CN108325537B - 蒽醌加氢双氧水用类球形微米级γ-三氧化二铝载体的制备方法 - Google Patents
蒽醌加氢双氧水用类球形微米级γ-三氧化二铝载体的制备方法 Download PDFInfo
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明是一种蒽醌加氢双氧水用类球形微米级γ‑三氧化二铝载体的制备方法,其步骤为:将无水葡萄糖和Al(NO3)3·9H2O分散到去离子水中,超声10min后加入尿素水溶液,再将混合溶液在180℃下水热8h,将水热产物用去离子水和乙醇交替洗涤,至滤液澄清;将滤饼在80℃鼓风干燥箱中干燥8h后,得到胶体碳/AlOOH复合物,将其在550℃的空气气氛下焙烧3h,得到类球形的微米级γ‑Al2O3粉体;以该粉体为载体,采用等体积浸渍法负载活性组分Pd‑,后经洗涤、干燥、焙烧制得Pd/γ‑Al2O3催化剂。在负载Pd‑之前,也可以采用与负载Pd‑相同的等体积浸渍法负载助剂Ni‑、Fe‑、Zn‑。该Pd/γ‑Al2O3催化剂在蒽醌加氢反应中表现出较高的氢化效率,可达11.30gH2O2/L工作液。
Description
技术领域
本发明涉及介孔Al2O3微球的制备方法及其在制备蒽醌法生产H2O2用钯催化剂中的应用,属于催化剂载体和催化剂的制备领域,提供了一种蒽醌加氢制H2O2用类球形微米级γ-Al2O3载体的制备方法。
背景技术
H2O2的合成方法有酸解过氧化物法、电解法、异丙醇法、蒽醌法和氢氧直接合成法等。目前国内普遍采用钯催化剂固定床蒽醌法生产H2O2,蒽醌法主要包括氢化、氧化和萃取等三个过程,氢化过程是整个生产工艺的控制过程,因为氧化过程能将氢化后的氢蒽醌完全氧化为H2O2。现有Pd-催化剂的载体主要是γ-Al2O3,目前国内主要采用中和法和碳化法制备,通过控制制备条件得到不同织构性质的γ-Al2O3,但很少有做出特定微观形貌的γ-Al2O3并且以其为载体时在加氢反应中表现出高的催化活性。
中国专利文献CN107185529A公布了一种以MCH为模板制备分等级球形Pd/γ-Al2O3催化剂的方法,该催化剂具有良好的蒽醌催化加氢性能。考虑到MCH制备过程复杂、繁琐,使得整个制备工艺的周期延长,不适合实际生产应用。碳模板作为一种硬模板已经被广泛的应用,因为它廉价易得,同时易于除去,此外,碳表面疏松多孔,能够吸附许多前驱物,这就促进了前驱物在其表面的生长过程。Naibo Chu等人(Naibo Chu,Jinqu Wang,Yan Zhang,Jianhua Yang,Jinming Lu,Dehong Yin.Nestlike hollow hierarchical MCM-22microspheres:synthesis and exceptional catalytic properties[J].Chemistry ofMaterials,2010,22(9):2757-2763.)直接从炭黑模板水热合成了蜂窝状MCM-22分等级微球,沸石自组装在其表面。但该方法需要先制备出炭黑,然后再进行水热,步骤稍繁琐。Jiabin Zhou等人(Jiabin Zhou,Chuan Tang,Bei Cheng,Jiaguo Yu,MietekJaroniec.Rattle-type carbon-alumina core-shell spheres:synthesis andapplication for adsorption of organic dyes[J].ACS Applied Materials&Interfaces,2012,4(4):2174-2179.)