CN111939952B - 一种多级孔催化剂及其制备方法与应用 - Google Patents
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Abstract
本发明涉及一种多级孔催化剂,该催化剂由占总质量30%~60%的活性组分和余量为具有三维有序多级孔道的SiO2载体制成;以重量份计,所述活性组分由17.66g/35.32g(NH4)6Mo7O24·4H2O、0.25g NH4VO3、0.42g Cu(CH3C00)2·2H2O、0.48g SbCl3、0.30g H3AsO4、1.09g H3PO4、0.35g La(CH3COO)3·1.5H2O、0.45g Ce(NO3)3·6H2O和2.12g CsOH·H2O构成。同时,本发明还公开了该催化剂的制备方法和应用。本发明可显著提高反应催化活性,其用于催化异丁醛氧化脱氢制备甲基丙烯酸能够在空气作为氧化剂,常压条件下进行,在较低的反应温度条件下,可得到较高的甲基丙烯酸收率和较低的COX生成率。
Description
技术领域
本发明涉及异丁醛转化利用领域,尤其涉及一种多级孔催化剂及其制备方法与应用。
背景技术
甲基丙烯酸(MAA)是生产甲基丙烯酸甲酯(MMA)及其它高级酯的基本原料。MAA和甲醇经酯化获得MMA单体,MMA单体经聚合的产物俗称有机玻璃,具有优越的透明性、机械强度、机加工性和耐候性,是丙烯酸酯类产品中产量最大,用途最广的品种。
以异丁醛为原料制甲基丙烯酸(MAA)是有机玻璃单体生产的最经济的工艺路线。该工艺路线主要由日本化学药品公司研发(日特开昭50-149611),吉林大学等在异丁酸氧化脱氢制甲基丙烯酸杂多酸催化剂研究的基础上,开展了异丁醛一步氧化脱氢制MAA的研究工作,开发了杂多酸催化剂及其担载型催化剂(吴通好等,异丁醛氧化制甲基丙烯酸杂多酸催化剂的研究,高等化学学报,1985, vol. 6,No.3:265;吴通好等,异丁醛一步氧化制甲基丙烯酸杂多酸系催化剂的研究,石油化工,1985,6:313)。该过程由于较高反应温度及氧的参与,反应物及产物容易发生深度氧化等副反应,限制了甲基丙烯酸选择性的提高。
由于异丁醛氧化脱氢制甲基丙烯酸反应过程是强放热反应,反应床层易形成热点。为有效提高甲基丙烯酸选择性和控制反应床层温度,催化剂制备及载体的选择尤为重要。复合型氧化物催化剂及传统载体负载型催化剂,如无定型SiO2、Al2O3等,热传导性能较差,反应床层易形成热点,反应过程难以有效控制,限制了其工业应用推广。
发明内容
本发明所要解决的技术问题是提供一种提高催化活性的多级孔催化剂及其制备方法与应用。
本发明所要解决的另一个技术问题是提供该多级孔催化剂的制备方法。
本发明所要解决的第三个技术问题是提供该多级孔催化剂的应用。
为解决上述问题,本发明所述的一种多级孔催化剂,其特征在于:该催化剂由占总质量30%~60%的活性组分和余量为具有三维有序多级孔道的SiO2载体制成;以重量份计,所述活性组分由17.66g/35.32g (NH4)6Mo7O24·4H2O、0.25g NH4VO3、0.42g Cu(CH3C00)2·2H2O、0.48g SbCl3、0.30g H3AsO4、1.09g H3PO4、0.35g La(CH3COO)3·1.5H2O、0.45g Ce(NO3)3·6H2O和2.12g CsOH·H2O构成。
所述SiO2载体是指使用硅源、大孔模板剂和介孔模板剂通过挥发自组装的方法合成SiO2前驱体,该前驱体先于100~120℃干燥12~24h,再于不低于600℃焙烧4~8h即得具有三维有序大孔-介孔结构的SiO2;所述大孔模板剂为聚甲基丙烯酸甲酯(PMMA);所述介孔模板剂为聚氧乙烯聚氧丙烯醚嵌段共聚物(Pluronic F127)。
