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PubMed2004

High yield bio-oil production from fast pyrolysis by metabolic controlling of Chlorella protothecoides.

The use of renewable energy sources is becoming increasingly necessary to mitigate global warming. Recently much research has been focused on identifying suitable biomass species, which can provide high-energy outputs, to replace conventional fossil fuels. This paper reports an approach for increasing the yield of bio-oil production from fast pyrolysis after manipulating the metabolic pathway in microalgae through heterotrophic growth. The yield of bio-oil (57.9%) produced from heterotrophic Chlorella protothecoides cells was 3.4 times higher than from autotrophic cells by fast pyrolysis. The bio-oil was characterized by a much lower oxygen content, with a higher heating value (41 MJ kg(-1)), a lower density (0.92 kg l(-1)), and lower viscosity (0.02 Pas) compared to those of bio-oil from autotrophic cells and wood. These properties are comparable to fossil oil. The research could contribute to the creation of a system to produce energy from microalgae, and also could have great commercial potential for liquid fuel production.

Chlorella↗

PubMed2004

Comparative study of carbon dioxide and nitrogen atmospheric effects on the chemical structure changes during pyrolysis of phenol-formaldehyde spheres.

The effect of CO(2) atmosphere on the chemical structure changes of resol-type phenol-formaldehyde spheres during pyrolysis was investigated, in comparison with that of N(2) atmosphere, using FT-IR, TGA, and elemental analysis techniques. It was found that, in contrast to the expectation that CO(2) may act as an oxidizing agent at high temperature, it behaves very similar to N(2) during pyrolysis of PF spheres up to 700 degree C, but results in a somewhat different extent of some specific reactions. That is, although the reactions occurring up to 700 degree C were dominated by crosslinking and/or polyaromatization under both CO(2) and N(2) atmospheres, fewer alkyl-phenolic ether bonds were formed under CO(2) than under N(2). As a consequence, the samples carbonized under CO(2) at 700 degree C were found to have more pendant groups on the edge carbon atoms of carbon in the carbonized samples than those prepared under N(2) atmosphere.

Journal Article↗

PubMed2006

Comparison of IR and UV cavity ring-down spectroscopy detection of transient intermediates: pyrolysis of methyl azide to form methyleneimine.

Mid-infrared cavity ring-down spectroscopy (CRDS) has been employed in this study to examine the hydride stretching region of methyl azide and its pyrolysis product methyleneimine. The absorption spectrum of methyl azide over 2835-3085 cm(-1) was recorded, and the integrated absorption cross section was determined. The pyrolysis of methyl azide and subsequent production of methyleneimine was observed at various wavenumbers. Using IR CRDS, we were able to observe vibrational transitions of methyleneimine without interference from the methyl azide precursor. Our previous UV CRDS study showed that electronic transitions of methyleneimine overlapped with those of methyl azide. IR CRDS should thus be useful for the detection of polyatomic transient intermediates without interference from precursors.

Azides↗

PubMed2005

Thermal pyrolysis of fresh and waste fishing nets.

Kinetic tests on the pyrolysis of nylon-6 taken from fresh (new) fishing nets and waste fishing nets were conducted using thermogravimetric analysis at heating rates of 0.5, 1.0 and 2.0 degrees C/min. The main region of decomposition of both materials was between 340 and 440 degrees C at each heating rate. The region of decomposition for the nylon-6 from the waste fishing nets was slightly lower than that of the fresh fishing nets. The result shows that the value of activation energies increased from 128 to 433 kJ mol(-1) as the conversion of the pyrolysis reaction increased from 5% to 95%. Nylon-6 from the fresh fishing nets was pyrolyzed in a micro-scale tubing bomb reactor for 60, 80 and 100 min at 440 degrees C. The yield of pyrolyzed gases increased from 3.94 to 5.50 wt% with reaction time. The selectivity to specific hydrocarbons was not detected from the pyrolyzed oil and the carbon number distribution of the pyrolyzed oil was random.

Animals↗

PubMed2006

Fungicidal value of wood tar from pyrolysis of treated wood.

The objective of the paper was to estimate the fungicidal value of wood tar extracted as a product of pyrolysis of wood previously treated with either creosote oil or CCB-type salt preservative. The effectiveness of wood treated with one of these two wood tar residuals was compared to the effectiveness of wood treated with virgin creosote oil (type WEI-B) and an untreated control. Wood was impregnated with alcohol solutions of the two extracted preservatives or virgin creosote oil and then subjected to the Coniophora puteana, Poria placenta and Coriolus versicolor fungi. The fungicidal values of the investigated preservatives were determined with the use of the short agar-block method and the aging test according to the standard EN 84. It was found that wood tar extracted by pyrolysis of old creosote-treated wood and then used to treat wood may have potential as a preservative for wood protection or as a component of preservatives.

