CN114210314B - 双前驱体炭基催化剂及其制备方法、脱除甲醛和汞的应用 - Google Patents
双前驱体炭基催化剂及其制备方法、脱除甲醛和汞的应用 Download PDFInfo
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Abstract
本发明公开了双前驱体炭基催化剂及其制备方法、脱除甲醛和汞的应用,所述催化剂包括:活性组分和双前驱体载体,活性组分为过渡金属氧化物和/或稀土金属氧化物,双前驱体载体以核桃壳和/或秸秆为原料;所述催化剂制备方法包括如下步骤:(1)将核桃壳和秸秆等粉碎成混合颗粒;(2)混合颗粒经过ZnCl2活化24h(混合颗粒与ZnCl2质量比3:4);(3)将活化后料干燥,N2保护下煅烧制得双前驱体炭基载体(4)硝酸处理后水洗至中性;(5)采用超声辅助等体积浸渍法,取载体浸渍在活性金属前体混合溶液中,超声、干燥煅烧后制得催化剂。还公开了该双前驱体炭基催化剂应用。本发明催化剂呈现协同高效脱除HCHO和Hg0性能,具有较好推广价值和广阔工业应用前景。
Description
技术领域
本发明涉及空气污染治理领域,特别是涉及一种双前驱体炭基催化剂及其制备方法、脱除HCHO和Hg0的应用。
背景技术
煤炭等在燃烧过程中会产生粉尘、NOx、SOx、Hg0和VOCs等大气污染物。据了解,对粉尘、SOx和NOx排放控制和处理技术已相对比较成熟,而针对Hg0和VOCs的控制仍处于起步阶段。Hg0的高毒性、持久性、挥发性和生物蓄积性对人类生活环境造成了严重的威胁,过多的汞积累会造成人体内脏和心脏机能破坏,甚至死亡。VOCs作为典型的大气污染物,在大气化学反应中扮演重要角色,会产生臭氧及二次气溶胶等污染物。燃煤烟气汞包含氧化态汞(Hg2+)、颗粒态汞(Hg P)以及元素态汞(Hg0)三种,由于Hg2+易溶于水,所以可以被现有的湿式烟气脱硫设备(WFGD)有效去除,Hg P也易于被布袋除尘设备(FF)或静电除尘设备(ESP)捕集。但是占比较多的Hg0极易挥发且难溶于水,现有的 WFGD 和除尘设备对其去除能力有限,故不能满足汞的排放标准。燃煤锅炉排放的VOCs,主要由醛类、脂肪烃和芳香烃以及氯化烃组成。甲醛(HCHO)作为其中代表性的挥发性有机化合物,具有致畸、致突变、致癌等特性,已被世界卫生组织认定为I类致癌物质。因此,加强燃煤烟气中HCHO和Hg0的管控对国家经济发展和国民身体健康具有重要意义。
目前,HCHO的处理方法主要包括光化学降解、催化氧化、等离子处理、微生物处理、催化燃烧等。光化学降解需要高能的紫外线,能耗高而且容易产生第二次污染;等离子处理技术不能应用于易燃易爆场合和废气浓度超高的工况;微生物处理需要的细菌和微生物所需生存条件极为苛刻,且效率较低;催化燃烧能耗高而难以大面积推广。相比之下,催化氧化法因HCHO转化效率高、无二次污染、能源消耗低、应用范围广而成为HCHO治理技术的最佳选择。它能将HCHO催化氧化为二氧化碳和水等无毒害或少毒害的小分子物质,是一种既经济环保又具有巨大前景的一种HCHO治理技术。此外,Hg0由于本身难溶于水且易挥发而难以被收集控制。尽管通过使用商用矾基催化剂的SCR系统可以将Hg0氧化为可以被后续的湿式脱硫设备(WFGD)吸收的Hg2+,但其氧化能力有限。如今,活性炭喷射技术(ACI)是最接近应用的Hg0控制技术。为了满足工业锅炉HCHO和Hg0的达标排放,需要另外增加单独收集它们的处理装置,那么必然会增加设备投资,扩大整个系统的运行和维护成本。为此,在现有烟气粉尘、SO2和NOx治理设备基础上,如果能开发一种兼具催化还原NOx和催化氧化HCHO和Hg0的催化剂,在还原NO为无害的N2同时,使HCHO和Hg0分别转化为无害化的二氧化碳(CO2)和水(H2O)及易净化处理的Hg2+等,将是一种事半功倍的处理工艺和方法。
