CN113101925A - 一种木质素基吸附-催化材料的制备方法及应用 - Google Patents
一种木质素基吸附-催化材料的制备方法及应用 Download PDFInfo
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Abstract
本发明为一种木质素基吸附‑催化材料的制备方法及应用,该制备方法采用木质素为碳源,首先对木质素进行强碱预处理,随后将预处理后的木质素与Ru盐溶液浸渍,最后在惰性气氛下碳化获得吸附‑催化材料。本发明实现氯代芳烃一步法“吸附‑催化”去除,解决了单一吸附法只吸附、不降解以及分开使用吸附剂与催化剂导致的处理效率低、能耗高等问题。吸附‑催化材料能彻底氧化降解污染物为CO2和H2O等无毒产物,且材料能够回收循环使用;另外本发明先负载再碳化,实现了吸附催化一体化的同时,降低了整体碳化温度,有助于气体中氯代芳烃的吸附‑催化作用,适用于大规模推广和工业化生产,提高生产效率。
Description
技术领域
本发明属于大气污染治理领域,具体涉及一种木质素基吸附-催化材料的制备及其去除气体中氯代芳烃的方法,尤其是对于低浓度氯代芳烃的去除。
背景技术
氯代芳烃类污染物具有“致癌、致畸、致突变”的三致特性及高毒性,对氯代芳烃的污染控制在国内外受到广泛关注。吸附法通过对污染物分子进行吸附,常被用于污染物去除。然而,吸附处理法只能对污染物分子富集,不能彻底降解污染物为无毒产物。另外,吸附剂吸附容量有限,重复回收需要升温处理,导致污染物脱附,造成二次污染。催化氧化可彻底降解氯代芳烃为CO2及H2O等无毒产物,然而现有的催化氧化方式对于低浓度污染物(<50ppm)处理效率较低,导致经济性较差。因此,本申请拟开发一种吸附-催化材料,首先吸附富集低浓度污染物随后彻底催化降解污染物为无毒产物。
目前已有联合吸附催化处理挥发性有机物(VOCs)的具体应用中往往将吸附剂和催化剂分开使用,导致处理过程中需要两次高温处理,第一次是高温下的污染物脱附,第二次是高温下的污染物催化燃烧,整个流程中能耗较高,经济性较差,开发新型的吸附-催化一体化材料,对提高氯代芳烃处理中的效率和经济性具有现实意义。
木质素是一种可再生的天然酚类聚合物,富含酚羟基、醇羟基、羧基等多种官能团。目前,已有专利报道木质素基碳材料制备及其吸附去除污染物,并都获得了较好的效果。专利(CN 106044744A)报道了一种石墨烯/木质素基碳材料的制备方法及其用途,该制备方法首先将混合氧化石墨烯与木质素磺酸钠碳化,再使用氢氧化钾活化,随后再碳化,最后洗涤得到石墨烯/木质素基复合多级孔碳片材料,结果表明石墨烯/木质素基复合多级孔碳片材料对环丙沙星有良好的吸附动力学性能。专利(CN 201910365919.3)报道了一种用于焚烧烟气中氯代芳烃净化的秸秆基复合吸附剂,该吸附剂以作物秸秆为原料,经过碱-尿素预处理,采用接枝聚合工艺对天然秸秆表面进行改性。将改性后的秸秆与高比表面积的碳质材料按照一定比例混匀,最后通过挤压造粒,制得秸秆基复合吸附剂。该材料对氯代芳烃的去除率可达95.7%。综上,利用木质素作为原材料制备木质素基吸附-催化材料,并通过改性和修饰优化其比表面积、微孔率,开发一体化去除低浓度氯代芳烃类极性污染物的方法具有创新性。
发明内容
为了克服现有技术对氯代芳烃类污染物中单一吸附或者单一催化效果较差的问题,本发明的目的是,提供一种木质素基吸附-催化材料的制备方法及应用。该方法中木质素经过碱处理后直接与Ru盐浸渍,再碳化,使碱处理后的木质素的官能团能与Ru盐发生相互作用降低碳化温度,能够获得高比表面积及高缺陷密度、Ru元素在材料表面以较高含量的Ru0形式存在的吸附-催化材料。
