Analysis of model dimensionality,particle shrinkage,boundary layer reactions on particle-scale modelling of biomass char conversion under pulverized fuel combustion conditions

In this work, the effects of model dimensionality, particle shrinkage, and boundary layer reactions on particle-scale modelling of biomass char conversion under pulverized fuel combustion conditions have been analysed by using six models: zero-dimensional models with constant particle size (0D_Cons) or shrinking particle size (0D_SPM), one-dimensional models with/without considering particle shrinkage (1D_Cons/1D_SPM), and 1D_Cons and 1D_SPM with considering boundary layer reactions (1D_Cons_BH and 1D_SPM_BH). A comparison with existing experimental data shows that the 1D_SPM_BH model with consideration of intra-particle heat and mass transfer, particle shrinkage, and boundary layer reactions is an appropriate model to describe biomass char conversion over a wide range of conditions. The 0D_Cons model is a good approximation for the conditions of small particle size (< 1 mm) at 1273–1473 K, but overestimates the char conversion rate for larger biomass char particle or at high temperatures (regime III). The 0D_SPM model gives a reasonable prediction on char conversion time but predicts a larger contribution of reaction between char and O₂ as compared to the 1D_SPM_BH model. The consideration of intra-particle heat and mass transfer in particle-scale modelling (1D_Cons and 1D_SPM) is beneficial to improving the model prediction of char conversion time and the contributions of char oxidation and gasification reactions. The boundary layer reactions have a significant effect on the prediction of char conversion for large particles (> 1 mm) and high temperatures (> 1473 K). An implication for the selection of a particle-scale model in CFD modelling is also given.     

Rapid pyrolysis of biochar prepared from slow and fast pyrolysis: The effects of particle residence time on char properties

This paper investigates the evolution of char properties with particle residence time during rapid pyrolysis of biochar under conditions pertinent to pulverized fuel (PF) applications. Two biochar samples were considered, prepared via slow (S-BC) and fast (F-BC) pyrolysis of mallee wood (150–250 µm) at 500 °C and two different heating rates (10 °C/s and ∼400 °C/s), respectively. The biochar samples were then subjected to rapid pyrolysis at 1300 °C using a novel drop-tube furnace (DTF), which enables direct determination of char yield experimentally. The evolution of char yield, the release of alkali and alkaline earth metallic (AAEM) species, and particle size and shape during rapid pyrolysis are investigated as a function of particle residence time (0.45 s to 1.4 s). The results show that char yields decrease from ∼77% to 75% when particle residence time increases from 0.45 s to 1.4 s. Rapid pyrolysis of F-BC has slightly higher char yields, due to the higher ash content of F-BC. More Cl in F-BC facilitates the release of Na during rapid pyrolysis, leading to the lower retention of Na in FC than in SC. Nevertheless, the retentions of K (∼90%), Mg (∼85%), and Ca (∼90%) are higher in FC, which can be ascribed to its higher contents of oxygen after rapid pyrolysis. The investigation of particle size and shape shows that biochar particles exhibit little changes after rapid pyrolysis, indicating their strong resistance to shrinkage and deformation even at high temperature.     

Pore-Resolving Simulations of Biomass Char Particle Combustion

Biomass char morphology affects combustion behavior at the particle scale for zone II conditions, in which both heterogeneous reaction and intra-particle diffusion govern the overall rate. Furthermore, particle-scale processes affect reactor-scale outputs, and reactor-scale simulations are sensitive to particle-scale models. However, most char particle combustion models employ coarse-grained, effective-continuum approaches, which treat all porosity at the subgrid-scale. Effective-continuum approaches are not valid or accurate in the presence of large, irregular pores which can approach the size of the particle. A 3-D, pore-resolving CFD simulation approach using real biomass char particle geometries obtained from X-ray micro-computed tomography (micro-CT) is therefore used to examine the impact of morphology on zone II combustion for pulverized (∼100 µm) biomass char particles for the first time. In contrast to larger, millimeter to centimeter sized particles, the sub-millimeter, high aspect ratio biomass char particles exhibited localized reactant penetration into the innermost regions of the particles, facilitated by the presence of large pores connected to the external surface. The oxygen mole fraction distributions were governed by the large pore morphology, were non-monotonic with distance from the surface, and achieved minima in thick microporous char regions surrounding the large pores. A comparison between the pore-resolving simulation and an equivalent, spatially resolved, effective-continuum simulation revealed that even in the microporous char, the effective-continuum model underpredicted reactant penetration. A careful comparison was then performed between 30 pore-resolving particle simulations and several effectiveness factor models that employed particle-specific parameters. Commonly used uniform cylinder models significantly underpredicted effectiveness factors for these real pulverized pine char particles, while accessible hollow cylinder models achieved less than 10% relative error when averaged over all 30 particles.     