所述H3AsO4与所述H3PO4的质量浓度均为85%。
如上所述的一种多级孔催化剂的制备方法,包括以下步骤:
⑴按配比称重;
⑵将(NH4)6Mo7O24·4H2O与NH4VO3溶于去离子水中,得到浸渍液A;将Cu(CH3C00)2·2H2O与SbCl3溶于去离子水中,得到浸渍液B;将H3AsO4与H3PO4溶于去离子水中,得到浸渍液C;将La(CH3COO)3·1.5H2O与Ce(NO3)3·6H2O溶于去离子水中,得到浸渍液D;将CsOH·H2O溶于去离子水中,得到浸渍液E;
⑶将所述浸渍液A于80℃~100℃浸渍到所述SiO2载体上,于120℃干燥3~12h;同理,依次将所述浸渍液B、所述浸渍液C、所述浸渍液D、所述浸渍液E浸渍到所述SiO2载体上,得到样品;
⑷所述样品120℃干燥过夜后,于350~450℃焙烧4~6h即得。
所述浸渍为等体积浸渍,且浸渍分多次进行。
如上所述的一种多级孔催化剂的应用,其特征在于:该催化剂在异丁醛制备甲基丙烯酸中催化异丁醛氧化脱氢制甲基丙烯酸反应。
本发明与现有技术相比具有以下优点:
1、本发明中以三维有序大孔-介孔结构的SiO2作为载体,载体中的大孔通道可以使原料、气体快速到达介孔表面的活性位点上,从而促进反应地快速进行;另外,有序介孔结构使得活性物种更好地分散,提高催化剂活性;同时,大孔结构可以加快流体扩散的速率和容量,反应产物快速地脱离反应活性中心,避免进一步深度氧化,从而降低COX生成率。
2、本发明使用多级孔道结构的SiO2为载体,对改善异丁醛氧化脱氢制甲基丙烯酸反应工艺过程有重要影响,大孔网络通道极易扩散的优势,使得催化剂具有较强的热传导能力,避免反应床层热点的形成,反应过程可得到有效控制,更有利于其工业应用。
3、本发明所得的催化剂使用的载体具有多级孔结构、比表面积较大的特点,该催化剂能够通过将活性组分以浸渍法负载到催化剂表面上及孔道中的方式进行制备,可以实现根据不同反应条件对催化剂反应活性的要求,灵活调整活性组分含量和配比。
4、本发明所得的催化剂可适应较宽泛的操作条件,异丁醛氧化脱氢制甲基丙烯酸性能优异。
附图说明
下面结合附图对本发明的具体实施方式作进一步详细的说明。
图1为本发明实施例1中的载体三维有序大孔-介孔SiO2的透射电子显微镜图(50nm)。
图2为本发明实施例1中的载体三维有序大孔-介孔SiO2的透射电子显微镜图(100nm)。
图3为本发明实施例1中的载体三维有序大孔-介孔SiO2的扫描电子显微镜图(1.00µm)。
具体实施方式
实施例1 一种多级孔催化剂,该催化剂由23.12g活性组分和53.95g的具有三维有序多级孔道的SiO2载体制成;活性组分由17.66g (NH4)6Mo7O24·4H2O、0.25g NH4VO3、0.42gCu(CH3C00)2·2H2O、0.48g SbCl3、0.30g H3AsO4、1.09g H3PO4、0.35g La(CH3COO)3·1.5H2O、0.45g Ce(NO3)3·6H2O和2.12g CsOH·H2O构成。
其中:SiO2载体是指使用硅源、大孔模板剂和介孔模板剂通过挥发自组装的方法合成SiO2前驱体,该前驱体先于100~120℃干燥12~24h,再于不低于600℃焙烧4~8h即得具有三维有序大孔-介孔结构的SiO2。具体方法如下:
①将50g甲基丙烯酸甲酯(MMA)溶于500g水中得到甲基丙烯酸甲酯的水溶液;在80℃、氮气气氛、搅拌条件下,缓慢向甲基丙烯酸甲酯的水溶液中加入0.05g连二亚硫酸钾,继续搅拌12h溶液逐渐变为乳白色,得到乳液;该乳液经离心纯化、蒸馏水洗涤除去未反应的单体和杂质后,于80℃干燥24h,得到大孔模板剂PMMA。
