铁铈钛沉淀,经烘干焙烧后,得到相应的催化剂,在低温条件下具有良好的脱硝活性与抗硫稳定性。
而以氧化锰为活性组分的脱硝或催化氧化磁性材料的报道,相对较少,如CN201010596024提出了一种磁性脱硝催化剂及应用,该催化剂以磁性氧化铁为活性组分,钙钛矿镧锰金属氧化物为载体,应用在磁场流化床中进行脱硝,在200-400℃条件下表现出良好的脱硝性能;CN201610119526提出了一种磁性铁基复合氧化物催化剂及制备方法,该催化剂采用碱性试剂沉淀可溶性亚铁与钛盐前驱体,经过过滤、洗涤、烘干焙烧后得到磁性铁基磁性复合氧化物催化剂,具有较好的低温活性。
上述专利大多采用共沉淀的方式制备锰系催化剂,强调催化剂的低温性能与抗硫中毒能力,而磁性脱硝催化剂大多以低温脱硝性能一般的氧化铁为活性组分,在磁场流化床中脱硝。但从根本上分析,低温条件下,锰系催化剂在烟气脱硝中一直没有得到工业应用,其根本原因在于以下两方面:(1)锰系催化剂的低温脱硝活性不足;(2)低温硫酸锰或是硫铵沉积导致失活。
发明内容
针对以上不足,本发明提出一种磁性稀土掺杂低温脱硝催化剂的制备方法及应用。实现催化剂良好的低温脱硝活性和抗失活性能,并在催化剂失活后可以有效分离循环,提高利用率。
本发明的一个方面,涉及一种磁性稀土掺杂低温脱硝催化剂的制备方法,包括以下步骤:
S1、将催化剂前驱体、稀土助剂氧化铈前驱体、磁性助剂前驱体溶于水中搅拌形成均相溶液;其中,催化剂前驱体为二价锰盐化合物,稀土助剂氧化铈前驱体为可溶性铈盐,磁性助剂前驱体为二价铁和/或钴的可溶性盐;
S2、加入碱性沉淀试剂,调节pH值到碱性,使前驱体在溶液中发生共沉淀反应;
S3、在搅拌条件下加入氧化剂,使溶液中沉淀发生价态转化,形成具有磁性的金属氧化物浆料;
S4、对纳米浆料进行连续磁分离、洗涤、烘干得到磁性稀土低温脱硝催化剂。
优选地,步骤S1中的催化剂前驱体为硫酸锰、硝酸锰中一种或两种混合物。
优选地,步骤S1中的稀土助剂氧化铈前驱体为硫酸铈、硝酸铈中的一种或两种混合物。
优选地,步骤S1中的磁性助剂前驱体硫酸盐、硝酸盐中的一种或两种混合物。
优选地,步骤S1中各前驱体质量含量组成范围为催化剂前驱体20%-80%、稀土助剂氧化铈前驱体10%-30%、磁性助剂前驱体的10-50%。
优选地,步骤S2中的碱性沉淀试剂主要为氨水、氢氧化钠水溶液或氢氧化钾水溶液;所述pH值在8-10之间。
优选地,步骤S3中的氧化剂为双氧水、臭氧或氧气。
本发明的另一个方面,一种磁性稀土掺杂低温脱硝催化剂的催化剂应用,包括以下步骤:
1)将催化剂填充固定床反应器中,与烟气进行接触,发生脱硝反应;
2)催化剂失活后,更换出失活催化剂,通过湿法研磨、连续磁力分离,利用催化剂的磁性与失效部分催化剂进行分离;
3)将分离出来的催化剂磁性部分重新造粒,得到新鲜催化剂样品;
4)将分离出来的催化剂失效部分溶解于水中,浓缩后,重复催化剂的制备过程。
本发明提出一种磁性稀土掺杂低温脱硝催化剂的制备方法及应用具有以下优势:
(1)通过原料的选择与制备方法的创新,有效调控了催化剂中锰、铁氧化物的价态,实现了磁性低温脱硝氧化物催化剂的制备;
(2)利用低温催化剂氧化物的磁性与失效催化剂溶解性和非磁性,实现失效后催化剂的有效分离。
(3)稀土助剂氧化铈的掺杂,有利于催化剂活性和结构的保持。
附图说明
附图是本发明实施例的脱硝率曲线图。
具体实施方式
下面结合附图并通过具体实施例来进一步说明本发明技术方案。
实施例1
将150g四水硫酸锰、40g硫酸亚铁,70g硫酸铈,加入1L去离子水,持续搅拌,溶解后形成均一体系,逐滴加入15%浓度的氨水,直到pH值达到9,逐渐形成褐色金属氧化物浆料。然后滴加双氧水,金属氧化物浆料颜色逐步变成黑褐色,并具有磁性,通过磁性分离洗涤后得到固定氧化物。