以葡萄糖和金属盐为原料,采用一锅水热法制备了核-壳结构碳铝复合物空心球,其对橙II染料的吸附量达到210mg/g。Guangxin Xue等人(Guangxin Xue,Xin Huang,Ning Zhao,Fukui Xiao,Wei Wei.Hollow Al2O3spheresprepared by a simple and tunable hydrothermal method[J].RSC Advances,2015,5:13385-13391.)通过简单可调的水热反应制备出了粒径大小均一的氧化铝空心球。相比之下,本发明采用简单、温和的方法制备了类球形的γ-Al2O3粉体及其负载的Pd/γ-Al2O3催化剂。
发明内容
本发明所要解决的技术问题是:提供一种蒽醌加氢制H2O2用类球形微米级γ-Al2O3载体的制备方法。所制得的催化剂在蒽醌加氢反应中表现出较高的催化活性、高蒽醌循环回收率和较高稳定性。
本发明解决其技术问题采用以下的技术方案:
(1)将一定量无水葡萄糖和Al(NO3)3·9H2O分散到90mL去离子水中,超声后加入沉淀剂;继续搅拌30min后在180℃下水热8h,将得到的黑色产物过滤,并用去离子水和乙醇交替洗涤至滤液澄清为止;将滤饼在80℃的鼓风干燥箱中干燥8h,得到细腻、质地蓬松的胶体碳/AlOOH复合材料粉体;将该粉体在550℃的空气气氛下焙烧3h,升温速率2℃/min,得到类球形微米级γ-Al2O3粉体;
(2)以该类球形微米级γ-Al2O3粉体为载体,按Pd-负载量为0.3wt%计,称取PdCl2和NaCl溶于0.6g载体对应的饱和吸水量,制得四氯钯酸钠溶液;将该四氯钯酸钠溶液加入到0.6g类球形微米级γ-Al2O3粉体中,搅拌均匀后密封并在60℃下静置2h,抽滤、去离子水洗涤滤饼至滤液中无Cl-时为止;将滤饼依次在120℃的静态空气氛下干燥2h、450℃的静态空气氛下焙烧4h,升温速率2℃/min,制得0.3wt%Pd/γ-Al2O3催化剂;
(3)添加助剂时助剂成分的添加在负载活性组分Pd-之前进行,采用与负载Pd-相同的等体积浸渍法负载。
步骤(1)中所述的Al(NO3)3·9H2O的物质的量为0.018mol,无水葡萄糖的物质的量为0.036-0.216mol,即无水葡萄糖与Al(NO3)3·9H2O的摩尔比为2:1-12:1。
步骤(1)中采用功率为100W进行超声,超声10min。
步骤(1)中所述的沉淀剂为尿素水溶液,其浓度为0.2mol/L,加入量为10mL。
步骤(2)中所述的四氯钯酸钠溶液由摩尔比为1:2的PdCl2和NaCl制得。
步骤(2)中所述催化剂的比表面积为31.9~79.4m2/g、孔容为0.02~0.09cm3/g、平均孔径为3.2~5.9nm。
步骤(3)中所述的助剂成分为Ni、Fe、Zn中的一种,负载量为2.0-5.0wt%。
催化剂的活性评价在自制的浆态床反应器中进行,该反应器由水浴锅、三颈烧瓶、冷凝管、温度计和附属部件组成。冷凝管连接三颈烧瓶的中间接口,另外两个接口分别为气体输入接口和取样口。实验用的工作液为工业用工作液,经液相色谱检测,其中有效蒽醌含量为:2-乙基蒽醌113.8g/L、四氢2-乙基蒽醌87.3g/L。将0.4g催化剂加入到上述自制的浆态床反应器中,加入6mL左右的工作液润湿催化剂,检查气密性,用N2置换烧瓶中的空气。在常压、60℃的条件下,用流速为60mL/min的H2/N2混合气体(V(N2):V(H2)=1:3)活化催化剂2h;再加入60mL工作液,在搅拌速度为30r/min、H2流速为75mL/min、60℃下进行氢化反应。