甘油催化氢解制1,2-丙二醇的研究进展

肖 飒，童东绅，赵立知，任倩倩，刘丰国，俞卫华，周春晖

（浙江工业大学化学工程学院，浙江 杭州 310014）

甘油主要来自动植物和化工产业（如肥皂、生物柴油产业），具有可降解、可再生等优点。因其独特的性质，甘油成为近年来的研究热点。目前，甘油可转化为各种高附加值的精细化学品[1-2]。其中，从甘油催化氢解制1,2-丙二醇（1,2-PDO）的技术最受关注。1,2-PDO 的传统生产工艺包括环氧丙烷水解法、丙烯氧化法和酯交换法。上述工艺原料来自不可再生的石油资源，流程复杂，环境污染严重，经济效益低。而甘油氢解法使用绿色清洁的甘油作原料，产物种类少、收率高、易分离提纯，具有替代传统生产工艺的潜力。

甘油催化氢解反应成功的关键是选择合适的催化剂。目前研究较多的催化剂有两大类：贵金属催化剂（如Ru、Rh、Pt、Pd）和过渡金属催化剂（如Cu、Ni、Co），载体研究较多的是碳材料、金属氧化物和层状双氢氧化物。这些催化剂所采用的制备方法不同，工艺参数不同，催化性能也有差异。

1 催化剂研究开发

1.1 贵金属催化剂

单一贵金属催化剂的选择性一般较差，添加其他组分可提高选择性。例如Ru/C 催化剂中加入12-磷钨酸作共催化剂后，大幅度提高了1,2-PDO 的收率[3]。

此外，载体表面的酸碱度也对催化剂的性能有一定影响[4]。酸性位有利于C-O 键断裂，但酸性位过多会促进C-C 键断裂。对Ru 催化剂，TiO2载体的酸性位数量较合适[5]，HZSM5 载体的酸性导致副产物CH4选择性提高，1,2-PDO 选择性降低[6]。碱性氧化物负载的Ru 催化剂中，因CeO2表面呈弱碱性，甘油转化率和1,2-PDO 选择性较高[7]。碱性的层状水滑石作载体对Pt 催化剂性能有促进作用[8]。

甘油氢解反应通常需在H2或合成气等还原性气氛下进行，存在一定的安全隐患。D’Hondt 等首次发现在不通氢气的条件下就能实现甘油氢解；采用Pt/NaY 催化剂，以20wt% 甘油水溶液为原料，在503 K 反应15 h 后，甘油转化率和1,2-PDO 选择性分别为85.4% 和64.0%[9]。同样在不加氢气条件下，Ru/Al2O3和Pt/Al2O3混合物[10]或Pd/Fe2O3催化剂[11]也能催化甘油氢解。

过去，Ag 基催化剂催化甘油转化制备1,2-PDO 的研究较少。最近研究表明，Ag 掺杂的分子筛催化剂[12]和Ag/γ-Al2O3催化剂[13]对于甘油催化氢解反应也具有活性和选择性。

1.2 Cu 催化剂

相对于贵金属催化剂，Cu 催化剂价格低廉，对C-O 键加氢活性较高，对C-C 键断裂活性较低，因此1,2-PDO 选择性较高。最近，开发高效Cu 催化剂成为研究热点。例如，在相对较低的压力下（1.4 MPa）使用Raney Cu 催化剂，甘油转化率可达100%，1,2-PDO 收率也高达94%[14]。

载体是影响催化性能的因素之一。对于氧化物改性的Raney Cu 催化剂，催化载体活性顺序是MgO>ZnO>SiO2>TiO2>ZrO2>Al2O3[15]。层状双氢氧化物作载体能提供碱性位[16]，例如层状双氢氧化物Cu0.4Mg5.6Al2(OH)16CO3热解产物作催化剂，在453 K，30 bar H2压力下，反应20 h 后，1,2-PDO选择性98.2%，甘油转化率80%[17]。介孔分子筛SBA-15 作载体，1,2-PDO 选择性和甘油转化率最高分别为92.4%和96.0%[18]。1173 K 预处理SBA-15，可提高催化剂结构稳定性[19]。在463 K 和0.64 MPa H2压力下，使用Cu/ZnO/Al2O3双载体催化剂，1,2-PDO 选择性为92%[20]。