Effect of pyrolysis conditions on gasification reactivity of woody biomass-derived char

The effect of pyrolysis conditions on char reactivity has been studied using Raman spectroscopy. This paper reports on the relationship between the properties of biomass char and the gasification rate. The gasification kinetics of biomass char have been revealed by measuring the rate of weight loss during its reaction with CO₂ as a function of temperature. First-order kinetic rate constants are determined by fitting the weight loss data using a random pore model. The relationship between the char structure and CO₂ gasification reactivity was investigated in the range of 15–600 °C/min at a constant pyrolysis pressure (0.1 MPa), and 0.1–3.0 MPa at a constant heating rate (15 °C/min). The experimental results reveal that the reactivity of biomass char is determined by the pyrolysis condition. The CO₂ gasification rates in char generated at 0.1 MPa exhibited approximately twice the values as compared to those obtained at 3 MPa. This is because the uniformity of the carbonaceous structure increases with the pyrolysis pressure. The uniformity of carbonaceous structures would affect the CO₂ gasification reactivity, and the decreasing uniformity would lead to the progression of cavities on the char surface during the CO₂ gasification process. The gasification rate of biomass char increases with the heating rate at pyrolysis. This is due to the coarseness (surface morphology) of biomass char and rough texture, which increases with the heating rate.     

Effect of high CO2 concentration on char formation through mineral reaction during biomass pyrolysis

O₂/CO₂ combustion has attracted considerable attention as a promising technology for CO₂ capture. Using biomass for fuel is considered carbon neutral, and O₂/CO₂ biomass combustion can mitigate the deleterious environmental effect of greenhouse. In this study, the effect of CO₂, the main component gas in O₂/CO₂ combustion, on the pyrolysis characteristics of biomass is investigated. Cellulose, lignin, and metal-depleted lignin pyrolysis experiments were performed using a thermobalance. Information on the surface chemistry of the chars was obtained by Fourier transform infrared (FTIR) spectroscopy to investigate changes in the surface chemistry during pyrolysis under different surrounding gasses. When the temperature increased to 1073 K at heating rate of 1 K s^?1, the char yield of lignin in the presence of CO₂ increased by about 10% compared with that under Ar. However, for cellulose and metal-depleted lignin, no significant difference appeared between pyrolysis under CO₂ and that under Ar. FT-IR showed that a strong peak corresponding to carbonate ions appeared in the char derived from lignin under CO₂. Therefore, salts such as Na₂CO₃ or K₂CO₃ formed during the lignin pyrolysis under CO₂. At around 1650–1770 cm^?1, a significant difference appeared in the FTIR spectra of chars formed under CO₂ and those formed under Ar. C=O groups not associated with an aromatic ring were found only in chars formed under CO₂. It was suggested that these salts affected the char formation reaction, in that the char formed during lignin pyrolysis under CO₂ had unique chemical bands that did not appear in the lignin-derived char prepared under Ar.     

Single particle ignition and combustion of pulverized pine wood,wheat straw,rice husk and grape pomace

This work examines the combustion behavior of single pulverized biomass particles from ignition to early stages of char oxidation. The biomass residues investigated were pine wood, wheat straw, rice husk and grape pomace. The biomass particles, in the size range 224–250 µm, were injected upward into a confined region with hot combustion products, produced by a flat flame McKenna burner, with a mean temperature of 1610 K and a mean O₂ concentration of 6.5 vol%. Temporally and spectrally resolved images of the single burning particles were recorded with an intensified charge-coupled device camera equipped with different band-pass spectral filters. Data are reported for CH*, C₂*, Na* and K* chemiluminescence, and thermal radiation from soot and char burning particles. The data on CH* and C₂* chemiluminescence and soot thermal radiation permits to identify important differences between the ignition delay time, volatiles combustion time and soot formation propensity of the four biomass residues, which are mainly affected by their volatile matter content. The Na* and K* emission signals follow the same trends of the CH* and C₂* emission signals until the end of the volatiles combustion stage, beyond which, unlike the CH* and C₂* emission signals, they persist owing to their release from the char burning particles. Moreover, during the volatiles combustion stage, the Na*/CH* and K*/CH* ratios present constant values for each biomass residue. The CH* and thermal radiation emission data suggest that all biomass char particles experienced heterogeneous oxidation at or immediately after the extinction of the homogeneous volatiles combustion.     