催化氧化法脱除HCHO将HCHO转化成CO2和H2O,没有紫外线与生物条件的限制,也没有吸附饱和的缺点。根据催化剂的组成可分为贵金属催化剂和过渡金属氧化物催化剂。目前用于HCHO氧化的贵金属催化剂通常以Pt、Pd、Au、Ag等为活性组分,而这些贵金属普遍价格昂贵难以广泛使用。过渡金属氧化物来源广泛,比贵金属热稳定性好且价格便宜。同时,过渡金属氧化物往往具有良好的电子结构、易于制备等特点,作为催化剂具有很大的潜力,如CN108940264A公开了一种Mn/Ce基催化剂,对甲醛的催化分解率保持在95%以上,最高可达99.3%。近些年,通过对过渡金属氧化物催化剂结构、形貌、缺陷等的研究和开发,其整体催化性能已接近甚至超过贵金属催化剂。
过渡金属氧化物催化剂多以载体催化剂为主。如中国专利CN104941669A公开了的一种V2O5-CeO2改性TiO2的SCR催化剂协同脱除NOx和Hg0,但它们所需最适温度区间较高(300-400℃)。再比如CN104338528A中公开的CeO2-ZrO2/海泡石催化剂仅是在常温下对HCHO具有良好催化活性,不适用燃煤烟气的工况条件。相较而言,利用秸秆与果壳这等廉价可再生的生物质原料来制备具有优异低温催化活性的生物质碳基催化剂以协同吸附-催化氧化燃煤烟气中HCHO和Hg0更有现实意义。活性炭产物的孔结构及应用与植物基前体的种类密切相关,当采用机械强度较低、较为疏松的花生壳、棉花、木屑、秸秆等原料作为前体时,制备出的炭材料一般孔径较大,孔隙率高,比表面积适中,对大分子的吸附能力较强。而以椰子壳、核桃壳等较为致密坚实的果壳类为前体时,制备出的活性炭往往孔径较小,比表面积高,机械强度大。现如今催化领域的多元化发展,通常单一前驱体所制备出来的生物质炭因其孔道结构的局限性已经难以适应现状。当采用多种前驱体通过调控前驱体的比例可以调控制备的活性炭的孔结构的分布,制备具有高比表面积、大孔容及分级孔结构的分级多孔炭,成为一大研究热点。
鉴于以上存在的问题,本发明采用两种生物质制备双前驱体生物质炭载体以及负载双活性金属氧化物的生物质炭催化剂来净化工业废气中的HCHO和Hg0,以达到将二者同时净化的目的。一方面采用多种生物质制备的多前驱体生物质活性炭,可通过调控各前驱体用量得到具有适宜比例的微孔-介孔-大孔比例的多级孔结构可以发挥各级孔的优点,有效解决了反应物与产物的传质,另一方面催化剂上各活性金属(以CrOx和CeOx为例)之间的相互作用增加了催化剂上活性氧物种的数目,促进了催化剂表面氧空穴的形成,提高了氧的流动性,从而有利于HCHO和Hg0的进一步降解和深度氧化,提高生成CO2和Hg2+的选择性。本发明为燃煤烟气去除HCHO和Hg0提供了新的技术方案。
发明内容
本发明的目的在于提供一种高效催化氧化HCHO和Hg0为无害的CO2、H2O和便于净化处理的Hg2+的多孔生物质炭催化剂制备及应用。
