Hao Zhan

The transformation pathways of nitrogen in sewage sludge during hydrothermal treatment

Hydrothermal treatment (HT) has been proved as a significant pretreatment in decreasing emissions of NOX pollutants from thermochemical utilization of sewage sludge (SS) derived solid fuel. This study aims to investigate the denitrification of HT and the redistribution of nitrogen (N) in different products so as to speculate the comprehensive pathway of N transformation during hydrothermal process. Results found that only 20% of N remained in hydrochar, whereas the rest of N (nearly 80%) was transformed into other phase. A majority of amino-N in SS was enriched in liquid phase in the form of Org-N at first, then further decomposed to NH4+-N. The remaining amino-N converted to pyrrole-N, pyridine-N and quaternary-N as temperature progresses. Meanwhile, amine-N derived from protein-N formed heterocyclic-N in oil phase via Diels-Alder reaction. NH3, the major nitrogenous gas, was dissolved in liquid as NH4+-N immediately after producing, but increased with prolonged reaction time.

Characteristics of NO x precursors and their formation mechanism during pyrolysis of herb residues

Abstract Based on two herb residues-herbal tea waste (HTW) and penicillin mycelial waste (PMW), characteristics of NOx precursors during their pyrolysis were investigated in a horizontal tubular reactor with the help of XPS and TGA technologies. Effects of thermal conditions and physicochemical properties of fuels were discussed and compared. The results demonstrate that protein-N is the main nitrogen form for both HTW and PMW, determining the dominance of NH3 among NOx precursors at any operational conditions. Thermal conditions would still change the ratio and total yield by intrinsically influencing their formation pathways. Subsequently, the effects could be sequenced as follows: high temperatures with rapid pyrolysis > high temperatures with slow pyrolysis > low temperatures with rapid pyrolysis ≈ low temperatures with slow pyrolysis. Moreover, at high temperatures with rapid pyrolysis, increase in particle size or decrease in moisture content would result in reduction of total yield by 5%–11% and 4%–6%, respectively. In addition, NH3 yield is produced at low temperatures or slow pyrolysis with sequence of PMW > HTW and vice versa, depending on components in the fuels. Consequently, analyses on nitrogen forms in char and nitrogen distribution indicate that total yield of 20%–45% is observed to be independent of fuel type under typical pyrolysis conditions, which may provide helpful guidance for the clean reutilization of herb residues.

Denitrification and desulphurization of industrial biowastes via hydrothermal modification

In attempt to decrease NOX and SO2 emission from thermochemical utilization, three industrial biowastes (penicillin mycelia waste, sewage sludge and peat waste) contained high nitrogen (N) and sulfur (S) were chosen to investigate the denitrification and desulphurization of hydrothermal modification. The results demonstrated that hydrothermal modification destroyed the structure of N- and S-containing components, thereby altering their existed conformations. Inorganic-N (N-IN) and most of amino-N/polyamide-N (N-A) were enriched by liquid phase in the forms of NH4+-N and soluble organic-N (Org-N), respectively; subsequently, Org-N could further decompose to NH4+-N at higher temperature. Residual N in hydrochars was converted from N-A to heterocyclic-N (pyrrolic-N, pyridinic-N and quaternary-N) via hydrolysis and cyclization. Similarly, over 60% of S was remove form biowastes at 240 °C. In solid phase, part of organic-S was altered to thiophenes-S after modified, while the remainder was transformed to inorganic-S; but the variation of inorganic-S in hydrochars strongly affected by its specific species.

Relevance between chemical structure and pyrolysis behavior of palm kernel shell lignin

Palm kernel shell (PKS) lignin obtained by enzymatic/mild acid hydrolysis (EMAL) was thoroughly elucidated by FTIR (fourier transform infrared), 13C-1H 2D-NMR (nuclear magnetic resonance), quantitative 31P NMR combined with DFRC (derivatization followed by reductive cleavage), and Py-GC/MS (pyrolysis-gas chromatography/mass spectrometry) with and without TMAH (tetramethylammonium hydroxide). Pyrolysis behavior was then characterized by TG-FTIR-MS (thermo-gravimetric-FTIR-mass spectrometry) and Py-GC/MS. The PKS lignin is demonstrated to be a p-hydroxyphenyl-guaiacyl-syringyl (H-G-S) lignin with abundances of p-hydrobenzoates and low S/G ratio of 0.15. 2D-NMR indicated that the main substructures are β-O-4-ethers (~85%), and 31P NMR/DFRC quantified the total β-O-4 content of 2295μmol/g. Py-GC/MS with and without TMAH confirmed that phenol mainly originated from p-hydroxybenzoates units. Thermal-stability, evolution behavior of typical volatiles, and selectivity of phenolic compounds (H-, G-, S-, C-type) during PKS lignin pyrolysis were explored. Relationship between chemical structure and pyrolysis behavior are also obtained. This work will provide a deep insight to the effective utilization of PKS.