化工学报 ›› 2019, Vol. 70 ›› Issue (12): 4519-4527.DOI: 10.11949/0438-1157.20190928
王文锦1,2,3(),徐莹1,2(),王东玲1,2,3,王晨光1,2,马隆龙1,2
收稿日期:
2019-08-13
修回日期:
2019-09-26
出版日期:
2019-12-05
发布日期:
2019-12-05
通讯作者:
徐莹
作者简介:
王文锦(1995—),男,硕士研究生,基金资助:
Wenjin WANG1,2,3(),Ying XU1,2(),Dongling WANG1,2,3,Chenguang WANG1,2,Longlong MA1,2
Received:
2019-08-13
Revised:
2019-09-26
Online:
2019-12-05
Published:
2019-12-05
Contact:
Ying XU
摘要:
木质素是由三种苯丙烷单元随机键合形成的复杂大分子物质,是自然界中唯一可直接提供芳环的可再生能源。以木质素为原料制取高品位液体燃料和高附加值化学品,特别是木质素氢解是国内外关注的热门研究领域之一。梳理了近年木质素催化氢解研究进展,针对木质素氢解过程中溶剂体系(水溶剂以及醇类溶剂)和催化剂体系(均相催化剂以及非均相金属催化剂)对木质素氢解效率、产物分布的影响机理,做了较全面的概述和分析。最后,针对木质素催化氢解领域目前尚存在的问题提出建议,期望为木质素高值化利用相关研究提供参考。
中图分类号:
王文锦,徐莹,王东玲,王晨光,马隆龙. 木质素氢解反应溶剂与催化剂研究进展[J]. 化工学报, 2019, 70(12): 4519-4527.
Wenjin WANG,Ying XU,Dongling WANG,Chenguang WANG,Longlong MA. Progress in solvent and catalyst for hydrogenolysis of lignin[J]. CIESC Journal, 2019, 70(12): 4519-4527.
Solvent | Catalyst | Reaction conditions | Reactant | Product | Conversion/% | Selectivity/% |
---|---|---|---|---|---|---|
basic water | NiAl alloy | 220℃,Ar | poplar wood lignin | monomer+oligomer | 86.8 | 18.9 |
basic water | Ni/ZSM-5 | 200℃,4 MPa | OKL | bio-oil | 83 | — |
water | Pd1Ni4/MIL-100(Fe) | 180℃,6 h | organosolv lignin | phenol and guaiacol derivates | 100 | — |
methanol | Raney Ni | 300℃,8 h | organosolv lignin | unsaturates | 86 | — |
methanol | Pd/C+CrCl3 | 300℃,4 h | hydrolysis lignin | monomer | 81.4 | 26.3 |
ethanol | Ru/C | 300℃,10 h | lignin | oil | — | 75.8 |
ethanol | Ni/Al-SBA-15 | 300℃,4 h | hydrolysis lignin | phenolic monomers | >90 | 21.9 |
2-propanol | Raney Ni | 300℃,8 h | organosolv lignin | saturates | 91 | — |
isopropanol | Ni-Cu/H-Beta | 330℃,3 h | lignin | monomer | 98.8 | 50.83 |
isopropanol | Pt Re/TiO2 | 240℃,He | lignin | monomer phenol | — | 18.7 |
ethanol/1,4-dioxane | formic | 300℃,2 h | kraft lignin | monomer phenol | — | 22.4 |
SC-ethanol/phenol | Cu Ni Al | 290℃,3 h | alkali lignin | bio-oil | 81.8 | — |
表1 木质素氢解反应溶剂
Table 1 Solvent for hydrogenolysis of lignin
Solvent | Catalyst | Reaction conditions | Reactant | Product | Conversion/% | Selectivity/% |
---|---|---|---|---|---|---|
basic water | NiAl alloy | 220℃,Ar | poplar wood lignin | monomer+oligomer | 86.8 | 18.9 |
basic water | Ni/ZSM-5 | 200℃,4 MPa | OKL | bio-oil | 83 | — |
water | Pd1Ni4/MIL-100(Fe) | 180℃,6 h | organosolv lignin | phenol and guaiacol derivates | 100 | — |
methanol | Raney Ni | 300℃,8 h | organosolv lignin | unsaturates | 86 | — |
methanol | Pd/C+CrCl3 | 300℃,4 h | hydrolysis lignin | monomer | 81.4 | 26.3 |
ethanol | Ru/C | 300℃,10 h | lignin | oil | — | 75.8 |
ethanol | Ni/Al-SBA-15 | 300℃,4 h | hydrolysis lignin | phenolic monomers | >90 | 21.9 |
2-propanol | Raney Ni | 300℃,8 h | organosolv lignin | saturates | 91 | — |
isopropanol | Ni-Cu/H-Beta | 330℃,3 h | lignin | monomer | 98.8 | 50.83 |
isopropanol | Pt Re/TiO2 | 240℃,He | lignin | monomer phenol | — | 18.7 |
ethanol/1,4-dioxane | formic | 300℃,2 h | kraft lignin | monomer phenol | — | 22.4 |
SC-ethanol/phenol | Cu Ni Al | 290℃,3 h | alkali lignin | bio-oil | 81.8 | — |
Catalyst | Reaction condition | Reactant | Product | Conversion/% | Selectivity/% |
---|---|---|---|---|---|
Pd/C+CrCl3 | 280℃,5 h | alkali lignin | monophenols | — | 28.5 |
Ni/Al-SBA-15 | 300℃,4 h | hydrolysis lignin | monophenol | >90 | 21.9 |
Co-phen/C | 200℃,2 h | birch lignin | monophenol | — | 34 |
Ni7Au3 | 170℃,12 h | organoslov lignin | aromatic monomers | — | 14 |
Pd Ni/ZrO2 | 80℃,6 h | model compounds | aromatic monomers | >80 | — |
Pt Re/TiO2 | 240℃,12 h | birch lignin | monophenol | — | 18.71 |
Ni Fe/AC | 225℃,2 MPa H2 | organosolv lignin | monophenol | — | 23.2 |
Au1Pd1/CeO2 | 180℃,6 h | organosolv lignin | monophenol | — | 44.1 |
表2 木质素氢解非均相催化剂
Table 2 Heterogeneous catalyst of lignin hydrogenolysis
Catalyst | Reaction condition | Reactant | Product | Conversion/% | Selectivity/% |
---|---|---|---|---|---|
Pd/C+CrCl3 | 280℃,5 h | alkali lignin | monophenols | — | 28.5 |
Ni/Al-SBA-15 | 300℃,4 h | hydrolysis lignin | monophenol | >90 | 21.9 |
Co-phen/C | 200℃,2 h | birch lignin | monophenol | — | 34 |
Ni7Au3 | 170℃,12 h | organoslov lignin | aromatic monomers | — | 14 |
Pd Ni/ZrO2 | 80℃,6 h | model compounds | aromatic monomers | >80 | — |
Pt Re/TiO2 | 240℃,12 h | birch lignin | monophenol | — | 18.71 |
Ni Fe/AC | 225℃,2 MPa H2 | organosolv lignin | monophenol | — | 23.2 |
Au1Pd1/CeO2 | 180℃,6 h | organosolv lignin | monophenol | — | 44.1 |
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