每隔30min移取3mL反应液,冷却后放入离心管中,在8000r/min下离心3min后去除固体催化剂,移取2mL滤液于分液漏斗;加入20mL去离子水,滴加2滴浓磷酸,通入流速为35mL/min的O2进行氧化反应产生H2O2,至工作液呈现亮黄色(耗时约0.5~1h)后,用去离子水萃取产生的H2O2(共萃取5次)并收集于锥形瓶中,加入5mL浓度为20wt%的硫酸,随后用0.02mol/L的KMnO4标准溶液滴定,计算氢化效率。
式中:C为KMnO4溶液的实际浓度(mol/L);V0为消耗KMnO4溶液的体积(mL);M为H2O2的相对分子量(34g/mol);V为参加氧化的工作液体积(mL)。
蒽醌循环回收率的测定采用Agilent HP1260高效液相色谱仪进行。检测条件为:柱温25℃,色谱柱zorbox Eclipse XDB-C18(4.6mm×250mm、5μm),流动相体积比甲醇:水=90:10,流速1mL/min,检测波长254nm,进样量10μL。采用外标法作标准曲线,检测样品中2-乙基蒽醌与四氢-2-乙基蒽醌的含量,以获得催化剂的蒽醌循环回收率数据,其计算公式为:
式中,n为氧化反应后工作液中有效蒽醌的物质量(mol);n0为原始工作液中有效蒽醌的物质量(mol)。这种方法有效地避免了转化率为100%的假设问题,又能如实反映氢化反应选择性的变化。
与现有技术相比,本发明具有以下主要优点:
(1)采用一锅水热法制备碳模板及粒子表现为类球形微米级的γ-Al2O3粉体,通过控制葡萄糖与Al(NO3)3·9H2O的摩尔比,将其类球形结构调整到最佳。
(2)所制备的类球形微米级γ-Al2O3具有较高的比表面积,同时在催化反应中能提供更多的活性位点,并且具有传质方面的优势。
(3)以廉价易得的葡萄糖为碳源,制备成本较低。
(4)所制备的催化剂在蒽醌加氢制H2O2的反应中具有较高的氢化效率和蒽醌循环回收率。
图1为实施例1-3所制备催化剂的N2吸附-脱附等温线。
图2为实施例1-3所制备催化剂的N2吸附-脱附孔径分布曲线。
图3为实施例4-6所制备催化剂的N2吸附-脱附等温线。
图4为实施例4-6所制备催化剂的N2吸附-脱附孔径分布曲线。
图5-图8为实施例1-4所制备催化剂的SEM图片。
具体实施方式
下面结合实施例和附图对本发明作进一步的说明,这些实施例仅仅是对本发明较佳实施方式的描述,但并不限定本发明。
以下各实施例中N2吸附-脱附曲线的测定在美国麦克公司生产的TriStar Ⅱ3020型吸附分析仪上进行。
以下各实施例中蒽醌循环回收率的测定在Agilent HP1260高效液相色谱仪上进行。检测条件为:柱温25℃,色谱柱zorbox Eclipse XDB-C18(4.6mm×250mm、5μm),流动相体积比甲醇:水=90:10,流速1mL/min,检测波长254nm,进样量10μL。采用外标法作标准曲线,检测样品中2-乙基蒽醌与四氢-2-乙基蒽醌的含量,以获得催化剂的蒽醌循环回收率数据。
【实施例1】
(1)将0.036mol无水葡萄糖和0.018mol Al(NO3)3·9H2O分散到90mL去离子水中(二者摩尔比为2:1),超声10min(超声功率100W)后,加入10mL、0.2mol/L的尿素溶液作为沉淀剂,搅拌30min后,在180℃下水热8h,将得到的黑色产物过滤,并用去离子水和无水乙醇交替洗涤至滤液澄清为止,在80℃下的鼓风干燥箱中干燥8h,得到细腻、质地蓬松的胶体碳/AlOOH复合材料粉体。将该粉体在550℃的空气气氛下焙烧3h(升温速率2℃/min),得到γ-Al2O3粉体。