Basidiomycota↗

PubMed1989

Carcinogenic tryptophan pyrolysis products in human lens.

Mutagenic and carcinogenic tryptophan pyrolysis products, 3-amino-1,4-dimethyl-5H-pyrido-[4,3-b]indole (Trp-P-1) and 3-amino-1-methyl-5H-pyrido[4,3-b]indole (Trp-P-2), have been identified in human cataractous lenses, but not in young bovine lenses. The amounts of Trp-P-1 and Trp-P-2 in senile cataractous lenses were 156.34 +/- 35.63 fmol (mean +/- S.D., n = 10) and 128.27 +/- 40.45 fmol (n = 10), respectively, while those of Trp-P-1 and Trp-P-2 in diabetic cataractous lenses were 158.29 +/- 40.06 fmol (n = 10) and 150.34 +/- 23.77 fmol (n = 10), respectively. In both senile and diabetic cataractous lenses, the concentrations of Trp-P-1 and Trp-P-2 in the insoluble protein fraction (fmol mg-1 protein) were significantly higher than those in the water-soluble protein fraction. Moreover, proteinase-K treatment of lens protein before extraction with methylene chloride significantly increased the recoveries of Trp-P-1 and Trp-P-2. These results clearly indicate that carcinogenic tryptophan pyrolysis products, gamma-carboline derivatives, are present in human cataractous lenses and that these fluorescent carcinogens are significantly concentrated in the insoluble lens proteins.

Adult↗

PubMed2001

Pyrolysis-capillary gas chromatography-mass spectrometry for the determination of polyvinyl chloride traces in solid environmental samples.

A novel method based on pyrolysis-capillary gas chromatography-mass spectrometry (CGC-MS) was developed for the quantitative analysis of polyvinylchloride (PVC) in solid environmental samples like sludge and dust. The samples are extracted and the extract is fractionated by solid-phase extraction (SPE). Possibly interfering biological and frequently occuring synthetic polymers are removed by this clean-up. The final extract is analyzed by pyrolysis-CGC-MS. Selective detection of PVC is performed by using specific markers in the pyrogram. Quantitation is done on naphthalene. Good linearity was obtained in a range from 0.5 to 100 microg applied to the pyrolyser. The limit of quantitation (LOQ) in sludge and dust samples is 10 mg/kg dry mass. A correlation between PVC and phthalates was made for sewage sludge samples.

Environmental Pollutants↗

PubMed1986

Identification of soy protein in meat by pyrolysis-high-resolution gas chromatography.

Pyrolysis-gas chromatography was applied to the characterization of ground beef and soy protein isolate and its mixtures at the 50, 30 and 10% levels. A cryogenic trap pyrolysis mode was employed and the volatile pyrolysates were analysed by a high-resolution capillary gas chromatograph. Two phenolic derivatives, o-methoxy- and dimethoxyphenol, as well as 2,3-dithiabutane are uniquely observed at a large concentration in the soy pyrolysate. Quantification of these characteristic compounds allow the estimation of the level of soy inclusion in the mixture. This approach effectively denotes soy addition up to the 10% level in comminuted beef.

Animals↗

PubMed2003

Pyrolysis-gas chromatography-mass spectrometry of cured phenolic resins.

A previously described pyrolysis device with a movable reaction zone was used in the present work for thermal degradation of cured novolac and resol resins. After the pyrolysis the usual major components were identified, as well as relatively low-volatile aromatic compounds which were revealed after their separation in a capillary chromatographic column. Among the latter components, for both types of cured resins, xanthene and its methyl derivatives were found. The isomers of bis(hydroxyphenyl)methane were found in considerable quantities only in the case of partially cured novolac resins which contained any linear sequences in their structure.

Gas Chromatography-Mass Spectrometry↗

PubMed1999

Introduction to pyrolysis-capillary gas chromatography.

By breaking large molecules into characteristic smaller fragments, analytical pyrolysis extends the use of gas chromatography to the analysis of polymeric materials, including natural polymers such as cellulose as well as synthetics. An understanding of the chemistry involved permits interpretation of the information present in these molecular fragments, with application to polymer and copolymer microstructure in addition to routine identification and quality control. Whether microfurnace, Curie-point or resistively heated filament, the pyrolysis device must be interfaced efficiently to the gas chromatography to make use of the resolving power afforded by capillary columns.

