Catalytic depolymerization of kraft lignin for liquid fuels and phenolic monomers over molybdenum-based catalysts: The effect of supports
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摘要: 本文研究了不同载体(黏土(海泡石(SEP)、凹凸棒石(ATP)、蒙脱土(MTM))和氧化物(Al2O3和SiO2)及其负载的Mo基催化剂对超临界乙醇体系中催化解聚木质素制备液体燃料和酚类单体的影响。催化剂表征结果证明，不同结构性质的载体会影响Mo基催化剂结构、表面Mo5+含量和酸性位分布。与Al2O3和SiO2相比，黏土基载体具有更多的强酸位，不利于木质素油(LO)的生成，形成更多的固体产物。仅使用载体获得的LO中得到的石油醚溶性产物(PEsp)主要为烷基/烷氧基取代苯酚，而Mo基催化剂中Mo物种(尤其是Mo5+)显著提高了LO和PEsp的产量。Mo/SiO2表面Mo5+物种最多，LO产率最高，为85.2%，其中生成的烷基/烷氧基取代苯酚达450.3 mg/glignin。在黏土负载的Mo催化剂中，Mo/SEP的LO产率(82.3%)和PEsp产率(70.8%)较高，所获得取代酚达到398.8 mg/glignin。本研究系统地报道了绿色环保型黏土基材料在木质素转化中的应用，为黏土基材料在生物质转化中的应用提供了关键信息。Abstract: Catalytic lignin depolymerization (CCLD) for liquid fuels and phenolic monomers was investigated over various supports including clays (e.g., sepiolite (SEP), attapulgite (ATP), and montmorillonite (MTM)), and oxides (e.g., Al2O3 and SiO2) as well as their supported Mo-based catalysts under supercritical ethanol. The characterization results demonstrated that different supports with diverse structural properties could affect the textural structures, surface Mo5+ content, and acid sites distribution. Clay-based supports had more strong acid sites as compared with Al2O3 and SiO2, which went against the production of lignin oil (LO) and led to form more solid products during CLD experiments. Meanwhile, the obtained petroleum ether-soluble product (PEsp) in LO catalyzed by sole supports was mainly alkyl/alkoxy substituted phenols. Additionally, Mo species (especially Mo5+) significantly increased the yields of LO and PEsp. Mo/SiO2 had the highest surface Mo5+ species, showing the highest LO yield of 85.2%, in which the produced alkyl/alkoxy substituted phenols reached 450.3 mg/glignin. Among the clay-supported Mo catalysts, Mo/SEP presented superior LO (82.3%) and PEsp (70.8%) yields and the generated substituted phenols reached 398.8 mg/glignin. This paper systematically reported the application of green and environmentally friendly clay-based materials in lignin conversion, which provides some key information for the development of clay catalysts for biomass conversion.
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Key words:
- kraft lignin /
- catalytic depolymerization /
- lignin oil /
- Mo-based catalysts /
- clay materials /
- phenolic monomers
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Figure 3 N2 adsorption-desorption isotherms and pore size distribution profiles of the supports and Mo-based catalysts
Table 1 Ultimate and proximate analysis of lignin
Ultimate analysis w/% Proximate analysis w/% C H O N S M A V FC 57.84 4.63 22.98 0.89 2.28 5.78 4.05 55.79 34.38 
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Table 2 Textural properties of supports and Mo-based catalysts
Sample SBET /(m2·g−1)* v /(cm3·g−1)** d /nm** NH3 monolayer uptake /(mol NH3·g−1 sample)*** SEP 9.346 0.060 18.7 1443.2 Mo/SEP 5.632 0.037 25.6 1268.7 ATP 127.571 0.449 15.8 5593.4 Mo/ATP 6.904 0.056 22.4 1195.3 MTM 64.227 0.134 5.7 3044.0 Mo/MTM 8.961 0.052 10.1 1462.2 Al2O3 92.224 0.226 6.1 777.5 Mo/Al2O3 34.835 0.099 7.6 679.9 SiO2 234.081 1.647 30.3 1176.1 Mo/SiO2 65.317 0.530 27.9 1040.4 * SBET was calculated using the BET method;