为实现上述目的,本发明的技术方案是:
第一方面,本发明提供一种木质素基吸附-催化材料的制备方法,该方法采用木质素为碳源,首先对木质素进行强碱预处理,随后将预处理后的木质素与Ru盐溶液浸渍,最后在惰性气氛下碳化获得吸附-催化材料。
上述木质素基吸附-催化材料的制备方法,具体包括如下步骤:
(1)木质素预处理:将木质素放入pH大于10的碱溶液中进行预处理,随后将预处理后的木质素调节中和,再用去离子水洗涤至中性后干燥;
(2)吸附-催化材料制备:将步骤(1)中所得预处理的木质素与Ru盐溶液浸渍,干燥;随后将干燥后的前驱体在惰性气氛下碳化得到吸附-催化材料,碳化温度保持在280-350℃,Ru的负载量为1.0-2.5wt%。
优选地,步骤(1)中的碱溶液为浓度范围为0.1-1mol/L的KOH、NaOH溶液等;中和时使用盐酸、硫酸等强酸性溶液进行中和,去掉碱溶液预处理过程中多余的氢氧根。
优选地,步骤(2)中Ru盐为三氯化钌,负载量为2.0wt%。该三氯化钌中的Cl元素能部分附着于最后的吸附-催化材料,提高对氯代芳烃的催化效果。
优选地,步骤(2)所述浸渍的时间3h以上,优选为4h-12h,时间太短,不能完全浸渍;碳化过程优选在氮气或者氩气下进行,所述氮气或者氩气的流量优选为75-150mL/min;碳化温度保持在300-350℃,升温速率为10-60℃/min。
优选地,步骤(1)所述木质素的粒径为2mm-4mm。较小的粒径有助于增加吸附催化剂的比表面积和孔隙容积,更有利于吸附低浓度的氯代芳烃,但粒径也不能太小,粒径太小会产生压降,反应不容易进行且增加成本。
第二方面,本发明提供一种上述木质素基吸附-催化材料在气体中氯代芳烃处理的应用,该应用的过程是:将上述木质素基吸附-催化材料用于去除氯代芳烃类污染物,以邻二氯苯(o-DCB)作为氯代芳烃模型化合物,利用固定床吸附-在线检测装置对木质素基吸附-催化材料吸附催化性能进行测试,在同一个反应室内分两段进行,第一阶段在50-200℃下进行吸附处理,直至吸附饱和(750-1500min.);然后升温至300-400℃,进入第二阶段,进行30min左右(30-40min.)的催化降解,完全反应,利用木质素基吸附-催化材料中的催化剂组分将氯代芳烃催化氧化为CO2和H2O;污染物尾气经GC-FID检测,计算得到木质素基吸附-催化材料去除邻二氯苯的效率及CO2的产率。此时,不仅污染物被彻底降解,木质素基吸附催化材料也脱附再生,进而吸附-催化一体化材料可以循环使用。
或者设置两个平行使用的吸附催化室,将木质素基吸附-催化材料放入第一个吸附催化室中,在低于催化降解阶段反应温度的温度下,利用木质素基吸附-催化材料中的木质素组分对低浓度氯代芳烃充分富集,当尾气中再次检测到o-DCB(即吸附饱和)后,再将木质素基吸附-催化材料置于第二个吸附催化室,在300-400℃的温度下进行催化降解,两个吸附催化室的温度条件分别为较低吸附温度和较高催化温度,第一个吸附催化室的反应温度比第二个吸附催化室的反应温度低,在第二个吸附催化室内不需要外加催化剂;每隔750-1500min.,将木质素基吸附-催化材料在两吸附催化室中交换,以实现吸附-催化材料的高效循环应用及提高吸附-催化处理的效率。
利用固定床吸附-在线检测装置对木质素基吸附-催化材料吸附催化性能进行测试时总气体流量为50-200mL/min,o-DCB浓度为10-50ppm,吸附-催化剂的质量为50-500mg。
本发明与传统木质素应用和单一吸附或单一催化材料处理氯代芳烃相比,具有以下优点:
1.本发明所制备的木质素基吸附-催化材料以木质素为原材料。木质素来源丰富,价格低廉,其以下特点为本工艺提供了有利条件:木质素的基本结构单元包括多种紫丁香基、愈创木基及对羟基等芳香结构,这些基本结构单元再由C-O/C-C链接构成复杂三维网状结构。对木质素进行碱性pH下的预处理,使木质素的三维网状结构发生一定程度的水解后加入Ru盐溶液,Ru离子进入木质素的隧道孔隙,对吸附剂的表面起到了很好的支撑作用,可提高材料的稳定性和比表面积,利于氯代芳烃吸附降解;同时,加入的Ru金属与木质素预处理中得到的产物可形成有机金属螯合物,有机金属螯合物对氯代芳烃C-Cl的键具有特定的识别功能,经过低温碳化处理,部分有机金属螯合物未发生反应,还有另一部分有机金属螯合物发生反应。未反应的有机金属螯合物与氯代芳烃接触后弱化C-Cl键的离解能,有利于Cl的脱除;反应的有机金属螯合物碳化后形成网状结构,锚定钌位点,使其高度分散,高效氧化脱氯后的芳香环,进而实现负载Ru后木质素基吸附-催化材料在低温下对氯代芳烃进行吸附降解。
2.本发明实现氯代芳烃一步法“吸附-催化”去除,解决了单一吸附法只吸附、不降解以及分开使用吸附剂与催化剂导致的处理效率低、能耗高等问题。吸附-催化材料能彻底氧化降解污染物为CO2和H2O等无毒产物,且材料能够回收循环使用;另外本发明先负载再碳化,实现了吸附催化一体化的同时,降低了整体碳化温度,有助于气体中氯代芳烃的吸附-催化作用,适用于大规模推广和工业化生产,提高生产效率。
具体实施方式
下面结合实施例对本发明作进一步详细的描述,但本发明的实施方式不限于此。
实施例1
一、木质素预处理
称取10g碱性木质素,过60目筛,取得筛下部分放入干燥箱中进行24h干燥处理。随后称取5g氢氧化钾粉末溶于去离子水中制成pH=11的碱性KOH溶液;
将5g干燥后的木质素与25mL上述的KOH溶液分别混合,并在室温下搅拌2h。
加入浓度为1mol/L的HCl溶液,进行中和,再用去离子水洗涤至中性,抽滤,把得到的滤饼置于烘箱进行干燥,干燥温度为105℃,干燥时间为13h;
二、吸附-催化材料制备
采用等体积浸渍法制备,将蒸馏水分别慢慢滴入5g上述的预处理后的木质素(LC-B),直到上述材料吸水恰好达到饱和,得到浸渍液体积。
称取一定质量的氯化钌粉末溶于去离子水中制成浓度为0.5mol/L的RuCl3溶液,使得溶液体积恰好等于浸渍液体积。
另取5g木质素(LC-B)与上述RuCl3溶液混合之后搅拌均匀,常温下放入通风橱4h以上,之后放入烘箱干燥10-12h,即制得负载量为2wt%木质素基混合材料。
将上述木质素基混合材料置于热解炉中碳化。氮气流量为100ml/min,升温速率为60℃/min,碳化温度分别为300℃,处理时间为1h,最终得到吸附-催化材料(碱性吸附-催化材料(Ru/LC-B))。
对比例1
本对比例的吸附-催化材料各步骤同实施例1,不同之处在于:
将质量分数为85wt%的H3PO4加水稀释制成pH=4的酸性溶液,
预处理时选择25mL的去离子水、和25mL的H3PO4溶液对木质素进行预处理,对应的磷酸处理后用1mol/L的KOH溶液中进行中和,再用去离子水洗涤至中性;分别得到中性木质素(LC-A)和酸性木质素(LC-C),
之后再分别让上述的两种处理方式的木质素浸渍Ru盐,对应获得中性条件吸附-催化材料(Ru/LC-A)和酸性吸附-催化材料(Ru/LC-C);
使用N2-物理吸附测定上述三种吸附-催化材料比表面积,结果如表1所示。
表1不同pH预处理下吸附-催化材料的比表面积
将上述三种吸附-催化材料分别置于吸附催化反应室内进行吸附-催化性能测试,第一阶段吸附催化反应室升温至50℃,将邻二氯苯通入进行吸附处理;第二阶段升温至300℃,在该温度下进行催化降解反应。利用固定床气相色谱GC-FID对于组分进行分离和检测,并根据结果分别计算对应的吸附性能和催化效果。测试结果如表2及表3所示:
表2邻二氯苯在50℃下通过不同吸附-催化材料的吸附性能
表3邻二氯苯在300℃下不同吸附-催化材料的CO2产率
综上,采用本申请中强碱性处理获得的碱性吸附-催化材料(Ru/LC-B)比表面积更大,更有利于低浓度氯代芳烃的吸附,吸附性能及催化效果均较好。碱预处理后的吸附催化材料的吸附性能明显更优,在50℃低温下能实现99%以上的邻二氯苯去除率,且在300℃下能够实现100%的CO2产率,实现邻二氯苯的无毒降解。
实施例2
本实施例各步骤同实施例1,不同之处在于,本实施例中Ru负载量为1wt%。
对比例2
本对比例各步骤同实施例1不同之处在于,本实施例中Ru负载量为5wt%。
通过X射线光电子光谱(XPS)对上述实施例1-2和对比例2中不同Ru负载量催化剂表面Ru物种进行测定,对比结果见表4。
表4不同Ru负载量下Ru的价态
综上,在负载量为1wt%或2wt%时,催化剂表面同时存在Ru0和Ru3+,Ru0的存在对Ru的催化氧化性能具有关键作用,同时较高的Ru0将促进有机螯合物的形成,从而降低氯代芳烃的C-Cl键能。负载量为2wt%的吸附-催化材料效果最佳,有利于氯代芳烃催化降解。当Ru含量太低时,催化效率低;Ru含量太高容易发生团聚,不能与反应物良好的接触,且表面无Ru0,吸附催化性能显著降低。
对比例3
本对比例各步骤同实施例1,不同之处在于,本对比例中,碳化温度分别为280℃,300℃,350℃,400℃,处理时间为1h。
使用拉曼光谱仪对实施例1与对比例3的吸附-催化材料进行分析,结果见表5。
表5不同碳化温度下吸附-催化材料ID/IG的强度比
ID/IG的强度比反应了这些碳材料的缺陷密度和石墨化程度,指拉曼光谱中D线与G线的积分强度比。其中在碳化温度为300℃的时候,ID/IG的比值最大为1.036,与其他温度的ID/IG的比值(小于1)比较,说明在300℃下碳化Ru/LC-B有更高的缺陷密度。且吸附-催化试验表明,碳化温度为300℃的吸附-催化材料的效果最佳,更有利于吸附富集低浓度污染物随后彻底降解为无毒产物。
实施例3
本实施例以实施例1制备获得的吸附-催化材料(Ru/LC-B)处理氯代芳烃。
以邻二氯苯(o-DCB)作为氯代芳烃代表性化合物,利用固定床气相色谱GC-FID对于经过吸附-催化材料(Ru/LC-B)处理的氯代芳烃组分别进行分离和检测。
称取100mg吸附-催化材料(Ru/LC-B)装填于石英管吸附床中,吸附-催化材料两端装填石英棉垫层。邻二氯苯初始浓度为30ppm,总气体流量为60mL/min,反应温度分别为50℃,100℃,150℃,200℃,250℃,280℃,300℃,并根据检测结果计算得到不同温度下邻二氯苯的去除率及CO2产率,见表6。同时将实施例1的催化剂在300℃下进行多次吸附-催化循环使用,效果见表7。
表6不同反应温度下邻二氯苯去除率及CO2产率
表7 300℃下吸附-催化材料循环使用下的邻二氯苯去除率
可见,本申请的木质素基吸附-催化材料(Ru/LC-B)在50-300℃时具有良好的吸附催化性能,邻二氯苯的去除率均在80%以上,且在300℃可完全降解邻二氯苯为无毒CO2,成功实现了氯代芳烃的无害化处理(表6)。同时该吸附-催化材料经可循环使用5次仍能保持较高污染物去除效率(表7),材料使用寿命长,可循环使用,更加经济。
本实施例中使吸附-催化材料置于同反应温度下的一体化处理效果,提高吸附-催化材料在实际中的应用性能。
本发明制备方法在给定的条件下均能够获得高比表面积、高缺陷、表面负载Ru0的高效吸附-催化材料,能使气体中氯代芳烃的去除率保持在80%以上,同时能够实现氯代芳烃的完全降解,不需要引入新的催化剂,使用回收方便。