Chromatography, Gas↗

PubMed2001

Residue characteristics and pore development of petrochemical industry sludge pyrolysis.

Petrochemical industry bio-sludge was pyrolyzed to investigate the composition and pore size distribution of pyrolytic residue. Results indicated that the carbon, nitrogen, and hydrogen concentrations could be reduced after an increase in pyrolytic temperature. The trace element analysis indicated that Al, Ca, Fe, Mg. K, Cu, Sr, and Sb concentrated during the pyrolytic process. When forty grams of pre-dried sludge were pyrolyzed at various pyrolytic temperatures, the transfers from the gas phase to liquid phase to residue were from 21.2 to 36.0%, from 49.0 to 70.0%, and from 8.3 to 16.5%. Results of the pore size distribution examination indicated that the mesopore had the greatest effect on the bio-sludge pyrolysis. The optimal pyrolytic temperatures and times were approximately 800 degrees C for 30 min and 900 degrees C for 10 min. The conceptual model can reasonably explain the pore structure development during the pyrolysis process.

Chemical Industry↗

PubMed2002

Microwave-induced pyrolysis of sewage sludge.

This paper describes a new method for pyrolyzing sewage sludge using a microwave furnace. It was found that if just the raw wet sludge is treated in the microwave, only drying of the sample takes place. However, if the sludge is mixed with a small amount of a suitable microwave absorber (such as the char produced in the pyrolysis itself) temperatures of up to 900 degrees C can be achieved, so that pyrolysis takes place rather than drying. Microwave treatments were also compared with those carried out in a conventional electric furnace, as well as the characteristics of their respective carbonaceous solid residues.

Electricity↗

PubMed1998

Pyrolysis-GC-MS and CuO-oxidation-HPLC in the characterization of HMMs from sediments and surface waters downstream of a pulp mill.

High molecular mass fractions of lignin and humic compounds in sediments and waters downstream of a pulp mill were characterized applying pyrolysis-gas chromatography-mass spectrometry. The results were compared to those obtained using reversed phase HPLC on the cupric oxide oxidation products. The chromatographic data of both pyrolysis and cupric oxide oxidation were also subjected to the principal component analysis (PCA). The sediment samples and fractions obtained by ultrafiltration of river water samples were freeze dried prior to characterization. The sediment samples were also extracted using 2 M sodium hydroxide solution. The extracts were ultrafiltrated, freeze dried and compared to the freeze dried original sediments using the procedures mentioned above. The amounts of HMMs obtained from the sediments ranged from 62 mg to 97 mg per one gram of sediment. Gel permeation chromatography was applied to samples obtained from sediments by extraction with tetrahydrofuran. The weight average molecular weights of these fractions were in the range of 1500-2300 amu.

Chromatography, High Pressure Liquid↗

PubMed2000

Characterisation of riverine particulate organic matter by pyrolysis-gas chromatography-mass spectrometry.

Particulate matter samples were collected in the mountainous section and river mouth at the Tech River basin, south France, during flood (December 1996) and summer (September 1997) periods. Suspended material was analysed by pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS) and 23 identified pyrolysis products were divided into five main fractions: aminosugars, aromatic hydrocarbons, polysaccharides, phenols and nitrogenous compounds. Analysis of relative amounts of these fractions revealed neither significant spatial nor temporal changes in the particulate organic matter composition. Nevertheless, their specific composition showed that during flooding there is a certain homogeneity in the composition of the riverine particulate organic matter, with more degraded material of pedogenic (allochthonous) character, and during the summer the results suggest the presence of two components, allochthonous and autochthonous.

Disasters↗

PubMed2002

Use of pyrolysis molecular beam mass spectrometry (py-MBMS) to characterize forest soil carbon: method and preliminary results.

