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Preparation and characterization of activated carbon derived from the thermo-chemical conversion of chicken manure.

Physico-chemical properties of a bioorganic char were modified by pyrolysis in the presence of NaOH, and with subsequent physical activation of carbonaceous species with CO2 a value-added activated carbon was fabricated. Bioorganic char is produced as a co-product during the production of bio-fuel from the pyrolysis of chicken litter. Untreated char contains approximately 37 wt% of C and approximately 43-45 wt% of inorganic minerals containing K, Ca, Fe, P, Cu, Mg, and Si. Carbonization and chemical activation of the char at 600 degrees C in the presence of NaOH in forming gas (4% H2 balanced with Ar) produced mainly demineralized activated carbon having BET (Brunauer, Emmett, and Teller) surface area of 486 m2/g and average pore size of 2.8 nm. Further physical activation with CO2 at 800 degrees C for 30 min resulted in activated carbon with BET surface area of 788 m2/g and average pore size of 2.2 nm. The mineral content was 10 wt%. X-ray photoelectron spectroscopy (XPS) indicated that the latter activation process reduced the pyrrolic- and/or pyridonic-N, increased pyridinic-N and formed quaternary-N at the expense of pyrrolic- and/or pyridonic-N found in the untreated char.

Animals↗

Spiramycin fermentation residue-derived biochar regulates soil nutrient cycling, microbial communities, and antibiotic resistance gene dynamics.

Spiramycin fermentation residues (SFR) are hazardous wastes enriched with residual antibiotics, yet they can serve as potential feedstocks for resource recovery after appropriate treatment. In this study, SFR-derived biochar (SFR-BC) was produced by pyrolysis and applied to agricultural soil to evaluate its effects on soil properties, microbial communities, potential pathogenic bacteria, antibiotic resistance genes (ARGs), and mobile genetic elements (MGEs). A 60-day soil incubation experiment was conducted with one control and three SFR-BC application rates of 0.5%, 1.0%, and 2.0%. SFR-BC improved soil physicochemical properties, nutrient status, enzyme activities, and microbial alpha diversity. Metagenomic analysis showed that SFR-BC altered the abundance of functional genes associated with carbon and nitrogen cycling, indicating shifts in microbial functional potential. SFR-BC also changed bacterial co-occurrence patterns, with the high-dose treatment showing a more complex and highly connected network structure during incubation. In addition, high-dose SFR-BC reduced several potential pathogenic bacteria, including major plant pathogenic taxa. SFR-BC decreased soil ARG abundance by 9.38%-33.67% and MGE abundance by 6.49%-27.89% relative to the control, showing a dose-dependent reduction in antibiotic resistance-related genetic elements. Network and PLS-PM analyses further indicated that ARG variation was statistically associated with soil physicochemical properties, microbial diversity, potential bacterial hosts, and MGEs. Overall, these results suggest that SFR-BC can improve short-term soil nutrient status and reduce ARGs, MGEs, and several potential pathogenic taxa under controlled incubation conditions, providing useful evidence for the potential valorization of antibiotic fermentation residues through pyrolysis.

Charcoal↗

Enhancement of photocatalytic activity of sprayed nitrogen-containing ZnO powders by coupling with metal oxides during the acetaldehyde decomposition.

Colored N-containing MOx-ZnO (M = W, V) composite powders with high surface area were synthesized by spray pyrolysis. The nitrogen content was controlled from 600 to 3000 ppm by changing the powder ingredients and the spray pyrolysis temperature. Ultraviolet-visible spectra indicated that the N-containing MOx-ZnO powders absorbed not only ultraviolet light like pure ZnO powder, but also some visible-light. Acetaldehyde decomposition was used as a probe reaction to evaluate the photocatalysis of these MOx-ZnO powders. The photocatalytic activity of the N-containing ZnO powder was pronouncedly enhanced by the WO3 or V2O5 addition under both UV and visible-light irradiation. This enhancement was ascribed to the MOx acting as a sink for photogenerated electrons in the UV case, and to a synergistic effect of N-doping and MOx-ZnO coupling in the case of visible-light.

Acetaldehyde↗

Sonolytic reactions of phenanthrene in organic extraction solutions.