②将65g的F127与40g浓度为0.2mol/L HCl溶液和300mL无水乙醇混合,得到混合液;向混合液中加入100g的硅酸四乙酯并升温至60℃搅拌1h后静置过夜。
③将步骤①合成的全部大孔模板剂PMMA加入到步骤②静置过夜后的溶液中,在60℃下挥发,于100~120℃下干燥12~24h,然后在不低于600℃下焙烧4~8h,即得具有三维有序大孔-介孔结构的SiO2。
该具有三维有序大孔-介孔结构的SiO2经透射电子显微镜以及扫描电子显微镜测试,结果显示如图1~图3所示。该三维有序大孔-介孔结构的SiO2的比表面积为320m2·g-1,其大孔的平均孔径为170nm,大孔孔壁厚度为8nm,介孔的平均孔径为6nm,
该多级孔催化剂的制备方法,包括以下步骤:
⑴按配比称重;
⑵将17.66g (NH4)6Mo7O24·4H2O与0.25g NH4VO3溶于100mL去离子水中,得到浸渍液A;将0.42g Cu(CH3C00)2·2H2O与0.48g SbCl3溶于100mL去离子水中,得到浸渍液B;将0.30g H3AsO4与1.09g H3PO4溶于100mL去离子水中,得到浸渍液C;将0.35g La(CH3COO)3·1.5H2O与0.45g Ce(NO3)3·6H2O溶于100mL去离子水中,得到浸渍液D;将2.12g CsOH·H2O溶于100mL去离子水中,得到浸渍液E;
⑶采用等体积浸渍法,将浸渍液A于80℃浸渍到53.95g SiO2载体(筛选40~60目的载体)上,于120℃干燥12h;同理,依次将浸渍液B、浸渍液C、浸渍液D、浸渍液E浸渍到SiO2载体上,得到样品;
⑷样品120℃干燥过夜后,于400℃焙烧6h即得催化剂A1。
实施例2 一种多级孔催化剂,该催化剂由40.78g活性组分和95.15g具有三维有序多级孔道的SiO2载体制成;活性组分由35.32g (NH4)6Mo7O24·4H2O、0.25g NH4VO3、0.42g Cu(CH3C00)2·2H2O、0.48g SbCl3、0.30g H3AsO4、1.09g H3PO4、0.35g La(CH3COO)3·1.5H2O、0.45g Ce(NO3)3·6H2O和2.12g CsOH·H2O构成。
其中:SiO2载体同实施例1。
该多级孔催化剂的制备方法,包括以下步骤:
⑴按配比称重;
⑵将35.32g (NH4)6Mo7O24·4H2O与0.25g NH4VO3溶于100mL去离子水中,得到浸渍液A;浸渍液B、浸渍液C、浸渍液D、浸渍液E同实施例1;
⑶采用等体积浸渍法,将浸渍液A于100℃浸渍到95.15g SiO2载体(筛选40~60目的载体)上,于120℃干燥3h;同理,依次将浸渍液B、浸渍液C、浸渍液D、浸渍液E浸渍到SiO2载体上,得到样品;
⑷样品120℃干燥过夜后,于350℃焙烧6h即得催化剂B1。
实施例3 一种多级孔催化剂,该催化剂由23.12g活性组分和28.25g具有三维有序多级孔道的SiO2载体制成;活性组分由17.66g (NH4)6Mo7O24·4H2O、0.25g NH4VO3、0.42g Cu(CH3C00)2·2H2O、0.48g SbCl3、0.30g H3AsO4、1.09g H3PO4、0.35g La(CH3COO)3·1.5H2O、0.45g Ce(NO3)3·6H2O和2.12g CsOH·H2O构成。
其中:SiO2载体同实施例1。
该多级孔催化剂的制备方法,包括以下步骤:
⑴按配比称重;
⑵将17.66g (NH4)6Mo7O24·4H2O与0.25g NH4VO3溶于50mL去离子水中,得到浸渍液A;浸渍液B、浸渍液C、浸渍液D、浸渍液E同实施例1;