为实现上述发明目的,本发明采用如下技术方案:一种双前驱体催化剂,其特征在于,所述催化剂包括:活性组分和双前驱体载体,所述活性组分为过渡金属氧化物和/或稀土金属氧化物,双前驱体载体以核桃壳和/或秸秆为原料制备而成。
本发明可采用椰子壳、核桃壳等较为致密坚实的果壳类为前驱载体原料。
本发明可采用水稻秸秆等类似的秸秆为前驱载体原料。
进一步的,所述催化剂包括:活性组分和双前驱体载体,所述活性组分包括Cr氧化物、Ce氧化物、Mn氧化物、Fe氧化物中的一种或多种氧化物的混合,双前驱体载体是以核桃壳和秸秆为原料制备。
进一步的,所述催化剂包括:活性组分和双前驱体载体,所述活性组分为稀土金属或过渡金属氧化物,所述活性组分以CrOx和CeOx为例,双前驱体载体是以核桃壳和水稻秸秆为原料制备。
所述CrOx包括,CrO、Cr2O3、CrO3、CrO2中的一种或多种的混合;所述CeOx包括,CeO2、Ce2O3中的一种或多种的混合。
所述催化剂还包括制备载体的活化剂ZnCl2。
本发明中,所述催化剂中活性组分的含量为6wt.%~24wt.%,优选为18wt.%。
本发明中,所述CeOx和CeOx中,所述Cr占Cr+Ce摩尔比为0.25~0.75,Ce占Cr+Ce摩尔比为0.25~0.75,均优选为0.5。
在研究催化剂的基础上,本发明还提出了一种催化剂的制备方法,所述制备方法包括如下步骤:
(1)将核桃壳和秸秆,制成颗粒;
(2)将步骤(1)中等质量的两种颗粒混合均匀,后加入制备的ZnCl2水溶液,所述ZnCl2与两种混合颗粒质量比为4:3;
(3)将混合均匀的核桃壳和秸秆颗粒倒入步骤(2)ZnCl2溶液中搅拌均匀,静置24个小时,随后110℃干燥24h,后在750℃炭化2小时;
(4)6mol/L的硝酸溶液浸泡步骤(3)制备的材料,随后用水洗至中性,所得产物干燥,所得即为双前驱体载体WSAC;
(5)采用等体积浸渍法,取WSAC载体浸渍在铬盐和铈盐混合溶液中,超声,静置,干燥,煅烧,制得催化剂。
进一步的,所述制备方法包括如下步骤:
(1)将核桃壳和秸秆,制成颗粒;
(2)将步骤(1)中等质量的两种颗粒混合均匀,后加入制备的ZnCl2水溶液,所述ZnCl2与两种混合颗粒质量比为4:3;
(3)将混合均匀的核桃壳和秸秆颗粒倒入步骤(2)ZnCl2溶液中搅拌均匀,静置24个小时,随后110℃干燥24h,后在750℃炭化2小时;
(4)6mol/L的硝酸溶液浸泡步骤(3)制备的材料,随后用水洗至中性,所得产物进行干燥,即得双前驱体载体WSAC;
(5)采用等体积浸渍法,取WSAC载体浸渍在铬盐和铈盐混合溶液中,超声处理1h,随后静置23小时,干燥至恒重,然后在N2保护下550°C煅烧4.5小时,制得催化剂。
在本发明的具体实施方式中,所述ZnCl2水溶液为600~700g/L, 本发明的一个具体实施例中为666.6g/L;
本发明中,所述制备方法步骤(5)中,制得催化剂中所述铬盐和铈盐,以金属氧化物计含量为6wt.%~ 24wt.%,优选为18wt.%,所述Cr占Cr+Ce摩尔比为0.25~0.75,Ce占Cr+Ce摩尔比为0.25~0.75,均优选为0.5。
在研究催化剂的基础上,本发明还发现了一种双前驱体催化剂脱除甲醛、汞的应用,上述催化剂在脱除甲醛、汞中的应用。
本发明中,所述制备方法包括如下步骤:
(1)将核桃壳和秸秆,制成颗粒;
