CN117563661A - 一种用于催化热解塑料高选择性转化制芳香烃的混合催化剂及其制备方法 - Google Patents
一种用于催化热解塑料高选择性转化制芳香烃的混合催化剂及其制备方法 Download PDFInfo
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- B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
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Abstract
本申请公开了一种用于催化热解塑料高选择性转化制芳香烃的混合催化剂及其制备方法。通过廉价的金属M改性镓基HZSM‑5分子筛催化剂,再与介孔MCM‑41分子筛组合得到的一种混合催化剂。该催化剂可用于塑料定向催化热转化为芳香烃化合物。其中,所述金属M选自Zr、Ce、Fe、Zn中的任意一种。通过本申请提供的催化剂,将LLDPE在较为温和的催化热解条件下,达到了93.11%的总芳烃选择性,单环芳烃也达到了73.46%。本发明的催化剂具有良好的催化活性和价格低廉等优点,工业化应用前景明朗。通过合理有效地再次利用废弃塑料,缓解了资源紧张问题。
Description
技术领域
本发明涉及催化剂材料及塑料热解领域,尤其涉及聚烯烃选择性转化制芳香烃及其制备方法。
背景技术
在催化热解中,沸石分子筛催化剂由于具有独特的孔道结构、较强的酸性、良好的芳烃选择性,使其在催化热解领域得到广泛的研究。其中,HZSM-5分子筛是一类具有MFI型拓扑结构,属高硅五元环型的沸石分子筛,其独特的交叉二维孔道为择形催化提供了空间限制作用,还有较强的酸性位点及酸量,被认为是现阶段塑料催化转化为芳烃最有效的催化剂。为了获得更高产率的芳香烃,需要沸石具有适度的酸性,为此,还可以选择对沸石进行改性。在诸多改性方法中,贵金属、碱土金属、稀土金属等改性方法最为常见,这主要是因为金属物种可以显著提高沸石的脱氢活性,并催化烷烃转化为烯烃,进而催化烯烃转化为芳烃。芳烃分类主要为单环芳烃、双环芳烃和多环芳烃,其中单环具有更高的经济和应用价值,例如BTEX中的苯(Benzene)、甲苯(Toluene)、乙苯(Ethylbenzene)和二甲苯(Xylene)应用最为广泛。现阶段芳烃的生产主要依靠高烷烃含量的原油经催化重整和石脑油等重油经蒸汽裂解工艺为主。随着芳烃原料的工业需求量不断提升,在全球日益严峻的能源利用形式下,对不可再生能源消耗又提出了新的挑战,这为废塑料与生物质利用热转化技术回收高附加值芳烃提供了契机。
专利申请CN 116179234 A生物质与废塑料协同在线催化热解制备芳香烃,选择性只达到了30.16%。专利申请CN 112029528 A通过酸改性活性炭在线催化热解低密度聚乙烯,得到单环芳烃的选择性为41.7%。专利申请CN 110819372 A将预处理后的聚乙烯进料至高压釜反应器中,采用3wt%锌负载的ZSM-5作为催化剂,可获得选择性为92.72%的单环芳烃。专利申请CN 107903932 A在微波热解下通过ZSM-5催化剂制备的航空煤油中芳香烃组分含量最高可达96.3%,但是煤油的产率较低都不超过40%。
由以上技术可知,在没有加压或者微波等苛刻的条件下得到的芳香烃选择性都很低,而在外场力的作用下又导致低的液相收率,因此,为了解决上述缺陷,提供一种性能优良、制备条件友好,并且尤其在废弃物芳构化方面有较温的条件及高的选择性和收率的催化剂,成为亟待解决的技术问题。
发明内容
针对上述现有技术中的缺陷,本发明的目的在于提供一种改性的微孔与介孔组合的芳构化催化剂,在其催化作用下,塑料能够在较温和的条件下实现高效转化制芳香烃。
