By-product Of Pyrolysis Research Articles

Biopolymers production from mixed cultures and pyrolysis by-products

Polyhydroxyalkanoates (PHAs) production from low value substrates and/or byproducts represents an economical and environmental promising alternative to established industrial manufacture methods. Bio-oil resulting from the fast-pyrolysis of chicken beds was used as substrate to select a mixed microbial culture (MMC) able to produce PHA under feast/famine conditions. In this study a maximum PHA content of 9.2% (g/g cell dry weight) was achieved in a sequencing batch reactor (SBR) operated for culture selection. The PHA obtained with bio-oil as a carbon source was a copolymer composed by 70% of hydroxybutyrate (HB) and 30% of hydroxyvalerate (HV) monomers. Similar results have been reported by other studies that use real complex substrates for culture selection indicating that bio-oil can be a promising feedstock to produce PHAs using MMC. To the best of our knowledge this is the first study that demonstrated the use of bio-oil resulting from fast pyrolysis as a possibly feedstock to produce short chain length polyhydroxyalkanoates.

Hydrogen Production From Crude Bio-oil and Biomass Char by Electrochemical Catalytic Reforming

We reports an efficient approach for production of hydrogen from crude bio-oil and biomass char in the dual fixed-bed system by using the electrochemical catalytic reforming method. The maximal absolute hydrogen yield reached 110.9 g H2/kg dry biomass. The product gas was a mixed gas containing 72%H2, 26%CO2, 1.9%CO, and a trace amount of CH4. It was observed that adding biomass char (a by-product of pyrolysis of biomass) could remarkably increase the absolute H2 yield (about 20%-50%). The higher reforming temperature could enhance the steam reforming reaction of organic compounds in crude bio-oil and the reaction of CO and H2O. In addition, the CuZn-Al2O3 catalyst in the water-gas shift bed could also increase the absolute H2 yield via shifting CO to CO2.

Biochar adsorbed ammonia is bioavailable

Biochar is produced as a by-product of the low temperature pyrolysis of biomass during bioenergy extraction and its incorporation into soil is of global interest as a potential carbon sequestration tool. Biochar influences soil nitrogen transformations and its capacity to take up ammonia is well recognized. Anthropogenic emissions of ammonia need to be mitigated due to negative environmental impacts and economic losses. Here we use an isotope of nitrogen to show that ammonia-N adsorbed by biochar is stable in ambient air, but readily bioavailable when placed in the soil. When biochars, containing adsorbed 15N labelled ammonia, were incorporated into soil the 15N recovery by roots averaged 6.8% but ranged from 26.1% to 10.9% in leaf tissue due to differing biochar properties with plant 15N recovery greater when acidic biochars were used to capture ammonia. Recovery of 15N as total soil nitrogen (organic+inorganic) ranged from 45% to 29% of 15N applied. We provide a proof of concept for a synergistic mitigation option where anthropogenic ammonia emissions could be captured using biochar, and made bioavailable in soils, thus leading to nitrogen capture by crops, while simultaneously sequestering carbon in soils.

Terra Pretas: Charcoal Amendments Influence on Relict Soils and Modern Agriculture

Most soils found in the Amazon region are characterized by highly weathered profiles that are incapable of long‐term agricultural production. However, small patches of highly fertile relict soil referred to as Terra Pretas, are also found in the Amazon region, and have maintained their integrity for thousands of years. These soils were anthropologically formed, being of pre‐Columbian origin and are unique in their high amounts of charcoal and nutrients compared to the surrounding soils. The charcoal serves to stabilize the organic matter in the soil, increase cation exchange capacity, and increase water retention due to its porous structure and high surface area. Organic wastes, such as bones and manure are thought to be the source of additional nutrients. To improve the overall productive capacity of the soil in this region, slash and char has been proposed to replace the traditional practice of slash and burn to mimic the high amounts of charcoal found in Terra Pretas soils. Instead of burning the vegetation and releasing the carbon into the atmosphere, the vegetation would be charred and the carbon would be sequestered in the soil on a small scale. Furthermore, based on the stability of charcoal and its ability to sequester carbon, some scientists are suggesting we consider pyrolysis (the process that creates charcoal by heating organic material with low amounts of oxygen) and its byproducts as a solution to soil quality issues, global warming, and peak oil. This concept is very controversial and relatively unstudied; further research is needed to truly understand the feasibility and consequences of sequestering large amounts carbon in the soil and the use of biofuels formed as byproducts of pyrolysis.

