Production of levulinic acid from cellulose by hydrothermal decomposition combined with aqueous phase dehydration with a solid acid catalyst

被引:323
作者
Weingarten, Ronen [1 ]
Conner, Wm. Curt, Jr. [1 ]
Huber, George W. [1 ]
机构
[1] Univ Massachusetts, Dept Chem Engn, Amherst, MA 01003 USA
基金
美国国家科学基金会;
关键词
LIQUID-HYDROCARBON FUELS; HOT-COMPRESSED WATER; HIGH-SURFACE-AREA; GAMMA-VALEROLACTONE; HIGH-TEMPERATURE; IONIC LIQUIDS; FORMIC-ACID; CONVERSION; GLUCOSE; BIOMASS;
D O I
10.1039/c2ee21593d
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
In this paper we introduce a process to produce levulinic acid from cellulose without the use of a homogeneous acid catalyst. The process consists of 2 reaction steps: (1) non-catalytic hydrothermal decomposition of cellulose at moderate temperatures (190-270 degrees C) to produce organic water-soluble compounds including glucose and HMF; (2) water-soluble compounds are further reacted with a solid acid catalyst at relatively low temperatures (160 degrees C) to produce levulinic acid and formic acid. Unreacted cellulose can be recycled back to the first reactor for further decomposition. The cellulose hydrothermally decomposes at high initial cellulose concentrations of 29 wt% while maintaining high selectivity towards water-soluble compounds, which are levulinic acid precursors. The maximum amounts of usable water soluble organics are produced at relatively higher temperatures and shorter residence times (220 degrees C and 30 min). Amberlyst 70 was used as a solid acid catalyst for conversion of the water soluble organics into HMF, levulinic acid and formic acid. Amberlyst 70 has comparable activity to HCl, with a slightly lower selectivity towards levulinic acid. The maximum obtainable yield of levulinic acid we obtained was 28% of the theoretical. This study lays the grounds for further optimization to produce levulinic acid from cellulose without using homogeneous acid catalysts.
引用
收藏
页码:7559 / 7574
页数:16
相关论文
共 96 条
[1]   DILUTE ACID DEPOLYMERIZATION OF CELLULOSE IN AQUEOUS PHASE - EXPERIMENTAL-EVIDENCE OF THE SIGNIFICANT PRESENCE OF SOLUBLE OLIGOMERIC INTERMEDIATES [J].
ABATZOGLOU, N ;
BOUCHARD, J ;
CHORNET, E ;
OVEREND, RP .
CANADIAN JOURNAL OF CHEMICAL ENGINEERING, 1986, 64 (05) :781-786
[2]   Roles of water for chemical reactions in high-temperature water [J].
Akiya, N ;
Savage, PE .
CHEMICAL REVIEWS, 2002, 102 (08) :2725-2750
[3]   CHARACTERIZATION OF SYNTHETIC CARBOHYDRATE-DERIVED HUMIC-LIKE POLYMERS [J].
ALMENDROS, G ;
SANZ, J ;
SOBRADOS, I .
SCIENCE OF THE TOTAL ENVIRONMENT, 1989, 81-2 :91-98
[4]   Production of Biofuels from Cellulose and Corn Stover Using Alkylphenol Solvents [J].
Alonso, David Martin ;
Wettstein, Stephanie G. ;
Bond, Jesse Q. ;
Root, Thatcher W. ;
Dumesic, James A. .
CHEMSUSCHEM, 2011, 4 (08) :1078-1081
[5]   Production of liquid hydrocarbon transportation fuels by oligomerization of biomass-derived C9 alkenes [J].
Alonso, David Martin ;
Bond, Jesse Q. ;
Serrano-Ruiz, Juan Carlos ;
Dumesic, James A. .
GREEN CHEMISTRY, 2010, 12 (06) :992-999
[6]  
[Anonymous], 2002, COMM BIOF TECHN LEV
[7]   Conversion of Japanese red pine wood (Pinus densiflora) into valuable chemicals under subcritical water conditions [J].
Asghari, Feridoun Salak ;
Yoshida, Hiroyuki .
CARBOHYDRATE RESEARCH, 2010, 345 (01) :124-131
[8]   Hydrothermal conversion of glucose in a batch reactor. A detailed study of an experimental key-parameter: The heating time [J].
Barbier, J. ;
Charon, N. ;
Dupassieux, N. ;
Loppinet-Serani, A. ;
Mahe, L. ;
Ponthus, J. ;
Courtiade, M. ;
Ducrozet, A. ;
Fonverne, A. ;
Cansell, F. .
JOURNAL OF SUPERCRITICAL FLUIDS, 2011, 58 (01) :114-120
[9]  
Bayan S., 1941, La Chimica e L'Industria, V23, P432
[10]   Fermentable sugars by chemical hydrolysis of biomass [J].
Binder, Joseph B. ;
Raines, Ronald T. .
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA, 2010, 107 (10) :4516-4521