⑶采用等体积浸渍法,将浸渍液A于90℃浸渍到28.25g SiO2载体(筛选40~60目的载体)上,于120℃干燥8h;同理,依次将浸渍液B、浸渍液C、浸渍液D、浸渍液E浸渍到SiO2载体上,得到样品;
⑷样品120℃干燥过夜后,于450℃焙烧4h即得催化剂A2。
实施例4 一种多级孔催化剂,该催化剂由40.78g活性组分和49.84g具有三维有序多级孔道的SiO2载体制成;活性组分由35.32g (NH4)6Mo7O24·4H2O、0.25g NH4VO3、0.42g Cu(CH3C00)2·2H2O、0.48g SbCl3、0.30g H3AsO4、1.09g H3PO4、0.35g La(CH3COO)3·1.5H2O、0.45g Ce(NO3)3·6H2O和2.12g CsOH·H2O构成。
其中:SiO2载体同实施例1。
该多级孔催化剂的制备方法,包括以下步骤:
⑴按配比称重;
⑵将35.32g (NH4)6Mo7O24·4H2O与0.25g NH4VO3溶于50mL去离子水中,得到浸渍液A;浸渍液B、浸渍液C、浸渍液D、浸渍液E同实施例1;
⑶采用等体积浸渍法,将浸渍液A于90℃浸渍到49.84g SiO2载体(筛选40~60目的载体)上,于120℃干燥8h;同理,依次将浸渍液B、浸渍液C、浸渍液D、浸渍液E浸渍到SiO2载体上,得到样品;
⑷样品120℃干燥过夜后,于450℃焙烧4h即得催化剂B2。
实施例5 一种多级孔催化剂,该催化剂由23.12g活性组分和15.41g具有三维有序多级孔道的SiO2载体制成;活性组分由17.66g (NH4)6Mo7O24·4H2O、0.25g NH4VO3、0.42g Cu(CH3C00)2·2H2O、0.48g SbCl3、0.30g H3AsO4、1.09g H3PO4、0.35g La(CH3COO)3·1.5H2O、0.45g Ce(NO3)3·6H2O和2.12g CsOH·H2O构成。
其中:SiO2载体同实施例1。
该多级孔催化剂的制备方法,包括以下步骤:
⑴按配比称重;
⑵将17.66g (NH4)6Mo7O24·4H2O与0.25g NH4VO3溶于50mL去离子水中,得到浸渍液A;浸渍液B、浸渍液C、浸渍液D、浸渍液E同实施例1;
⑶采用等体积浸渍法,将浸渍液A于85℃浸渍到15.41g SiO2载体(筛选40~60目的载体)上,于120℃干燥12h;同理,依次将浸渍液B、浸渍液C、浸渍液D、浸渍液E浸渍到SiO2载体上,得到样品;
⑷样品120℃干燥过夜后,于400℃焙烧5h即得催化剂A3。
实施例6 一种多级孔催化剂,该催化剂由40.78g活性组分和27.19g具有三维有序多级孔道的SiO2载体制成;活性组分由35.32g (NH4)6Mo7O24·4H2O、0.25g NH4VO3、0.42g Cu(CH3C00)2·2H2O、0.48g SbCl3、0.30g H3AsO4、1.09g H3PO4、0.35g La(CH3COO)3·1.5H2O、0.45g Ce(NO3)3·6H2O和2.12g CsOH·H2O构成。
其中:SiO2载体同实施例1。
该多级孔催化剂的制备方法,包括以下步骤:
⑴按配比称重;
⑵将35.32g (NH4)6Mo7O24·4H2O与0.25g NH4VO3溶于50mL去离子水中,得到浸渍液A;浸渍液B、浸渍液C、浸渍液D、浸渍液E同实施例1;
⑶采用等体积浸渍法,将浸渍液A于85℃浸渍到27.19g SiO2载体(筛选40~60目的载体)上,于120℃干燥12h;同理,依次将浸渍液B、浸渍液C、浸渍液D、浸渍液E浸渍到SiO2载体上,得到样品;
⑷样品120℃干燥过夜后,于400℃焙烧5h即得催化剂B3。