Biopolymers production from mixed cultures and pyrolysis by-products

Biopolymers production from mixed cultures and pyrolysis by-products

Brown coal tar hydrotreatment

The paper deals with the outcomes of laboratory experiments concerning brown coal tar hydrotreatment, in which tar was a by-product of brown coal pyrolysis. The experiments were carried out in pressure reactor at 300 °C and at varied operational pressures of hydrogen used as hydrotreatment medium. The brown coal tar samples earmarked for the hydrotreatment tests had been prepared through pyrolysis of samples of brown coal, in which samples represented, in terms of qualitative parameters, the brown coal types to be found in individual districts of the North Bohemian Coal Basin. During the experiments the qualitative parameters were determined both of the feed material (brown coal tar) and of the products generated (gaseous, water and organic phases and the hydrotreatment residue). The yields of these products as per on the operational hydrogen pressure used during the hydrotreatment process were also determined.

Hydrogen-rich gas production by steam gasification of char derived from cyanobacterial blooms (CDCB) in a fixed-bed reactor: Influence of particle size and residence time on gas yield and syngas composition

Char derived from cyanobacterial blooms (CDCB), by-product of fast pyrolysis of cyanobacterial blooms from Dianchi Lake (Yunnan Province, China) at a final pyrolysis temperature of 500 °C were used as feedstock material in this study. Steam gasification characteristics of CDCB were investigated in a fixed-bed reactor to evaluate the effect of particle size (below 0.15 mm, 0.15–0.3 mm, 0.3–0.45 mm, 0.45–0.9 mm, 0.9–3 mm) and solid residence time (3, 6, 9, 12, 15 min) on gas yield and composition, and experiments were carried out at bed temperature range of 600–850 °C, steam flow rate of 0.178 g/min. The results showed that solid residence time played an important role on steam gasification process, while particle size presented less effect on gasification process; proper particle size and longer residence time were favorable for dry gas yield and carbon conversion efficiency (CCE). At the same time, higher reaction temperature reduced influence of particle size on gasification process, and smaller particle size required less residence time for reaction completed. Maximum dry gas yield and CCE reached 1.84 Nm 3 kg −1 and 98.82%, respectively, achieved at a temperature of 850 °C, flow rate of 0.178 g/min, solid residence time of 15 min and particle size range of 0.45–0.9 mm.

On the rank-dependence of coal tar secondary reactions

The secondary reactions of volatile compounds, including coal tar and light gases, accounts for a great portion of soot formation and the subsequent heat release and pollutant emissions in the combustion zone. While coal primary pyrolysis has been extensively studied over the last few decades and several network pyrolysis models has been developed to describe this process, coal secondary pyrolysis is still not well understood. The Babcock and Wilcox Company has been investigating coal secondary pyrolysis in order to develop a comprehensive mechanism for inclusion in predictive computational fluid dynamics and coal combustion models. Supportive experiments were carried out in an entrained-flow reactor. Tar was extracted from the pyrolysis byproducts of seven coals of widely-distributed rank at temperatures ranging from 923 to 1473 K, and analyzed by 13C NMR. Tars formed from higher rank coals generally demonstrated higher sooting propensities. This rank-dependent sooting propensity is associated with tar’s chemical structure properties. With increased heat treatment severity, tar molecules lose a substantial amount of aliphatic attachments, and the average size of substitution per cluster decreases. Compared to tars formed from high-rank bituminous coals, those formed from low-rank sub-bituminous coals have a larger attachment portion, higher averaged substitution, and higher oxygen-containing functional groups. These differences contribute to the higher cracking propensity observed for low-rank coal tars.

Biochar based solid acid catalyst for biodiesel production

A promising catalyst based on a biomass pyrolysis by-product, biochar, has been developed for the production of biodiesel. Two carbon-based solid acid catalysts were prepared by sulfonating pyrolysis char with concentrated or fuming sulfuric acids. Prepared catalysts were studied for their ability to catalyze transesterification of vegetable oils and esterification of free fatty acids. The catalyst sulfonated with the concentrated sulfuric acid demonstrated considerable conversion in free fatty acid esterification, while indicating limited transesterification activity. Using the stronger sulfonating reagent, fuming sulfuric acid, resulted in much higher transesterification activity. Further investigation of the latter catalyst was conducted to determine the effect of sulfonation time (5 and 15 h) and surface area on the transesterification reaction. The surface area of the biochar was increased by chemical treatment using 10 M potassium hydroxide through porosity development. The resulting four catalysts were compared for their catalytic activity. Results showed the catalyst with the highest surface area and acid density to have the highest catalytic activity for the production of biodiesel from canola oil in the presence of methanol as the reagent. Furthermore, the catalyst with the higher surface area indicated higher transesterification activity among the catalyst with similar acid densities. The effects of alcohol to oil (A:O) molar ratio, reaction time and catalyst loading on the esterification reaction catalyzed by the sulfonated biochar were also investigated. Free fatty acid (FFA) conversion increased with increasing A:O molar ratio, reaction time and catalyst loading. The catalyst has a tremendous potential to be used in a process converting a high FFA feedstock to biodiesel.

