新型高分散纳米铜基催化剂的制备及其催化1，4-环己烷二甲酸二甲酯加氢反应的研究
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摘要
1,4-环己烷二甲醇(CHDM)是工业上重要的聚酯生产原料，以其生产的聚酯纤维具有更高的热稳定性、光透过率和机械强度。因此，CHDM代替乙二醇(EG)成为生产高端聚酯纤维的主力将是大势所趋。到目前为止，仅有1,4-环己烷二甲酸二甲酯(DMCD)加氢制备CHDM的路线实现了工业化，但是该工艺采用亚铬酸铜作为催化剂会来带严重的铬污染。因此，开发新一代用于DMCD加氢的高性能无铬催化剂是CHDM产业发展的重要挑战。铜基催化剂以其较高的催化活性和选择性被广泛应用于各种有机反应中，并且与贵金属相比具有价格低廉的先天优势，仍然是新型DMCD加氢催化剂开发的不二之选。以传统的沉淀沉积、湿式浸渍等方法制备的铜基催化剂，存在铜粒子分散不均或者负载量有限等缺点，很难得到具有高性能的铜基催化剂。此外铜基催化剂在反应过程中会因铜原子的迁移而逐渐长大，导致催化剂逐渐失活。
本论文通过在铜基催化剂中添加具有不同性质的高性能助剂与通过形成层状前驱体的方法分别制备出了高分散的铜基催化剂，并在DMCD加氢制备CHDM的反应得到了很好的催化性能。同时通过对催化剂的系统表征揭示了催化剂的结构性质与催化性能的关系。
(一)采用成核晶化隔离法制备出具有不同ZrO_2含量的Cu/ZnO/ZrO_2催化剂，并用于催化DMCD加氢制备CHDM的反应中。通过表征和催化评价发现锆的加入对催化剂的结构和催化性能具有显著的影响。在所合成的催化剂中ZrO_2含量为35%的催化剂表现出了优秀的催化性能，其CHDM的产率达到96.8%。这可以归结为适量的ZrO_2的加入可以使铜基催化剂的分散度显著提高，进而形成了大量的Cu~0和Cu~+催化活性中心。
(二)通过Cu~-Zn-Al水滑石单源前驱体经过焙烧和还原制备出高分散的铜基催化剂，并用于催化DMCD加氢制备CHDM的反应中。采用XRD、TG-MS、TPR、SEM、TEM、XPS和XAES等方法对催化剂前驱体及催化剂进行了系统的表征。由表征结果发现层状前驱体经过不同焙烧温度处理后所得催化剂的组成，结构和性质具有非常大的变化。从DMCD加氢评价结果发现，层状前驱体在600oC下焙烧所得催化剂表现出了最优秀的催化性能，其CHDM的收率达到了95.6%，不仅高于其它温度焙烧所得的催化剂，还高于经典的铜铬催化剂。这是因为该催化剂具有最高的铜分散度，最大的铜表面积，最发达的孔结构和适合的表面化学性质促进了酯基的反应的进行，并提出了Cu~0与Cu~+在DMCD加氢反应中的作用机理。
(三)通过Cu~-Mg-Al水滑石单源前驱体经过焙烧和还原制备出具有Lewis碱增强的高分散铜基催化剂，并用于催化DMCD加氢制备CHDM的反应中。通过XRD、TPR、SEM、TEM和CO~(2-)TPD等方法对催化剂前驱体及催化剂进行表征发现镁的加入对催化剂的结构、铜的分散性和表面碱性都有非常显著的影响。从催化结果上发现Cu:Mg:Al为6:6:6的样品其CHDM的产率高达99.8%，并在200小时内不失活。该结果超越了所有经过报道的催化剂的性能。这是因为在镁的加入后不仅提高了催化剂的分散性还增加了催化剂的碱性。在铜表面积相近的条件下具有更高碱性的催化剂将表现出更优秀的催化性能。此外，结合XAES和in situ FT-IR的表征结果提出了DMCD在Cu~0与Lewis碱两种活性位上的协同加氢机理。
1,4-cyclohexane dimethanol (CHDM), which is one of the mostimportant chemical intermediates, has been preferred over ethylene glycol as astepping stone in the production of polyester fibers having excellent thermalresistance, transparency, and physical strength. To date, on an industrial scale,the only reported feasible route to CHDM is the catalytic hydrogenation ofdimethyl1,4-cyclohexane dicarboxylate (DMCD) by using Cr2O3promotedcopper-based heterogeneous catalysts. The toxicity of such type ofCr-containing catalysts, however, can cause a severe environmental pollution,and thus limits their practical applications, in addition to the high yield ofdesired product. Therefore, it has always been a challenge or a hot issue todevelop Cr-free catalysts with high activity and selectivity in thehydrogenation of DMCD. In addition, the Cu-based catalysts have been ofgreat interest due to their good activities and selectivities in a wide range ofreactions of various organic compounds. The most widely used preparation techniques for supported Cu~-based catalysts are deposition-precipitation andincipient wetness impregnation, which easily lead to the formation of copperparticles with large diameters and low metal loading amounts. In additional,the copper particle is easily sintered to large copper size during long termreaction, which inevitably leads to deactivation of copper-based catalyst.