Ultrasonic extraction is a common method used to extract semi-volatile and nonvolatile organic compounds such as polycyclic aromatic hydrocarbons (PAHs) from solid matrices. However, ultrasonic energy has been suspected to lead to undesired reactions of the solute and thus affect qualitative and quantitative results. In this paper, sonolytic reactions of phenanthrene in common organic extraction solutions were examined using a 20kHz ultrasonic probe under conditions commonly used for ultrasonic extraction. Extraction parameters including phenanthrene concentration, solvent type, pulse length, and sonication time were investigated. Hexane:acetone (1:1 V/V) resulted in less phenanthrene degradation than dichloromethane (DCM):acetone (1:1 V/V). Initial solute concentration, length of sonication time, and solvent type affected the degradation of phenanthrene. Reaction byproducts including methylphenanthrene and methylnaphthalene detected after sonication indicate that phenanthrene reacts by both direct pyrolysis and reaction with methyl or ethyl radicals formed from solvent pyrolysis.

Organic Chemicals↗

Phytoextraction crop disposal--an unsolved problem.

Several methods of contaminated crop disposal after phytoextraction process (composting, compaction, incineration, ashing, pyrolysis, direct disposal, liquid extraction) have been described. Advantages and disadvantages of methods are presented and discussed. Composting, compaction and pyrolysis are the pretreatment steps, since significant amount of contaminated biomass will still exist after each of the process. Four methods of final disposal were distinguished: incineration, direct disposal, ashing and liquid extraction. Among them, incineration (smelting) is proposed as the most feasible, economically acceptable and environmentally sound.

Biodegradation, Environmental↗

Study on tobacco components involved in the pyrolytic generation of selected smoke constituents.

The aim of this study was to investigate the contribution of various tobacco components to the generation of smoke constituents using a tobacco pyrolysis model. We analyzed the amounts of primary tobacco components (sugars, protein, polyphenols, alkaloids, organic acids, inorganics etc.) in flue-cured and burley tobacco leaves. Each of the components was added to the tobacco leaves at the 0.5-fold and 1.0-fold amount naturally present in the leaves. The treated tobacco samples were pyrolyzed at 800 degrees C in a nitrogen atmosphere with an infrared image furnace, and the selected smoke constituents (benzo[a]pyrene, hydrogen cyanide, carbonyl compounds, aromatic amines, volatile organic compounds and phenolics) were quantitatively analyzed by several methods, including high performance liquid chromatography (HPLC) and gas chromatography/mass spectrometry (GC-MS). The contribution of each tobacco component to the generation of selected smoke constituents was estimated from a regression line determined by the three yields (no addition, 0.5-fold addition, and 1.0-fold addition). The results of this study can provide useful and comprehensive information on the relationship between tobacco components and selected smoke constituents during pyrolysis.

Gas Chromatography-Mass Spectrometry↗

A study of interface-sustained ferromagnetism in 1/2(1-x)Ln2O3-xSrO/1/3Co3O4 nano-composite.

The binary oxide composite, consisting of rock salt-type SrO and spinel Co3O4 nano-domains, exhibits soft ferromagnetic properties at ambient temperature. This ferromagnetism is originated from interface-induction, and the magnitude of the magnetic properties can be enhanced when the spinel phase of the composite is doped by a small amount of Ln2O3 (Ln = La, Nd, for instance). In this work, we study the composites of tri-oxide, 1/2(1-x)Ln2O3-xSrO/1/3Co3O4, where 0.01 < or =1-x < or = 0.6, by focusing on three areas: (i) generation of nano-composite dominant by interfacial phase via the pyrolysis of preceramic metallo-organic gel; (ii) influence of post-pyrolysis calcination and Ln2O3 content on the phase composition of the composite; and (iii) elucidation of different magnetic responses caused by the nature of Ln2O3 dissolved in the Co3O4 phase. The Ln(3+)-doped Co3O4 oxide displays only paramagnetic behavior at room temperature, but the ferromagnetic response is attained upon its mixing with SrO in nano-scale. The SrO phase plays the role in assisting Co3O4 phase with aligning unpaired electrons through interfacial induction.

Journal Article↗

Direct aerosol synthesis of carboxy-functionalized iron oxide colloids displaying reversible magnetic behavior.

A simple and rapid synthetic strategy for fabricating carboxy-functionalized iron oxide colloidal particles displaying reversible magnetic behavior is reported. The method is based on the pyrolysis of aerosols generated from ethanol/water solutions containing iron inorganic salts and mono- or polysaccharides. Essential to the success of the method are the use of hybrid (organo-inorganic) aerosols and the temperature of pyrolysis. The resulting material could be used in advanced biotechnological applications such as the magnetically assisted chemical separation of biocompounds.

Journal Article↗

Dechlorination of auto shredder residues.

