CN114100644A - 一种固体酸催化分离一体化填料及其制备方法和应用 - Google Patents
一种固体酸催化分离一体化填料及其制备方法和应用 Download PDFInfo
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 77
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- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims abstract description 6
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- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 3
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Abstract
本发明属于催化分离领域,具体为一种固体酸催化分离一体化填料及其制备方法和应用。以规整填料为载体,以高硅分子筛为活性涂层,并以磷钨酸、磷钼酸、硅钨酸、硅钼酸等杂多酸或磷钨酸盐、磷钼酸盐、硅钨酸盐、硅钼酸盐等杂多酸盐或氧化锆、氧化钨、氧化铌等超强酸对高硅分子筛涂层进一步修饰,形成具有固体酸催化性能和分离特性的规整催化分离填料。本发明解决了常规固体酸催化剂不具备宏观几何外形、不易分离操作,高温环境不稳定的问题,实现催化和精馏的原位耦合,高度融合固体酸催化剂的环保优势和规整填料的高理论塔板数优势,可在保证绿色合成的前提下,提高催化精馏效率。
Description
技术领域
本发明属于催化分离领域,具体为一种固体酸催化分离一体化填料及其制备方法和应用。
背景技术
反应精馏技术被认为是过程耦合强化概念在化工领域应用最为成功的经典案例之一,其将反应与精馏耦合集成于同一设备同时进行,为受化学平衡限制的化学反应过程强化带来了巨大的进步。然而,在催化精馏过程中所使用的催化分离材料的性能与结构成为限制这一过程广泛应用的瓶颈难题。通常,催化精馏过程使用强酸(如:硫酸)作为催化剂,副反应多,产品等级不高,设备腐蚀严重,产生大量含酸废水,污染环境,且催化剂不能重复使用。因此,亟需一种新型固体酸催化剂以解决液体酸催化剂带来的问题。然而,迄今为止,唯一商品化的用于酯化反应的固体酸催化剂只有阳离子交换树脂,但它缺乏足够的机械强度和热稳定性,且会膨胀失活,限制了通过提高反应温度来提高反应物转化率的可能。另外,阳离子交换树脂不能制备成规整结构,限制了其分离效果。
最近,沸石尤其是等级孔沸石,由于可以提供大量的可接触的酸性位,在催化酯化反应方面表现优异。但相对于硫酸和阳离子交换树脂,其酸强度还稍弱,催化活性还有待进一步提高。杂多酸是一种固体超强酸,由于具有强而均一的质子酸特性和独特的“准液相”行为在酸催化反应中表现优异。但是,纯杂多酸比表面积小(<10m2/g),且易溶于极性溶剂,使得回收及重复使用困难,限制了其作为多相催化剂使用。将杂多酸分散于等级孔沸石孔道内,不仅可以与沸石表面酸性位协同作用提高沸石酸强度,还可以通过等级孔道限制杂多酸流失,在乙酸正丁酯、乙酸异丁酯酯化反应合成中表现出良好的稳定性、活性和产物选择性。如果进一步将杂多酸修饰等级孔沸石负载到规整结构填料表面制成结构化沸石催化剂并应于反应精馏过程,不仅可以利用载体的分散作用将沸石稳定化并提高其利用率,还可以改善催化反应精馏体系中流体传递性能,在保持沸石高反应活性、高目标选择性等优点的前提下,有利于开发新的反应技术和过程集成技术,提高乳酸乙酯生产的节能、高效、清洁、安全水平。