该芳构化催化剂是以另一种廉价的金属来改性镓基HZSM-5,换而言之也可以称之为一种双金属改性HZSM-5分子筛催化剂,再与介孔MCM-41组合催化,用于催化热解塑料制备芳香烃,具有较高的催化活性、芳烃选择性以及传质传热效率。
为达到上述目的,本发明采用如下技术方案:
一种改性镓基HZSM-5分子筛催化剂,组成记为M-Ga/HZSM-5,其中金属M为Zr、Ce、Fe、Zn,负载量为2%~5%,金属Ga的负载量为3%~5%,所用载体HZSM-5的硅铝比为25。
一种改性镓基HZSM-5分子筛催化剂的制备方法,将Ga(NO3)3·xH2O和M的硝酸盐溶于超纯水中,并于水浴搅拌器中搅拌得到均匀的混合盐溶液,在混合溶液中缓慢加入HZSM-5分子筛,搅拌成糊状,烘箱干燥,研磨筛分,最后在马弗炉中焙烧即可获得。所述的金属盐水浴混合温度为80℃,时间为30min;加入分子筛后的水浴温度调整为60℃;焙烧温度为550℃,时间3h。
所述的一种用于塑料选择性转化制芳香烃的催化剂,是一种金属改性HZSM-5分子筛再与介孔MCM-41分子筛组合的催化剂,用于塑料催化热解制备芳烃。
整个反应过程一直保持着惰性气体氛围,以100mL/min的氮气作为载气,等反应温度达到500℃保持30min以活化催化剂再开始投料进行异位催化热解反应,反应时间为20min。反应在固定床反应器上进行。
相对于现有技术,本发明技术方案取得的有益效果是:
通过本发明所制备金属改性镓基HZSM-5分子筛催化剂联合介孔MCM-41分子筛组合催化剂具有很好的催化热解塑料芳构化活性。具体地,首先通过廉价的金属物种来调控HZSM-5分子筛的酸性位点及活性中心,使得芳香烃选择性得到了不错的提升,再进一步将其与介孔MCM-41组合定向调控,并且是在没有外场力的作用下,最后能达到了93.11%的芳香烃选择性,而且液相产物的收率均超过40%。
据我们所知,本发明制备的M-Ga/HZSM-5催化剂联合介孔MCM-41分子筛组合催化剂鲜有报导,并将之用于塑料的催化热解的研究更是缺乏,而本催化剂的应用还取得了高的芳构化效果,因此有很好的运用与发展前景。
附图说明
图1为本发明实施例5所得的复合催化剂的离子色谱图(图1(a)总离子色谱图;图1(b)局部离子色谱图)。
图2为实施例1-4所得的催化剂以及未改性的HZSM-5的XRD谱图(母体和金属改性镓基HZSM-5沸石的XRD谱图)。
图3为母体HZSM-5以及实施例1的扫描电镜图(母体(a)和实例1(b)的SEM图)。
图4为母体HZSM-5的元素映射。
图5为实施例1的元素映射。
图6为流程图。
具体实施方式
为了使本发明所要解决的技术问题、技术方案及有益效果更加清楚、明白,以下例举实施例,对本发明做进一步详细说明。所述的实施例是本发明的一部分实施例,而不是全部的实施例。
实施例1
制备2Zr-3Ga/HZSM-5催化剂并进行塑料催化热解芳构化测试分别称取0.471g硝酸锆五水合物、0.550g硝酸镓(III)水合物配成15mL混合硝酸盐溶液。在温度为80℃,转速为518rpb搅拌条件下持续搅拌30min得到均匀的硝酸盐溶液;在搅拌均匀的混合溶液中缓慢加入5g HZSM-5分子筛,并在60℃下搅拌成糊状;在105℃烘箱中干燥过夜24h;干燥后的催化剂研磨筛分后在马弗炉中焙烧,焙烧温度为550℃,时间为3h;焙烧后过100目筛网,得到的催化剂记为2Zr-3Ga/HZSM-5,其中2为Zr的质量分数,3为Ga的质量分数。
称取1.4g制备好的2Zr-3Ga/HZSM-5催化剂装入石英反应管下级的砂芯中,并将7g的塑料预装在上级的悬挂坩埚中。之后设置100mL/min的N2对体系进行吹扫,排除体系中存在的空气。随后以10℃/min升温速度程序升温升至500℃,并保持30min来活化催化剂。活化完成之后开始投料进行异位催化热解反应,反应时间为20min,整个反应过程一直保持N2氛围。值得注意的是,本发明的催化热解条件并没有涉及到高压等苛刻条件。最后反应产物通过冰水混合物冷凝收集并通过GC-MS对产物进行定性定量分析。催化剂评价结果见表1。