Dechlorination of ASR (auto shredder residual) wastes has been studied in the present work. ASR was predechlorinated with Ca(OH)(2) extraction as well as dechlorinated with Ca(OH)(2) during incineration or pyrolysis. Experimentally, pre-dechlorination of ASR via extraction of Cl with a Ca(OH)(2) solution (pH 12.5) may reduce Cl contain in the ASR by 15%. Extraction of Cl at elevated temperatures (such as 373 K), interestingly, led to a further reduction of Cl in the ASR to 33.5%. A small amount of HCl and light hydrocarbons (C(1)-C(5)) were yielded during pyrolysis of the ASR in the presence of Ca(OH)(2) at 773 K. On the contrary, 75-85% of Cl may be mineralized (CaCl(2)) with Ca(OH)(2) (or CaO) during incineration at 1100 K.

Chlorine↗

Comparison of polycyclic aromatic hydrocarbon distributions and sedimentary organic matter characteristics in contaminated, coastal sediments from Pensacola Bay, Florida.

In this study, we examined the distribution of polycyclic aromatic hydrocarbons (PAHs) in a contaminated coastal area and the characteristics of the natural organic matter in tandem. We present a detailed study of PAH concentration, distribution, and organic matter characteristics of three core samples from Pensacola Bay, Florida. Solid-state 13C Nuclear Magnetic Resonance (NMR), pyrolysis gas chromatography coupled with mass spectrometry (GC-MS), and tetramethyl ammonium hydroxide (TMAH) thermochemolysis GC-MS were applied to obtain structural details about the sedimentary organic matter. Elemental compositions (carbon and nitrogen) and estimates of black carbon contents are also reported. These coastal sediments were found to contain more PAHs in the upper 15 cm layers than in the bottom 15-25 cm samples. The samples that contained the most PAHs also contained the least amount of aromatic carbon and contained a significant amount of paraffinic carbon. Lignin-derived pyrolysis and TMAH thermochemolysis products were abundant and generally higher in all of the samples in comparison to those reported for modern coastal sediments, indicating a large flux of terrestrial carbon. The black carbon contents were found to range from 4.3% to 6.8%, which are significantly lower than other reports of black carbon in sediments, which represent as much as 65% of the total organic carbon content. The low black carbon content suggests that this type of refractory carbon may not be as responsible for regulating PAH distribution as indicated by other researchers.

Carbon Isotopes↗

Sonochemical reaction of selected cyclic C6Hx hydrocarbons in organic solvents.

The rates and products of the sonochemical reactions of benzene, 1,4-cyclohexadiene, 1,3-cyclohexadiene, cyclohexene, and cyclohexane in selected organic solvents have been investigated. The sonochemical reactions of these educts in the investigated organic solvents follow first-order kinetics. Generally, they are sonicated more rapidly in polar than in non-polar solvent; higher volatility of the solute results in faster sonolysis in the organic solvents. However, the sonication of cyclohexane in n-decane and the sonication of benzene in n-propanol are exceptional cases. Since cyclohexane exhibits a much higher lipophilicity and benzene a much higher hydrophilicity than other educts, it might be more difficult to transfer either educt from the bulk liquid into the cavitation bubbles. In tetrachloroethylene, the reactivity of the tested educts with in situ generated chlorine as well as chlorine-containing radical intermediates can accelerate the rate of sonochemical reactions under the employed conditions. In n-propanol and n-decane, the pyrolysis during the collapse of the cavitation bubbles is the only reaction pathway of sonolysis. In tetrachloroethylene, the pyrolysis during the collapse of the cavitation bubbles and the free radical reaction in the bulk liquid may occur simultaneously. Except for the products generated from sonolysis, products formed from chlorine transformations (substitution or addition reactions) are detected. Benzene is hardly decomposed in tetrachloroethylene. However, when FeCl3 is added into the reaction system, benzene is sonoconverted rapidly, and the product chlorobenzene was detected. In organic solvents, the sonoreaction rates and the sonoproducts are dependent on the physicochemical properties of the solvents used, as well as the volatility, the polarity and the reactivity of educts.

Hydrocarbons, Cyclic↗

Thermal degradation of PMMA in fluidised beds.