Simultaneous in-situ measurements of gas temperature and pyrolysis of biomass smoldering via X-ray computed tomography

In-situ X-ray computed tomography (XCT) imaging is employed to investigate the smoldering dynamics of biomass at the sub-millimeter scale. This technique provides simultaneous and spatially-resolved information about the gas temperature and the biomass density, thereby enabling tracking of the pyrolysis and char oxidation fronts. To achieve well-controlled heating and flow conditioning, oak biomass samples are instrumented above a diffusion flame inside a tube, with total oxygen concentrations of 6% and 11% per volume. Experiments are performed on a laboratory XCT system. The flow is diluted with Kr to increase X-ray attenuation in the gas phase thus allowing for simultaneous 3D measurements of sample density and surrounding temperature. XCT scans are acquired every 90 s at a spatial resolution of 135 µm. The high spatial resolution enables the volumetric visualization of the smoldering process that is associated with pyrolysis and char oxidation. These measurements show how the grain structure affects flame stabilization and induces fingering of the pyrolysis front, while crack formation accelerates the char oxidation locally. Evaluations of the sample mass via XCT are compared with load cell measurements, showing good agreement. A low-order model is developed to evaluate the propagation speeds of pyrolysis and oxidation fronts from the X-ray data over time, and comparisons are made with the surface recess speed.     

Characteristics of chars formed during rapid pyrolysis of biomass model components at high temperature

This paper reports char formation and inherent inorganic transformation during rapid pyrolysis of various biomass model components under simulated pulverized fuel (PF) conditions at 1300 °C. A drop-tube furnace with a novel double-tube configuration was deployed to achieve direct determination of char yield. The results show that rapid pyrolysis of xylan and water-washed lignin (W-L) under the conditions results in char yields of 3.4 wt.% and 12.6 wt.%, respectively, while no char was founded during rapid pyrolysis of water-washed cellulose (W-C). After loading K₂CO₃ into the W-C (i.e. KW-C) and W-L (i.e. KW-L), the char yields increase to 2.1 wt.% and 15.6 wt.%, respectively. The retentions of Na and S are low in chars after pyrolysis. After rapid pyrolysis, W-L and KW-L chars have higher retentions of AAEM species than xylan, W-C and KW-C chars. Micromorphology analysis shows char particles formed after rapid pyrolysis of all biomass components have a cenospheric structure and a rough surface with many bubbles and pores, demonstrating strong melting processes. For xylan and KW-L, the abundant inorganics accelerate char formation with swelling and reduce the extent of particle shrinkage, resulting in char particles with apparent sizes bigger than the parent feedstock particles. Oppositely, for KW-C and W-L that have low contents of inorganic species, the pyrolyzing particles experience significant shrinkage, resulting in formed char particles with apparent sizes that are much smaller than feedstock particles.     

Effect of gasification reactions on biomass char conversion under pulverized fuel combustion conditions

The effect of gasification reactions on biomass char conversion under pulverized fuel combustion conditions was studied by single particle experiments and modelling. Experiments of pine and beech wood char conversion were carried out in a single particle combustor under conditions of 1473-1723 K, 0.0-10.5% O₂, and 25-42% H₂O. A comprehensive progressive char conversion model, including heterogeneous reactions (char oxidation and char gasification with CO₂ and H₂O), homogeneous reactions (CO oxidation, water-gas shift reaction, and H₂ oxidation) in the particle boundary layer, particle shrinkage, and external and internal heat and mass transfer, was developed. The modelling results are in good agreement with both experimental char conversion time and particle size evolution in the presence of oxygen, while larger deviations are found for the gasification experiments. The modelling results show that the char oxidation is limited by mass transfer, while the char gasification is controlled by both mass transfer and gasification kinetics at the investigated conditions. A sensitivity analysis shows that the CO oxidation in the boundary layer and the gasification kinetics influence significantly the char conversion time, while the water-gas shift reaction and H₂ oxidation have only a small effect. Analysis of the sensitive parameters on the char conversion process under a typical pulverized biomass combustion condition (4% O₂, 13% CO₂, 13% H₂O), shows that the char gasification reactions contribute significantly to char conversion, especially for millimeter-sized biomass char particles at high temperatures.     