热解产物评价分析指标
SAHs=SMAHs+SPAHs (1-3)
式(1-1)中SMAHs表示单环芳烃的选择性,∑PMAHs表示单环芳烃化合物的总峰面积,Ptotal表示总峰面积;式(1-2)中SPAHs表示稠环芳烃的选择性,∑PPAHs表示稠环芳烃化合物的总峰面积;式(1-3)中SAHs表示芳香烃的选择性;式(1-4)中SOlefins表示烯烃的选择性,∑POlefins表示烯烃化合物的总峰面;式(1-5)中SAlkanes表示烷烃的选择性;∑PAlkanes表示烷烃化合物的总峰面积。
实施例2
制备2Zn-3Ga/HZSM-5催化剂并进行塑料催化热解芳构化测试
分别称取0.450g六水合硝酸锌、0.550g硝酸镓(III)水合物配成15mL混合硝酸盐溶液。其它制备及反应性能评价步骤与实施例1相同,得到的催化剂记为2Zn-3Ga/HZSM-5,并与实施例1的步骤一样用于催化热解塑料的反应的性能评价,催化剂评价结果见表1。
实施例3
制备2Fe-3Ga/HZSM-5催化剂并进行塑料催化热解芳构化测试
分别称取0.721g硝酸铁(III)九水合物、0.550g硝酸镓(III)水合物配成15mL混合硝酸盐溶液。其它制备及反应性能评价步骤与实施例1相同,得到的催化剂记为2Fe-3Ga/HZSM-5,催化剂评价结果见表1。
实施例4
制备2Ce-3Ga/HZSM-5催化剂并进行塑料催化热解芳构化测试
分别称取0.308g硝酸铈(III)六水合物、0.550g硝酸镓(III)水合物配成15mL混合硝酸盐溶液。其它制备及反应性能评价步骤与实施例1相同,得到的催化剂记为2Ce-3Ga/HZSM-5,催化剂评价结果见表1。
实施例5-8
上述实施例1-4制备所得的样品分别掺入0.7g硅铝比为25的介孔MCM-41分子筛并混合均匀,得到新的实施例5-8催化剂,并与实施例1的步骤一样用于催化热解塑料的反应的性能评价,评价结果见表2。
实施例9-10
上述实施例1制备所得的样品分别掺入0.47g、1.4g硅铝比为25的介孔MCM-41分子筛并混合均匀,得到新的实施例9-10催化剂,并与实施例1的步骤一样用于催化热解塑料的反应的性能评价,评价结果见表3。
对比例1
分别称取0.471g五水合硝酸锆、0.917g硝酸镓(III)水合物配成15mL混合硝酸盐溶液。得到的催化剂记为2Zr-5Ga/HZSM-5,并与实施例1的步骤一样用于催化热解塑料的反应的性能评价,催化剂评价结果见表4。
对比例2
分别称取0.450g六水合硝酸锌、0.917g硝酸镓(III)水合物配成15mL混合硝酸盐溶液。其它制备及反应性能评价步骤与实施例1相同,得到的催化剂记为2Zn-5Ga/HZSM-5,并与实施例1的步骤一样用于催化热解塑料的反应的性能评价,催化剂评价结果见表4。
表1不同金属组合改性HZSM-5分子筛的催化热解产物
表2不同金属组合改性HZSM-5分子筛与MCM-41组合的催化热解产物
表3不同比例组分的混合催化剂的催化热解产物
表4不同比例的金属组合改性HZSM-5分子筛的催化热解产物
由表1的结果可知,本发明提供的芳构化催化剂的制备方法均能得到高于60%的芳烃选择性,特别是实例5得到的催化剂在催化热解塑料芳构化中的活性最为优异,能得到选择性为93.11%的芳烃,单环芳烃的选择性也达到了73.46%。
通过实例1与实例5、实例2与实例6、实例3与实例7、实例4与实例8,两两对比可知,MCM-41的掺入对一开始就是低选择性的稠环芳烃的催化剂的芳构化活性起到抑制的作用,而对有些高选择性稠环芳烃的催化剂的芳构化带来了很大的促进作用,把总芳烃的选择性从84.01%优化到93.11%。这些结果表明,合适的酸性位点以及孔道结构的催化剂对于原料与产物之间的转化才是最重要的。
