Hanwu Lei

A review of catalytic hydrodeoxygenation of lignin-derived phenols from biomass pyrolysis

Catalytic hydrodeoxygenation (HDO) of lignin-derived phenols which are the lowest reactive chemical compounds in biomass pyrolysis oils has been reviewed. The hydrodeoxygenation (HDO) catalysts have been discussed including traditional HDO catalysts such as CoMo/Al(2)O(3) and NiMo/Al(2)O(3) catalysts and transition metal catalysts (noble metals). The mechanism of HDO of lignin-derived phenols was analyzed on the basis of different model compounds. The kinetics of HDO of different lignin-derived model compounds has been investigated. The diversity of bio-oils leads to the complexities of HDO kinetics. The techno-economic analysis indicates that a series of major technical and economical efforts still have to be investigated in details before scaling up the HDO of lignin-derived phenols in existed refinery infrastructure. Examples of future investigation of HDO include significant challenges of improving catalysts and optimum operation conditions, further understanding of kinetics of complex bio-oils, and the availability of sustainable and cost-effective hydrogen source.

Production of phenols and biofuels by catalytic microwave pyrolysis of lignocellulosic biomass

Catalytic microwave pyrolysis of biomass using activated carbon (AC) was investigated to determine the effects of pyrolytic conditions on the yields of phenol and phenolics. Bio-oils with high concentrations of phenol (38.9%) and phenolics (66.9%) were obtained. These levels were higher than those obtained by pyrolysis without AC addition and were closely related to the decomposition of lignin. A high concentration of esters (42.2% in the upgraded bio-oil) was obtained in the presence of Zn powder as catalyst and formic acid/ethanol as reaction medium. Most of the esters identified by GC-MS were long chain fatty acid esters. The high content of phenols and esters obtained in this study can be used as partial replacement of petroleum fuels after separation of oxygenates or as feedstock for organic syntheses in the chemical industry after purification.

Phenol and phenolics from lignocellulosic biomass by catalytic microwave pyrolysis

Catalytic microwave pyrolysis of biomass using activated carbon was investigated to determine the effects of pyrolytic conditions on the yields of phenol and phenolics. The high concentrations of phenol (38.9%) and phenolics (66.9%) were obtained at the temperature of 589 K, catalyst-to-biomass ratio of 3:1 and retention time of 8 min. The increase of phenol and its derivatives compared to pyrolysis without catalysts has a close relationship with the decomposition of lignin under the performance of activated carbon. The concentration of esters was also increased using activated carbon as a catalyst. The high content of phenols obtained in this study can be used either directly as fuel after upgrading or as feedstock of bio-based phenols for chemical industry.

Catalytic pyrolysis of microalgae and their three major components: Carbohydrates, proteins, and lipids

To better understand the pyrolysis of microalgae, the different roles of three major components (carbohydrates, proteins, and lipids) were investigated on a pyroprobe. Cellulose, egg whites, and canola oil were employed as the model compounds of the three components, respectively. Non-catalytic pyrolysis was used to identify and quantify some major products and several reaction pathways were proposed for the pyrolysis of each model compound. Catalytic pyrolysis was then carried out with HZSM-5 for the production of aromatic hydrocarbons at different temperatures and catalyst to feed ratios. The aromatic yields of all feedstocks were significantly improved when the catalyst to biomass ratio increased from 1:1 to 5:1. Egg whites had the lowest aromatic yield among the model compounds under all reaction conditions, which suggests that proteins can hardly be converted to aromatics with HZSM-5. Lipids, although only accounted for 12.33% of Chlorella, contributed about 40% of aromatic production from algal biomass.

The effects of torrefaction on compositions of bio-oil and syngas from biomass pyrolysis by microwave heating.

Microwave pyrolysis of torrefied Douglas fir sawdust pellet was investigated to determine the effects of torrefaction on the biofuel production. Compared to the pyrolysis of raw biomass, the increased concentrations of phenols and sugars and reduced concentrations of guaiacols and furans were obtained from pyrolysis of torrefied biomass, indicating that torrefaction as a pretreatment favored the phenols and sugars production. Additionally, about 3.21-7.50 area% hydrocarbons and the reduced concentration of organic acids were obtained from pyrolysis of torrefied biomass. Torrefaction also altered the compositions of syngas by reducing CO2 and increasing H2 and CH4. The syngas was rich in H2, CH4, and CO implying that the syngas quality was significantly improved by torrefaction process.

Bio-based phenols and fuel production from catalytic microwave pyrolysis of lignin by activated carbons

The aim of this study is to explore catalytic microwave pyrolysis of lignin for renewable phenols and fuels using activated carbon (AC) as a catalyst. A central composite experimental design (CCD) was used to optimize the reaction condition. The effects of reaction temperature and weight hourly space velocity (WHSV, h(-1)) on product yields were investigated. GC/MS analysis showed that the main chemical compounds of bio-oils were phenols, guaiacols, hydrocarbons and esters, most of which were ranged from 71% to 87% of the bio-oils depending on different reaction conditions. Bio-oils with high concentrations of phenol (45% in the bio-oil) were obtained. The calorific value analysis revealed that the high heating values (HHV) of the lignin-derived biochars were from 20.4 to 24.5 MJ/kg in comparison with raw lignin (19 MJ/kg). The reaction mechanism of this process was analyzed.

