Efficient Treatment of Oily Sludge via Fast Microwave-Assisted Pyrolysis, Followed by Thermal Plasma Vitrification.

Oily sludge, as a critical hazardous waste, requires appropriate treatment for resource recovery and harmfulness reduction. Here, fast microwave-assisted pyrolysis (MAP) of oily sludge was conducted for oil removal and fuel production. The results indicated the priority of the fast MAP compared with the MAP under premixing mode, with the oil content in solid residues after pyrolysis reaching below 0.2%. The effects of pyrolysis temperature and time on product distribution and compositions were examined. In addition, pyrolysis kinetics can be well described using the Kissinger-Akahira-Sunose (KAS) and the Flynn-Wall-Ozawa (FWO) methods, with the activation energy being 169.7-319.1 kJ/mol in the feedstock conversional fraction range of 0.2-0.7. Subsequently, the pyrolysis residues were further treated by thermal plasma vitrification to immobilize the existing heavy metals. The amorphous phase and the glassy matrix were formed in the molten slags, resulting in bonding and, hence, immobilization of heavy metals. Operating parameters, including working current and melting time, were optimized to reduce the leaching concentrations of heavy metals, as well as to decrease their volatilization during vitrification.

Pyrolysis of Methyl Ricinoleate: Distribution and Characteristics of Fast and Slow Pyrolysis Products.

A stable temperature site and the speed of heating the feedstocks play a key role in pyrolysis processes. In this study, the product distribution arising from pyrolysis of methyl ricinoleate (MR) at 550 °C with low and high heating rates was first studied by pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). The results show that fast pyrolysis of MR favored the production of undecylenic acid methyl ester (UAME) and heptanal (HEP). Density functional theory (DFT) calculations were employed to reveal the UAME and HEP formation process from pyrolysis of MR. The bond dissociation energies (BDEs) of C-C bonds in MR showed that the C11-C12 bond is the weakest. This suggests that UAME and HEP are two major products. The process of slow and fast MR pyrolysis was the dehydration-first and the pyrolysis-first trend, respectively. The calculated activation energies of MR pyrolysis to UAME and HEP and MR dehydration to 9,12-octadecadienoic acid methyl ester were 287.72 and 238.29 kJ/mol, respectively. The much higher product yields obtained in the fast pyrolysis reactors than those from conventional tubular reactors confirmed the proposed process.

Sulfonated Sargassum horneri carbon as solid acid catalyst to produce biodiesel via esterification.

A solid acid catalyst prepared by sulfonated Sargassum horneri carbon was utilized for the esterification reaction of oleic acid and methanol. The formed amorphous carbon layers during carbonization and the access of sulfonic acid groups during sulfonation can catalyze the esterification reaction for biodiesel preparation efficiently. The catalyst was characterized by various methods to investigate its physical and chemical properties. With carbonization at 300 °C for 2 h followed by sulfonation at 90 °C for 5 h, the catalyst reached acid density of 1.40 mmol/g. The catalyst dosage, methanol/oleic acid (molar ratio), reaction temperature, and reaction time were optimized to 10 wt%, 15:1, 70 °C, and 3 h, respectively. Under the optimal condition, the conversion of oleic acid reached 96.4%. Additionally, the catalyst was regenerated after four cycles, with the conversion of oleic acid still reaching 95.4%.

Biosorption of hexavalent chromium from aqueous solution by polyethyleneimine-modified ultrasonic-assisted acid hydrochar from Sargassum horneri.

In this study, an efficient route to synthesizing polyethyleneimine-modified ultrasonic-assisted acid hydrochar (PEI-USAH) is developed and reported. Ultrasonic irradiation technique was used as surface modification method to shorten the crosslinking reaction for hydrochar and polyethyleneimine (PEI). The PEI-USAH showed an excellent adsorption capacity for Cr(VI) from aqueous solution. The physicochemical properties of this PEI-modified adsorbent were comparatively characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, X-ray photoelectron spectroscopy, Brunauer-Emmett-Teller analysis and CNHS analysis. The effects of contact time, initial pH, and biosorbent dose on adsorption capacities were investigated. The batch adsorption experiments showed that PEI-USAH possessed the maximum adsorption capacities of 94.38 mg/g and 330.84 mg/g for initial Cr(VI) concentration of 100 mg/L and 500 mg/L, respectively. Furthermore, this adsorption process could be fitted to Langmuir adsorption and described by the pseudo second order kinetic model. Based on the above findings, PEI-USAH could be used as a potential adsorbent for removal of Cr(VI) from wastewater.

Room-temperature production of bio-based aldehydes from vegetable oil-derived epoxide via H2WO4@Al-MCM-41 as recyclable catalyst.

