Influences of the Reaction Temperature and Catalysts on the Pyrolysis Product Distribution of Lignocellulosic Biomass (Aspen Wood and Rice Husk).

It is important to clarify the distribution of pyrolysis products from lignocellulosic biomass for its thermal transformation to produce high-quality bio-oil. Influences of the reaction temperature and catalysts on the pyrolysis product distribution from aspen wood (AW) and rice husk (RH) were studied by pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). The difference in components from the lignocellulosic biomass results in different pyrolysis characteristics of the biomass raw materials. The reaction temperature significantly influences the product distribution from AW and RH pyrolysis. In all AW catalysis experiments, acids (8.35%), ketones (3.79%), phenols (4.73%), and esters (1.50%) have the lowest content while carbohydrates (48.75%) demonstrate the highest content when taking zinc chloride (ZnCl2) as the catalyst; the HZSM-5 molecular sieve (HZSM-5) promotes the generation of esters (7.97%) and N-compounds (22.43%) while inhibiting production of aldehydes (2.41%); addition of an MCM-41 molecular sieve (MCM-41) is conducive to increasing the contents of aldehydes (21.29%), furans (5.88%), ketones (22.30%), acids (20.46%), and hydrocarbons (4.85%), while reducing the contents of alcohols (0) and carbohydrates (0). In all RH catalysis experiments, the addition of ZnCl2 helps increase the content of carbohydrates (39.16%) and decrease the contents of ketones (3.89%), phenols (5.20%), alcohols (2.34%), esters (1.13%), and N-compounds (3.09%); when applying HZSM-5 as the catalyst, hydrocarbons (18.28%) and alcohols (6.66%) reach their highest content while acids (13.21%) have the lowest content; MCM-41 promotes the generation of aldehydes (25.33%) and furans (5.55%) while inhibiting that of carbohydrates (1.42%).

Enhanced degradation of VOCs from biomass gasification catalyzed by Ni/HZSM-5 series catalyst.

Volatile organic compounds (VOCs) evolved from biomass gasification plays a positive role in the formation of PM2.5 and odor pollution. In order to improve the removal rate of various VOCs produced by biomass gasification, a nickel-based supported HZSM-5 cataly st (Ni/HZSM-5 and Ni-Ca-Co/HZSM-5) was prepared by different auxiliary methods, Ni loadings, and pyrolysis temperatures. The catalytic cracking performance of Ni/HZSM-5 catalysts for different VOCs model compounds such as toluene, phenol, furan, acetic acid and cyclohexane were studied in a fixed-bed reactor. The catalysts were further characterized and analyzed by XRD, SEM, XPS and BET. The results showed that the Ni/HZSM--C-Co5 catalyst prepared by ultrasonic-assisted excess impregnation method with Ni loading of 8 wt%, Ca loading of 4 wt%, Co loading of 0.1 wt% had strong catalytic activity for VOCs degradation. With the increase of the cracking temperature, the conversion rate and gas yield of from model compound cracking improved significantly. At 800 °C, the conversion of each model compound was more than 90%, accompanied by the generation of cracking gases such as H2 and CH4. The selectivity of H2 and CH4 from toluene cracking reached 93%, and cyclohexane reached 98%. The models with higher oxygen content and lower bond energy were more likely to undergo reforming reaction to form small molecular gas. Model compounds with large molecular weight and high carbon content provided more carbon sources. Under the conversion degree towards the gas direction was high. This study provides a new idea on the removal of VOCs for the efficient utilization of biomass resources.

Effect of Evolution of Carbon Structure during Torrefaction in Woody Biomass on Thermal Degradation.

Torrefaction is an effective method for upgrading biomass. Cedar torrefaction is carried out in a fixed bed reactor at the temperature of 200-300 °C. The structural parameters are obtained from elemental analysis and 13C nuclear magnetic resonance (NMR). Thermal degradation behavior of raw and torrefied cedar is monitored by thermogravimetry analysis. The results show that carbon structure varied during torrefaction has a significant effect on thermal degradation of cedar. Some unstable oxygen functional groups, such as C1 of hemicellulose, ß-O-4 linked bonds, and amorphous C6 of cellulose, are decomposed at mild torrefaction of torrefied temperature ≤ 200 °C. The temperature of maximum weight loss rate increases from 348 °C of raw cedar to 373 °C of C-200. The amorphous cellulose is partly re-crystallized at moderate torrefaction of torrefied temperature 200-250 °C. The aromaticity of torrefied cedar increases from 0.45 of C-200 to 0.73 of C-250. The covalent bond in the side chain of aromatic rings in cedar was further broken during torrefaction at severe torrefaction of torrefied temperature 250-300 °C. The area percentage of DTG mainly signed at 387 °C of C-300. The proton aromatic carbon increases from 12.35% of C-250 to 21.69% of C-300. These results will further facilitate the utilization of biomass for replacing fossil fuel to drive carbon neutrality.