** v and d were calculated using the BJH method based on the desorption isotherms;
*** data was obtained from NH3-TPD analysis
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Table 3 Yields of identified monomer products in PEsp obtained over various supports
SN Monomer name ${\rm{Yields} } /({\rm{mg} }\cdot{\rm{g} }_{ {\rm{lignin} } }^{ - 1})$ PEsp-a PEsp-b PEsp-c PEsp-d PEsp-e 2 1,2-dimethoxy-4-(1-methoxyethenyl) benzene 10.2 13.3 3.8 − 14.3 4 phenol,3-(1,1-dimethylethyl)-4-methoxy- 11.4 12.8 − − 13.9 6 2-hexenoic acid, ethyl ester 4.4 4.2 5.8 6.6 − 8 1,6-heptadien-4-ol 3.9 4.4 6.5 5.7 4.3 9 phenol,2-methoxy- 24.4 30.1 27.6 14.3 32.5 11 octanoic acid, ethyl ester 3.0 − 3.5 − − 13 phenol,2-ethoxy- 8.7 5.5 9.7 30.0 5.1 14 phenol,4-methoxy-3-methyl- 27.0 21.1 29.0 13.3 21.2 15 ethyl P-hydroxybenzoate 3.1 3.4 3.9 3.2 3.5 16 benzene,1-ethoxy-4-methoxy- 3.1 3.2 4.1 7.9 6.2 17 2-pentenoic acid,4-methyl-, ethyl ester, 3.4 3.6 3.0 3.1 − 18 2-ethoxy-4-methylphenol 5.1 4.5 6.7 9.7 − 20 phenol,4-ethyl-2-methoxy- 15.9 21.7 15.8 13.2 12.2 23 P-cymene-2,5-diol 3.1 4.0 3.8 5.4 3.3 24 phenol,2-methoxy-4-propyl- 9.8 11.4 7.9 5.99 12.54 25 durohydroquinone − − − 6.1 − 26 1,4-benzenediol,2,3,5-trimethyl- − − − 2.6 − 27 propofol − − − 3.0 − 28 benzene,2-(1,1-dimethylethyl)-1,4-methoxyl- − − − 3.1 − 29 phenol,3,5-bis(1,1-dimethylethyl)- − − − 4.9 − 31 benzene,1,4-dimethoxy-2-methyl-5-isopropyl- − − − 2.8 − Aliphatic oxygenates 14.7 12.2 18.8 15.4 4.3 Alkyl and oxyalkylated benzenes 13.3 16.5 7.9 13.8 20.5 Alkyl and alkoxy substituted phenols 108.5 114.5 104.2 111.6 104.2 Total 136.5 143.2 130.9 140.8 129.0
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Table 4 Yields of identified monomer products in PEsp obtained over various Mo-based catalysts
SN Monomer name Yields/(mg·${\rm{g} }_{ {\rm{lignin} } }^{ - 1}$) PEsp-A PEsp-B PEsp-C PEsp-D PEsp-E 1 pentanoic acid,3-methyl-, ethyl ester 20.4 4.8 11.4 22.4 22.2 3 2-hexenoic acid, ethyl ester 76.2 6.9 45.6 37.8 78.0 5 3-hexenoic acid, ethyl ester 71.6 10.1 35.2 33.9 73.2 7 6-hepten-1-ol,5-methyl- 8.0 4.5 3.3 9.3 10.3 9 phenol,2-methoxy- 34.8 17.3 14.8 23.1 32.5 10 octanoic acid,2-ethyl-, ethyl ester 36.0 16.1 9.3 34.1 18.7 11 octenoic acid, ethyl ester 50.4 12.7 11.5 53.3 30.6 12 phenol,2-ethoxyl- 35.9 18.4 16.4 23.7 34.5 13 phenol,3-ethoxyl- 9.3 8.4 2.7 13.9 6.9 16 benzene,1-ethoxy-4-methoxy- 16.5 18.8 5.0 35.9 17.2 17 2-pentenoic acid,4-methyl-, ethyl ester, 19.8 6.9 4.8 23.5 14.6 19 2,5-diethylphenol 6.1 − 3.4 9.9 7.0 21 1,4-benzenediol,2,6-dimethyl- 7.8 4.0 4.7 12.1 6.4 22 phenol,2-(1,1-dimethylethyl)-6-methyl- 15.1 11.1 6.2 19.3 16.2 27 propofol 41.9 26.7 30.7 83.8 64.9 29 phenol,3,5-bis(1,1-dimethylethyl)- 16.9 15.5 13.6 35.0 28.9 30 phenol,2,6-bis(1,1-dimethylethyl)- 182.5 96.8 46.7 200.7 189.9 32 phenol,2,4,6-tris(1-methylethyl)- 15.6 16.5 8.5 24.8 22.4 33 4-tert-butyl-2,6-diisopropylphenol 32.9 30.4 17.6 49.6 40.7 Aliphatic oxygenates 282.4 62.0 121.1 214.3 247.6 Alkyl and oxyalkylated benzenes 16.5 18.8 5.0 35.9 17.2 Alkyl and alkoxy substituted phenols 398.8 245.1 165.3 496.2 450.3 Total 697.7 325.9 291.4 746.4 715.1
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