In recent years, the production and consumption of plastics have increased significantly and wastes are commonly incinerated or dumped in a landfill. Plastics pyrolysis, on the other hand, may provide an alternative means for disposal of plastic wastes with recovery of valuable gasoline-range hydrocarbons or the monomer. Pyrolysis of polymethyl methacrylate (PMMA) may result in very high recycling rates (90-98%) of the monomer methylmethacrylate (MMA) since the cracking of MMA to lighter molecules (CO2, CO and light hydrocarbons) is limited. The MMA-yield is mainly dependent on the residence time of the gas in the reactor and to a lesser extent on the operating temperature. The paper presents experimental work performed in a lead bath and in a fluidised bed. At low temperatures, the reaction is kinetically controlled, whereas at high temperatures, heat transfer restricts the overall reaction rate. It was demonstrated that the heat transfer in the fluid bed could be estimated by the equation of Kothari. A design procedure for a fluid bed PMMA-depolymerisation reactor is outlined and illustrated for a process of 1 tpd PMMA.

Bone Cements↗

Agro-industry sugarcane residues disposal: the trends of their conversion into energy carriers in Cuba.

The goal of the present work was to carry out a review of the disposal practices for the agro-industry's sugarcane residue and the trends of energy use in Cuba. The lack of an alternative energy carrier to electricity with storage capability for use in off-season has to date been an unsolvable question. The improvement of cogeneration capacity via implementation of CEST or BIG/GTCC and the barriers for their implementation, the introduction of a medium size (3 ton/h) fast pyrolysis module (FPM3) as a solution for off-season energy demand in the agro-industry, and an assessment of the energy required to do so, were also analyzed. Bio-oil production from bagasse and sugarcane agriculture residues (SCAR) and their particularities at the sugar mill are treated. The influence of sugar facility production process configuration is analyzed. The fast pyrolysis products and the trends of their end uses in Cuba are presented. The production cost of a ton of Bio-oil for FPM3 conditions was calculated at 155 USD/ton and the payback time as a function of selling price between 160 and 110 USD/ton was estimated to be from 1.5 to 4 years. The economic feasibility of the FPM3 was estimated, comparing the added values for three scenarios: 1st case, currently-used sugar production, 16.5 USD/ton of cane; 2nd case, factoring in the cogeneration improvement, 27 USD/ton of cane; and 3rd case, with cogeneration improvement and Bio-oil production, 40 USD/ton of cane. The energy use of SCAR and the introduction of FPM3 in the sugar mill are promising improvements that could result in a potential surplus of 80 kWh(e)/ton of cane in-season, or 6 x 10(6)ton of Bio-oil (LHV=15 MJ/kg) for use off-season in a milling season of 4 million tons of raw sugar.

Agriculture↗

Comparison between thermal and ozone regenerations of spent activated carbon exhausted with phenol.

Thermal and ozone regenerations of granular activated carbons (GAC) used in the removal of phenol from aqueous solution have been studied. The phenol isotherms for virgin GAC could be well represented by the Langmuir equation. Direct ozonation of GAC introduced large amounts of acidic surface oxygen groups, which caused a decrease in the phenol uptake. Thermogravimetric methods were used to investigate the mechanism of phenol adsorption onto virgin and ozonated carbons. Thermal regeneration was carried out at 1123K using nitrogen (pyrolysis alone) or nitrogen and carbon dioxide (pyrolysis plus oxidation). Results showed that spent carbons do not recover their adsorption characteristics when heated under inert conditions whereas carbon dioxide regeneration was effective at about 15% wt burn-off. Regeneration of GAC was also carried out with ozone as oxidizing gas at room temperature. Ozone dose and the nature of GAC have much influence on the regeneration performance. For an individual GAC there exits an optimum ozone dose for which phenol is eliminated together with most of its oxidation by-products without incurring in carbon surface chemical alterations. However, if excessive ozone is applied some acidic surface groups are formed on the GAC, thereby decreasing the adsorption capacity for phenol. Results showed that spent carbons can recover most of their adsorption characteristics and specific surface areas when regenerated through a number of adsorption-ozone regeneration cycles.

Adsorption↗

2. Comparison of the disinfection by-product formation potentials between a wastewater effluent and surface waters.

In this study, the chemical reactivity with chlorine as measured by disinfection by-product formation potential (DBPFP) is compared among samples of a wastewater effluent and surface waters. Water samples that had higher anthropogenic impacts were found to have higher overall DBPFP due primarily to higher dissolve organic carbon (DOC) concentrations. Effluent-derived organic matter (EfOM), however, was found to be less reactive with chlorine on a per DOC concentration basis. Yet, EfOM had higher proportions of brominated DBP, which may be associated with greater health risks. In this research, pyrolysis-GC/MS was used to establish relationship between structural features of DOC and DBPFP. We show that there is a critical set of pyrolysis fragments that separates the waters based on the degree of anthropogenic influence. Even though no single chemical marker was found to be indicative of the formation potentials of different classes of DBP, combinations of chemical fragments were found to be associated with the formation potentials of total trihalomethane (THM), brominated THM, total haloacetic acid (HAA), and brominated HAA for this set of samples. In contrast to previous work, the phenolic signature of these samples was negatively correlated to DBPFP, whereas strong relationships were found between DBPFP and the organic nitrogen and halogenated signatures.