Cannabinoid Receptor 1 Binding Activity and Quantitative Analysis of Cannabis sativa L. Smoke and Vapor

Cannabis sativa L. (cannabis) extracts, vapor produced by the Volcano vaporizer and smoke made from burning cannabis joints were analyzed by GC-flame ionization detecter (FID), GC-MS and HPLC. Three different medicinal cannabis varieties were investigated Bedrocan, Bedrobinol and Bediol. Cannabinoids plus other components such as terpenoids and pyrolytic by-products were identified and quantified in all samples. Cannabis vapor and smoke was tested for cannabinoid receptor 1 (CB1) binding activity and compared to pure Delta(9)-tetrahydrocannabinol (Delta(9)-THC). The top five major compounds in Bedrocan extracts were Delta(9)-THC, cannabigerol (CBG), terpinolene, myrcene, and cis-ocimene in Bedrobinol Delta(9)-THC, myrcene, CBG, cannabichromene (CBC), and camphene in Bediol cannabidiol (CBD), Delta(9)-THC, myrcene, CBC, and CBG. The major components in Bedrocan vapor (>1.0 mg/g) were Delta(9)-THC, terpinolene, myrcene, CBG, cis-ocimene and CBD in Bedrobinol Delta(9)-THC, myrcene and CBD in Bediol CBD, Delta(9)-THC, myrcene, CBC and terpinolene. The major components in Bedrocan smoke (>1.0 mg/g) were Delta(9)-THC, cannabinol (CBN), terpinolene, CBG, myrcene and cis-ocimene in Bedrobinol Delta(9)-THC, CBN and myrcene in Bediol CBD, Delta(9)-THC, CBN, myrcene, CBC and terpinolene. There was no statistically significant difference between CB1 binding of pure Delta(9)-THC compared to cannabis smoke and vapor at an equivalent concentration of Delta(9)-THC.

Laboratory analogs of carbonaceous matter: Soot and its precursors and by-products

AbstractCarbonaceous materials have been prepared in the laboratory by laser-induced pyrolysis of a mixture of hydrocarbons under different conditions and laser ablation of graphite in reactive gas atmospheres. We have investigated the soluble and insoluble parts of the condensed carbon powders with several spectroscopic and chromatographic methods in order to obtain information on the composition of the condensate. The results of these experiments have demonstrated that, at temperatures lower than 1700 K, the pyrolysis by-products are mainly PAHs, whereas at higher temperatures fullerenes and polyyne-based compounds are formed. The experimental findings point to different soot formation mechanisms with variable intermediates and end products. It has been found that soot extracts can contain more than 65 different polycyclic aromatic hydrocarbons (PAHs). Eventually, the study of the condensation pathways of soot particles and their precursors and by-products will permit the prediction of the spectral properties of carbonaceous matter in space.

Preparation of nanostructured nitrogen-containing carbon catalysts for the oxygen reduction reaction from SiO 2- and MgO-supported metal particles

Nitrogen-containing carbon was prepared from the vapor deposition of acetonitrile at 900 °C over silica- or magnesia-supported Fe, Co, and Ni particles. The byproducts of pyrolysis were monitored by mass spectrometry. The carbon formed from silica precursors was washed with KOH to remove the silica and HCl to remove metal particles, whereas the carbon formed from magnesia samples was washed with HCl to remove the support and the metal. The solid carbon product was characterized with N 2 physisorption to measure surface area and pore volume distribution, X-ray diffraction to determine the crystalline phases present, and temperature-programmed oxidation to determine ash and nitrogen content. Magnesia was more readily removed from the carbon compared with silica. A significant amount of metal, encased in carbon, remained in the samples after washing. The Co particles led to a higher content of bulk nitrogen in the carbon, as high as 2.9% based on oxidation measurements. Electron microscopy imaging confirmed that all of the metal particles catalyzed the formation of various types of carbon nanofibers, with the diameter and structure of the fibers varying with different metal–support precursor combinations. A possible application for these fibers is oxygen reduction reaction catalysts for proton-exchange membrane fuel cell cathodes.