(2)以上述γ-Al2O3粉体为载体,采用等体积浸渍法负载助剂成分Ni,按添加量为2wt%称取0.0594g Ni(NO3)2·6H2O溶于0.6g载体对应的饱和吸水量,将得到的溶液滴入γ-Al2O3中搅拌均匀,封膜后在60℃下静置2h,然后在120℃的静态空气气氛下干燥2h,进一步将该干燥产物在450℃的静态空气气氛下焙烧4h(升温速率2℃/min)。
(3)将步骤(2)中载体采用等体积浸渍法负载活性组分Pd-制备成Pd/γ-Al2O3催化剂。按Pd-负载量为0.3wt%称取0.003g PdCl2和0.002g NaCl,溶于0.6g载体对应的饱和吸水量制得四氯钯酸钠溶液,滴入到γ-Al2O3粉体中搅拌均匀,封膜后在60℃下静置2h,抽滤、去离子水洗至滤液中无Cl-,将滤饼在120℃的静态空气气氛下干燥2h,进一步将该干燥产物在450℃的静态空气气氛下焙烧4h(升温速率2℃/min),制得0.3wt%Pd-2.0wt%Ni/γ-Al2O3催化剂。
催化剂的活性评价在自制的浆态床反应器中进行。该反应器由水浴锅、三颈烧瓶、冷凝管、温度计以及一些附属部件组成,冷凝管连接烧瓶的中间接口,另外两个接口分别为气体输入接口和取样口。实验用的工作液为工业用工作液,经液相色谱检测,其中有效蒽醌含量为:2-乙基蒽醌113.8g/L、四氢2-乙基蒽醌87.3g/L。将0.4g催化剂加入上述自制浆态床反应器中,加入6mL工作液润湿催化剂,检查气密性;用N2置换三颈烧瓶中的空气。在常压、60℃下,用流速为60mL/min的H2/N2混合气体(V(N2):V(H2)=1:3)活化催化剂2h,再加入60mL工作液,在搅拌速度为30r/min、H2流速为75mL/min、60℃下进行氢化反应。每隔30min移取3mL反应液,冷却后放入离心管中,在8000r/min下离心3min,去除固体催化剂;移取2mL滤液于分液漏斗,加入20mL去离子水,滴加2滴浓磷酸,通入流速为35mL/min的O2进行氧化反应产生H2O2,至工作液呈现亮黄色(耗时约0.5~1h)后,用去离子水萃取产生的H2O2(共萃取5次)收集于锥形瓶中,加入5mL浓度为20wt%的硫酸,随后用0.02mol/L的KMnO4标准溶液滴定,计算氢化效率。
所制备催化剂的比表面积为31.9m2/g、孔容为0.02cm3/g、平均孔径为3.2nm;氢化效率为9.16g H2O2/L工作液,最高蒽醌循环回收率为87.9%。
【实施例2】
(1)将0.072mol无水葡萄糖和0.018mol Al(NO3)3·9H2O分散到90mL去离子水中(二者摩尔比为4:1),超声10min(超声功率100W)后,加入10mL、0.2mol/L的尿素溶液作为沉淀剂,搅拌30min后,在180℃下水热8h,将得到的黑色产物过滤,并用去离子水和无水乙醇交替洗涤至滤液澄清为止,在80℃的鼓风干燥箱中干燥8h,得到细腻、质地蓬松的胶体碳/AlOOH复合材料粉体。将该粉体在550℃的空气气氛下焙烧3h(升温速率2℃/min),得到γ-Al2O3载体。
(2)以上述γ-Al2O3粉体为载体,采用等体积浸渍法负载助剂成分Fe,按添加量为3wt%称取0.1298g Fe(NO3)3·9H2O溶于0.6g载体对应的饱和吸水量,将得到的溶液滴入γ-Al2O3中搅拌均匀,封膜后在60℃下静置2h,然后在120℃的静态空气气氛下干燥2h,进一步将该干燥产物在450℃的静态空气气氛下焙烧4h(升温速率2℃/min)。