(2)将步骤(1)中等质量的两种原料粉末混合均匀,称量适量的ZnCl2制备ZnCl2溶液(ZnCl2与二种原料混合粉末质量比为4:3);
(3)将混合均匀的核桃壳和水稻秸秆混合粉末倒入步骤(2)ZnCl2溶液中搅拌均匀,室温静置一昼夜,随后置于110℃环境下干燥24h后,在750℃的N2保护的管式炉炭化2小时;
(4)分别用6mol/L的硝酸溶液浸泡步骤(3)制备的材料,随后用去离子水清洗数次至中性,最后将所得产物干燥并过60-80目筛,所得即为核桃壳和水稻秸秆双前驱体生物质炭载体WSAC;
(5)称量适量的铬盐和铈盐前躯体配置成前驱体溶液,取适量WSAC载体浸渍在上述铬盐和铈盐前躯体溶液中,超声处理1h,随后静置23小时,而后在105°C干燥箱干燥至恒重,然后在N2保护下550°C煅烧4.5小时,制得过渡金属氧化物CrOx和稀土金属氧化物CeOx共同改性的双前驱体生物质炭催化剂CrCe/WSAC。
所述X表示金属氧化物可能同时呈现多种价态。
本发明中,核桃壳和水稻秸秆经清洗、干燥和破碎后得到对应的原料颗粒,取它们的原料颗粒各250g,按ZnCl2与二种原料混合粉末质量比为4:3称量ZnCl2(即333.3g)制备500mLZnCl2溶液,再将混合粉末与ZnCl2溶液混合搅拌均匀,待其静置一昼夜后,放入干燥箱在110℃下干燥24小时,然后在N2保护下750℃炭化2小时,取出后用6mol/L硝酸溶液浸泡,并用水洗涤样品至至中性。然后将样品干燥24小时后研磨并过筛(60-80目),所得即为WSAC;
采用等体积浸渍法将3gWSAC浸渍于Cr(NO3)3·9H2O(1.37g)和Ce(NO3)2·6H2O(1.48g)混合溶液(加水3mL制成)中,并超声处理1h,待其静置23小时后,放入在105°C干燥箱干燥至恒重,最后通过管式炉在N2保护下550°C煅烧4.5小时,制得过渡金属氧化物CrOx和稀土金属氧化物CeOx共同改性的双前驱体生物质炭催化剂18 wt.%Cr0.5Ce0.5/WSA。
与现有技术相比,本发明的有益效果在于:
(1)本发明所述的双前驱体生物质炭催化剂CrCe/WSAC采用两种植物前体进行复配制备生物质炭载体,具有较高的比表面积、特定微孔-介孔-大孔比例的多级孔结构,后者可以发挥各级孔的优点,有利于反应物和产物的传质,在催化领域具有显著优势。
(2)本发明所述的超声辅助等体积浸渍法制备的Cr和Ce共同改性的双前驱体生物质炭催化剂制作方式简单,能表现出较高的HCHO和Hg0的催化氧化活性。
(3)本发明所述的双前驱体生物质炭基催化剂具有良好的抗SO2抗H2O中毒特性,具有广泛的应用前景。
附图说明
图1是本发明催化剂的SEM图(a:WSAC的SEM图,b:6 wt.%Cr0.5Ce0.5/WSAC的SEM图,c:12 wt.%Cr0.5Ce0.5/WSAC的SEM图,d:18 wt.%Cr0.5Ce0.5/WSAC的SEM图,e:24 wt.%Cr0.5Ce0.5/WSAC的SEM图);
图2是本发明的实施例2制备催化剂测试结果图(a:18wt.%Cr0.5Fe0.5/WSAC,18wt.%Cr0.5Mn0.5/WSAC,18 wt.%Cr0.5Ce0.5/WSAC,18 wt.%Mn0.5Ce0.5/WSAC,18 wt.%Fe0.5Ce0.5/WSAC甲醛脱除率结果图,b:18wt.%Cr0.5Fe0.5/WSAC,18 wt.%Cr0.5Mn0.5/WSAC,18 wt.%Cr0.5Ce0.5/WSAC,18 wt.%Mn0.5Ce0.5/WSAC,18 wt.%Fe0.5Ce0.5/WSAC汞脱除率图);
