CN117258752A - 一种利于挥发性有机物吸附的核壳沸石吸附剂 - Google Patents
一种利于挥发性有机物吸附的核壳沸石吸附剂 Download PDFInfo
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Abstract
本发明属于精细化工和无机材料领域,具体涉及一种利于挥发性有机物吸附的核壳沸石吸附剂;其以低硅铝比高比表面积沸石为核相载体,加入结构导向剂,并提供壳层生长的硅源等,凝胶晶化得到以低硅高比表面积沸石为核;所述核壳型吸附剂是以具有FAU拓扑结构的沸石为核,以具有较高硅铝比的疏水性材料为壳的核壳型沸石吸附材料,壳层厚度为15~100 nm。本发明通过提高核相沸石硅铝比以及合成体系中硅源和核相沸石的相对比例等来调变壳层的厚度,进一步改善核壳沸石吸附剂对挥发性有机化合物的吸附能力;该核壳沸石吸附剂结合了FAU沸石吸附量大和高硅壳层疏水的优点,使得其在VOCs捕集与有效脱除中有很重要的实用价值。
Description
技术领域
本发明属于精细化工和无机材料领域,具体涉及一种利于挥发性有机物吸附的核壳沸石吸附剂的制备方法。
技术背景
挥发性有机化合物(Volatile Organic Compounds , VOCs)是指在常压下沸点范围为50 ~260 ℃的有机化合物,其来源广泛,大多数被证明具有高毒性。
目前基于VOCs的脱除主要分为吸附分离,催化吸收,生物降解,光催化,催化氧化等。吸附法因其净化效率高、运行成本低而被公认为最有效、最经济的方法之一。
吸附技术的进步与吸附剂的更新换代密切相关。许多吸附剂如硅胶、活性炭、金属有机骨架(Metal Organic Frameworks,MOFs)和沸石已被用于吸附VOCs。硅胶主要用于干燥吸附和变压吸附。活性炭作为传统大宗吸附剂,价格低廉,吸附容量大,应用广泛,是吸附VOCs的常用材料。然而,在脱附过程中,一些高沸点物质不断堆积在材料内,导致吸附效率下降,其自身的可燃性限制了其循环利用。MOFs目前仍存在水热稳定性差、成本高等缺点。
沸石具有较高的比表面积、丰富的孔隙度、良好的水热稳定性、不可燃性和稳定的再生性,是作为VOCs吸附的优良备选材料。沸石分子筛也是一种离子型极性吸附剂,由于其高比表面积,高度有序的微孔孔道,可以实现VOCs分子的选择性吸附。同时由于其孔道表面高度极化,即沸石孔道内部有强大的库仑场和极性使其易于吸附极性较强、极化率较大的分子。目前广泛认为的观点是:硅铝酸盐类物质的组成,尤其是骨架中铝含量(骨架硅铝比),影响材料的亲疏水性,同时也是影响其吸附性能的重要参数。
具有FAU拓扑结构的低硅铝比沸石如Y,USY, 13X等相对而言具有较高的孔体积和比表面积,为VOCs 的吸附提供了更多的吸附位点从而具有较大的吸附量。其三维孔道体系,由12元环(0.74 nm×0.74 nm)组成,并通过超笼(1.1 nm×1.3 nm)相互连接,其较大的比表面积适合甲苯(分子尺寸为0.59 nm)等大分子进入通道进行吸附。然而,一般工业尾气中的挥发性有机化合物具有浓度低,含水量高的特点。具有FAU拓扑结构的沸石具有较低的硅铝比,使得尾气中ppm级的较低浓度的有机废气和水分子之间产生强烈的竞争吸附,低硅铝比沸石更亲水,因此优先吸附水分子,从而对VOCs的吸附性能显著下降。
值得注意的是,一些高硅材料,如SiO2, 高硅ZSM-5(纯硅Silicate-1),还有一些常见的有序介孔分子筛(如MCM-41和SBA-15)体相硅含量较高,这些材料高硅铝比组成赋予了其在湿条件下较好的疏水性。
发明内容
针对上述情况,本发明的目的是提供一种利于挥发性有机物吸附的核壳沸石吸附剂的制备方法,通过比表面积大吸附量大的低硅铝比沸石为核,在其上包裹一层高硅疏水化合物为壳的核@壳型复合分子筛材料的制备方法,以解决目前沸石吸附剂在湿环境下的VOCs吸附与脱除问题,使沸石吸附剂在湿环境下也有较好的VOCs控制脱除效果。
