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%).
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%).
Melamine-impregnated paper waste (MIPW) is an unavoidable byproduct of the melamine-impregnated paper production process, and it must be urgently disposed. In this paper, due to its high N content, MIPW was used as a N source to co-pyrolyze with camellia oleifera shell (COS). By changing the proportion of MIPW in the raw materials, the migration path of the N was studied during the co-pyrolysis process. X-ray photoelectron spectroscopy (XPS), elemental analysis (EA), total nitrogen analysis (TN) and ultraviolet spectrophotometry were used to determine the content and the types of N-containing components in raw materials and products. The results showed that during the co-pyrolysis process, the N in MIPW and COS would be converted into different types of N-containing components, and the proportion of MIPW in raw materials directly impacts the product distribution and the N migration path. With the increase in the proportion of MIPW from 10 to 50 wt.% (daf, mass ratio), the proportion of N in raw materials that migrated into the solid phase decreased from 27.58 to 16.31 wt.%, while that which migrated to the gas and liquid phases increased from 24.92 and 47.50 wt.% to 25.97 and 57.72 wt.%, respectively. The proportions of N in the raw materials that changed into pyridinic-N, pyrrolic-N and graphitic-N in the solid phase and N2-N in the gas phase were decreased. The proportions of NH3-N and HCN-N in the gas phase and NH3-N and organic-N in the liquid phase were increased. Moreover, synergies were observed during the co-pyrolysis process, which affected the N migration path in the raw material. This study will provide policy directions and theoretical support for the comprehensive utilization of MIPW and COS.
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, β-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.
Solid oxide fuel cell power generation systems are devices that utilize solid electrolytes to transfer ions for electrochemical energy conversion. A wide range of gases can be used as fuel gas, including hydrogen, natural gas, and carbon monoxide. Considering the high cost of pure hydrogen, hydrogen production from natural gas reforming has become a hot research area. In this study, the 4F-LCA method was employed to construct an evaluation framework, with a particular emphasis on the cost analysis of solid oxide fuel cell power generation systems, and uses a bottom-up approach to build a system economic analysis model to visualize the major costs involved in the system. An economic benefit analysis and sensitivity analysis were carried out for the 2 kW natural gas solid oxide fuel cell as a case by taking the financial net present value (NPV), internal rate of return (IRR) and payback period into account. In this study, the investment cost and payback period of a 2 kW solid oxide fuel cell system are obtained, which can provide a reference for the project construction and operation of solid oxide fuel cell systems.
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.