(3)将步骤(2)中载体采用等体积浸渍法负载活性组分Pd-制备成Pd/γ-Al2O3催化剂。按Pd-负载量为0.3wt%称取0.003g PdCl2和0.002g NaCl溶于0.6g载体对应的饱和吸水量制得四氯钯酸钠溶液,滴入γ-Al2O3中搅拌均匀,封膜后在60℃下静置2h,抽滤、去离子水洗至滤液中无Cl-,将滤饼在120℃的静态空气气氛下干燥2h,进一步将该干燥产物在450℃的静态空气气氛下焙烧4h(升温速率2℃/min),制得0.3wt%Pd-3.0wt%Fe/γ-Al2O3催化剂。
采用与实施例1相同的催化性能评价方法检测所制备催化剂的性能。
所制备催化剂的比表面积为79.4m2/g、孔容为0.09cm3/g、平均孔径为5.2nm;氢化效率为10.70g H2O2/L工作液,最高蒽醌循环回收率为92.5%。
【实施例3】
(1)将0.144mol无水葡萄糖和0.018mol Al(NO3)3·9H2O分散到90mL去离子水中(二者摩尔比为8:1),超声10min(超声功率100W)后,加入10mL、0.2mol/L的尿素溶液作为沉淀剂,搅拌30min后,在180℃下水热8h,将得到的黑色产物过滤,并用去离子水和无水乙醇交替洗涤至滤液澄清为止,在80℃的鼓风干燥箱中干燥8h,得到细腻、质地蓬松的胶体碳/AlOOH复合材料粉体。将该粉体在550℃的空气气氛下焙烧3h(升温速率2℃/min),得到γ-Al2O3载体。
(2)以上述γ-Al2O3粉体为载体,采用等体积浸渍法负载助剂成分Zn,按添加量为5wt%称取0.1373g Zn(NO3)2·6H2O溶于0.6g载体对应的饱和吸水量,将得到的溶液滴入γ-Al2O3中搅拌均匀,封膜后在60℃下静置2h,然后在120℃的静态空气气氛下干燥2h,进一步将该干燥产物在450℃的静态空气氛围焙烧4h(升温速率2℃/min)。
(3)将步骤(2)中载体采用等体积浸渍法负载活性组分Pd-制备成Pd/γ-Al2O3催化剂。按Pd-负载量为0.3wt%称取0.003g PdCl2和0.002g NaCl溶于0.6g载体对应的饱和吸水量制得四氯钯酸钠溶液,滴入γ-Al2O3中搅拌均匀,封膜后在60℃下静置2h,抽滤、去离子水洗至滤液中无Cl-,将滤饼在120℃的静态空气气氛下干燥2h,进一步将该干燥产物在450℃的静态空气氛围焙烧4h(升温速率2℃/min),制得0.3wt%Pd-5.0wt%Zn/γ-Al2O3催化剂。
采用与实施例1相同的催化性能评价方法检测所制备催化剂的性能。
所制备催化剂的比表面积为39.5m2/g、孔容为0.08cm3/g、平均孔径为5.9nm;氢化效率为10.07g H2O2/L工作液,最高蒽醌循环回收率为89.3%。
【实施例4】
(1)将0.216mol无水葡萄糖和0.018mol Al(NO3)3·9H2O分散到90mL去离子水中(二者摩尔比为12:1),超声10min(超声功率100W)后,加入10mL、0.2mol/L的尿素溶液作为沉淀剂,继续搅拌30min后,在180℃下水热8h,将得到的黑色产物过滤,并用去离子水和无水乙醇交替洗涤至滤液澄清为止,在80℃的鼓风干燥箱中干燥8h,得到细腻、质地蓬松的胶体碳/AlOOH复合材料粉体。将该粉体在550℃的空气气氛下焙烧3h(升温速率2℃/min),得到γ-Al2O3载体。