泡沫碳化硅是一种高导热能力、高化学稳定性的结构化载体材料。中国科学院金属研究所在多个国家课题支持下,研发出具有全部自主知识产权的高性能、低成本泡沫碳化硅制备技术,并开展了泡沫碳化硅基结构化沸石催化剂在甲醇制丙烯反应中的应用研究,为开发具有工业应用价值的新型乳酸乙酯合成结构化催化剂奠定了良好的基础。最近,中国科学院金属研究所和天津大学合作开展了结构化沸石催化剂固定床连续流催化合成乙酸正戊酯的研究,对比了间歇反应与平推流反应两种装置,建立了反应动力学模型,该模型与实验显示出良好的一致性。近期,中国科学院金属研究所发明了一种高强度二维陶瓷丝网材料及其制备方法(申请公布号:CN 112174678 A)。该材料宏观上为一层或多层的平薄片或波纹片结构,丝网网丝自身为实心或空心结构,网丝所围的丝网孔孔径为2~60目,丝网孔面积占比为50%~95%,其组成材质优选但不限于碳化硅和/或氮化硅陶瓷,制备方法优选但不限于反应烧结。该材料作为规整填料使用,相对于金属规整填料,具有强度高、耐高温、耐腐蚀、耐氧化等特点,解决制造苛刻环境服役的工业装置或零部件所需丝网结构基础材料的力学强度低、不耐腐蚀、不耐高温等问题。发展以规整填料、特别是以多孔碳化硅为载体的结构化功能化修饰等级孔沸石催化剂(以下简称结构化沸石催化剂),对于提高我国溶剂绿色化和制备绿色化具有重要意义。
发明内容
为了解决上述阳离子交换树脂、分子筛催化剂和杂多酸催化剂存在的的局限性,本发明的目的在于提供一种具有固体酸特性、兼具催化和分离功能的结构化固体酸催化分离一体化填料及其制备方法和应用。
本发明的技术方案是:
一种固体酸催化分离一体化填料,以规整填料为载体,以高硅分子筛为活性涂层,并以杂多酸或杂多酸盐或超强酸对高硅分子筛涂层进一步修饰,形成具有固体酸催化性能和分离特性的规整催化分离填料;其中,杂多酸为磷钨酸、磷钼酸、硅钨酸或硅钼酸,杂多酸盐为磷钨酸盐、磷钼酸盐、硅钨酸盐或硅钼酸盐,超强酸为氧化锆、氧化钨或氧化铌。
所述的固体酸催化分离一体化填料,高硅分子筛涂覆于载体表面,分子筛涂层的厚度为5~100微米。
所述的固体酸催化分离一体化填料,分子筛的负载量为5~50wt%;杂多酸或杂多酸盐或超强酸的负载量为1~30wt%。
所述的固体酸催化分离一体化填料,规整填料为商业化的金属丝网填料或陶瓷丝网填料。
所述的固体酸催化分离一体化填料,陶瓷丝网填料宏观上为一层或两层以上叠合的平薄片或波纹片结构,陶瓷丝网填料的网丝自身为实心或空心结构,网丝所围的丝网孔孔径为2~60目,丝网孔面积占比为50%~95%,其组成材质优选但不限于碳化硅和/或氮化硅陶瓷,制备方法优选但不限于反应烧结。
所述的固体酸催化分离一体化填料,高硅分子筛为高硅MFI型沸石分子筛、高硅beta型沸石分子筛、高硅Y型沸石分子筛、MCM-41分子筛、高硅SBA-15分子筛、微孔二氧化硅或介孔二氧化硅。
所述的固体酸催化分离一体化填料,高硅MFI型沸石分子筛的硅铝原子比大于50,高硅beta型沸石分子筛的硅铝原子比大于20,高硅Y型沸石分子筛的硅铝原子比大于20。
所述的固体酸催化分离一体化填料的制备方法,包括如下步骤:
(1)通过原位水热合成,或涂覆,或涂覆结合蒸汽转晶,或涂覆结合水热转晶的方法,将高硅分子筛以涂层形式负载于规整填料表面;
(2)通过水热合成、浸渍或离子交换的方法,将杂多酸、杂多酸盐或超强酸负载于分子筛孔道中和表面。
所述的固体酸催化分离一体化填料的应用,固体酸催化分离一体化填料作为催化剂,用于催化精馏合成乳酸乙酯、丙二酸、乙酸乙酯和醋酸二甲酯的过程中。
本发明的设计思想是:
针对目前工业上生产各类酯多是以液体酸(如:硫酸)为催化剂,会带来设备腐蚀以及含酸废水处理的问题。树脂类固体强酸催化剂,虽然活性较高,但其热稳定性差、结构难以加工的问题。杂多酸修饰等级孔沸石可以提供大量可接触的酸性位,在酯化、水解和合成反应中表现出优异性能,成为替代树脂类固体酸催化剂的一种选择。如果进一步将杂多酸修饰等级孔沸石负载到泡沫碳化硅(SiC)载体表面制成结构化沸石催化材料,使催化材料兼具固体酸特性和结构可调变性的特点,实现催化材料设计和分离材料结构设计的结合,对于实现乳酸乙酯低碳、绿色合成具有重要意义。
