Wu-Jun Liu

Modification of bio-char derived from fast pyrolysis of biomass and its application in removal of tetracycline from aqueous solution.

In this work, bio-char, a mass productive by-product of biomass fast pyrolysis, was adopted as an adsorbent to remove tetracycline (TC) from aqueous solution. To enhance the adsorption capacity, a simple modification of bio-char with acid and alkali was carried out. Bio-char samples were characterized by Fourier transform infrared (FTIR), X-ray photoelectron spectroscopy (XPS), and nitrogen adsorption-desorption isotherm. The results show that the alkali treated bio-char possesses larger surface area than those of raw and acid treated bio-chars, and accordingly exhibits a more excellent adsorption performance (58.8 mg/g) than the other two bio-chars and other adsorbents reported previously. The graphite-like structure of bio-char facilitates the formation of π-π interactions between ring structure in tetracycline molecule and graphite-like sheets. The surface area showed significant effects on TC adsorption as well as O-containing functional groups, whereas the initial pH of solution has small effects on TC adsorption under the experimental conditions.

Preparation of high adsorption capacity bio-chars from waste biomass.

Bio-chars with high adsorption capacity derived from rice-husks and corncobs were prepared at different retention times (RTs) in a pyrolysis reactor. At a fixed pyrolysis temperature, the pyrolysis RT is a key factor influencing the surface areas and functional group contents of the bio-chars, and further influencing their adsorption capacities. The results indicate that the bio-char prepared at RT of 1.6s exhibits a higher phenol adsorption capacity (589 mg g(-1)) than other bio-chars and many activated carbons reported in the literature. An adsorption mechanism based on acid-base interaction and hydrogen binding between phenol and the functional groups was proposed to elucidate the adsorption process. An economic evaluation of the use of bio-chars as adsorbents was made.

Thermochemical conversion of lignin to functional materials: a review and future directions

Lignin valorization is considered an important part of the modern biorefinery scheme. The unique structure and composition of lignin may offer many effective routes to produce several bulk chemicals and functional materials. Thermochemical conversion of lignin to synthesize value-added functional materials has recently attracted a lot of attention. In this review, we have presented currently available approaches and strategies for the thermochemical conversion of lignin to functional carbon materials. The transformation behavior and mechanism of lignin during the thermochemical process (e.g., pyrolysis and hydrothermal carbonization) are illuminated. The characteristics (structure and surface chemistry) of lignin-based functional carbon materials are summarized systematically. The advances in the functionalization of lignin-based carbon materials (surface functionality tuning and porosity tailoring) and the applications of lignin-based functional carbon materials in the fields of catalysis, energy storage, and pollutant removal are reviewed. Perspectives on how lignin-based functional materials would develop and, especially, in which fields the use of these functionalized materials could be expanded are discussed. This review clearly shows that a rational design of the functionalized lignin-based materials will lead to a rich family of hybrid functional carbon materials with various applications toward a green and sustainable future.

Polyethylenimine modified biochar adsorbent for hexavalent chromium removal from the aqueous solution

A chemical modified biochar with abundant amino groups for heavy metal removal was prepared using polyethylenimine (PEI) as a modification reagent, and used as an adsorbent for the removal of Cr(VI) from aqueous solution. The biochars before and after modification were characterized by Fourier transformed infrared spectroscopy, X-ray photoelectron spectroscopy etc. The adsorption of Cr(VI) by the modified biochar was obeyed pseudo-second-order kinetic model and Langmuir adsorption isotherm model. Its maximum adsorption capacity was 435.7 mg/g, which was much higher than that of pristine biochar (23.09 mg/g). Results also indicated that the removal of Cr(VI) by the PEI modified biochar depended on solution pH, and a low pH value was favorable for the Cr(VI) removal. The results herein revealed that the PEI modified biochar had a good potential as a suitable material for sorption and detoxification of Cr(VI) from aqueous solution.

Mesoporous Carbon Stabilized MgO Nanoparticles Synthesized by Pyrolysis of MgCl2 Preloaded Waste Biomass for Highly Efficient CO2 Capture

Anthropogenic CO2 emission makes significant contribution to global climate change and CO2 capture and storage is a currently a preferred technology to change the trajectory toward irreversible global warming. In this work, we reported a new strategy that the inexhaustible MgCl2 in seawater and the abundantly available biomass waste can be utilized to prepare mesoporous carbon stabilized MgO nanoparticles (mPC-MgO) for CO2 capture. The mPC-MgO showed excellent performance in the CO2 capture process with the maximum capacity of 5.45 mol kg(-1), much higher than many other MgO based CO2 trappers. The CO2 capture capacity of the mPC-MgO material kept almost unchanged in 19-run cyclic reuse, and can be regenerated at low temperature. The mechanism for the CO2 capture by the mPC-MgO was investigated by FTIR and XPS, and the results indicated that the high CO2 capture capacity and the favorable selectivity of the as-prepared materials were mainly attributed to their special structure (i.e., surface area, functional groups, and the MgO NPs). This work would open up a new pathway to slow down global warming as well as resolve the pollution of waste biomass.