Cu 还能与载体MxOy结合形成CuMxOy晶相。例如Cu 和CuCr2O4[21-22]之间有明显的相互作用，Cu/CuCr2O4活性比Cu/Cr2O3高。Cu-Fe 催化剂含有CuFe2O4晶相，在463 K，4.1 MPa H2压力下反应10 h，甘油转化率和1,2-PDO 选择性分别为47% 和92%[23]。纳米CuAl2O4催化剂只有CuAl2O4一个晶相，还原性高，对氢气吸附-脱附能力强，甘油转化率和1,2-PDO 选择性都大于90%[24]。

此外，制备方法不同，催化剂的催化性能也有差异。浸渍法制备的Cu/SiO2催化剂比离子交换法活性好，在1.5 MPa，528 K，300 mL/min H2反应条件下，甘油可完全转化，1,2-PDO 的选择性为87%[25]。共沉淀法制备的Cu/Al2O3催化剂，甘油转化率和1,2-PDO 选择性最高分别为63%和88%，而使用固态熔融法制备的Cu/Al2O3催化剂，甘油转化率最高仅39%[26]。溶胶凝胶法制备的Cu/ZnO催化剂表面积约为共沉淀法的两倍，因此活性更高[29]。

影响催化性能的因素还有负载量、甘油浓度、溶剂类型、氢气压力、pH 和反应温度等。Cu 负载量较低时，Cu/MgO 催化剂活性较高[27]。添加少量NaOH 进一步提高了Cu/MgO 的活性，可代替Ru/C (或Rh/SiO2)+Amberlyst、Pt/C (或Ru/C) +NaOH 催化剂体系[28]。反应中生成的水会造成Cu/ZnO 催化剂失活，改用1,2-丁二醇作溶剂，甘油转化率从5%增至55%[29]。Cu 催化剂添加助剂（如Ba[30]、Ga2O3[31]）也可使催化剂抗失活。

1.3 Ni、Co 催化剂

除了Cu 催化剂，Raney Ni[32-33]，Ni/AC[34]，Ni/NaX[35]，Ni/SiO2-Al2O3[36]，Ni/Mg/Al 层状双氢氧化物[37]同样对甘油催化氢解具有很好的活性。Raney Ni 作催化剂时，可使用粗甘油作原料[38]。KBH4处理Ni/AC 催化剂，使得AC 表面的羰基还原为酚基，大大提高了催化剂酸性[34]。此外，Ni 还可以作为掺杂剂或者载体。例如，将金属Ni 掺在Cu-Cr催化剂中有助于提高1,2-PDO 的选择性[39]。若增加原料中水的含量，甘油的转化率和1,2-PDO 的选择性都会增加，这是因为低浓度甘油可减少脱水反应和加氢裂化[40]。

Co 催化剂的研究相对较少。在较高温度下处理Co/MgO 催化剂时，Co3O4和MgO 之间的相互作用得到了加强，形成了MgCo2O4晶体和Mg-Co-O 固溶体[41]，减少了钴氧化物的还原性，同时阻止了Co 粒子的聚集，所得的Co/MgO 催化剂表现出良好的稳定性。Co/Zn/Al 催化剂在反应前后物理性质能保持几乎不变，可重复使用[42]。

1.4 双金属催化剂

使用双金属催化剂如Pt-Ru、Au-Ru 可提高1,2-PDO 的收率[43]。Re 的加入对抑制C-C 键断裂发挥了作用，Ru-Re[44-46]、Pd-Re[47]、Pt-Re[48]催化剂均比单一Ru、Pd、Pt 或Re 催化剂活性好。

