CN109553129B - 纳米级高分散氧化锆及其制备方法与在合成气制备芳烃中的应用 - Google Patents
纳米级高分散氧化锆及其制备方法与在合成气制备芳烃中的应用 Download PDFInfo
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Abstract
本发明公开了一种纳米级高分散氧化锆及其制备方法与在合成气制备芳烃中的应用。该制备纳米级高分散氧化锆的方法,包括:1)将锆盐、螯合剂溶于溶剂中,记为混合液A;2)向所述混合液A中加入矿化剂,得到混合液B;3)将所述混合液B进行水热反应,反应完毕将所得产物过滤、洗涤、干燥,焙烧,得到所述纳米级高分数氧化锆。该方法操作简单、重复性强,产物晶粒小、分散度高,具有较高的CO转化率,低的CO2选择性,且产物中多以芳烃为主,具有极高的芳烃选择性。
Description
技术领域
本发明涉及一种催化剂及其制备方法与应用,具体的说,本发明涉及一种纳米级高分散氧化锆及其制备方法与在合成气制备芳烃中的应用。
背景技术
苯(benzene)、甲苯(toluene)、二甲苯(xylene),简称BTX,作为一级化工原料,是石化工业的基本有机化工原料,可用来生产合成橡胶,合成纤维和合成树脂等多种化工产品,也可用来生产多种精细化学产品,还可作为高辛烷值汽油的调和成分。BTX约占汽油组成的21%,经济效益高、市场需求量大。目前,BTX主要来自石油炼制,以催化重整油和裂解汽油为主要原料,但由于石油资源匮乏导致这些化学品的价格居高不下,同时,我国的原油以石蜡基原油为主,不利于重整反应的进行,芳烃产量较低。寻找新的BTX生产路线变得尤为迫切,相较于烃类重整、甲醇芳构化等技术路线而言,合成气直接制芳烃可以缩短工艺流程,产物易于分离,能够显著提高煤化工过程效率,大大降低生产成本。
氧化锆作为异构化催化剂[Ind.Eng.Chem.,Prod.Res.Dev.176,15(2),123],可以在较高反应温度、压力下,将合成气转化为烃类化合物;Pichler等[Brennst.Chem.,1949,30,13-22.]首次研究了合成气异构化反应,指出ZrO2具有较高的异丁烯/烷的选择性;Yingwei Li等[J.Cat.,2004,221,584-593.]对ZrO2上的合成气异构化反应做了大量研究,认为ZrO2表面的酸、碱性对催化合成气转化起着决定性的作用,酸性位活化CO,而碱性位则起到异构化的作用。目前对ZrO2上能直接合成芳烃的研究报告不多,且以金属氧化物作为催化剂活性相,催化活性比较低:Clarence D.Chang等[J.Catal.,1979,56,268-273]在400℃,8Mpa下将合成气直接转化为芳烃,但反应的C5 +只有24%,且C5 +中芳烃含量只有53%。
目前纳米ZrO2的制备方法主要有溶胶-凝胶法、水热法和共沉淀法:GeorgGarnweitner等[Small,2007,9,1626-1632]以异丙醇锆为锆源采用溶胶-凝胶法制备得到3nm左右的ZrO2;Weizhen Li等[Langmuir,2008,24,8358-8366]采用水热法制备得到的ZrO2尺寸集中在7nm;共沉淀法合成的ZrO2其实际颗粒尺寸往往大于10nm,且这些方法都存在成本高、颗粒尺寸难以控制等问题。
发明内容
本发明的目的是提供一种纳米级高分散氧化锆及其制备方法与在合成气制备芳烃中的应用。
本发明提供的制备纳米级高分散氧化锆的方法,包括:
1)将锆盐、螯合剂溶于溶剂中,记为混合液A;
2)向所述混合液A中加入矿化剂,得到混合液B;
3)将所述混合液B进行水热反应而得。
上述方法步骤1)中,锆盐选自硝酸锆、氯化锆、醋酸锆、硫酸锆、硝酸氧锆、氧氯化锆、丙醇锆和丁醇锆中至少一种;
螯合剂选自对苯二甲酸、均苯三甲酸、联苯二甲酸、甲基咪唑和反丁烯二酸中至少一种;
溶剂选自N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、甲醇、乙醇和水中至少一种;
所述溶剂的量具体可为100-1000mL,更具体可为100、200、300或1000mL;