Facile synthesis of highly efficient and recyclable magnetic solid acid from biomass waste

In this work, sawdust, a biomass waste, is converted into a magnetic porous carbonaceous (MPC) solid acid catalyst by an integrated fast pyrolysis–sulfonation process. The resultant magnetic solid acid has a porous structure with high surface area of 296.4 m2 g−1, which can be attributed to the catalytic effect of Fe. The catalytic activity and recyclability of the solid acid catalyst are evaluated during three typical acid-catalyzed reactions: esterification, dehydration, and hydrolysis. The favorable catalytic performance in all three reactions is attributed to the acids high strength with 2.57 mmol g−1 of total acid sites. Moreover, the solid acid can be reused five times without a noticeable decrease in catalytic activity, indicating the stability of the porous carbon (PC)–sulfonic acid group structure. The findings in the present work offer effective alternatives for environmentally friendly utilization of abundant biomass waste.

Selectively improving the bio-oil quality by catalytic fast pyrolysis of heavy-metal-polluted biomass: take copper (Cu) as an example.

Heavy-metal-polluted biomass derived from phytoremediation or biosorption is widespread and difficult to be disposed of. In this work, simultaneous conversion of the waste woody biomass into bio-oil and recovery of Cu in a fast pyrolysis reactor were investigated. The results show that Cu can effectively catalyze the thermo-decomposition of biomass. Both the yield and high heating value (HHV) of the Cu-polluted fir sawdust biomass (Cu-FSD) derived bio-oil are significantly improved compared with those of the fir sawdust (FSD) derived bio-oil. The results of UV-vis and (1)H NMR spectra of bio-oil indicate pyrolytic lignin is further decomposed into small-molecular aromatic compounds by the catalysis of Cu, which is in agreement with the GC-MS results that the fractions of C7-C10 compounds in the bio-oil significantly increase. Inductively coupled plasma-atomic emission spectrometry, X-ray diffraction, and X-ray photoelectron spectroscopy analyses of the migration and transformation of Cu in the fast pyrolysis process show that more than 91% of the total Cu in the Cu-FSD is enriched in the char in the form of zerovalent Cu with a face-centered cubic crystalline phase. This study gives insight into catalytic fast pyrolysis of heavy metals, and demonstrates the technical feasibility of an eco-friendly process for disposal of heavy-metal-polluted biomass.

Investigation on the Evolution of N‑Containing Organic Compounds during Pyrolysis of Sewage Sludge

Pyrolysis is an emerging technology for the disposal of huge amounts of sewage sludge. However, the thermochemical decomposition mechanism of organic compounds in sludge is still unclear. We adopt a novel online TG-FTIR-MS technology to investigate the pyrolysis of sludge. The sludge samples were pyrolyzed from 150 to 800 °C with heating rates of 10, 50, and 200 K min(-1). We found for the first time that the heating rate of pyrolysis can significantly change the species of liquid organic compounds produced, but cannot change the gaseous species produced under the same conditions. The contents of produced gas and liquid compounds, most of which were produced at 293-383 °C, are influenced by both the heating rate and temperature of pyrolysis. The results also showed that heterocyclic-N, amine-N, and nitrile-N compounds are obtained from the decomposition of N-compounds in sludge, such as pyrrolic-N, protein-N, amine-N, and pyridinic-N. Heterocyclic-N compounds are the dominant N-containing products, which can be due to the thermochemical decomposition of pyridine-N and pyrrole-N, whereas fewer amine-N compounds are produced during the pyrolysis. A mechanism for the decomposition of N-containing compounds in sludge is proposed based on the obtained data.

Harvest of Cu NP anchored magnetic carbon materials from Fe/Cu preloaded biomass: their pyrolysis, characterization, and catalytic activity on aqueous reduction of 4-nitrophenol

In the present study, a value-added Cu NP anchored magnetic carbon (Cu&Fe3O4-mC) material was obtained directly by fast pyrolysis of heavy metal polluted biomass (derived from a biosorption process using fir sawdust to remove Cu(II) from synthetic wastewater). The composition and structure of the Cu&Fe3O4-mC were characterized by various physicochemical techniques, which indicated that the Cu NPs were monodispersed on the mesoporous carbon support with an average particle size of 21.2 nm. The material shows favorable activity and separability on the catalytic reduction of 4-nitrophenol, and can be reused several times without a decrease in the catalytic activity. The maximum release concentration of Cu during the recycling process is 0.7 mg L−1, which is below the limit of the Cu concentration in the surface water. This study would provide a green and sustainable pathway for simultaneous disposal of the biomass waste, removal of the heavy metal pollution, and pretreatment of 4-nitrophenol.

Total recovery of nitrogen and phosphorus from three wetland plants by fast pyrolysis technology

Fast pyrolysis of three wetland plants (Alligator weed, Oenanthe javanica and Typha angustifolia) in a vertical drop fixed bed reactor was investigated in this study. The experiments were carried out at different pyrolysis temperatures, and the maximum bio-oil yields achieved were 42.3%, 40.2% and 43.6% for Alligator weed, Oenanthe javanica and Typha angustifolia, respectively. The elemental composition of the bio-oil and char were analyzed, and the results show that a low temperature was appropriate for the nitrogen and phosphorus enrichment in char. GC-MS analysis shows that nitrogenous compounds, phenols and oxygenates were the main categories in the bio-oil. A series of leaching tests were carried out to examine the recovery of the nitrogen and phosphorus in the char, and the results indicate that significant fractions of nitrogen and phosphorus could be recovered by leaching process.