为实现上述目的,本发明所采取的技术方案是提供:一种利于挥发性有机物吸附的核壳沸石吸附剂的制备方法,其以低硅铝比高比表面积沸石为核相载体,加入结构导向剂(Structure Directing Agent,SDA),并提供壳层生长的硅源等,凝胶晶化得到以低硅高比表面积沸石为核,高硅疏水材料为壳的一种利于挥发性有机物吸附的核壳沸石吸附剂。
所述一种利于挥发性有机物吸附的核壳沸石吸附剂,具体是在微/介孔低硅铝比沸石的表面外延生长一层高硅疏水材料。
所述一种利于挥发性有机物吸附的核壳沸石吸附剂,核相材料选择X型、Y型沸石或USY沸石。
所述一种利于挥发性有机物吸附的核壳沸石吸附剂,高硅疏水化合物壳可以是SiO2、MCM-41、SBA-15、ZSM-5或Silicate-1,壳层厚度为15~100 nm。
所述有利于挥发性有机化合物组分优先吸附的核壳沸石吸附剂的制备方法,具体包括以下步骤:
(1)疏水壳层凝胶体系的配制:其摩尔组分配比:SDA : SiO2 : H+ : OH-:Al2O3 :TPA+ : ROH : H2O=(0~0.0073): 1.0 :(0~1.81):(0~1.81):(0~0.02):(0~0.2):(64.6~645): 270.0;向一定量的蒸馏水中依次加入碱/酸(醇),结构导向剂(SDA)和硅源,在一定温度下预水解,充分搅拌均匀,备用;
(2)将核相沸石加入已经预水解好的步骤(1)中的疏水壳层凝胶体系;充分搅拌后,进行晶化;产物经过洗涤中性,干燥,焙烧后即可得到利于挥发性有机物吸附的核壳沸石吸附剂。
所述步骤(1)中合成疏水壳层的SDA为聚环氧乙烷-聚环氧丙烷-聚环氧乙烷三嵌段共聚物(PEO-PPO-PEO,P123),十六烷基三甲基溴化铵(CTABr)或四丙基氢氧化铵(TPAOH);硅源为正硅酸乙酯或硅溶胶;酸为盐酸;碱为氢氧化钠或氨水(25 wt%);铝源为偏铝酸钠、氯化铝或异丙醇铝;醇为异丙醇或乙醇。
本发明采用溶胶凝胶外延生长法。首先将FAU沸石作为核相添加到疏水高硅壳层的水解体系,在结构导向剂和沸石表面库仑力的作用下,初始凝胶体系中的硅源等围绕核相生长,在特定条件下最终完全包裹核相FAU沸石,因此形成核壳沸石吸附剂。
本发明提供的上述核壳沸石吸附剂可应用于有机挥发气体组分在0~83% 相对湿度下的有效脱除。
本发明的有益效果是:所制备的利于挥发性有机物吸附的核壳沸石吸附剂,有效结合了核相和壳层材料的优点;核相FAU材料的比表面积丰富,孔道有大量的有机挥发性气体分子的吸附位点。在其表面包覆/二次生长高硅材料形成的壳层高硅疏水壳,起到屏蔽水分子的作用,有效阻碍了在高湿环境下的水分子吸附,同时高硅材料的介孔通道与核相微孔通道贯通,有利于净化后的的相对干燥的有机挥发物组分的传输扩散与较弱的与水分子的竞争吸附。本发明的制备方法具有原料廉价易得、工艺流程简单易行,可操作性强的优点,在解决富含水汽的工业尾气中有机挥发性气体组分的高效吸附方面具有广泛的应用前景。
附图说明
图1为本发明核壳沸石吸附剂的制备工艺流程图;
图2为实施例1制备的核壳沸石吸附剂的粉末X-射线广角衍射图;
图3为实施例1制备的核壳沸石吸附剂的粉末X-射线小角衍射图;
图4为工业Y沸石的扫描电子显微镜和透射电子显微镜图;
图5实施例1制备的核壳沸石吸附剂的扫描电子显微镜图;
图6实施例1制备的核壳沸石吸附剂的透射电子显微镜图;
图7为工业Y沸石和实施例1制备的核壳沸石吸附剂的C/C0-T穿透曲线;
图8为工业Y沸石和实施例1制备的核壳沸石吸附剂的累计吸附量曲线;
图9为实施例1制备的核壳沸石吸附剂在55%相对湿度条件下甲苯吸附循环稳定性测试;
图10为实施例1核壳吸附剂的饱和吸附量及穿透时间与循环次数与关系图。
具体实施方式
下面结合实施例对本发明的具体实施方式作进一步描述。以下实施例仅用于更加清楚地说明本发明的技术方案,而不是限制本发明的保护范围。本领域普通技术人员在不脱离本发明原理和宗旨的情况下,针对这些实施例进行的各种变化、修改、替换和变型,均应包含在本发明的保护范围之内。