Fast Pyrolysis of Cellulose and the Effect of a Catalyst on Product Distribution.

Fast pyrolysis of microcrystalline cellulose (MC) was carried out by pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). The effects of temperature, time, and a catalyst on the distribution of the pyrolysis products were analyzed. The reaction temperature and time can significantly affect the types and yields of compounds produced by cellulose pyrolysis. A pyrolysis temperature of 500-600 °C and pyrolysis time of 20 s optimized the yield of volatile liquid in the pyrolysis products of cellulose. In all catalytic experiments, the relative contents of alcohols (1.97%), acids (2.32%), and esters (4.52%) were highest when K2SO4 was used as a catalyst. HZSM-5 promoted the production of carbohydrates (92.35%) and hydrocarbons (2.20%), while it inhibited the production of aldehydes (0.30%) and ketones (1.80%). MCM-41 had an obvious catalytic effect on cellulose, increasing the contents of aldehydes (41.58%), ketones (24.51%), phenols (1.82%), furans (8.90%), and N-compounds (12.40%) and decreasing those of carbohydrates (5.38%) and alcohols (0%).

Co-Thermal Oxidation of Lignite and Rice Straw for Synthetization of Composite Humic Substances: Parametric Optimization via Response Surface Methodology.

In this study, Baoqing lignite (BL) and rice straw (RS), which were the representatives of low-rank coal and biomass, were co-thermally oxidized to produce composite humic substances (HS), including humic acid (HA) and fulvic acid (FA). Taking HS content as the output response, the co-thermally oxidizing conditions were optimized through single factor experiment and response surface methodology (RSM). The structures of HA and FA prepared under optimized conditions were analyzed by SEM, UV, and FTIR. Results showed that HS content was clearly influenced by the material ratio, oxidation time, and oxidation temperature, as well as their interactions. The optimized co-thermal oxidization condition was as follows: BL and RS pretreated with a material ratio of 0.53, oxidation time of 59.50 min, and oxidation temperature of 75.63 °C. Through verification, the experimental value (62.37%) had a small relative error compared to the predicted value (62.27%), which indicated that the developed models were fit and accurate. The obtained HA had a tightly packed block structure; FA had a loosely spherical shape. The molecular weight of FA was 2487 Da and HA was 20,904 Da; both had a smaller molecular weight than that reported in other literature. FA showed strong bands at 1720 cm-1, thus confirming the presence of more oxygen-containing functional groups. The appearance of double peaks at 2900~2980 cm-1 indicated that HA contains more aliphatic chains. The co-thermal oxidation of BL and RS gives a new method for the synthesis of HS, and the optimization of co-thermal oxidation conditions will provide fundamental information for the industrialization of composite HS.

Fast corn stalk pyrolysis and the influence of catalysts on product distribution.

Fast pyrolysis of corn stalk (CS) was performed by pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) and the product distribution was measured as a function of temperature, time, and catalyst. The types and yields of product compounds were influenced dramatically by temperature, while the duration of the reaction had little effect on the type of compound. Three primary components in the biomass interacted during pyrolysis. The maximum proportions of aldehydes (27.26%), furans (5.93%), and olefins (6.46%), and the minimum proportions of alcohols (0%) and carbohydrates (0.74%) were obtained over MCM-41. HZSM-5 improved the selectivity of aromatic hydrocarbons while inhibiting acid formation. The proportion of N-compounds was maximal (23.39%) over ZrO2. ZnCl2 tended to generate the least amounts of ketones (2.02%), phenols (9.08%), and esters (2.16%), but the greatest amount of carbohydrates (37.31%). K2SO4 promoted the formation of acids, ketones, alcohols, and phenols, while reducing the production of N-compounds and aldehydes.