所述锆盐在混合液A的摩尔浓度为0.10~0.20mol/L,具体可为0.10、0.11、0.12、0.13、0.14、0.15或0.17mol/L;
所述锆盐与螯合剂的摩尔比为1:1~5,具体可以为1:1,1:2,1:3,1:4或1:5。
所述方法还包括:在所述步骤1)之后,步骤2)之前,将所述混合液A超声;
所述超声步骤中,时间具体为30~60min;功率为100W;温度为40-60℃;具体可为50℃。
所述步骤2)中,矿化剂选自硝酸、盐酸、硫酸、甲酸、乙酸和丙酸中至少一种;
所述矿化剂与锆盐的摩尔比为0.3~100:1,具体为0.5:1、1:1,5:1,10:1,20:1,30:1,40:1,50:1,60:1,70:1,80:1,90:1或100:1。
所述方法还包括:在所述步骤2)之后,步骤3)之前,将所述混合液B搅拌;
所述搅拌步骤中,温度为常温;时间为10~30min。
所述步骤3)水热反应步骤中,温度为100~150℃,具体可为100,110,120,130,140或150℃;时间为12~24h,具体可以为12,16,20或24h。
所述方法还包括:在所述步骤3)水热反应之后,将所得产物过滤、洗涤、干燥,焙烧;
所述过滤步骤中,滤孔的目数为325-400目;所述过滤可在真空度为-0.1至-0.05条件进行;所述过滤可为抽滤;
所述洗涤步骤中,洗涤剂为N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、甲醇、乙醇或水;洗涤温度为50~70℃;时间为10-60min;具体为30min;洗涤剂的用量为100~200ml;
所述洗涤为超声洗涤;功率为100W;上述洗涤步骤可根据实际需要重复,如可重复3次;
所述干燥步骤中,温度为100~120℃;时间为12~24h;
所述焙烧步骤中,焙烧温度为350~750℃,具体为350,400,450,500,550,600,650,700或750℃;焙烧时间为6~12h,具体为6,7,8,9,10,11或12h;焙烧气氛为纯氧气或合成空气;所述合成空气的组成如下:20%O2/He或20%O2/Ar。
另外,按照上述方法制备得到的纳米级高分散氧化锆及该纳米级高分散氧化锆在合成气催化转化中的应用,也属于本发明的保护范围。其中,所述纳米级高分散氧化锆为四方相ZrO2;尺寸为3-12纳米;具体为4-11nm;
所述H2与CO的摩尔比为0.5~5.0,优选1.0~3.0,具体为1:1、1.5:1、2:1、2.5:1或3:1;
温度为350~550℃;具体为400~500℃,更具体为400、425、450、475或500℃;
压力为0.5~10Mpa,优选4~6Mpa、具体为4、4.5、5、5.5或6Mpa;
空速为500~5000ml/gcat·h-1;具体为1000~2000ml/gcat·h-1、1000、1250、1500、1750或2000ml/gcat·h-1;
所述合成气催化转化具体为催化合成气制备芳烃。所述芳烃的碳原子数具体可为6-12。
与现有技术相比,本发明具有以下优点:
1、该方法操作简单、重复性强,产物具有晶粒小、分散度高等特点;
2、通过控制焙烧条件可实现氧化锆晶粒尺寸的调节,表征结果显示得到的氧化锆高度分散,呈单晶分布,催化剂比表面积较高;
3、该方法合成的氧化锆催化剂具有较高的CO转化率,低的CO2选择性,且产物中多以芳烃为主,具有极高的芳烃选择性;
4、该发明制备方案均为常压操作,实验结果重复性好,前驱物低温活化,能耗较低,设备投资及操作费用低,有利于工业化生产。
附图说明
图1为实施例1氧化锆的前驱物X-射线衍射谱图;
图2为实施例1氧化锆的X-射线衍射谱图;
图3为实施例1氧化锆的N2-吸脱附曲线谱图。
具体实施方式
下面结合具体实施例对本发明作进一步阐述,但本发明并不限于以下实施例。所述方法如无特别说明均为常规方法。所述原材料如无特别说明均能从公开商业途径获得。
实施例1、纳米级高分散氧化锆的可控合成及其催化合成气直接转化制备芳烃:
称量硝酸氧锆4.60g,对苯二甲酸3.32g,溶于100ml N,N-二甲基甲酰胺中,50℃下超声30min,得到混合液A;
加入1.26g矿化剂硝酸,常温下磁力搅拌10min,得到混合液B;