Rational design of thermogravimetric experiments to determine intrinsic char gasification kinetics

The Boudouard reaction is an important heterogeneous reaction that takes place inside the gasifier during char gasification. To evaluate the gasification performance of solid fuels, it is important to know the intrinsic rate of the Boudouard reaction of that particular fuel. Incorrect determination of this rate results in error when used for modelling or gasifier scaling purposes. The thermo-gravimetric analyser (TGA) is an instrument that is widely used for gasification studies, particularly to explore the intrinsic gasification kinetics of coal or biomass char in a controlled environment. As in a real gasifier environment, several experimental parameters in TGA experiments can influence the intrinsic reactivity of the sample char; however, this is rarely discussed in the literature. It is essential to carefully differentiate the physical effects from the pure chemical reaction and to consider their interactions to obtain reliable kinetic parameters. No systematic experimental procedures to minimize the effects of the rate-influencing parameters during TGA experiments are available in the literature. This article presents an analysis for this purpose and demonstrates the variation in the gasification rate when the experimental conditions are not properly optimized. A mathematical model is also presented to explain the possible diffusional interactions with chemical kinetics during un-optimized TGA experiments.     

Char characteristics and particulate matter formation during Chinese bituminous coal combustion

The characteristics of char particles and their effects on the emission of particulate matter (PM) from the combustion of a Chinese bituminous coal were studied in a laboratory-scale drop tube furnace. The raw coal was pulverized and divided into three sizes, <63, 63–100, and 100–200 μm. These coal samples were subjected to pyrolysis in N₂ and combusted in 20 and 50% O₂ at 1373, 1523, and 1673 K, respectively. Char samples were obtained by glass fiber filters with a pore size of 0.3 μm, and combustion-derived PM was size-segregated by a low pressure impactor (LPI) into different sizes ranging from 10.0 to 0.3 μm. The characteristics of char particles, including particle size distribution, surface area, pore size distribution, swelling behavior and morphology property, were studied. The results show that, coal particle size and pyrolysis temperature have significant influence on the char characteristics. The swelling ratios of char samples increase with temperature increasing from 1373 to 1523 K, then decrease when the temperature further increases to 1623 K. At the same temperature, the swelling ratios of the three size fractions are markedly different. The finer the particle size, the higher the swelling ratio. The decrease of swelling ratio at high temperature is mainly attributed to the high heating rate, but char fragmentation at high temperature may also account for the decrease of swelling ratio. The supermicron particles (1–10 μm) are primarily spherical, and most of them have smooth surfaces. Decreasing coal particle size and increasing the oxygen concentration lead to more supermicron-sized PM formation. The influence of combustion temperature on supermicron-sized PM emission greatly depends on the oxygen concentration.     

Study of the competing chemical reactions in the initiation and spread of smouldering combustion in peat

Smouldering combustion of natural fuel layers such as peatlands leads to the largest fires on Earth and posses a possible positive feedback mechanism to climate change. In this paper, we use an experimental methodology to study the smouldering combustion of samples of peat under a wide range burning conditions. Vertical samples (30 mm deep and 125 mm in diameter) are ignited by radiation on the top free surface and the smouldering front propagates downward against a forced flow of oxidizer. By varying the oxygen concentration ([O₂]) and the ignition conditions we investigate the competing pyrolysis and oxidation reactions. A reaction framework with two regimes is consistently observed. The measurements show that a char species is formed by the competing pyrolysis and oxidation reactions in the first regime resulting in net char production and in the second regime char oxidation results in conversion of the char to ash. Lower mass loss rates and the larger residual mass at lower [O₂] suggest that a wider smouldering front is required to sustain combustion as the [O₂] is decreased. These results improve our understanding of smouldering phenomena and the role of the competing chemical reactions.     