上述实施例为本发明较佳的实施方式,但本发明的实施方式并不受上述实施例的限制,其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化,均应为等效的置换方式,都包含在本发明的保护范围之内。
本发明未述及之处适用于现有技术。
Claims (9)
1.一种木质素基吸附-催化材料的制备方法,其特征在于,该制备方法采用木质素为碳源,首先对木质素进行强碱预处理,随后将预处理后的木质素与Ru盐溶液浸渍,最后在惰性气氛下碳化获得吸附-催化材料。
2.根据权利要求1所述的制备方法,其特征在于,所述吸附-催化材料为高比表面积、高缺陷密度、Ru元素在材料表面以较高含量的Ru0形式存在;吸附-催化材料的比表面积为1000-1800m2/g;缺陷密度用ID/IG表示,ID/IG的比值不小于1;在材料表面Ru0的相对浓度为62-65%。
3.一种木质素基吸附-催化材料的制备方法,该制备方法包括以下步骤:
(1)木质素预处理:将木质素放入pH大于10的碱溶液中进行预处理,随后将预处理后的木质素调节中和,再用去离子水洗涤至中性后干燥;
(2)吸附-催化材料制备:将步骤(1)中所得预处理的木质素与Ru盐溶液浸渍,干燥;随后将干燥后的前驱体在惰性气氛下碳化得到吸附-催化材料,碳化温度保持在280-350℃,Ru的负载量为1.0-2.5wt%。
4.根据权利要求3所述的制备方法,其特征在于,步骤(1)中的碱溶液为浓度范围为0.1-1mol/L的KOH溶液或NaOH溶液;中和时使用盐酸或硫酸溶液进行中和。
5.根据权利要求3所述的制备方法,其特征在于,步骤(2)中Ru盐为三氯化钌,负载量为2.0wt%;步骤(2)所述浸渍的时间为4h-12h;碳化过程在氮气或者氩气下进行,所述氮气或者氩气的流量为75-150mL/min;碳化温度保持在300-350℃,升温速率为10-60℃/min。
6.根据权利要求3所述的制备方法,其特征在于,步骤(1)中所述木质素的粒径为2mm-4mm。
7.一种权利要求1-6任一所述的制备方法获得的木质素基吸附-催化材料在气体中氯代芳烃处理的应用,其特征在于,该应用的过程是:将上述木质素基吸附-催化材料用于去除氯代芳烃类污染物,以邻二氯苯o-DCB作为氯代芳烃模型化合物,利用固定床吸附-在线检测装置对木质素基吸附-催化材料吸附催化性能进行测试,在同一个反应室内分两段进行,第一阶段在50-200℃下进行吸附,至吸附饱和;然后升温至300-400℃,进入第二阶段,进行催化降解,利用木质素基吸附-催化材料中的催化组分将催化材料吸附的高浓度氯代芳烃催化氧化为CO2和H2O;污染物尾气经GC-FID检测,计算得到木质素基吸附-催化材料去除邻二氯苯的效率及CO2的产率。
8.根据权利要求7所述的应用,其特征在于,利用固定床吸附-在线检测装置对木质素基吸附-催化材料吸附催化性能进行测试时总气体流量为50-200mL/min,o-DCB浓度为10-50ppm,吸附-催化剂的质量为50-500mg。
9.一种权利要求1-6任一所述的制备方法获得的木质素基吸附-催化材料在气体中氯代芳烃处理的应用,其特征在于,设置两个平行使用的吸附催化室,将木质素基吸附-催化材料放入第一个吸附催化室中,在低于催化降解阶段反应温度的温度下,利用木质素基吸附-催化材料中的木质素组分对低浓度氯代芳烃充分富集,至吸附饱和,再将木质素基吸附-催化材料置于第二个吸附催化室,在300-400℃的温度下进行催化降解,第一个吸附催化室的反应温度比第二个吸附催化室的反应温度低;每隔达到吸附饱和的时间,将木质素基吸附-催化材料在两吸附催化室中交换,以实现吸附-催化材料的高效循环应用及提高吸附-催化处理的效率。
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