The oxidative cleavage of vegetable oils and their derivatives to produce bio-based aldehydes is a potentially useful process, although the aldehyde products are readily oxidized to carboxylic acids and thus seldom obtained in high yields. The present study developed a room-temperature method for the synthesis of bio-aldehydes via the oxidative cleavage of vegetable oil-derived epoxides, using H2WO4 as the catalyst, H2O2 as the oxidant, and t-BuOH as the solvent. Reactions were carried out at temperatures ranging from 25 to 35 °C for 3.5-10.5 h, and provided >99% conversion and >90% aldehyde yield. In particular, an approximately 97% yield was obtained at 25 °C after 10.5 h. As the reaction proceeded, the H2WO4 dissolved to form a W-containing anion. Several mesoporous Al-MCM-41 materials having different Si/Al ratios were hydrothermally synthesized and used as adsorbents to recover the catalyst by adsorbing these anions. The adsorption capacity of the Al-MCM-41 was found to increase with decreases in the Si/Al ratio. The Al-MCM-41 had little effect on the oxidative cleavage reaction at 25 °C, and thus could be directly added to the reaction system. The excellent anion adsorption performance of the Al-MCM-41 greatly improved the reusability of the H2WO4 catalyst. When using the Al-MCM-41 with the best adsorption performance, there was no significant decrease in the activity of the catalyst following five reuses.

Degradation of methylene blue by dielectric barrier discharge plasma coupled with activated carbon supported on polyurethane foam.

The degradation of methylene blue (MB) using a novel dielectric barrier discharge plasma reactor coupled with activated carbon supported polyurethane foam (AC/PUF) was investigated in this paper. The plasma reactor combining a glass bead-packed bed and a microporous plate was developed. The AC/PUF provided sufficient contact area between carbon media and pollutants and hence revealed a good MB removal capacity. The effects of input voltage and initial MB solution concentration on MB degradation efficiency were examined. Kinetic study indicated that plasma and AC/PUF in the coupled system had a good synergistic effect in MB degradation. The degradation efficiency of 100 ppm MB solution could reach 97.9% with 10 min treatment in the coupled system, which was close to that obtained by plasma treatment alone for 30 min (97.5%). The COD removal in the plasma and AC/PUF coupled system (90.7%) was much higher than that obtained by plasma treatment followed by AC/PUF adsorption (58.3%). In addition, the energy yield (G 50) of the coupled system was up to 38.3 g kW-1 h-1, suggesting great energy efficiency of the system. Moreover, repeated use experiments of AC/PUF showed the good utilization potential of the coupled system. Finally, a possible degradation pathway of MB was proposed.

Two-step fast microwave-assisted pyrolysis of biomass for bio-oil production using microwave absorbent and HZSM-5 catalyst.

A novel technology of two-step fast microwave-assisted pyrolysis (fMAP) of corn stover for bio-oil production was investigated in the presence of microwave absorbent (SiC) and HZSM-5 catalyst. Effects of fMAP temperature and catalyst-to-biomass ratio on bio-oil yield and chemical components were examined. The results showed that this technology, employing microwave, microwave absorbent and HZSM-5 catalyst, was effective and promising for biomass fast pyrolysis. The fMAP temperature of 500°C was considered the optimum condition for maximum yield and best quality of bio-oil. Besides, the bio-oil yield decreased linearly and the chemical components in bio-oil were improved sequentially with the increase of catalyst-to-biomass ratio from 1:100 to 1:20. The elemental compositions of bio-char were also determined. Additionally, compared to one-step fMAP process, two-step fMAP could promote the bio-oil quality with a smaller catalyst-to-biomass ratio.

Utilization of municipal solid and liquid wastes for bioenergy and bioproducts production.

Municipal wastes, be it solid or liquid, are rising due to the global population growth and rapid urbanization and industrialization. Conventional management practice involving recycling, combustion, and treatment/disposal is deemed unsustainable. Solutions must be sought to not only increase the capacity but also improve the sustainability of waste management. Research has demonstrated that the non-recyclable waste materials and bio-solids can be converted into useable heat, electricity, or fuel and chemical through a variety of processes, including gasification, pyrolysis, anaerobic digestion, and landfill gas in addition to combustion, and wastewater streams have the potential to support algae growth and provide other energy recovery options. The present review is intended to assess and analyze the current state of knowledge in the municipal solid wastes and wastewater treatment and utilization technologies and recommend practical solution options and future research and development needs.

Fast microwave-assisted catalytic co-pyrolysis of corn stover and scum for bio-oil production with CaO and HZSM-5 as the catalyst.