Heterogeneous fixation of N2: Investigation of a novel mechanism for formation of NO

Formation of NO initiated by heterogeneous fixation of N₂ during pyrolysis is investigated experimentally and theoretically. The experiments were conducted with beech wood as well as with the pure biomass components cellulose, xylan, and lignin. The NO formation during char oxidation was recorded as function of pyrolysis atmosphere (N₂ or Ar), pyrolysis temperature (700–1050 °C), and oxidizing atmosphere (O₂ in N₂ or Ar). The results confirm earlier reports that biomass char may be enriched in N during pyrolysis at 900 °C and above. The N-uptake involves re-capture of N-volatiles as well as uptake of N₂. During char oxidation, the captured N is partly oxidized to NO, resulting in increased NO formation. The NO yield from oxidation of beech wood char made in N₂ increases with pyrolysis temperature, and is about a factor of two higher at 1050 °C than the corresponding yield from chars made in Ar. The experiments with pure materials show that the lignin char has the strongest ability to form NO from uptake of N₂, while xylan char forms only small amounts of NO from N₂. Density Functional Theory (DFT) calculations on model chars have revealed a number of chemisorption sites for N₂, many of which are weakly bound and therefore expected to have a short half-life at the higher pyrolysis temperatures. However, the chemisorption of N₂ across a single ring of the armchair surface was found to have an activation energy of 344 ± 30 kJ mol⁻¹ and form a stable, exothermic product with cyano groups. This demonstrates that at least one channel exists for the high-temperature incorporation of N₂ into a char which could give rise to the observed increase in NO release in subsequent char oxidation.     

木质装饰板材贫氧条件下燃烧和热解特性研究

本文利用热重差热分析仪,在各种不同的氧气浓度下对落叶松、红木和红松样品进行实验。通过对TG、DTG和DTA曲线的分析,样品干燥基要经历两个失重过程,第一个失重过程主要是纤维素和半纤维素的热解,第二个失重过程主要是木质素的炭化分解和燃烧。在各氧气浓度条件下,热解失重的第一个阶段TG和DTG曲线差异很小;在各样品失重的第二个阶段,随着氧气浓度的增加,TG和DTG曲线左移,反应结束的温度明显降低。氧气能使木质素的炭化物氧化并进而可能使其着火燃烧,从而使反应进程加快。当氧气浓度大于6.32%时,各样品DTA曲线上均有两个明显放热峰,并且随着氧气浓度的增加,DTA曲线放热峰越尖锐,放热峰面积越大,说明氧气浓度越大,在两阶段失重过程中更多的挥发分物质和固体炭化物参与燃烧。     

Effect of pyrolysis conditions on the char gasification with mixtures of CO2 and H2O

Two kinds of char were prepared from a lignite by fast pyrolysis using a drop tube furnace and by slow pyrolysis using a fixed-bed furnace at the temperature of 1273 K. Scanning electron microscopy, X-ray diffractometry and the BET method were employed to characterize char properties. The chars were gasified with CO₂, H₂O and their mixtures in a thermogravimetric analyzer (TGA) system to investigate gasification kinetics and derive the rate expression. To validate the gasification rate equation derived from TGA, a fluidized-bed gasification experiment was also carried out. The results showed that both fast-char and slow-char were mainly composed of dense char. The shrinking core model was applicable to predict both gasification of fast-char and slow-char. It was found that the char gasification rate in the mixtures of CO₂ and H₂O was obviously lower than the sum of the two rates of the char independently reacting with CO₂ and H₂O but higher than the rate of each independent reaction, for both the fast-char gasification and slow-char gasification. Both of the results from the TGA and the fluidized-bed reactor showed that char-H₂O reaction was independent on char-CO₂ reaction, while char-CO₂ reaction was inhibited by char-H₂O reaction.     

金属盐对生物质热解特性影响试验研究

基于深入了解生物质热解行为的目的,在自行研制的热解机理试验台上系统研究了金属盐对生物质热解的影响规律。试验结果表明,钾离子对生物油中的一些大分子量组分发生重聚反应生成焦炭和小分子气体产物具有强烈的催化作用,从而降低了热解生物油产量而得到更多的焦炭和气体产物。相比钾离子而言,钙离子对焦炭生成的促进作用更为强烈;镁离子对白松热解的影响远没有钾离子和钙离子明显。     

Detailed and simplified kinetic models of n-dodecane oxidation: The role of fuel cracking in aliphatic hydrocarbon combustion

A detailed kinetic model is proposed for the combustion of normal alkanes up to n-dodecane above 850 K. The model was validated against experimental data, including fuel pyrolysis in plug flow and jet-stirred reactors, laminar flame speeds, and ignition delay times behind reflected shock waves, with n-dodecane being the emphasis. Analysis of the computational results reveal that for a wide range of combustion conditions, the kinetics of fuel cracking to form smaller molecular fragments is fast and may be decoupled from the oxidation kinetics of the fragments. Subsequently, a simplified model containing a minimal set of 4 species and 20 reaction steps was developed to predict the fuel pyrolysis rate and product distribution. Combined with the base C₁-C₄ model, the simplified model predicts fuel pyrolysis rate and product distribution, laminar flame speeds, and ignition delays as close as the detailed reaction model.     

