Catalytic co-pyrolysis of oil sludge and biomass over ZSM-5 for production of aromatic platform chemicals.

Hazardous oil sludge (OS) poses a great challenge to the environment, whereas conventional treatment methods (i.e., incineration or pyrolysis-incineration) are relatively less value-added and will bring about air pollution problems. To realize the high-value utilization of OS, catalytic co-pyrolysis with waste biomass to produce platform chemicals was studied using TG-FTIR and Py (pyrolyzer)-GC/MS methods. Results showed that for the non-catalytic co-pyrolysis of RH (rice husk) and OS, the main synergy on weight loss was the greatly lowered initial pyrolysis temperature of RH (for ∼55 °C) at the lower temperatures and the reduced weight loss ratio of OS (∼10-18 wt%) within the higher temperature range. ZSM-5 catalyst promoted the degradation of OS and RH mixtures at < 150 °C, yet showed minor effects on their weight loss at higher temperatures. The oxygenated and aliphatic compounds from non-catalytic co-pyrolysis were efficiently converted, resulting in an increased relative yield of aromatics to the highest of 46% and an elevated selectivity to BTX (as high as 60%). Despite the relatively short carbon chain length of OS components, ZSM-5 was proved effective to activate the OS pyrolysis products, thus enhancing the further aromatization reactions with biomass pyrolysis intermediates. This study provides a novel method for value-added co-utilization of hazardous OS waste and abundant biomass waste, and thus is beneficial to producing renewable chemicals while reducing the environment pollutant.

Soil microbial community and association network shift induced by several tall fescue cultivars during the phytoremediation of a petroleum hydrocarbon-contaminated soil.

Biodegradation of soil contaminants may be promoted near plant roots due to the "rhizosphere effect" which may enhance microbial growth and activity. However, the effects of different plant cultivars within a single species on degradation remains unclear. Here, we evaluated the removal of soil total petroleum hydrocarbons (TPHs) by ten different cultivars of tall fescue grass (Festuca arundinacea L.) and their associated rhizosphere microbiomes. TPH removal efficiency across the ten different cultivars was not significantly correlated with plant biomass. Rhizing Star and Greenbrooks cultivars showed the maximum (76.6%) and minimum (62.2%) TPH removal efficiencies, respectively, after 120 days. Significant differences were observed between these two cultivars in the composition of rhizosphere bacterial and fungal communities, especially during the early stages (day 30) of remediation but the differences decreased later (day 90). Putative petroleum-degrading bacterial and fungal guilds were enriched in the presence of tall fescue. Moreover, the complexity of microbial networks declined in treatments with higher TPH removal efficiency. The relative abundances of saprotrophic fungi and putative genes alkB and C12O in bacetria involved in petroleum degradation increased, especially in the presence of Rhizing Star cultivar, and this was consistent with the TPH removal efficiency results. These results indicate the potential of tall fescue grass cultivars and their associated rhizosphere microbiomes to phytoremediate petroleum hydrocarbon-contaminated soils.

Improving hydrocarbon yield via catalytic fast co-pyrolysis of biomass and plastic over ceria and HZSM-5: An analytical pyrolyzer analysis.

The excessive oxygen content in biomass obstructs the production of high-quality bio-oils. In this work, we developed a tandem catalytic bed (TCB) of CeO2 and HZSM-5 in an analytical pyrolyzer to enhance the hydrocarbon production from co-pyrolysis of corn stover (CS) and LDPE. Results indicated that CeO2 could remove oxygen from acids, aldehydes and methoxy phenols, producing a maximum yield of hydrocarbons of 85% and highest selectivity of monocyclic aromatics of 73% in the TCB. The addition of LDPE exhibited a near-complete elimination of oxygenates, leaving hydrocarbons as the overwhelming products. With increasing LDPE proportion, the yield of aliphatics and the selectivity of BTX kept increasing. An optimum H/Ceff of 0.7 was superior to that reported in literature. Mechanisms consisting of deoxygenation, Diels-Alder reactions, hydrocarbon pool and hydrogen transfer reactions were discussed extensively. Our findings provide an efficient method to produce high-quality biofuels from renewable biomass resources.

Improving hydrocarbon yield from catalytic fast co-pyrolysis of hemicellulose and plastic in the dual-catalyst bed of CaO and HZSM-5.

The high concentration of oxygenated compounds in pyrolytic products prohibits the conversion of hemicellulose to important biofuels and chemicals via fast pyrolysis. Herein a dual-catalyst bed of CaO and HZSM-5 was developed to convert acids in the pyrolytic products of xylan to valuable hydrocarbons. Meanwhile, LLDPE was co-pyrolyzed with xylan to supplement hydrogen during the catalysis of HZSM-5. The results showed that CaO could effectively transform acids into ketones. A minimum yield of acids (2.74%) and a maximum yield of ketones (42.93%) were obtained at a catalyst to feedstock ratio of 2:1. The dual-catalyst bed dramatically increased the yield of aromatics. Moreover, hydrogen-rich fragments derived from LLDPE promoted the Diels-Alder reactions of furans and participated in the hydrocarbon pool reactions of non-furanic compounds. As a result, a higher yield of hydrocarbons was achieved. This study provides a fundamental for recovering energy and chemicals from pyrolysis of hemicellulose.