上述实施例1~6中,H3AsO4与H3PO4的质量浓度均为85%。
上述实施例1~6中所得的多级孔催化剂的应用:该催化剂在异丁醛制备甲基丙烯酸中催化异丁醛氧化脱氢制甲基丙烯酸反应。具体过程如下:
在反应管内径为12mm的常压石英固定床反应器中,分别使用催化剂A1、催化剂B1、催化剂A2、催化剂B2催化异丁醛氧化脱氢制甲基丙烯酸反应,从而实现异丁醛制甲基丙烯酸。其中反应条件是指压力为常压,空气为氧化剂,液体原料(异丁醛和水)经两台液体进样泵泵入后(液体空速0.8h-1),经200℃预热汽化进入反应体系,反应炉控制温度285℃,反应物料异丁醛、水与空气的摩尔比为1:7:12.5,总气体空速为1300h-1。
反应产物中气相组成由装备热导检测器气相色谱仪在线分析,O2、N2、CO、CO2等,液相产物经冷凝收集,由装备FID(火焰离子检测器)气象色谱分析异丁醛、乙酸,甲基丙烯醛、甲基丙烯酸等产物。采用校正因子面积归一化法计算异丁醛转化率和甲基丙烯酸选择性等,性能评价结果如下表1所示。
表1
从表1可以看出,本发明所得催化剂异丁醛转化率≈100%、甲基丙烯酸选择性≥70%、甲基丙烯醛选择性≥5%,乙酸选择性≥9%,COx选择性<8%,表现出优异的反应性能,说明该催化剂用于催化异丁醛氧化脱氢制备甲基丙烯酸时能够在空气作为氧化剂,常压条件下进行,在较低的反应温度条件下,可得到较高的甲基丙烯酸收率和较低的COX生成率,适合工业化应用推广。
Claims (4)
1.一种多级孔催化剂,其特征在于:该催化剂由占总质量30%~60%的活性组分和余量为具有三维有序多级孔道的SiO2载体制成;以重量份计,所述活性组分由17.66g或35.32g(NH4)6Mo7O24·4H2O、0.25g NH4VO3、0.42g Cu(CH3COO )2·2H2O、0.48g SbCl3、0.30g H3AsO4、1.09g H3PO4、0.35g La(CH3COO)3·1.5H2O、0.45g Ce(NO3)3·6H2O和2.12g CsOH·H2O构成;所述SiO2载体是指使用硅源、大孔模板剂和介孔模板剂通过挥发自组装的方法合成SiO2前驱体,该前驱体先于100~120℃干燥12~24h,再于不低于600℃焙烧4~8h即得具有三维有序大孔-介孔结构的SiO2;所述大孔模板剂为聚甲基丙烯酸甲酯;所述介孔模板剂为聚氧乙烯聚氧丙烯醚嵌段共聚物;
该多级孔催化剂的制备方法,包括以下步骤:
⑴按配比称重;
⑵将(NH4)6Mo7O24·4H2O与NH4VO3溶于去离子水中,得到浸渍液A;将Cu(CH3COO )2·2H2O与SbCl3溶于去离子水中,得到浸渍液B;将H3AsO4与H3PO4溶于去离子水中,得到浸渍液C;将La(CH3COO)3·1.5H2O与Ce(NO3)3·6H2O溶于去离子水中,得到浸渍液D;将CsOH·H2O溶于去离子水中,得到浸渍液E;
⑶将所述浸渍液A于80℃~100℃浸渍到所述SiO2载体上,于120℃干燥3~12h;同理,依次将所述浸渍液B、所述浸渍液C、所述浸渍液D、所述浸渍液E浸渍到所述SiO2载体上,得到样品;
⑷所述样品120℃干燥过夜后,于350~450℃焙烧4~6h即得。
2.如权利要求1所述的一种多级孔催化剂,其特征在于:所述H3AsO4与所述H3PO4的质量浓度均为85%。
3.如权利要求1所述的一种多级孔催化剂,其特征在于:所述浸渍为等体积浸渍,且浸渍分多次进行。
4.如权利要求1所述的一种多级孔催化剂的应用,其特征在于:该催化剂在异丁醛制备甲基丙烯酸中催化异丁醛氧化脱氢制甲基丙烯酸反应。
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