Production of aromatic hydrocarbons by catalytic pyrolysis of microalgae with zeolites: catalyst screening in a pyroprobe.

Catalytic pyrolysis of microalgae and egg whites was investigated to evaluate the performance of different zeolites for the production of aromatic hydrocarbons. Three zeolites with different structures (H-Y, H-Beta and H-ZSM5) were used to study the effect of catalyst type on the aromatic yield. All three catalysts significantly increased the aromatic yields from pyrolysis of microalgae and egg whites compared with non-catalytic runs, and H-ZSM5 was most effective with a yield of 18.13%. Three H-ZSM5 with silica-to-alumina ratios of 30, 80 and 280 were used to study the effect of Si/Al ratio on the aromatic yield. The maximum yield was achieved at the Si/Al ratio of 80, which provides moderate acidity to achieve high aromatic production and reduce coke formation simultaneously. Aromatic production increased with the incorporation of copper or gallium to HZSM-5. However, other studied metals either had no significant influence or led to a lower aromatic yield.

Microwave pyrolysis of distillers dried grain with solubles (DDGS) for biofuel production

Microwave pyrolysis of distillers dried grain with solubles (DDGS) was investigated to determine the effects of pyrolytic conditions on the yields of bio-oil, syngas, and biochar. Pyrolysis process variables included reaction temperature, time, and power input. Microwave pyrolysis of DDGS was analyzed using response surface methodology to find out the effect of process variables on the biofuel (bio-oil and syngas) conversion yield and establish prediction models. Bio-oil recovery was in the range of 26.5-50.3 wt.% of the biomass. Biochar yields were 23.5-62.2% depending on the pyrolysis conditions. The energy content of DDGS bio-oils was 28 MJ/kg obtained at the 650°C and 8 min, which was about 66.7% of the heating value of gasoline. GC/MS analysis indicated that the biooil contained a series of important and useful chemical compounds: aliphatic and aromatic hydrocarbons. At least 13% of DDGS bio-oil was the same hydrocarbon compounds found in regular unleaded gasoline.

Catalytic co-pyrolysis of lignocellulosic biomass with polymers: a critical review

The increasing demand for renewable chemicals and fuels requires the exploitation of alternative feedstock to replace petroleum-derived chemicals and fuels. Lignocellulosic biomass has been considered as the most promising feedstock for the production of sustainable biofuels. Catalytic fast pyrolysis (CFP) is more amenable to directly converting biomass into high quality biofuel. However, even in the presence of a highly efficient catalyst, the CFP of biomass can solely manufacture a low yield of aromatic hydrocarbon but a high formation of coke. The addition of a hydrogen-rich co-reactant (e.g. waste plastics) in CFP can significantly improve the yield of aromatics and lower the coke formation. Catalytic co-pyrolysis can also reduce the disposal of waste polymers (plastics and waste tires) in landfills, solve some environmental issues, and further increase energy security. In this regard, this article reviews the catalytic co-pyrolysis process from several points of view, starting from feedstock characteristics and availability, current understanding of the chemistry in non-catalytic co-pyrolysis, and focusing on the chemistry in the catalytic co-pyrolysis of biomass with various categories of polymers. Recent progress in the experimental studies on both the non-catalytic pyrolysis and catalytic co-pyrolysis of biomass with polymers is also summarized with the emphasis on the liquid yield and quality. In addition, reaction kinetics and several outlooks in the light of current studies are also presented in the review. Consequently, this review demonstrates both highlights of the remarkable achievement of catalytic co-pyrolysis and the milestones that are necessary to be garnered in the future.

Comparative study of organosolv lignin extracted from prairie cordgrass, switchgrass and corn stover

Lignin extracted from prairie cordgrass, switchgrass, and corn stover (using ethyl acetate-ethanol-water organosolv pretreatment) was analyzed and characterized using several methods. These methods included analysis of purity (by determination of Klason lignin, carbohydrate, and ash contents), solubility (with several organic solvents), phenolic group analysis (ultraviolet ionization difference spectra, and nitrobenzene oxidation), and general functional group analysis (by (1)H NMR). Results showed that all the examined lignin samples were relatively pure (contained over 50% Klason lignin, less than 5% carbohydrate contamination, and less than 3% ash), but switchgrass-derived lignin was observed to be the purest. All the lignins were found to contain high amounts of phenolic groups, while switchgrass-derived lignin was the most phenolic, according to the ionization difference spectra. Nitrobenzene oxidation revealed that all the lignin samples contained available guaiacyl units in high amounts.