(2)以上述γ-Al2O3粉体为载体,采用等体积浸渍法负载助剂成分Ni,按添加量为5wt%称取0.1485g Ni(NO3)2·6H2O溶于0.6g载体对应的饱和吸水量,将得到的溶液滴入γ-Al2O3中搅拌均匀,封膜后在60℃下静置2h,然后在120℃的静态空气气氛下干燥2h,进一步将该干燥产物在450℃静态空气氛围焙烧4h(升温速率2℃/min)。
(3)将步骤(2)中载体采用等体积浸渍法负载活性组分Pd-制备成Pd/γ-Al2O3催化剂。按Pd-负载量为0.3wt%称取0.003g PdCl2和0.002g NaCl溶于0.6g载体对应的饱和吸水量制得四氯钯酸钠溶液,滴入γ-Al2O3中搅拌均匀,封膜后在60℃下静置2h,抽滤、去离子水洗至滤液中无Cl-,将滤饼在120℃的静态空气气氛下干燥2h,进一步将该干燥产物在450℃的静态空气氛下焙烧4h(升温速率2℃/min),制得0.3wt%Pd-5.0wt%Ni/γ-Al2O3催化剂。
采用与实施例1相同的催化性能评价方法检测所制备催化剂的性能。
所制备催化剂的比表面积为50.8m2/g、孔容为0.08cm3/g、平均孔径为5.7nm;氢化效率为8.69gH2O2/L工作液,最高蒽醌循环回收率为84.7%。
【实施例5】
(1)采用实施例2步骤(1)方法制备γ-Al2O3载体。
(2)以上述γ-Al2O3粉体为载体,载体采用等体积浸渍法负载助剂成分Zn,按添加量为2wt%称取0.0549g Zn(NO3)2·6H2O溶于0.6g载体对应的饱和吸水量,将得到的溶液滴入γ-Al2O3中搅拌均匀,封膜后在60℃下静置2h,然后在120℃的静态空气气氛下干燥2h,进一步将该干燥产物在450℃静态空气氛围焙烧4h(升温速率2℃/min)。
(3)将步骤(2)中载体采用等体积浸渍法负载活性组分Pd-制备成Pd/γ-Al2O3催化剂。按Pd-负载量为0.3wt%称取0.003gPdCl2和0.002gNaCl溶于0.6g载体对应的饱和吸水量制得四氯钯酸钠溶液,滴入γ-Al2O3中搅拌均匀,封膜后在60℃下静置2h,抽滤、去离子水洗至滤液中无Cl-,将滤饼在120℃的静态空气气氛下干燥2h,进一步将该干燥产物在450℃的静态空气气氛下焙烧4h(升温速率2℃/min),制得0.3wt%Pd-2.0wt%Zn/γ-Al2O3催化剂。
采用与实施例1相同的催化性能评价方法检测所制备催化剂的性能。
所制备催化剂的比表面积为79.4m2/g、孔容为0.09cm3/g、平均孔径为5.2nm;氢化效率为11.30g H2O2/L工作液,最高蒽醌循环回收率为93.1%。
【实施例6】
(1)采用实施例3步骤(1)方法制备γ-Al2O3载体。
(2)γ-Al2O3载体采用等体积浸渍法负载助剂成分Fe,按添加量为2wt%称取0.0866g Fe(NO3)3·9H2O溶于0.6g载体对应的饱和吸水量,将得到的溶液滴入γ-Al2O3中搅拌均匀,封膜后在60℃下静置2h,然后在120℃的静态空气气氛下干燥2h,进一步将该干燥产物在450℃的静态空气气氛下焙烧4h(升温速率2℃/min)。
(3)将步骤(2)中载体采用等体积浸渍法负载活性组分Pd-制备成Pd/γ-Al2O3催化剂。按Pd-负载量为0.3wt%称取0.003g PdCl2和0.002g NaCl溶于0.6g载体对应的饱和吸水量制得四氯钯酸钠溶液,滴入γ-Al2O3中搅拌均匀,封膜后在60℃下静置2h,抽滤、去离子水洗至滤液中无Cl-,将滤饼在120℃的静态空气气氛下干燥2h,进一步将该干燥产物在450℃静态空气氛下焙烧4h(升温速率2℃/min),制得0.3wt%Pd-2.0wt%Fe/γ-Al2O3催化剂。
采用与实施例1相同的催化性能评价方法检测所制备催化剂的性能。