Avaliação dos produtos de emissão a partir da pirólise de assentos automotivos feitos de fibra de coco e de espuma de poliuretano

O presente trabalho visa comparar assentos automobilísticos feitos de manta de fibra de coco com látex (MFCL) em relação à espuma de poliuretano (EPU), avaliando a possibilidade do primeiro substituir o segundo, devido ao fato da fibra natural ser biodegradável e renovável. Esses materiais foram submetidos à análise termogravimétrica (TGA), pirólise e análise dos produtos de pirólise por cromatografia gasosa acoplada ao espectrômetro de massa. Verificou-se que a pirólise a 800ºC apresentou grande número de gases tóxicos, e comparando os materiais observou-se que a EPU emitiu gases mais tóxicos na combustão que aqueles produzidos pelos outros materiais sob as mesmas condições, tais como o cianeto de hidrogênio e compostos de nitrila. Quanto às análises de TGA, verificou-se que acima de 270ºC inicia-se a degradação térmica de todos materiais.

Cannabis Vaporizer Combines Efficient Delivery of THC with Effective Suppression of Pyrolytic Compounds

Cannabis vaporization is a technology designed to deliver inhaled cannabinoids while avoiding the respiratory hazards of smoking by heating cannabis to a temperature where therapeutically active canna- binoid vapors are produced, but below the point of combustion where noxious pyrolytic byproducts are formed. This study was designed to evaluate the efficacy of an herbal vapor- izer known as the Volcano ® , produced by Storz & Bickel GmbH&Co. KG, Tuttlingen, Germany (http://www.storz-bickel.com). Three 200 mg samples of standard NIDA cannabis were vaporized at temperatures of 155°-218°C. For comparison, smoke from combusted samples was also tested.

Thermal and Base-Induced Cyclizations of N-Heteroarylamidinopropanoates

The potential cyclization of N-heteroarylamidines to annelated pyrimidines by flash vacuum pyrolysis or by treatment with bases has been investigated. The pyrolytic process with the title compounds is complicated by competing formation and rearrangement of an imidoylketene. The major pyrolysis products, the 4-aminopyrimidin-6-ones, were best prepared from the title compounds by reaction with hindered alkoxides, while the pyrolysis byproducts, the 4-alkoxypyrimidin-6-ones, were conveniently prepared from the appropriate isoxazol-5(2H)-one by reaction with the appropriate alkoxide, followed by acidic workup.

Use of pyrolysis GC/MS for predicting emission byproducts from the incineration of double-base propellant.

Gas chromatography/mass spectrometry was used to analyze the pyrolytic byproducts from an Army-unique propellant compound (AA2) that is composed of predominantly nitrocellulose and nitroglycerin. Compounds produced by AA2 pyrolysis were compared to compounds detected in the gaseous effluent from AA2 incineration. The light permanent gases and most of the higher molecular weight byproducts produced by AA2 incineration are replicated by laboratory pyrolysis on AA2. The reverse case also holds whereby 18 out of 24 high molecular weight AA2 pyrolytic byproducts are found in the incinerator emissions. Poor matching, however, was obtained between the two processes for the volatile, water-soluble species. None of these low molecular weight compounds produced under pyrolytic conditions were detected in the AA2 incinerator samples, likely indicating inefficient capture of these compounds from the effluent stream. Separate pyrolytic degradation of the individual components of AA2 provides evidence that nearly all of the incomplete combustion products detected during incineration originate not from the prevalent energetic ingredients but rather from the minor and trace additives in AA2. In addition, pyrolysis successfully identified the AA2 components capable of surviving the incineration process intact. This work illustrates the potential of bench-scale pyrolysis for predicting incineration behavior.