Thermal Characteristics of Hyperaccumulator and Fate of Heavy Metals during Thermal Treatment of Sedum plumbizincicola.

Thermal treatment is one of the most promising disposal techniques for heavy metal- (HM)-enriched hyperaccumulators. However, the thermal characteristics and fate of HMs during thermal treatment of hyperaccumulator biomass need to be known in detail. A horizontal tube furnace was used to analyze the disposal process of hyperaccumulator biomass derived from a phyto-extracted field in which the soil was moderately contaminated with heavy metals. Different operational conditions regarding temperature and gas composition were tested. A thermo-dynamic analysis by advanced system for process engineering was performed to predict HM speciation during thermal disposal and SEM-EDS, XRD and sequential chemical extraction were used to characterize the heavy metals. The recovery of Zn, Pb and Cd in bottom ash decreased with increasing temperature but recovery increased in the fly ash. Recovery of Zn, Pb and Cd fluctuated with increasing air flow rate and the metal recovery rates were higher in the fly ash than the bottom ash. Most Cl, S, Fe, Al and SiO2 were found as alkali oxides, SO2, Fe2(SO4)3, iron oxide, Ca3Al2O6, K2SiO3 and SiO2 instead of reacting with HMs. Thus, the HMs were found to occur as the pure metals and their oxides during the combustion process and as the sulfides during the reducing process.

Emission and control characteristics for incineration of Sedum plumbizincicola biomass in a laboratory-scale entrained flow tube furnace.

Experiments were conducted to investigate and control pollutant emission from incineration of Sedum plumbizincicola plants on a laboratory scale using an entrained flow tube furnace. Without control technologies, the flue gas contained 0.101 mg Nm(-3) of Cd, 46.4 mg Nm(-3) of Zn, 553 mg Nm(-3) of NOx, 131 pg Nm(-3) of polychlorinated dibenzo-p-dioxin and polychlorinated dibenzofuran (PCDD/Fs) and 35.4 mg Nm(-3) of polycyclic aromatic hydrocarbons (PAHs). In pollutants control experiments. Al2O3, CaO, and kaolin were compared as adsorbents and activated carbon was used as an end-of-pipe method for the capture of pollutants. Kaolin, the most effective of the three adsorbents, removed 91.2% of the Cd in flue gas. While 97.6% of the Cd and 99.6% of the PAHs were removed by activated carbon. Incineration may therefore be regarded as a viable option for the safe disposal of the biomass of the zinc and cadmium hyperaccumulator species S. plumbizincicola.

Comparison of trace element emissions from thermal treatments of heavy metal hyperaccumulators.

Phytoextraction has become one of the most promising remediation techniques for heavy metal (HM) contaminated soils. However, the technique invariably produces large amounts of HM-enriched hyperaccumulators, which need further safe disposal. In this study, two different thermal treatment methods are investigated as potential options for evaporative separation of HMs from the residues. A horizontal tube furnace and a vertical entrained flow tube furnace were used for testing the disposal of grounded hyperaccumulators. The release characteristics of HMs (Cd, Cu, Pb, and Zn) into flue gas and residues were investigated for thermal treatment of the Cd and Zn hyperaccumulators Sedum plumbizincicola and Sedum alfredii. In a horizontal tube furnace, incineration favors the volatilization of Cu and Cd in contrast to pyrolysis. The percentages of HMs in residues after incineration are lower than those after pyrolysis, especially for Cd, Pb, and Zn. However, in an entrained flow tube furnace, Zn content in flue gas increases with increasing temperature, but Cu and Cd contents are fluctuated. In addition, a higher incineration temperature enhances the Cu content in residues.

Cadmium distribution in rice plants grown in three different soils after application of pig manure with added cadmium.

A glasshouse pot experiment was conducted to investigate Cd concentrations in the aboveground parts of two consecutive crops of rice and Cd availability in three different soils (loam, silt loam, and sandy loam) after application of pig manure with added Cd. Soil pH tended to increase with increasing application rate of pig manure from 1 to 3% (w/w, oven dry basis). Soil diethylene triamine pentaacetic acid (DTPA) extractable Cd showed a clear positive correlation with soil total Cd content and increased with increasing Cd amendment of the manure but showed no difference between the two manure application rates. Cd concentrations in the grain, husk, and straw were significantly and positively correlated with soil DTPA-extractable Cd (p < 0.001). Within each level of manure Cd, the higher rate (3%) of manure produced lower Cd concentrations in the grain, husk, and straw on all three soils than did the lower rate (1%) after the first crop, but this no longer occurred after the growth of the second crop. Grain Cd concentrations exceeded the Chinese National Food Quality Standard (0.2 mg kg(-1)) most often on the loam, with intermediate frequency on the silt loam, and least often on the sandy loam, the soil with the highest pH and lowest organic carbon content and cation exchange capacity.