所制备催化剂的比表面积为39.5m2/g,孔容为0.08cm3/g,平均孔径为5.9nm;氢化效率为10.45g H2O2/L工作液,最高蒽醌循环回收率为90.5%。
表1各实施例所制备催化剂的织构性质数据
样品 | 比表面积S<sub>BET</sub>(m<sup>2</sup>/g) | 孔容V<sub>t</sub>(cm<sup>3</sup>/g) | 平均孔径D(nm) |
实施例1 | 31.9 | 0.02 | 3.2 |
实施例2 | 79.4 | 0.09 | 5.2 |
实施例3 | 39.5 | 0.08 | 5.9 |
实施例4 | 50.8 | 0.08 | 5.7 |
实施例5 | 79.4 | 0.09 | 5.2 |
实施例6 | 39.5 | 0.08 | 5.9 |
表2各实施例所制备催化剂对蒽醌加氢反应的氢化效率及其蒽醌循环回收率
Claims (6)
1.一种蒽醌加氢双氧水用类球形微米级γ-三氧化二铝载体的制备方法,其特征在于,采用一锅水热法制备碳模板及粒子表现为类球形微米级的γ-Al2O3粉体,通过控制葡萄糖与Al(NO3)3·9H2O的摩尔比,将其类球形结构调整到最佳;
包括以下步骤:
(1)将一定量无水葡萄糖和Al(NO3)3·9H2O分散到90mL去离子水中,超声后加入沉淀剂;继续搅拌30min后在180℃下水热8h,将得到的黑色产物过滤,并用去离子水和乙醇交替洗涤至滤液澄清为止;将滤饼在80℃的鼓风干燥箱中干燥8h,得到细腻、质地蓬松的胶体碳/AlOOH复合材料粉体;将该粉体在550℃的空气气氛下焙烧3h,升温速率2℃/min,得到类球形微米级γ-Al2O3粉体;所述的Al(NO3)3·9H2O的物质的量为0.018mol,无水葡萄糖的物质的量为0.036-0.216mol,即无水葡萄糖与Al(NO3)3·9H2O的摩尔比为2:1-12:1;
(2)以该类球形微米级γ-Al2O3粉体为载体,按Pd-负载量为0.3wt%计,称取PdCl2和NaCl溶于0.6g载体对应的饱和吸水量,制得四氯钯酸钠溶液;将该四氯钯酸钠溶液加入到0.6g类球形微米级γ-Al2O3粉体中,搅拌均匀后密封并在60℃下静置2h,抽滤、去离子水洗涤滤饼至滤液中无Cl-时为止;将滤饼依次在120℃的静态空气氛下干燥2h、450℃的静态空气氛下焙烧4h,升温速率2℃/min,制得0.3wt%Pd/γ-Al2O3催化剂;
(3)添加助剂时助剂成分的添加在负载活性组分Pd-之前进行,采用与负载Pd-相同的等体积浸渍法负载;
所制备的催化剂在蒽醌加氢制双氧水的反应中具有较高的蒽醌循环回收率,蒽醌循环回收率最高可达到93.1%。
2.根据权利要求1所述的制备方法,其特征在于步骤(1)中,采用功率为100W进行超声,超声10min。
3.根据权利要求1所述的制备方法,其特征在于步骤(1)中,所述的沉淀剂为尿素溶液,其浓度为0.2mol/L,加入量为10mL。
4.根据权利要求1所述的制备方法,其特征在于步骤(2)中,所述的四氯钯酸钠水溶液由物质的量为1:2的PdCl2和NaCl制得。
5.根据权利要求1所述的制备方法,其特征在于步骤(2)中,所述催化剂的比表面积为31.9~79.4m2/g、孔容为0.02~0.09cm3/g、平均孔径为3.2~5.9nm。
6.根据权利要求1所述的制备方法,其特征在于步骤(3)中,所述的助剂成分为Ni、Fe、Zn中的一种,负载量为2.0-5.0wt%。
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