Xiao-ning Ye

Catalytic fast pyrolysis of cellulose and biomass to produce levoglucosenone using magnetic SO42−/TiO2–Fe3O4

Magnetic superacid (SO4(2-)/TiO2-Fe3O4) was prepared for catalytic fast pyrolysis of cellulose and poplar wood to produce levoglucosenone (LGO). Its catalytic activity was evaluated via pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) experiments, and compared with the non-magnetic SO4(2-)/TiO2, phosphoric acid (H3PO4) and sulfur acid (H2SO4) catalysts. Moreover, the LGO yield was quantitatively determined. The results indicated that the magnetic SO4(2-)/TiO2-Fe3O4 was effective to selectively produce LGO from both cellulose and poplar wood. Its catalytic capability was a little better than the non-magnetic SO4(2-)/TiO2 and H3PO4, and much better than the H2SO4. The maximal LGO yields from both cellulose and poplar wood were obtained at 300 °C with the feedstock/catalyst ratio of 1/1, reaching as high as 15.43 wt% from cellulose and 7.06 wt% from poplar wood, respectively.

Effects of biopretreatment on pyrolysis behaviors of corn stalk by methanogen.

The study investigated the effects of methanogen pretreatment on pyrolysis behaviors of corn stalk (CS) by using Py-GC/MS analysis and thermogravimetric analysis. Results indicated that biopretreatment changed considerably the pyrolysis behaviors of CS from four weight loss stages to two weight loss stages. Increasing biopretreatment time from 5 days to 25 days enhanced the kinds and contents of chemicals in volatile products. In pyrolysis products, the contents of sugars, linear ketones and furans decreased from 1.43%, 12.60% and 7.38% to 1.25%, 10.22% and 3.25%, respectively, and the contents of phenols increased from 15.08% to 27.84%. The most content change from 6.83% to 13.63% indicated that methanogen pretreatment improved the pyrolysis selectivity of CS to product the 4-VP, but it was disadvantageous to 5-hydroxymethyl furfural, levoglucose and furfural. The changes of chemical compositions and structure of CS after biopretreatment were the main reason of the differences.

Fast pyrolysis product distribution of biopretreated corn stalk by methanogen.

After pretreated by methanogen for 5, 15 and 25 days, corn stalk (CS) were pyrolyzed at 250, 300, 350, 400, 450 and 500 °C by Py-GC/MS and product distribution in bio-oil was analyzed. Results indicated that methanogen pretreatment changed considerably the product distribution: the contents of sugar and phenols increased; the contents of linear carbonyls and furans decreased; the contents of linear ketones and linear acids changed slightly. Methanogen pretreatment improved significantly the pyrolysis selectivity of CS to phenols especially 4-VP. At 250 °C, the phenols content increased from 42.25% for untreated CS to 79.32% for biopretreated CS for 5 days; the 4-VP content increased from 28.6% to 60.9%. Increasing temperature was contributed to convert more lignin into 4-VP, but decreased its content in bio-oil due to more other chemicals formed. The effects of biopretreatment time on the chemicals contents were insignificant.

Interaction characteristics and mechanism in the fast co-pyrolysis of cellulose and lignin model compounds

During biomass fast pyrolysis process, the interactions among biomass components will affect the pyrolytic products distribution. In this study, d-glucose and a β-O-4 type lignin model dimer (LMD, 1-(4-hydroxy-3-methoxyphenyl)-2-(2-methoxyphenoxy)propane-1,3-diol) were selected as the model compounds of cellulose and lignin. The interaction characteristics and mechanism during their fast co-pyrolysis process were investigated by combined pyrolysis–gas chromatography/mass spectrometry (Py–GC/MS) experiments and density functional theory (DFT) calculations. The Py–GC/MS results indicated that during fast co-pyrolysis process, the presence of LMD significantly decreased the formation of levoglucosan (LG) from d-glucose, while promoted the formation of linear carbonyls and furans. Meanwhile, the presence of d-glucose enhanced the decomposition of LMD to generate phenolic compounds. The DFT calculations revealed that d-glucose would interact with a homolysis radical of LMD to form a ten-membered ring transition state. The formed complex transition state changed the energy barriers of certain pyrolytic reactions of d-glucose and LMD, thus affecting the pyrolytic products distribution.

Pyrolytic characteristics of sweet potato vine

To utilized biomass for optimum application, sweet potato vine (SPV) was studied on its pyrolytic characteristics by TGA and Py-GC/MS analysis as a representative of biomass with low lignin content and high extractives content. Results indicated that lignin, cellulose, hemicellulose and extractives contents were 7.85 wt.%, 33.01 wt.%, 12.25 wt.% and 37.12 wt.%, respectively. In bio-oil, sugars content firstly increased from 8.76 wt.% (350 °C) to 13.97 wt.% (400 °C) and then decreased to 9.19 wt.% (500 °C); linear carbonyls and linear acids contents decreased from 16.58 wt.% and 17.45 wt.% to 5.26 wt.% and 4.03 wt.%, respectively; furans content increased from 7.10 wt.% to 15.47 wt.%. The content 11.86 wt.% of levoglucose at 400 °C, 15.41 wt.% of acetic acid at 350 °C and 6.94 wt.% of furfural at 500 °C suggested good pyrolysis selectivity of SPV.