催化剂表面的硫酸盐失活后,更换出失活催化剂,通过湿法研磨、使失活催化剂溶于水,通过连续磁力分离,利用催化剂的磁性与失效部分催化剂进行分离;
将分离出来的催化剂磁性部分重新造粒,得到新鲜催化剂样品;
将分离出来的催化剂失效部分溶解于水中,浓缩后,重复催化剂的制备过程。
实施例2
将150g硝酸锰、40g七水硫酸钴,40g硫酸铈20g硝酸铈,加入1L去离子水,持续搅拌,溶解后形成均一体系,逐滴加入15%浓度的氨水,直到pH值达到9,逐渐形成褐色金属氧化物浆料。然后滴加双氧水,金属氧化物浆料颜色逐步变成黑褐色,并具有磁性,通过磁性分离洗涤后得到固定氧化物。
实施例3
将160g四水硫酸锰、20g硝酸亚铁、20g七水硫酸钴,70g硝酸铈,加入1L去离子水,持续搅拌,溶解后形成均一体系,逐滴加入15%浓度的氨水,直到pH值达到9,逐渐形成褐色金属氧化物浆料。然后滴加双氧水,金属氧化物浆料颜色逐步变成黑褐色,并具有磁性,通过磁性分离洗涤后得到固定氧化物。
在模拟烟气环境下,进行脱硝评价,测试各实施例的在130~180oC的脱硝率。各实施例脱硝率(%)曲线见附图。
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,在不脱离本发明技术原理的前提下,还可以做出若干改进和变形,这些改进和变形也应视为本发明的保护范围。
Claims (8)
1.一种磁性稀土掺杂低温脱硝催化剂的制备方法,其特征在于,包括以下步骤:
S1、将催化剂前驱体、稀土助剂氧化铈前驱体、磁性助剂前驱体溶于水中搅拌形成均相溶液;其中,催化剂前驱体为二价锰盐化合物,稀土助剂氧化铈前驱体为可溶性铈盐,磁性助剂前驱体为二价铁和/或钴的可溶性盐;
S2、加入碱性沉淀试剂,调节pH值到碱性,使前驱体在溶液中发生共沉淀反应;
S3、在搅拌条件下加入氧化剂,使溶液中沉淀发生价态转化,形成具有磁性的金属氧化物浆料;
S4、对纳米浆料进行连续磁分离、洗涤、烘干得到磁性稀土低温脱硝催化剂。
2.根据权利要求1所述的一种磁性稀土掺杂低温脱硝催化剂的制备方法,其特征在于,步骤S1中的催化剂前驱体为硫酸锰、硝酸锰中一种或两种混合物。
3.根据权利要求1所述的一种磁性稀土掺杂低温脱硝催化剂的制备方法,其特征在于,步骤S1中的稀土助剂氧化铈前驱体为硫酸铈、硝酸铈中的一种或两种混合物。
4.根据权利要求1所述的一种磁性稀土掺杂低温脱硝催化剂的制备方法,其特征在于,步骤S1中的磁性助剂前驱体硫酸盐、硝酸盐中的一种或两种混合物。
5.根据权利要求1所述的一种磁性稀土掺杂低温脱硝催化剂的制备方法,其特征在于,步骤S1中各前驱体质量含量组成范围为催化剂前驱体20%-80%、稀土助剂氧化铈前驱体10%-30%、磁性助剂前驱体的10-50%。
6.根据权利要求1所述的一种磁性稀土掺杂低温脱硝催化剂的制备方法,其特征在于,步骤S2中的碱性沉淀试剂主要为氨水、氢氧化钠水溶液或氢氧化钾水溶液;所述pH值在8-10之间。
7.根据权利要求1所述的一种磁性稀土掺杂低温脱硝催化剂的制备方法,其特征在于,步骤S3中的氧化剂为双氧水、臭氧或氧气。
8.根据权利要求1所述的一种磁性稀土掺杂低温脱硝催化剂的催化剂应用,其特征在于,包括以下步骤:
1)将催化剂填充固定床反应器中,与烟气进行接触,发生脱硝反应;
2)催化剂失活后,更换出失活催化剂,通过湿法研磨、连续磁力分离,利用催化剂的磁性与失效部分催化剂进行分离;
3)将分离出来的催化剂磁性部分重新造粒,得到新鲜催化剂样品;
4)将分离出来的催化剂失效部分溶解于水中,浓缩后,重复催化剂的制备过程。
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