图3是本发明的实施例3制备催化剂测试结果图(a:6 wt.% Cr0.5Ce0.5/WSAC,12wt.% Cr0.5Ce0.5/WSAC,18 wt.% Cr0.5Ce0.5/WSAC,24 wt.% Cr0.5Ce0.5/WSAC,WSAC甲醛、汞的脱除率图;b:WSAC,18wt.%Cr0.5Fe0.5/WSAC,18wt.%Cr0.33Fe0.67/WSAC,18wt.%Cr0.67Fe0.33/WSAC),18wt.%Cr0.25Fe0.75/WSAC,18wt.%Cr0.75Fe0.25/WSAC甲醛脱除率图;c:WSAC,18wt.%Cr0.5Fe0.5/WSAC,18wt.%Cr0.33Fe0.67/WSAC,18wt.%Cr0.67Fe0.33/WSAC,18wt.%Cr0.25Fe0.75/WSAC,18wt.%Cr0.75Fe0.25/WSAC汞脱除率图);
图4是本发明的实施例4制备催化剂测试结果图;
图5是本发明的实施例5制备催化剂测试结果图。
具体实施方式
为更好地理解本发明的技术方案,下面用具体实例来说明本发明。有必要指出的是,实施例只是对本发明作出进一步说明,而可实施的情况并不限于实施例的范围,本发明不以任何方式局限于此。该领域的技术熟练人员可以根据上述发明的内容做出一些非本质性的改进和调整。
实施例1
本实施例中,核桃壳和水稻秸秆经清洗、干燥和破碎后得到对应的原料颗粒。取它们的原料颗粒各250g,按ZnCl2与二种原料混合粉末质量比为4:3称量ZnCl2(即约333.3g)制备约500mLZnCl2溶液,再将混合粉末与ZnCl2溶液混合搅拌均匀,待其静置一昼夜后放入干燥箱在110℃下干燥24小时。然后通过管式炉在N2保护下750℃炭化2小时,取出后用6mol/L硝酸溶液浸泡,并用去离子水洗涤样品至中性。然后将样品干燥24小时后研磨并过筛(60-80目),所得即为WSAC。
以上述3gWSAC为载体,制备多孔生物质炭催化剂(18 wt.%Cr0.5Ce0.5/WSAC)。其中,对应活性组分的含量均按照各自对应的氧化物计,并换算所需硝酸盐的量,具体如表一所示:
表一18 wt.%Cr0.5Ce0.5/WSAC所需原料量
活性炭质量(g) | 金属氧化物质量百分比(%) | Cr/Ce摩尔比 | <![CDATA[CrO<sub>x</sub>的摩尔质量(mol)]]> | <![CDATA[CeO<sub>x</sub>的摩尔质量(mol)]]> | <![CDATA[Cr(NO<sub>3</sub>)<sub>3</sub>·9H<sub>2</sub>O的质量(g)]]> | <![CDATA[Ce(NO<sub>3</sub>)<sub>2</sub>·6H<sub>2</sub>O的质量(g)]]> |
3 | 18 | 1 | 0.0034 | 0.0034 | 1.370 | 1.480 |
所述X表示金属氧化物可能同时呈现多种价态。
根据上表所需原料量,采用等体积浸渍法将3gWSAC浸渍于Cr(NO3)3·9H2O(1.37g)和Ce(NO3)2·6H2O(1.48g)混合溶液中,并超声处理1h。待其静置23小时后,放入在105°C干燥箱干燥至恒重。最后通过管式炉在N2保护下550°C煅烧4.5小时,制得过渡金属氧化物CrOx和稀土金属氧化物CeOx共同改性的双前驱体生物质炭催化剂18 wt.%Cr0.5Ce0.5/WSA。