实施例1
如图1所示,制备一种利于挥发性有机物吸附的核壳沸石吸附剂,其具体制备方法如下:
(1)疏水壳层凝胶体系的配制:将20 mL异丙醇和1 mL的氨水(25 wt%)加入200 mL的蒸馏水中,加入0.5 g CTABr充分溶解后缓慢加入12 g 正硅酸乙酯(TEOS),充分搅拌均匀,备用;
(2)将核相沸石Y加入已经预水解好的步骤(1)中的疏水壳层凝胶体系。充分搅拌后,将得到的混合液在45 ℃水解8 h。产物经过洗涤中性,干燥,焙烧后即可得到核壳沸石吸附剂实施例1。
图2、3为核壳沸石吸附剂的X-射线衍射图,从图2中可以看到所制备的核壳材料在2θ为6.3°,10.3°,20.8°,24.1°以及31.4°显示出FAU分子筛的特征衍射峰,分别对应于(111),(220),(331),(440),(533)以及(555)晶面;同时,从图3中的小角XRD衍射图在2.2°出现了较宽泛的衍射峰,这归属于MCM-4二维六方有序的(100)晶面;XRD图表明两相存在,即本发明实施例1制备的核壳材料具有FAU拓扑结构的沸石材料以及MCM-41材料的共同存在。
图4-6所示为本发明相关材料的扫描电子显微镜和透射电子显微镜图;图4中工业Y沸石呈现大小约为1 μm的八面体形貌,其表面非常光滑、致密。从图5可以看到制备的实施例1核壳吸附剂的粒径略大于工业Y沸石,但是表面变得粗糙,明显凸起;从图6的透射电镜图可以进一步清晰观察到制备的核壳吸附剂具有明显的核壳结构,其壳层厚度约为40 nm。
图7、8为本发明相关材料在83%相对湿度条件下的甲苯吸附性能测试。图7为工业Y沸石和本发明实施例1核壳吸附剂的甲苯C/C0-T穿透曲线,C0表示吸附床层入口甲苯的浓度,标定为初始浓度C0,C为在线色谱实时监测到的吸附床层出口甲苯的浓度;当开始通入甲苯气时,开始计时;可以从图7中看到,工业Y沸石和核壳吸附剂在吸附前期时C/ C0为0,吸附床层尾气出口检测不到甲苯,说明甲苯全部被吸附。而随着吸附时间延长,工业Y沸石很快达到吸附饱和(C/ C0=1),并且以极快的穿透速度出现了甲苯的脱附峰, C/C0值出现远大于1的情况,近乎达到6,这意味着尾气出口甲苯的浓度甚至超过入口甲苯浓度的5倍。由于水分子的存在,工业Y沸石的亲水性使得其优先吸附水分子而非甲苯等挥发性有机物,并且吸附床层中吸附了的甲苯吸附位点也进一步被水分子取代,这大大减少了工业Y沸石在湿条件下对甲苯气体的吸附量。而实施例1制备的核壳吸附剂的甲苯C/C0-T穿透曲线线型有着明显的不同,仍然呈现吸附剂典型的“S”型曲线,并未出现C/ C0大于1的情况,即吸附床层未被“穿透”。由于壳层的阻隔,有效的屏蔽了水分子,减弱了水与甲苯分子的竞争吸附,提高了核壳吸附剂的疏水性。从图8累计吸附量与时间的关系图也可以看出,实施例1所制备的核壳吸附剂的饱和吸附量为94.3 mg甲苯/g,远远高于工业Y沸石的1.1 mg甲苯/g。该核壳吸附剂优异的疏水性能使其具有高湿度条件下良好的甲苯吸附性能表现, 为具有较高湿度的工业VOCs尾气的脱除提供了解决思路。
图9、10为本发明实施例1核壳沸石吸附剂在55%相对湿度条件下甲苯吸附循环稳定性测;可以看到,每次甲苯循环C/C0-T穿透曲线的线型类似,且三次循环吸附量分别为111.9,114.2和108.8 mg甲苯/g,三次循环测试的穿透时间也很稳定,基本在103分钟,说明所制备的核壳沸石吸附具有良好的吸附性能稳定性和重复使用性,是在湿条件下优先对有机挥发物组分吸附的可循环利用的优良吸附剂。
实施例2
如图1所示,制备一种利于挥发性有机物吸附的核壳沸石吸附剂,其具体制备方法如下:
(1)76.1 mL的蒸馏水中加入0.58 g P123充分溶解后,缓慢加入3.47 g TEOS和60mL 1M的盐酸混合液,充分搅拌均匀后,备用;