The components of soil organic matter (SOM) and their degradation dynamics in forest soils are difficult to study and thus poorly understood, due to time-consuming sample collection, preparation, and difficulty of analyzing and identifying major components. As a result, changes in soil organic matter chemical composition as a function of age, forest type, or disturbance have not been examined. We applied pyrolysis molecular beam mass spectrometry (py-MBMS), which provides rapid characterization of SOM of whole soil samples. to the Tionesta soil samples described by Hoover, C.M., Magrini, K.A., Evans, R.J., 2002. Soil carbon content and character in an old growth forest in northwestern Pennsylvania: a case study introducing molecular beam mass spectrometry (PY-MBMS). Environmental Pollution 116 (Supp. 1), S269-S278. Our goals in this work were to: (1) develop and demonstrate an advanced, rapid analytical method for characterizing SOM components in whole soils, and (2) provide data-based models to predict soil carbon content and residence time from py-MBMS analysis. Using py-MBMS and pattern recognition techniques we were able to statistically distinguish among four Tionesta sites and show an increase in pyrolysis products of more highly decomposed plant materials at increasing sample depth. For example, all four sites showed increasing amounts of older carbon (phenolic and aromatic species) at deeper depths and higher amounts of more recent carbon (carbohydrates and lignin products) at shallower depths. These results indicate that this type of analysis could be used to rapidly characterize SOM for the purpose of developing a model, which could be used in monitoring the effect of forest management practices on carbon uptake and storage.

Carbon↗

PubMed2002

Soil carbon content and character in an old-growth forest in northwestern Pennsylvania: a case study introducing pyrolysis molecular beam mass spectrometry (py-MBMS).

This study was conducted to: (1) test the utility of a new and rapid analytical method, pyrolysis molecular beam mass spectrometry (py-MBMS), for the measurement and characterization of carbon in forest soils, and (2) examine the effects of natural disturbance on soil carbon dynamics. An additional objective was to test the ability of py-MBMS to distinguish recent from more stable humic substances, and to relate this information to the ecology and history of the sites. To test the utility of the py-MBMS technique, we investigated soil carbon stocks in a chronosequence of stands arising from natural disturbance in the Tionesta Scenic and Research Natural Areas. Soil carbon increased with increasing time since disturbance; although the exact shape of the carbon accumulation curve is not known, it appears that the rate of carbon accretion is initially rapid and then levels off, with a possible maximum of 86 metric tons/ha to a depth of 30 cm. This study also demonstrates that py-MBMS is a valid method for characterizing soil carbon and can be used with little sample preparation. In addition, multivariate analysis of the mass spectra from Tionesta soils can distinguish both sites and depths on the basis of their pyrolysis products; both long-lived and short-lived carbon forms were identified.

Carbon↗

PubMed2001

Survivability of biomolecules during extraterrestrial delivery: new results on pyrolysis of amino acids and poly-amino acids.

The hypothesis on exogenous origin of organic matter on the early Earth is strongly supported by the detection of a large variety of organic compounds (including amino acids and nucleobases) in carbonaceous chondrites. Whether such complex species can be successively delivered by other space bodies (comets, asteroids and interplanetary dust particles) is unclear and depends primarily on capability of the biomolecules to survive high temperatures during atmospheric deceleration and impacts to the terrestrial surface. Recent simulation experiments on amino acid and nucleic acid base pyrolysis under oxygen-free atmosphere demonstrated that simple representatives of these (considered thermally unstable) compounds can survive at 1-10% level a rapid heating at 500-600 degrees C. In the present work, we report on new data on the pyrolysis of amino acids and their homopolymers and discuss implications of their thermal behavior for extraterrestrial delivery.

Amino Acids↗

PubMed1997

Analysis of wool fiber by alkali-catalyzed pyrolysis gas chromatography.

Alkali-catalyzed pyrolysis gas chromatography (PyGC) has been used to identify minute samples of wool fiber. The wool sample to which aqueous sodium hydroxide was added was pyrolyzed in a Curie-point pyrolyzer attached to a gas chromatograph or a gas chromatograph-mass spectrometer. The addition of an aqueous solution of sodium hydroxide increased the production of specific volatile pyrolysis products from the constitutive amino acid residues of wool protein, i.e. acetaldehyde from alanine or proline, isobutyronitrile from valine, 2-methylbutyronitrile from isoleucine, isovaleronitrile from leucine and toluene from phenylalanine. Compared with conventional non-catalyzed PyGC, the alkali-catalyzed PyGC was found to greatly improve the detection limit of wool fiber and make it possible to analyze very minute samples. The alkali-catalyzed PyGC presented here has been shown to be applicable to minute thermally-denatured samples of wool fiber which cannot be identified successfully by morphological inspection using a microscope or by using Fourier-transform infrared microspectroscopy. Furthermore, the present PyGC method was successfully used for several protein samples and was shown to be useful for analysis of proteins other than wool fibers by using different special pyrograms reflecting different amino acid compositions.

Alkalies↗