Effect of phosphorus (P) on the structure and reactivity of biochars produced from the pyrolysis of acid-washed biomass loaded with P of various forms

This paper investigates the effect of phosphorus (P) on char structure and reactivity of char prepared from the fast pyrolysis of purposely-prepared P-loaded biomass samples at 1000 °C in absence of other inorganic species. Biomass was first acid-washed then loaded with P of three different occurrence forms (one organic P i.e. phytic acid, and two inorganic P i.e. orthophosphoric acid and polyphosphoric acid) at the same P content of 0.8 wt%. Experimental results show that both organic and inorganic P substantially increase char yields during pyrolysis from 6.2% for the biomass sample without P to 23.0–26.0% for P-loaded samples due to the enhanced crosslinking by P-containing structures in char, leading to increases in the char C and H contents and decrease in O content. The presence of P in biochars from fast pyrolysis of various P-loaded biomass samples plays important role in the evolution of char structure and intrinsic reactivity measured during low-temperature oxidation at 500 °C in air under chemical-reaction-controlled regime. After pyrolysis and subsequent char oxidation, all P in biomass either as organic or inorganic P are found to be present in forms of acid-insoluble organic structures. For char prepared from acid-washed wood, char reactivity increases with char conversion due to the increasing pore surface area at higher conversion. Comparatively, for char prepared from acid-washed wood loaded with various P at char conversion below 60%, the presence of P increases char intrinsic reactivity due to the enhanced crosslinking of reactive carbon structures and reduced condensation of char structures. However, at conversions above 60%, P-containing species in char lead to a significant decrease in char reactivity, due to the formation of abundant CO-P bonds, that is highly resistant to the oxidation in air, in the reacting chars.     

Measurement and kinetics of elemental and atomic potassium release from a burning biomass pellet

Combining polarizing-filtered planar laser-induced fluorescence (PLIF) with simultaneous laser absorption, quantitative laser-induced breakdown spectroscopy (LIBS) and two-color pyrometry, the potassium release during the combustion of biomass fuels (corn straw and poplar) has been investigated. The temporal release profiles of volatile atomic potassium and potassium compounds from a corn straw show a single peak. The woody biomass, poplar, produces a dual-maxima distribution for potassium and potassium compounds. For both biomass samples, the highest concentrations of released atomic potassium and potassium compounds occur in the devolatilization stage. The mass ratios between volatile atomic potassium and potassium compounds in the corn straw and poplar cases are 0.77% and 0.79%, respectively. These values agree well with chemical equilibrium predictions that 0.68% of total potassium will be in atomic form. A two-step kinetic model of potassium release has been developed, which gives better predictions during the devolatilization stage than the existing single-step model. Finally, a map of potassium transformation processes during combustion is developed. Starting with inorganic and organic potassium, there are eight proposed transformation pathways including five proposed release pathways that occur during the combustion. The pathways describe the transformation of potassium between the fuel volatile matter, char, and ash. Potassium release during the devolatilization stage is due to pyrolysis and evaporation; during the char burnout stage, potassium release is due to char oxidation and decomposition; and during the ash cooking stage, potassium release is caused by reactions between the ash and H₂O in the co-flow.     

Combustion chemistry probed by synchrotron VUV photoionization mass spectrometry

Combustion is directly related to energy conversion and the environment. Gas-phase chemical reactions such as thermal decomposition, oxidation and recombination play a critical role in combustion processes. Here we review six applications of synchrotron vacuum-ultraviolet (VUV) photoionization mass spectrometry (PIMS) in fundamental studies of combustion chemistry. These applications range from the use of flow reactors to probe elementary reaction kinetics, studies of pyrolysis in plug-flow reactors and oxidation in jet-stirred reactors, studies of spatial evolution of species concentrations in premixed and non-premixed flames, product distributions in pyrolysis of biomass, and analysis of polycyclic aromatic hydrocarbon (PAH) formation. These experiments provide valuable data for the development and validation of detailed chemical kinetic models. Furthermore, some additional potential applications are proposed.