Rock-Eval 6 Technology: Performances and Developments

The Rock-Eval 6 apparatus is the latest version of the Rock-Eval product line, commercialized since 1996 by Vinci Technologies. The present work describes the methodology developed at IFP for reliable data acquisition and endorses the quality of geochemical parameters acquired with Rock-Eval 6. Data were obtained on 147 source rocks from various sedimentary basins, of different organic matter types and maturity stages. Intrinsic correlations for two different Rock-Eval 6 apparatus were performed and the obtained data set shows an excellent consistency and good reproducibility conditions for the whole set of Rock-Eval parameters. Complete recovery of total carbon (TC) by Rock-Eval 6 was confirmed by comparison with elemental analysis. In order to check the carbon partition (mineral vs. organic) determined by Rock-Eval 6, measurements of mineral carbon (MinC) and total organic carbon (TOC) were performed by alternative techniques. TOC measured by Rock-Eval 6 was compared to that obtained either by: the Leco apparatus for bulk rocks; elemental analysis for kerogens; and calculation from the mass balance determined after destruction of mineral matrix and the carbon concentration determined by elemental analysis on recovered kerogens for bulk rocks. The results display a good correlation for the whole concentration range (0-90 wt% TOC), when comparing elemental analyses and Rock-Eval 6 for source rocks and kerogens. However, comparison of Rock-Eval 6 with Leco data leads to larger deviations while correlation factors are still good. For a subset of kerogen samples, preparative pyrolysis was performed in order to confirm the value of 83 wt% for the organic carbon of the total S2 peak for any rock with any organic type and to check the absolute value of the S2 peak by gas chromatography analysis of pyrolysis by-product. MinC measured with Rock-Eval 6 was compared to that determined by: weight loss after HCl treatment; the acidimetry technique; and calculation after TC, mass balance from kerogen isolation and organic carbon measurement on kerogen by elemental analysis. The results display a good correlation for the whole concentration range (0-12 wt% MinC), when comparing elemental analyses and Rock-Eval 6. However, comparison of Rock-Eval 6 with acidimetry data leads to larger deviations while correlation factors are still good while comparison with weight loss is poor. As a whole an excellent reliability of TOC and MinC obtained by Rock-Eval 6 was demonstrated, and consequently, it is now possible to get at once the total organic and mineral carbon mass balance for a given rock. Recommendations are proposed regarding the standard samples and analytical methods selected for calibrating the Rock-Eval 6 over a large mineral and organic carbon range. Consistency between S2 and Tmax measured by Rock-Eval 2 and Rock-Eval 6 for Types I and II bulk rocks was also checked. A good correlation was obtained for S2, even though S2 values are slightlyhigher when measured with Rock-Eval 2. It was demonstrated that this is due to carrier gas (nitrogen vs. helium) by running measurements with a Rock-Eval 6 under helium, the difference ranging from 5 to 10 relative wt% for most studied samples. For Tmax correlation, data are much more scattered and as a general trend Tmax obtained by Rock-Eval 6 are higher than Tmax obtained by Rock-Eval 2 and the difference increases with Tmax: this is due to the fact that the probe measuring the temperature in the Rock-Eval 2 is located in the oven wall, consequently Tmax determination is highly dependent on the setup and calibration of the apparatus. A special attention was given for temperature measurement in the Rock-Eval 6, where the probe is in contact with the crucible containing the sample, leading to much more reliable data.

Heat-treated timber: potentially toxic byproducts presence and extent of wood cell wall degradation

C NMR to determine which type of loose chemical compounds were produced by the thermal treatment. The formation of some toxic polynuclear aromatic hydrocarbons derivatives of phenantrene as well as other classes of polyaromatics compounds was detected. It is most likely that the presence of all such compounds contributes, perhaps to a relatively substantial extent, to the reported resistance of heat treated timber to fungal and other biological attack. Other allegedly non-toxic compounds due to wood constituents degradation were also found, mainly the by-products of lignin pyrolysis. The extent of toxic and non-toxic compounds in the heat treated wood were not quantified, but it can be stated that their proportion appears to be quite small. The lack of quantification of the concentration of these products does not allow to ascertain if the final product is toxic or not, and to what extent. Nonetheless, the amount of polynuclear aromatic hydrocarbon-type derivatives should be quantified and related to the type of heat treatment process undertaken before assigning to this type of wood treatment a completely clean health safety label.

Liquid phase sintering of iron-copper-carbon

GaInP nucleation on Ge(100) often starts by annealing of the Ge(100) substrates under supply of phosphorus precursors. However, the influence on the Ge surface is not well understood. Here, we studied vicinal Ge(100) surfaces annealed under tertiarybutylphosphine (TBP) supply in MOVPE by in situ reflection anisotropy spectroscopy (RAS), X-ray photoelectron spectroscopy (XPS), and low energy electron diffraction (LEED). While XPS reveals a P termination and the presence of carbon on the Ge surface, LEED patterns indicate a disordered surface probably due to by-products of the TBP pyrolysis. However, the TBP annealed Ge(100) surface exhibits a characteristic RA spectrum, which is related to the P termination. RAS allows us to in situ control phosphorus desorption dependent on temperature.

Direct observation of the formation of aromatic pollutants in waste incineration flue gases by on-line REMPI-TOFMS laser mass spectrometry.

On-line REMPI-TOFMS laser mass spectrometry (Resonance Enhanced Multi-Photon Ionization-Time-Of-Flight Mass Spectrometry) was used to monitor combustion and pyrolysis byproducts from industrial combustion processes, including polycyclic aromatic hydrocarbons (PAH) and monochlorobenzene in the flue gas of an industrial 22 MW hazardous waste incineration plant. Sampling at different places in the flue gas stream revealed the complexity of the processes responsible for the formation of the different chemical species, while time resolved measurements depicted the emission dynamics.