This study investigated fast microwave-assisted catalytic co-pyrolysis of corn stover and scum for bio-oil production with CaO and HZSM-5 as the catalyst. Effects of reaction temperature, CaO/HZSM-5 ratio, and corn stover/scum ratio on co-pyrolysis product fractional yields and selectivity were investigated. Results showed that co-pyrolysis temperature was selected as 550°C, which provides the maximum bio-oil and aromatic yields. Mixed CaO and HZSM-5 catalyst with the weight ratio of 1:4 increased the aromatic yield to 35.77 wt.% of feedstock, which was 17% higher than that with HZSM-5 alone. Scum as the hydrogen donor, had a significant synergistic effect with corn stover to promote the production of bio-oil and aromatic hydrocarbons when the H/C(eff) value exceeded 1. The maximum yield of aromatic hydrocarbons (29.3 wt.%) were obtained when the optimal corn stover to scum ratio was 1:2.

Glycerin esterification of scum derived free fatty acids for biodiesel production.

Scum is an oily waste stream of the wastewater treatment process that can be used to produce biodiesel. Combining acid hydrolysis and solvent extraction, a free fatty acid and acyl-glycerol rich product was produced. Free fatty acids (FFAs) present were converted to acyl-glycols via a high temperature (238°C) glycerin esterification process known as glycerolysis. The inorganic catalysts zinc aluminum oxide and sodium sulfate were tested during glycerolysis to compare the reaction kinetics of converting FFA to acyl-glycerols. It was concluded that the zinc-based catalyst increased the reaction rate significantly, from a "k" value of 2.57 (uncatalyzed) to 5.63, completing the reaction in 60min, half the time it took the uncatalyzed reaction (120min). Sodium sulfate's presence however slowed the reaction, resulting in a "k" value of 1.45, completing the reaction in 180min. Use of the external catalyst Zn-Al2O3 showed the greatest catalytic potential, but also assumes additional costs.

Catalytic fast co-pyrolysis of biomass and food waste to produce aromatics: Analytical Py-GC/MS study.

In this study, catalytic fast co-pyrolysis (co-CFP) of corn stalk and food waste (FW) was carried out to produce aromatics using quantitative pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS), and ZSM-5 zeolite in the hydrogen form was employed as the catalyst. Co-CFP temperature and a parameter called hydrogen to carbon effective ratio (H/C(eff) ratio) were examined for their effects on the relative content of aromatics. Experimental results showed that co-CFP temperature of 600 °C was optimal for the formation of aromatics and other organic pyrolysis products. Besides, H/C(eff) ratio had an important influence on product distribution. The yield of total organic pyrolysis products and relative content of aromatics increased non-linearly with increasing H/C(eff) ratio. There was an apparent synergistic effect between corn stalk and FW during co-CFP process, which promoted the production of aromatics significantly. Co-CFP of biomass and FW was an effective method to produce aromatics and other petrochemicals.

Process development for scum to biodiesel conversion.

A novel process was developed for converting scum, a waste material from wastewater treatment facilities, to biodiesel. Scum is an oily waste that was skimmed from the surface of primary and secondary settling tanks in wastewater treatment plants. Currently scum is treated either by anaerobic digestion or landfilling which raised several environmental issues. The newly developed process used a six-step method to convert scum to biodiesel, a higher value product. A combination of acid washing and acid catalyzed esterification was developed to remove soap and impurities while converting free fatty acids to methyl esters. A glycerol washing was used to facilitate the separation of biodiesel and glycerin after base catalyzed transesterification. As a result, 70% of dried and filtered scum was converted to biodiesel which is equivalent to about 134,000 gallon biodiesel per year for the Saint Paul waste water treatment plant in Minnesota.

Fast microwave-assisted catalytic pyrolysis of sewage sludge for bio-oil production.

In this study, fast microwave-assisted catalytic pyrolysis of sewage sludge was investigated for bio-oil production, with HZSM-5 as the catalyst. Pyrolysis temperature and catalyst to feed ratio were examined for their effects on bio-oil yield and composition. Experimental results showed that microwave is an effective heating method for sewage sludge pyrolysis. Temperature has great influence on the pyrolysis process. The maximum bio-oil yield and the lowest proportions of oxygen- and nitrogen-containing compounds in the bio-oil were obtained at 550°C. The oil yield decreased when catalyst was used, but the proportions of oxygen- and nitrogen-containing compounds were significantly reduced when the catalyst to feed ratio increased from 1:1 to 2:1. Essential mineral elements were concentrated in the bio-char after pyrolysis, which could be used as a soil amendment in place of fertilizer. Results of XRD analyses demonstrated that HZSM-5 catalyst exhibited good stability during the microwave-assisted pyrolysis of sewage sludge.

Fast microwave-assisted pyrolysis of microalgae using microwave absorbent and HZSM-5 catalyst.