通过实施例1与对比例1、实施例2与对比例2的实验分析结果可知,当镓金属负载量从3%增加到5%,总芳烃的选择性分别从84.01%、82.74%降至77.72%、57.87%,单环芳烃的选择性也下降了不少。说明金属活性位不是越多越好,而适宜的金属活性位点,才更有利于芳构化效果的进一步提升。因此,在本发明的应用中,3%的镓基HZSM-5催化剂比5%的镓基HZSM-5催化剂更具有优势。
图1(a)和图1(b)分别是实例5中液相产物的GCMS的总离子色谱图、局部离子色谱图。在检测分析的过程中,使用氦气作为载气,进样口的温度为280℃,分流进样,分流比为60:1。柱温采用程序升温的方式,温度最初在40℃保持2min,以5℃/min的速度从40℃升至280℃,并保持5min。对于质谱条件,使用的电离方法为EI,电离能量为70eV,质量扫描范围在40~350amu(m/z),离子源的温度为200℃。
图2为实例1-4制备的催化剂的XRD图,该图是通过D/MAX-2500X射线多晶衍射仪使用Cu Kα辐射源,在工作压力和电流分别为10kV和40mA进行测量,2θ扫描范围为5°至90°之间,扫描速率为10°min-1。从图2表征中可以看出,所有双金属改性后的催化剂均保留了HZSM-5的MFI结构,且没有观察到任何金属物种的衍射峰,说明这种方法负载的金属物种都呈均匀分散状态。
图3、图4、图5为母体HZSM-5与实例5的SEM图及能谱图,该方法用于表征催化剂的形貌特征。使用仪器型号为捷克TESCAN MIRA LMS电子扫描显微镜用于观察改性前后沸石分子筛催化剂表面的形貌结构和表面元素的定性和半定量分析。取微量样品直接粘到导电胶上,形貌拍摄时加速电压为3kV,能谱mapping拍摄时加速电压为15kV,探测器为SE2二次电子探测器。该方法可以观察到金属物种分布在载体的表面,并且是没有团聚的,这与XRD的表征结果是一致的。
对于本领域技术人员而言,显然本发明不限于上述示范性实施例、对比例以及应用例的细节,而且在不背离本发明的精神或基本特征的情况下,能够以其他的具体形式实现本发明。因此,无论从哪一点来看,均应将实施例、对比例以及应用例看作是示范性的,而且是非限制性的,本发明的范围由所附权利要求而不是上述说明限定,因此旨在将落在权利要求的等同要件的含义和范围内的所有变化囊括在本发明内。不应将权利要求中的任何标记视为限制所涉及的权利要求。
Claims (4)
1.一种用于催化热解塑料高选择性转化制芳香烃的混合催化剂,所述的催化剂包含:
组分(1):改性镓基HZSM-5催化剂;和
组分(2):介孔MCM-41分子筛;
组分(1)和组分(2)的比例以质量比计为0.5~5。其中,组分(1)是以一种廉价的金属M来改性镓基HZSM-5催化剂,所述金属M选自Zr、Ce、Fe、Zn中的任意一种,所述的塑料为聚烯烃。
2.一种权利要求1所述的组分(1)中的改性方法,其特征在于,包括以下步骤:
(1)将Ga(NO3)3·xH2O和金属M的硝酸盐化合物溶于水中,混合均匀;
(2)加入HZSM-5载体,水浴搅拌至糊状;
(3)烘箱干燥,马弗炉焙烧,研磨过筛,得到镓基改性分子筛M-Ga/HZSM-5。
3.根据权利要求2所述的改性方法,其特征在于,在步骤(1)中,金属盐混合物首先溶于超纯水中,然后再置于80℃的水浴搅拌器搅拌30min,以致金属盐溶液混合均匀。所述的镓基HZSM-5分子筛为负载量3%~5%Ga的HZSM-5;所述的金属M的负载量为2%~5%。
4.根据权利要求1所述的催化热解塑料高选择性转化制芳香烃,其特征在于,所述催化热解塑料的条件为:在固定床反应器上进行异位催化热解反应,反应器以10℃/min升至500℃并保持30min来活化催化剂再开始投料反应,反应时间为20min,并用冰水混合物冷凝裂解气,整个过程始终保持100mL/min的N2吹扫。
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