本发明具有如下优点及有益效果:
(1)高硅介孔分子筛具有一定的固体酸特性和介孔结构来限域锚定杂多酸、杂多酸盐和氧化锆、氧化钨、氧化铌等纳米粒子。本发明通过酸性位的协同作用,达到协同高效催化的目的。同时,高硅介孔分子筛具有良好的耐酸特性,适用于酸性介质下的酯化反应、水解反应等。
(2)将上述活性组分负载于具有规整结构的载体上,解决了常规固体酸催化剂不具备宏观几何外形、不易分离操作,高温环境不稳定的问题。从而,实现催化和精馏的原位耦合,高度融合固体酸催化剂的环保优势和规整填料的高理论塔板数优势,可在保证绿色合成的前提下,提高催化精馏效率。
附图说明
图1为泡沫碳化硅规整填料作为载体,在其上负载高硅Y型分子筛作为活性组分,又通过杂多酸修饰高硅Y型分子筛所得的固体酸催化分离一体化填料实物图及扫描及投射电镜图。其中,(a)为波纹板精馏填料实物图,(b)为泡沫碳化硅骨架扫面电镜图,(c)为高硅分子筛涂层扫描电镜图,(d)为高硅分子筛透射电镜图,(e)为杂多酸负载于高硅分子筛介孔中的透射电镜图和结构示意图。
具体实施方式
在具体实施过程中,本发明方法以规整填料为载体,以高硅分子筛为活性涂层,并以磷钨酸、磷钼酸、硅钨酸、硅钼酸等杂多酸或磷钨酸盐、磷钼酸盐、硅钨酸盐、硅钼酸盐等杂多酸盐或氧化锆、氧化钨、氧化铌等超强酸对高硅分子筛涂层进一步修饰而形成的具有固体酸催化性能和分离特性的规整催化分离填料,作为催化剂。
该催化剂的制备方法如下:(1)通过原位水热合成、涂覆,涂覆结合蒸汽转晶或涂覆结合水热转晶的方法将高硅多级孔分子筛以涂层形式负载于规整填料表面。(2)通过水热合成、浸渍、或离子交换等方法将上述杂多酸、杂多酸盐或超强酸负载于分子筛孔道中和表面。
下面,通过实施例对本发明进一步详细阐述。
实施例1
本实施例中,以泡沫碳化硅陶瓷为载体,泡沫碳化硅载体具有三维连通孔道结构,孔径1毫米,孔体积分数70%。泡沫碳化硅载体表面涂覆高硅Y型介孔分子筛涂层,Y型分子筛的硅铝原子比为40;分子筛涂层的厚度为30微米,通过浸渍方法在分子筛涂层中负载硅钨酸,获得固体酸催化分离一体化填料。其中,分子筛的负载量为20wt%;硅钨酸的负载量为5wt%。
实施例2
本实施例中,以碳化硅丝网填料为载体,碳化硅丝网填料宏观上为一层或多层的平薄片或波纹片结构,网丝所围的丝网孔孔径为10目,丝网孔面积占比为75%。碳化硅丝网填料载体表面水热合成高硅ZSM-5型介孔分子筛涂层,ZSM-5型分子筛的硅铝原子比为200;分子筛涂层的厚度为80微米,通过离子交换方法在分子筛涂层中负载磷钼酸,获得固体酸催化分离一体化填料。其中,分子筛的负载量为30wt%;磷钼酸的负载量为23wt%。
实施例3
本实施例中,以金属丝网填料为载体,金属丝网填料宏观上为一层或多层的平薄片或波纹片结构,网丝所围的丝网孔孔径为60目,丝网孔面积占比为95%。金属丝网填料载体表面涂覆全硅silicalite-1型介孔分子筛涂层;分子筛涂层的厚度为100微米,通过水热合成方法在分子筛涂层中负载磷钨酸,获得固体酸催化分离一体化填料。其中,分子筛的负载量为30wt%;磷钨酸的负载量为15wt%。
实施例4
本实施例中,以金属波纹板填料为载体,金属波纹板填料宏观上为一层或多层的平薄片或波纹片结构。金属波纹板表面通过涂覆结合蒸汽相转化法负载beta型介孔分子筛涂层;分子筛涂层的厚度为10微米,通过浸渍方法在分子筛涂层中负载氧化锆,获得固体酸催化分离一体化填料。其中,分子筛的负载量为10wt%;氧化锆的负载量为8wt%。
实施例5
本实施例中,以泡沫碳化硅陶瓷为载体,泡沫碳化硅载体具有三维连通孔道结构,孔径1毫米,孔体积分数70%。泡沫碳化硅载体表面涂覆高硅Y型介孔分子筛涂层,Y型分子筛的硅铝原子比为100;分子筛涂层的厚度为20微米,通过浸渍方法在分子筛涂层中负载氧化钨,获得固体酸催化分离一体化填料。其中,分子筛的负载量为20wt%;氧化钨的负载量为8wt%。