此外，铜和贵金属结合的双金属催化剂的研究也有较多报道。例如，在453 K、2.0 MPa 氢气下，使用Pd0.04Cu0.4/Mg5.5Al2O8.56催化剂，反应10 h后，甘油的转化率为88.0%，1,2-PDO 选择性为99.6%[49]。使用Rh0.02Cu0.4/Mg5.6Al1.98O8.57催化剂，甘油转化率和1,2-PDO 的选择性最高分别为91.0%和98.7%[50]。此外，碳纳米管[51]、膨润土[52]、HMS[53]也可作为Cu-Ru 催化剂的载体。对于Cu-Ag/γ-Al2O3催化剂，Ag 的加入使CuO 原位还原为Cu，这有助于提高铜在载体表面上分散性[54]，还能抑制甘油C-C 键断裂生成乙二醇，1,2-PDO 的选择性最高98.3%，此时甘油转化率为100%[55]。Ni-Cu/Al2O3催化剂能将溶剂中的氢转移到甘油之上[56-58]。当甲酸作氢源，45 bar N2，493 K，Ni-Cu/Al2O3催化剂，反应24 h，甘油转化率和1,2-PDO选择性分别为90% 和82%[59]。

2 反应机理

要想设计出高效的催化剂，认识甘油氢解反应的机理至关重要，根据文献报道，可能的反应机理有5 种。其中脱氢-脱水-加氢机理[60]、脱水-加氢机理[61]和螯合氢解机理[62]已有较多综述提到，本文不予赘述，只对直接氢解机理和原位氢解机理进行解释说明。

图1 甘油氢解过渡态模型[63]

直接氢解机理由Shinmi 等提出，后来被该研究小组进一步完善[63-64]。首先，甘油的-CH2OH 基团吸附在ReOx表面上形成醇盐，然后活化氢攻击醇盐的3 号位，使C-O 键断裂，最后醇盐水解得到产物1,2-PDO（见图1）。

Chia 等提出了一种不同的直接氢解路径[65]。第一步甘油通过质子化-脱水反应形成碳正离子，-CH2OH 基团发生氢转移，碳正离子形成更稳定的含氧碳正离子。最后氢转移生成1,2-PDO 或1,3-PDO[65]。这与Qin 等的研究结果一致[66]。反应过程如下所示：

原位氢解机理是基于脱水-加氢机理发展而来的，理论上甘油自身可以通过水相重整（APR）产生氢气[67]，将甘油制氢和甘油氢解结合起来，使生成的氢气被消耗,即APR 原位氢解机理（见图2）。除甘油本身作氢源，乙醇[11]、甲酸[56]、异丙醇[56]、甲醇[58]等也可作氢源，通过催化转移加氢（CTH）实现甘油催化氢解，即CTH 原位氢解机理。首先载体酸中心吸附甘油形成醇盐，金属活性位活化氢源分解产生的氢，然后醇盐和吸附的活性氢原子相互作用生成1,2-PDO。

图2 甘油水相重整与氢解制备1,2-PDO[68]

3 结论

甘油催化氢解制1,2-PDO 已成为甘油转化的研究热点，近五年来有了新的进展。研究表明，金属催化剂性能顺序为Ru≈Cu≈Ni>Pt>Pd，其中Cu 催化剂价格相对低廉，1,2-PDO 选择性较高，具有工业化前景；双金属催化剂可提高金属分散性、减小金属粒径，不同金属针对不同反应步骤发挥作用，因此催化性能比单一金属好；载体、制备方法等也是影响催化剂性能的关键因素，特别是采用溶胶凝胶法制备的催化剂，甘油转化率和1,2-PDO 选择性较高；酸碱添加剂能提高催化剂的热稳定性，加快反应速率或减少副产物生成；金属氧化物类助剂可提高催化剂表面酸性，或使活性组分不易被氧化；此外，认识甘油氢解反应的各种机理，对设计高效催化剂具有重要意义。目前，甘油氢解制备1,2-PDO 的技术已趋于成熟，如何实现工业化应是未来探索的主要方向。

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