将混合液B置于具有聚四氟乙烯内衬的管弹反应器中,100℃下水热反应12h,待冷却至室温后取出;
后处理:分别用50℃热乙醇磁力搅拌30min、N,N-二甲基甲酰胺超声洗涤30min,重复上述洗涤过程3次,抽滤,100℃干燥24h,得到含有Zr的前驱物;
将前驱物置于管式炉中,通入50ml/min的20%O2/He,程序升温至400℃后停留6h,自然冷却至室温,得到氧化锆;
将焙烧得到的氧化锆经研磨、压片、破碎、筛分后,取1g 20~40目氧化锆催化剂在固定床装置中评价其催化转化合成气性能,催化剂织构性质、反应条件、CO转化率及产物分布见表-1、表-2。
本实施例中的氧化锆的前驱物X-射线衍射谱图如图1所示;在图1中,2θ=7.4、8.5、14.1、14.7、17.0、18.6和19.1°处的衍射峰归属于氧化锆的前驱物,表明该前驱物制备成功。
本实施例中的氧化锆的X-射线衍射谱图如图2所示;在图2中,2θ=30.2、35、50.4、60.0和62.9°处的衍射峰归属于氧化锆,表明得到的氧化锆为纯相的四方相氧化锆。
本实施例中的氧化锆的N2-吸脱附曲线谱图如图3所示;在图3中,得到的N2-吸脱附曲线具有明显的H-3回滞环,表明得到的氧化锆具有典型的介孔结构。
实施例2、纳米级高分散氧化锆的可控合成及其催化合成气直接转化制备芳烃:
称量硝酸锆9.45g,均苯三甲酸9.25g,溶于200ml N,N-二甲基乙酰胺中,50℃下超声40min,得到混合液A;
加入0.803g的盐酸,常温下磁力搅拌10min,得到混合液B;
将混合液B置于具有聚四氟乙烯内衬的管弹反应器中,110℃下水热反应12h,待冷却至室温后取出;
后处理:分别用50℃热乙醇磁力搅拌30min、N,N-二甲基乙酰胺超声洗涤30min,重复上述洗涤过程3次,抽滤,120℃干燥24h,得到含有Zr的前驱物;
将前驱物置于管式炉中,通入50ml/min的20%O2/Ar,程序升温至450℃后,停留8h,自然冷却至室温,得到氧化锆;
将焙烧得到的氧化锆经研磨、压片、破碎、筛分后,取1g 20~40目氧化锆催化剂在固定床装置中评价其催化转化合成气性能,催化剂织构性质、反应条件、CO转化率及产物分布见表-1、表-2。
实施例3、纳米级高分散氧化锆的可控合成及其催化合成气直接转化制备芳烃:
称量氯化锆5.59g,甲基咪唑5.91g,溶于200ml水中,50℃下超声40min,得到混合液A;
加入0.803g的盐酸,常温下磁力搅拌10min,得到混合液B;
将混合液B置于聚四氟乙烯内衬的管弹反应器中,110℃下水热反应12h,待冷却至室温后取出;
后处理:分别用50℃热乙醇磁力搅拌30min、水超声洗涤30min,重复上述洗涤过程3次,抽滤,120℃干燥24h,得到含有Zr的前驱物;
将前驱物置于管式炉中,通入50ml/min的20%O2/Ar,程序升温至450℃后,停留8h,自然冷却至室温,得到氧化锆;
将焙烧得到的氧化锆经研磨、压片、破碎、筛分后,取1g 20~40目氧化锆催化剂在固定床装置中评价其催化转化合成气性能,催化剂织构性质、反应条件、CO转化率及产物分布见表-1、表-2。
实施例4、纳米级高分散氧化锆的可控合成及其催化合成气直接转化制备芳烃:
称量醋酸锆8.51g,反丁烯二酸3.02g,溶于300ml甲醇中,50℃下超声60min,,得到混合液A;
加入30.18g的甲酸,常温下磁力搅拌20min,得到混合液B;
将混合液B置于聚四氟乙烯内衬的管弹反应器中,120℃下水热反应24h,待冷却至室温后取出;
后处理:分别用70℃热乙醇磁力搅拌30min、甲醇超声洗涤30min,重复上述洗涤过程3次,抽滤,120℃干燥24h,得到含有Zr的前驱物;
将前驱物置于管式炉中,通入50ml/min的纯氧气,程序升温至550℃后,停留12h,自然冷却至室温,得到氧化锆;
将焙烧得到的氧化锆经研磨、压片、破碎、筛分后,取1g 20~40目氧化锆催化剂在固定床装置中评价其催化转化合成气性能,催化剂织构性质、反应条件、CO转化率及产物分布见表-1、表-2。
实施例5、纳米级高分散氧化锆的可控合成及其催化合成气直接转化制备芳烃:
称量硫酸锆7.93g,联苯二甲酸13.56g,溶于1000ml乙醇中,50℃下超声30min,得到混合液A;
加入43.60g丙酸,常温下磁力搅拌30min,得到混合液B;
将混合液B置于聚四氟乙烯内衬的管弹反应器中,120℃下水热反应24h,待冷却至室温后取出;
后处理:分别用50℃热乙醇磁力搅拌30min、乙醇超声洗涤30min、重复上述洗涤过程3次,抽滤,100℃干燥24h,得到含有Zr的前驱物;
将前驱物置于管式炉中,通入50ml/min的20%O2/He,程序升温至600℃后,停留12h,自然冷却至室温,得到氧化锆;
将焙烧得到的氧化锆经研磨、压片、破碎、筛分后,取1g 20~40目氧化锆催化剂在固定床装置中评价其催化转化合成气性能,催化剂织构性质、反应条件、CO转化率及产物分布见表-1、表-2。
表-1、合成气在氧化锆催化剂催化转化制芳烃评价结果
表-2、合成气在氧化锆催化转化烃类产物分布
由表-1可以看出,采用该方法制备得到的纳米ZrO2,具有晶粒尺寸小,分散度高等特点,并且可以通过调节焙烧温度,得到不同晶粒尺寸的ZrO2,大量的实验表明,采用该方法制备纳米ZrO2,具有很强的可重复性。
将该方法制备得到的ZrO2用于催化合成气制芳烃反应,当温度为350~500℃,压力为0.5~10MPa,H2/CO为1~2,空速为1000~5000ml/gcat·h-1时,催化剂具有一定的活性,产物中烃类化合物的选择性高于60%,这其中甲烷的选择性低于10%,C2-C4的烃类仅为20%左右,具有高附加值的C5 +的选择性达到70%,这其中包含有90%以上的芳烃。
综上,采用该方法实现纳米ZrO2的可控合成,并且此技术制备得到的ZrO2在合成气催化转化制芳烃领域具有良好的应用前景。
Claims (7)
1.一种制备纳米级高分散氧化锆的方法,包括:
1)将锆盐、螯合剂溶于溶剂中,记为混合液A;
所述螯合剂选自对苯二甲酸、均苯三甲酸、联苯二甲酸、甲基咪唑和反丁烯二酸中至少一种;
所述锆盐在混合液A的摩尔浓度为0.10~0.20mol/L;
所述锆盐与螯合剂的摩尔比为1:1~5;
2)向所述混合液A中加入矿化剂,得到混合液B;
所述矿化剂与锆盐的摩尔比为0.3~100:1;
3)将所述混合液B进行水热反应而得;
所述步骤3)水热反应步骤中,温度为100~150℃;时间为12~24h;
所述方法还包括:在所述步骤3)水热反应之后,将所得产物过滤、洗涤、干燥,焙烧;
所述焙烧步骤中,焙烧温度为350~750℃;焙烧时间为6~12h;焙烧气氛为纯氧气或合成空气;所述合成空气的组成如下:20% O2/He或20% O2/Ar。
2.根据权利要求1所述的方法,其特征在于:所述步骤1)中,锆盐选自硝酸锆、氯化锆、醋酸锆、硫酸锆、硝酸氧锆、氧氯化锆、丙醇锆和丁醇锆中至少一种;
溶剂选自N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、甲醇、乙醇和水中至少一种。
3.根据权利要求1所述的方法,其特征在于:所述方法还包括:在所述步骤1)之后,步骤2)之前,将所述混合液A超声。
4. 根据权利要求3所述的方法,其特征在于:所述超声步骤中,时间为30~60min;功率为100 W;温度为40-60℃。
5.根据权利要求1-4中任一所述的方法,其特征在于:所述步骤2)中,矿化剂选自硝酸、盐酸、硫酸、甲酸、乙酸和丙酸中至少一种。
6.根据权利要求1-4中任一所述的方法,其特征在于:所述方法还包括:在所述步骤2)之后,步骤3)之前,将所述混合液B搅拌;
所述搅拌步骤中,温度为常温;时间为10~30min。
7.根据权利要求1-4中任一所述的方法,其特征在于:所述过滤步骤中,滤孔的目数为325-400目;
所述洗涤步骤中,洗涤剂为N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、甲醇、乙醇或水;洗涤温度为50~70℃;时间为10-60min;洗涤剂的用量为100~200ml;
所述洗涤为超声洗涤;功率为100W;
所述干燥步骤中,温度为100~120℃;时间为12~24h。
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