Therefore, different promoters and layered double hydroxides precursorare used to obtain highly dispersed copper-based catalyst, which exhibitexcellent performance in the catalytic hydrogenation of DMCD. Through aseries characterization, the relationship between the structure and catalyticperformance has been disclosed.
(1) The gas-phase hydrogenation of DMCD to CHDM was conducted onwell-dispersed supported Cu/ZnO/ZrO_2catalysts. The results indicated that thestructure and catalytic performance of resulting copper-based catalysts wereprofoundly affected by the addition of zirconium. Moreover, theas-synthesized catalyst with35.0wt.%ZrO_2component was found to exhibitsuperior catalytic performance with a high CHDM yield of96.8%to othercatalysts, which should be mainly attributed to the significant dispersion effectof ZrO_2on the copper-containing species resulting in the higher metalliccopper surface area as well as the larger number of Cu~+species.
(2) Copper-based catalysts for gas-phase hydrogenation of DMCD toCHDM were prepared from a single-source Cu-Zn-Al layered doublehydroxide (LDH) precursor. The materials were characterized by powder X-ray diffraction (XRD), thermogravimetry analysis coupled with massspectrometry (TG-MS), temperature programmed reduction (TPR), scanningelectron microscopy (SEM), transmission electron microscopy (TEM), andX-ray photoelectron spectroscopy (XPS). The results revealed that thecomposition, texture, and structure of copper-based catalysts weresignificantly affected by the calcination temperature for LDH precursor.Moreover, the as-synthesized catalyst calcined at600°C was found to exhibitsuperior catalytic hydrogenation performance with the high CHDM yield of95.6%to the catalysts calcined at other temperatures and the traditional one,which should be attributed to the presence of the highly-dispersed activemetallic copper species, as well as reasonable surface chemical state overmetal oxide-based matrix thus facilitating the activation of ester groups ofreactants.
(3) Lewis base promoted copper-based catalysts for gas-phasehydrogenation of DMCD to CHDM were prepared from Cu-Mg-Al layereddouble hydroxide (LDH) precursor with different Cu/Mg ratios. The materialswere characterized by XRD, TPR, SEM, TEM and CO~(2-)TPD. The resultsrevealed that the structure, dispersion and surface base property ofcopper-based catalysts were significantly affected by the addition ofmagnesium. Moreover, the as-synthesized catalyst with Cu~:Mg:Al=6:6:6achieved a lasting100%conversion with99.8%selectivity up to200hours.The unprecedented catalytic performance is ascribed to the synergistic effect between surface active Cu~0sites and Lewis base sites.
本论文通过在铜基催化剂中添加具有不同性质的高性能助剂与通过形成层状前驱体的方法分别制备出了高分散的铜基催化剂，并在DMCD加氢制备CHDM的反应得到了很好的催化性能。同时通过对催化剂的系统表征揭示了催化剂的结构性质与催化性能的关系。
(一)采用成核晶化隔离法制备出具有不同ZrO_2含量的Cu/ZnO/ZrO_2催化剂，并用于催化DMCD加氢制备CHDM的反应中。通过表征和催化评价发现锆的加入对催化剂的结构和催化性能具有显著的影响。在所合成的催化剂中ZrO_2含量为35%的催化剂表现出了优秀的催化性能，其CHDM的产率达到96.8%。这可以归结为适量的ZrO_2的加入可以使铜基催化剂的分散度显著提高，进而形成了大量的Cu~0和Cu~+催化活性中心。
(二)通过Cu~-Zn-Al水滑石单源前驱体经过焙烧和还原制备出高分散的铜基催化剂，并用于催化DMCD加氢制备CHDM的反应中。采用XRD、TG-MS、TPR、SEM、TEM、XPS和XAES等方法对催化剂前驱体及催化剂进行了系统的表征。由表征结果发现层状前驱体经过不同焙烧温度处理后所得催化剂的组成，结构和性质具有非常大的变化。从DMCD加氢评价结果发现，层状前驱体在600oC下焙烧所得催化剂表现出了最优秀的催化性能，其CHDM的收率达到了95.6%，不仅高于其它温度焙烧所得的催化剂，还高于经典的铜铬催化剂。这是因为该催化剂具有最高的铜分散度，最大的铜表面积，最发达的孔结构和适合的表面化学性质促进了酯基的反应的进行，并提出了Cu~0与Cu~+在DMCD加氢反应中的作用机理。
(三)通过Cu~-Mg-Al水滑石单源前驱体经过焙烧和还原制备出具有Lewis碱增强的高分散铜基催化剂，并用于催化DMCD加氢制备CHDM的反应中。通过XRD、TPR、SEM、TEM和CO~(2-)TPD等方法对催化剂前驱体及催化剂进行表征发现镁的加入对催化剂的结构、铜的分散性和表面碱性都有非常显著的影响。从催化结果上发现Cu:Mg:Al为6:6:6的样品其CHDM的产率高达99.8%，并在200小时内不失活。该结果超越了所有经过报道的催化剂的性能。这是因为在镁的加入后不仅提高了催化剂的分散性还增加了催化剂的碱性。在铜表面积相近的条件下具有更高碱性的催化剂将表现出更优秀的催化性能。此外，结合XAES和in situ FT-IR的表征结果提出了DMCD在Cu~0与Lewis碱两种活性位上的协同加氢机理。