实施例6
本实施例中,以碳化硅丝网填料为载体,碳化硅丝网填料宏观上为一层或多层的平薄片或波纹片结构,网丝所围的丝网孔孔径为10目,丝网孔面积占比为75%。碳化硅丝网填料载体表面水热合成高硅ZSM-5型介孔分子筛涂层,ZSM-5型分子筛的硅铝原子比为500;分子筛涂层的厚度为30微米,通过离子交换方法在分子筛涂层中负载氧化铌,获得固体酸催化分离一体化填料。其中,分子筛的负载量为30wt%;氧化铌的负载量为23wt%。
应用例
本应用例采用实施例1-6中得到的结构化固体酸作为催化剂,以乳酸乙酯、丙二酸、乙酸乙酯和醋酸二甲酯合成作为探针反应,结构化固体酸催化剂装填量为10升,结果见表1。
表1催化剂性能表
如图1所示,碳化硅规整填料宏观上具有波纹板结构,进一步观察可以看出每一片波纹板由三维联通的网孔组成,网孔尺度在毫米级。在毫米级网孔筋表面负载有厚度几十微米的分子筛涂层,分子筛涂层有几百纳米的分子筛颗粒组成。进一步通过投射电镜分析,几百纳米的分子筛晶体内部具有十几纳米的介孔,几纳米的杂多酸粒子被限域锚定在分子筛介孔孔道之中。
上述材料兼具催化与分离功能,实现了宏观结构设计和微观活性组分一体化设计。本发明结构化固体酸催化分离填料在催化精馏合成乳酸乙酯、丙二酸、乙酸乙酯和醋酸二甲酯等过程中表现出高活性、高目标产物选择性和高稳定性等优异性能。
Claims (9)
1.一种固体酸催化分离一体化填料,其特征在于,以规整填料为载体,以高硅分子筛为活性涂层,并以杂多酸或杂多酸盐或超强酸对高硅分子筛涂层进一步修饰,形成具有固体酸催化性能和分离特性的规整催化分离填料;其中,杂多酸为磷钨酸、磷钼酸、硅钨酸或硅钼酸,杂多酸盐为磷钨酸盐、磷钼酸盐、硅钨酸盐或硅钼酸盐,超强酸为氧化锆、氧化钨或氧化铌。
2.按照权利要求1所述的固体酸催化分离一体化填料,其特征在于,高硅分子筛涂覆于载体表面,分子筛涂层的厚度为5~100微米。
3.按照权利要求1所述的固体酸催化分离一体化填料,其特征在于,分子筛的负载量为5~50wt%;杂多酸或杂多酸盐或超强酸的负载量为1~30wt%。
4.按照权利要求1所述的固体酸催化分离一体化填料,其特征在于,规整填料为商业化的金属丝网填料或陶瓷丝网填料。
5.按照权利要求4所述的固体酸催化分离一体化填料,其特征在于,陶瓷丝网填料宏观上为一层或两层以上叠合的平薄片或波纹片结构,陶瓷丝网填料的网丝自身为实心或空心结构,网丝所围的丝网孔孔径为2~60目,丝网孔面积占比为50%~95%,其组成材质优选但不限于碳化硅和/或氮化硅陶瓷,制备方法优选但不限于反应烧结。
6.按照权利要求1所述的固体酸催化分离一体化填料,其特征在于,高硅分子筛为高硅MFI型沸石分子筛、高硅beta型沸石分子筛、高硅Y型沸石分子筛、MCM-41分子筛、高硅SBA-15分子筛、微孔二氧化硅或介孔二氧化硅。
7.按照权利要求6所述的固体酸催化分离一体化填料,其特征在于,高硅MFI型沸石分子筛的硅铝原子比大于50,高硅beta型沸石分子筛的硅铝原子比大于20,高硅Y型沸石分子筛的硅铝原子比大于20。
8.一种权利要求1至7之一所述的固体酸催化分离一体化填料的制备方法,其特征在于,包括如下步骤:
(1)通过原位水热合成,或涂覆,或涂覆结合蒸汽转晶,或涂覆结合水热转晶的方法,将高硅分子筛以涂层形式负载于规整填料表面;
(2)通过水热合成、浸渍或离子交换的方法,将杂多酸、杂多酸盐或超强酸负载于分子筛孔道中和表面。
9.一种权利要求1至7之一所述的固体酸催化分离一体化填料的应用,其特征在于,固体酸催化分离一体化填料作为催化剂,用于催化精馏合成乳酸乙酯、丙二酸、乙酸乙酯和醋酸二甲酯的过程中。
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