所述18 wt.%Cr0.5Ce0.5/WSAC的比表面积为301.624m2/g,总孔容为0.2107cm3/g,平均孔径为2.068nm。
以本发明中0.2g的18 wt.%Cr0.5Ce0.5/WSAC为实验对象,在80~400°C温度范围内,模拟烟气气氛(SFG)包括100 ppm HCHO、100 μg/m3 Hg0 (g)、6% O2和平衡气体N2(99.99%)。测试结果显示HCHO的去除效率在280°C的效率最佳,为99.7%,汞的去除效率也在99.3%。
实施例2
制备方法同实施例1,在不改变载体和其中一种活性组分的前提下,适当改变另外一种活性组分来制得多孔炭基催化剂,即替换其中一种硝酸盐溶液,并换算所需硝酸盐或醋酸盐的质量。且所述金属氧化物占炭基催化剂CrFe/WSAC,CrMn/WSAC,CrCe/WSAC,MnCe/WSAC,FeCe/WSAC的质量百分比和两种金属氧化物摩尔均为18 wt.%和1:1,应用如下:
以本发明中0.2g的18wt.%Cr0.5Fe0.5/WSAC,18 wt.%Cr0.5Mn0.5/WSAC,18 wt.%Cr0.5Ce0.5/WSAC,18 wt.%Mn0.5Ce0.5/WSAC,18 wt.%Fe0.5Ce0.5/WSAC为实验对象,在80~400°C温度范围内,模拟烟气气氛(SFG)包括100 ppm HCHO、100 μg/m3 Hg0 (g)、6% O2和平衡气体N2(99.99%)。测试结果显示, 18wt.%Cr0.5Ce0.5/WSAC相比于其他样品,均表现出较高的HCHO(99.7%)和Hg0(99.3%)的去除效率。具体测试结果见说明书附图2。
实施例3
制备方法同实施例1,在不改变载体前提下,适当改变活性组分的负载量制得多孔炭基催化剂,所述金属氧化物占炭基催化剂CrCe/WSAC的质量百分比为取6 wt.%,12 wt.%,18 wt.%,24 wt.%。应用如下:
以本发明中0.2g的生物质炭催化剂为实验对象,在80~400°C温度范围内,模拟烟气气氛(SFG)包括100 ppm HCHO、100 μg/m3 Hg0 (g)、6% O2和平衡气体N2(99.99%)。测试结果表明适量的金属氧化物负载量有利于HCHO和Hg0的去除,而过少或过量的金属氧化物则会使HCHO和Hg0的去除效果降低。另外,通过SEM表征结果(图1)可以看出金属氧化物的引入极大地改变了WSAC的表面结构,当金属氧化物负载量为12 wt.%的样品上仍有部分碳表面未被利用,而过量的24 wt.%负载量的样品上则出现大量金属氧化物的团聚现象甚至堵塞部分孔道,而18 wt.%Cr0.5Ce0.5/WSAC上的金属氧化物分布较为均匀,能为催化反应提供足够的吸附和催化活性位点,从而具有最高的HCHO和Hg0去除效率。具体测试结果见说明书附图3。
实施例4
制备方法同实施例1,以最佳负载量18 wt.%和Cr/Ce最佳摩尔比1:1为标准,改变制备的载体种类,即所述载体为单前驱体核桃制备的生物质炭(WAC)、单前驱体水稻秸秆制备的生物质炭(SAC)以及两种前驱体原料复配制备的生物质炭载体(WSAC)。应用如下:
以本发明中0.2g的制备的炭基催化剂为实验对象,在80~400°C温度范围内,模拟烟气气氛(SFG)包括100 ppm HCHO、100 μg/m3 Hg0 (g)、6% O2和平衡气体N2(99.99%)。结果显示双前驱体制备的生物质炭催化剂具有比单一前驱体制备的生物质炭催化剂更好协同脱除HCHO和Hg0效果,说明双前驱体制备的生物质炭催化剂具有特定微孔-介孔-大孔比例的多级孔结构,有利于反应物和产物的传质,有利于活性金属氧化物分散,有助于增加活性位点,有利于催化氧化反应的进行。具体结果见说明书附图4。
实施例5
制备方法同实施例1,在保证最佳反应温度的前提下,考察H2O和SO2对催化剂协同脱除HCHO和Hg0性能的影响。应用如下:
以本发明中0.2g的18 wt.%Cr0.5Ce0.5/WSAC为实验对象,程序温度控制在80~400°C温度范围内,模拟烟气气氛(SFG)包括100 ppm HCHO、6% O2、平衡气体N2(99.99%)。随后向SFG加入300ppmSO2或8%H2O,可见催化剂的协同脱除HCHO和Hg0性能受到了轻微地抑制,不过向SFG同时加入300ppmSO2和8%H2O运行24h后HCHO的去除效率仍可达到86.3%,Hg0去除效率仍达到92.1%。说明本发明设计的双前驱体生物质炭基催化剂在具有优异的催化氧化HCHO和Hg0的性能,也兼具良好的抗水抗硫性。具体测试结果见说明书附图5。
本发明通过上述实施例来详细说明本发明所述材料的详细组成及制备方法,但本发明可实施的情况并不限于实施例的范围,即不意味着本发明必须依赖上述详细组成及制备方法成才能实施。所述技术领域的技术人员应该明了,对本发明的任何改进,或对产品各原料和方法的等效替换及辅助成分的添加、删减、具体方式的选择等,均落在本发明的保护范围和公开范围之内。
Claims (1)
1.一种双前驱体碳基催化剂在脱除甲醛、汞中的应用,其特征在于,在80~400℃温度范围内,模拟烟气气氛包括100ppmHCHO、100μg/m3Hg0、6%O2和平衡气体N2;
将核桃壳和水稻秸秆经清洗、干燥和破碎后得到对应的原料颗粒,取它们的原料颗粒各250g,按ZnCl2与二种原料混合粉末质量比为4:3称量ZnCl2制备500mLZnCl2溶液,再将混合粉末与ZnCl2溶液混合搅拌均匀,待其静置一昼夜后放入干燥箱在110℃下干燥24小时,然后通过管式炉在N2保护下750℃炭化2小时,取出后用6mol/L硝酸溶液浸泡,并用去离子水洗涤样品至中性,然后将样品干燥24小时后研磨并过筛60-80目得到WSAC;
以3gWSAC为载体,制备多孔生物质炭催化剂18wt.%Cr0.5Ce0.5/WSAC,所述18wt.%Cr0.5Ce0.5/WSAC的比表面积为301.624m2/g,总孔容为0.2107cm3/g,平均孔径为2.068nm;
采用等体积浸渍法将3gWSAC浸渍于Cr(NO3)3·9H2O和Ce(NO3)2·6H2O混合溶液中,并超声处理1h,待其静置23小时后,放入在105℃干燥箱干燥至恒重,最后通过管式炉在N2保护下550℃煅烧4.5小时,制得过渡金属氧化物CrOx和稀土金属氧化物CeOx共同改性的双前驱体生物质炭催化剂18wt.%Cr0.5Ce0.5/WSAC。
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