1,4-cyclohexane dimethanol (CHDM), which is one of the mostimportant chemical intermediates, has been preferred over ethylene glycol as astepping stone in the production of polyester fibers having excellent thermalresistance, transparency, and physical strength. To date, on an industrial scale,the only reported feasible route to CHDM is the catalytic hydrogenation ofdimethyl1,4-cyclohexane dicarboxylate (DMCD) by using Cr2O3promotedcopper-based heterogeneous catalysts. The toxicity of such type ofCr-containing catalysts, however, can cause a severe environmental pollution,and thus limits their practical applications, in addition to the high yield ofdesired product. Therefore, it has always been a challenge or a hot issue todevelop Cr-free catalysts with high activity and selectivity in thehydrogenation of DMCD. In addition, the Cu-based catalysts have been ofgreat interest due to their good activities and selectivities in a wide range ofreactions of various organic compounds. The most widely used preparation techniques for supported Cu~-based catalysts are deposition-precipitation andincipient wetness impregnation, which easily lead to the formation of copperparticles with large diameters and low metal loading amounts. In additional,the copper particle is easily sintered to large copper size during long termreaction, which inevitably leads to deactivation of copper-based catalyst.
Therefore, different promoters and layered double hydroxides precursorare used to obtain highly dispersed copper-based catalyst, which exhibitexcellent performance in the catalytic hydrogenation of DMCD. Through aseries characterization, the relationship between the structure and catalyticperformance has been disclosed.
(1) The gas-phase hydrogenation of DMCD to CHDM was conducted onwell-dispersed supported Cu/ZnO/ZrO_2catalysts. The results indicated that thestructure and catalytic performance of resulting copper-based catalysts wereprofoundly affected by the addition of zirconium. Moreover, theas-synthesized catalyst with35.0wt.%ZrO_2component was found to exhibitsuperior catalytic performance with a high CHDM yield of96.8%to othercatalysts, which should be mainly attributed to the significant dispersion effectof ZrO_2on the copper-containing species resulting in the higher metalliccopper surface area as well as the larger number of Cu~+species.
(2) Copper-based catalysts for gas-phase hydrogenation of DMCD toCHDM were prepared from a single-source Cu-Zn-Al layered doublehydroxide (LDH) precursor. The materials were characterized by powder X-ray diffraction (XRD), thermogravimetry analysis coupled with massspectrometry (TG-MS), temperature programmed reduction (TPR), scanningelectron microscopy (SEM), transmission electron microscopy (TEM), andX-ray photoelectron spectroscopy (XPS). The results revealed that thecomposition, texture, and structure of copper-based catalysts weresignificantly affected by the calcination temperature for LDH precursor.Moreover, the as-synthesized catalyst calcined at600°C was found to exhibitsuperior catalytic hydrogenation performance with the high CHDM yield of95.6%to the catalysts calcined at other temperatures and the traditional one,which should be attributed to the presence of the highly-dispersed activemetallic copper species, as well as reasonable surface chemical state overmetal oxide-based matrix thus facilitating the activation of ester groups ofreactants.
(3) Lewis base promoted copper-based catalysts for gas-phasehydrogenation of DMCD to CHDM were prepared from Cu-Mg-Al layereddouble hydroxide (LDH) precursor with different Cu/Mg ratios. The materialswere characterized by XRD, TPR, SEM, TEM and CO~(2-)TPD. The resultsrevealed that the structure, dispersion and surface base property ofcopper-based catalysts were significantly affected by the addition ofmagnesium. Moreover, the as-synthesized catalyst with Cu~:Mg:Al=6:6:6achieved a lasting100%conversion with99.8%selectivity up to200hours.The unprecedented catalytic performance is ascribed to the synergistic effect between surface active Cu~0sites and Lewis base sites.
引文
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