Fast microwave-assisted pyrolysis (fMAP) in the presence of a microwave absorbent (SiC) and catalyst (HZSM-5) was tested on a Chlorella sp. strain and on a Nannochloropsis strain. The liquid products were characterized, and the effects of temperature and catalyst:biomass ratio were analyzed. For Chlorella sp., a temperature of 550 °C, with no catalyst were the optimal conditions, resulting in a maximum bio-oil yield of 57 wt.%. For Nannochloropsis, a temperature of 500 °C, with 0.5 of catalyst ratio were shown to be the optimal condition, resulting in a maximum bio-oil yield of 59 wt.%. These results show that the use of microwave absorbents in fMAP increased bio-oil yields and quality, and it is a promising technology to improve the commercial application and economic outlook of microwave pyrolysis technology. Additionally, the use of a different catalyst needs to be considered to improve the bio-oil characteristics.

Fast microwave assisted pyrolysis of biomass using microwave absorbent.

A novel concept of fast microwave assisted pyrolysis (fMAP) in the presence of microwave absorbents was presented and examined. Wood sawdust and corn stover were pyrolyzed by means of microwave heating and silicon carbide (SiC) as microwave absorbent. The bio-oil was characterized, and the effects of temperature, feedstock loading, particle sizes, and vacuum degree were analyzed. For wood sawdust, a temperature of 480°C, 50 grit SiC, with 2g/min of biomass feeding, were the optimal conditions, with a maximum bio-oil yield of 65 wt.%. For corn stover, temperatures ranging from 490°C to 560°C, biomass particle sizes from 0.9mm to 1.9mm, and vacuum degree lower than 100mmHg obtained a maximum bio-oil yield of 64 wt.%. This study shows that the use of microwave absorbents for fMAP is feasible and a promising technology to improve the practical values and commercial application outlook of microwave based pyrolysis.

Fast microwave-assisted catalytic gasification of biomass for syngas production and tar removal.

In the present study, a microwave-assisted biomass gasification system was developed for syngas production. Three catalysts including Fe, Co and Ni with Al2O3 support were examined and compared for their effects on syngas production and tar removal. Experimental results showed that microwave is an effective heating method for biomass gasification. Ni/Al2O3 was found to be the most effective catalyst for syngas production and tar removal. The gas yield reached above 80% and the composition of tar was the simplest when Ni/Al2O3 catalyst was used. The optimal ratio of catalyst to biomass was determined to be 1:5-1:3. The addition of steam was found to be able to improve the gas production and syngas quality. Results of XRD analyses demonstrated that Ni/Al2O3 catalyst has good stability during gasification process. Finally, a new concept of microwave-assisted dual fluidized bed gasifier was put forward for the first time in this study.

Fine root branch orders contribute differentially to uptake, allocation, and return of potentially toxic metals.

Growing evidence has revealed high heterogeneity of fine root networks in both structure and function, with different root orders corporately maintaining trees' physiological activities. However, little information is available on how fine root heterogeneity of trees responds to environmental stresses. We examined concentrations of seven potentially toxic metals (Cr, Ni, Cu, Zn, As, Cd, and Pb) within fine root networks and their correlations with root morphological and macro-elemental traits in six Chinese subtropical trees. The contributions of different orders of roots to fine-root metal storage and return were also estimated. Results showed no consistent pattern for the correlation among different metal concentration against root traits. Unlike root metal concentration that generally decreased with root order, root metal storage was commonly lowest in middle root orders. Root senescence was at least comparable to leaf senescence contributing to metal removal. Although the first-order roots constituted 7.2-22.3% of total fine root biomass, they disproportionately contributed to most of metal return fluxes via root senescence. The two distinct root functional modules contributed differentially to metal uptake, allocation, and return, with defensive (lower-order) roots effectively stabilizing and removing toxic metals and bulk buffering (higher-order) roots possessing a persistent but diluted metal pool. Our results suggest a strong association of physiological functions of metal detoxification and metal homeostasis with the structural heterogeneity in fine root architecture.

Syngas production by two-stage method of biomass catalytic pyrolysis and gasification.

A two-stage technology integrated with biomass catalytic pyrolysis and gasification processes was utilized to produce syngas (H(2)+CO). In the presence of different nickel based catalysts, effects of pyrolysis temperature and gasification temperature on gas production were investigated. Experimental results showed that more syngas and char of high quality could be obtained at a temperature of 750°C in the stage of pyrolysis, and in the stage of gasification, pyrolysis char (produced at 750°C) reacted with steam and the maximum yield of syngas was obtained at 850°C. Syngas yield in this study was greatly increased compared with previous studies, up to 3.29Nm(3)/kg biomass. The pyrolysis process could be well explained by Arrhenius kinetic first-order rate equation. XRD analyses suggested that formation of Mg(0.4)Ni(0.6)O and increase of Ni(0) crystallite size were two main reasons for the deactivation of nickel based catalysts at higher temperature.