(2)将核相沸石加入已经预水解好的步骤(1)中的疏水壳层凝胶体系;充分搅拌后,将得到的混合液在45 ℃继续水解2 h后转移至高压釜内,100 ℃进行水热晶化反应18h。产物经过洗涤中性,干燥,焙烧后即可得到核壳沸石吸附剂。
实施例3
如图1所示,制备一种利于挥发性有机物吸附的核壳沸石吸附剂,其具体制备方法如下:
(1)200 mL的蒸馏水中加入2.5 g CTABr充分搅拌均匀,0.56 g氢氧化钠加入,缓慢加入11.56 g TEOS充分水解后,备用;
(2)将步骤(1)中得到的核相沸石加入已经预水解好的步骤(1)中的疏水壳层凝胶体系。60 ℃充分搅拌12 h水解。产物经过洗涤中性,干燥,焙烧后即可得到核壳沸石吸附剂。
实施例4
如图1所示,制备一种利于挥发性有机物吸附的核壳沸石吸附剂,其具体制备方法如下:
(1)15.2 g的TPAOH(25 wt%)加入25 mL的蒸馏水中充分搅拌均匀,加入1.35 g偏铝酸钠,缓慢加入13.1 g TEOS充分搅拌后,备用;
(2)将步骤(1)中得到的核相沸石加入已经预水解好的步骤(1)中的疏水壳层凝胶体系,充分水解12 h后,将得到的混合液置于反应釜中, 160 ℃进行水热晶化反应72 h;产物经过洗涤中性,干燥,焙烧后即可得到核壳沸石吸附剂。
实施例5
如图1所示,制备一种利于挥发性有机物吸附的核壳沸石吸附剂,其具体制备方法如下:
(1)13.23 g的TPAOH(25 wt%)加入19.28mL的蒸馏水中充分搅拌均匀,加入19.28g 无水乙醇后缓慢加入14.05 g TEOS充分搅拌后,备用;
(2)将步骤(1)中得到的核相沸石加入已经预水解好的步骤(1)中的疏水壳层凝胶体系,充分水解12 h后,将得到的混合液置于反应釜中, 160 ℃进行水热晶化反应72 h。产物经过洗涤中性,干燥,焙烧后可得到核壳沸石吸附剂。
本发明所制备的利于挥发性有机物吸附的核壳沸石吸附剂,有效结合了核相和壳层材料的优点;核相FAU材料的比表面积丰富,孔道有大量的有机挥发性气体分子的吸附位点;在其表面包覆/二次生长高硅材料形成的壳层高硅疏水壳,起到屏蔽水分子的作用,有效阻碍了在高湿环境下的水分子吸附,同时高硅材料的介孔通道与核相微孔通道贯通,有利于净化后的的相对干燥的有机挥发物组分的传输扩散与较弱的与水分子的竞争吸附。本发明的制备方法具有原料廉价易得、工艺流程简单易行,可操作性强的优点,在解决富含水汽的工业尾气中有机挥发性气体组分的高效吸附方面具有广泛的应用前景。
Claims (2)
1.一种利于挥发性有机物吸附的核壳沸石吸附剂,其特征在于:所述核壳型吸附剂是以具有FAU拓扑结构的沸石为核,以具有较高硅铝比的疏水性材料为壳的核壳型沸石吸附材料,壳层厚度为15~100 nm;
所述的FAU沸石核相是13X型、Y型沸石或USY沸石中的任意一种;
所述的高硅疏水化合物壳是SiO2、MCM-41、SBA-15、ZSM-5或Silicate-1中的任意一种。
2.据权利要求1所述的一种利于挥发性有机物吸附的核壳沸石吸附剂,其特征在于:所述核壳型沸石吸附剂的制备方法,具体如下:
(1)疏水壳层凝胶体系的配制:其摩尔组分配比:SDA: SiO2: H+:OH-:Al2O3:TPA+:ROH:H2O=(0~0.0073):1.0:(0~1.81):(0~1.81):(0~0.02):(0~0.2):(64.6~645):270.0;向一定量的蒸馏水中依次加入碱/酸(醇),结构导向剂(SDA)和硅源,在一定温度下预水解,充分搅拌均匀,备用;
(2)将核相沸石加入已经预水解好的步骤(1)中的疏水壳层凝胶体系;充分搅拌后,进行晶化;产物经过洗涤中性,干燥,焙烧后即可得到具有核壳结构的FAU@高硅疏水复合材料;
所述步骤(2)中,核相FAU与高硅疏水化合物凝胶前驱体中氧化硅固相质量比为1.16~6.94;
所述步骤(2)中,焙烧温度为500~600 ℃。
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