Acetates↗

Sewage sludge stabilisation with calcium hydroxide: effect on physicochemical properties and molecular composition.

Raw primary sewage sludge (Wastewater Treatment Plant of Krotoszyn, SW Poland) and its mixtures with 3%d, 6%d, 9%d, 12%d and 24%d of calcium hydroxide were stabilised for 1 and 35 days. Changes of the sludge physicochemical properties and molecular composition, caused by alkaline agent in course of stabilisation process, are recognised. A basic physicochemical data on the sludge cake and filtrate after 1 and 35 days of stabilisation process are given. Soxhlet extracts from the sludge cakes stabilised for 35 days as well pyrolysis and pyrolysis in situ methylation (using tetramethylammonium hydroxide-TMAH) products of respective pre-extracted cake residues were analysed by gas chromatography-mass spectrometry (GC-MS). Increase of calcium hydroxide concentration in the sludge mixture causes enhanced ammonia release, preferential hydrolyses of fats and proteins from the sludge macromolecular network and transformation of free fatty acids contained in the sludge lipids, as well as these released hydrolytically, to their calcium salts. The sewage sludge stabilisation with calcium hydroxide has no effect on homological assemblage and content of unbound stanol and sterol compounds in the sludge lipids and these bound into macromolecular network. Biogenic n-alkanes and anthropogenic linear alkylbenzenes were detected as minor components in the lipids and pyrolytic products from the pre-extracted cake residue, respectively. The alkaline agent used for the sludge stabilisation accelerates equilibration of the process and reduces content of pathogenic microorganisms.

Ammonia↗

Analysis of pitch deposits produced in kraft pulp mills using a totally chlorine free bleaching sequence.

Two organic deposits accumulated in a Kraft pulp mill during pulping of Eucalyptus globulus wood and throughout a TCF (totally chlorine free) bleaching sequence were characterized. One deposit was collected after cooking and an oxygen delignification stage while the other was collected after bleaching with hydrogen peroxide. The deposits were Soxhlet extracted with acetone, and the extracts redissolved in chloroform and subsequently analyzed by gas chromatography (GC) and GC-mass spectrometry (MS) using short and medium length high temperature capillary columns, respectively. On the other hand, the insoluble residues left after the acetone extraction were analyzed by Curie-point flash pyrolysis-GC-MS and by pyrolysis-methylation-GC-MS. The compounds identified in the deposits arise from the E. globulus wood lipophilic extractives that survive the pulping and bleaching processes. Triglycerides were completely hydrolyzed during the Kraft cooking and the fatty acids dissolved. Steroids (alcohols, hydrocarbons, ketones and esters) and waxes were the main components in the deposit collected after the oxygen delignification stage. After the bleaching with hydrogen peroxide, content of the waxes were reduced and fatty acids appeared. High amounts of fatty acids salts were also identified in the deposit collected after the oxygen stage, and in minor amounts in the deposit collected after hydrogen peroxide bleaching. In contrast, this deposit was mainly made up of high amounts of lignin-derived phenolic moieties.

Acetone↗

Polychlorinated dibenzo-p-dioxins. Separation and identification of isomers by gas chromatography-mas spectrometry.

Attempts were made to synthesize all polychlorinated dibenzo-p-dioxin isomers containing six to eight chlorine atoms by micro-scale pyrolysis of different polychlorophenates. Eight of the ten possible hexachlorodibenzo-p-dioxins, the two hepta- and the octachlorodibenzo-p-dioxin were observed and separated by gas chromatography using glass capillary columns. Without actual isolation of these toxic materials, isomers were characterized by gas chromatography and mass spectrometry. Commercial chlorinate phenols were analyzed for the presence of these isomers. The major hexachlorodibenzo-p-dioxin observed in two commerical products was the unexpected 1,2,3,7,8,9-substituted isomer, which was not formed as the main dioxin component in any of the pyrolysis experiments. The same isomer was reported to be isolated from toxic fat and identified by X-ray crystallography.

Chlorobenzenes↗