Effect of cellulose–lignin interactions on char structural changes during fast pyrolysis at 100–350 °C

This study investigates the cellulose–lignin interactions during fast pyrolysis at 100–350 °C for better understanding fundamental pyrolysis mechanism of lignocellulosic biomass. The results show that co-pyrolysis of cellulose and lignin (with a mass ratio of 1:1) at temperatures < 300 °C leads to a char yield lower than the calculated char yield based on the addition of individual cellulose and lignin pyrolysis. The difference between the experimental and calculated char yields increases with temperature, from ～2% 150 °C to ～6% at 250 °C. Such differences in char yields provide direct evidences on the existence of cellulose–lignin interactions during co-pyrolysis of cellulose and lignin. At temperatures below 300 °C, the reductions in both lignin functional groups and sugar structures within the char indicate that co-pyrolysis of cellulose and lignin enhances the release of volatiles from both cellulose and lignin. Such an observation could be attributed to two possible reasons: (1) the stabilization of lignin-derived reactive species by cellulose-derived reaction intermediates as hydrogen donors, and (2) the thermal ejection of cellulose-derived species due to micro-explosion of liquid intermediates from lignin. In contrast, at temperatures ≥ 300 °C, co-pyrolysis of cellulose and lignin increases char yields, i.e., with the difference between the experimental and calculated char yields increasing from ～1% at 300 °C to ～8% at 350 °C. The results indicate that the cellulose-derived volatiles are difficult to diffuse through the lignin-derived liquid intermediates into the vapor phase, leading to increased char formation from co-pyrolysis of cellulose and lignin as temperature increases. Such an observation is further supported by the increased retention of cellulose functional groups in the char from co-pyrolysis of cellulose and lignin.     

Comparing reaction orders of anthracite chars with bituminous coal chars at high temperature oxidation conditions

The influence of concentration of oxygen on the oxidation rates of 5 anthracite chars is investigated at gas temperatures ranging from 1223 K to 1673 K. Reaction orders and kinetic parameters are determined with a multivariable optimization method in which modeled burnout profiles are fitted to experimental burnout profiles from a 4 m isothermal plug flow reactor operating at industrially realistic heating rates, i.e., 10⁴–10⁵ K/s. The determined reaction orders are compared to reaction orders of 10 bituminous coal chars investigated at similar conditions in a previous study. The results show that the optimized reaction order of the anthracite chars is zero, while the reaction order of the bituminous coal char is one. The difference in the reaction orders cannot be explained by using the two semi-global oxidation reactions: C(O) + O₂ → CO/CO₂ and C(O) → CO. However, by also considering 2C(O) → CO₂ + C as a possible reaction step, the reaction order difference between the anthracite chars and the bituminous coal chars can be explained. In addition, a first attempt to apply the same multivariable optimization method to determine the reaction order for a biomass char is presented.     

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.     

Pyrolysis study of poplar biomass by tunable synchrotron vacuum ultraviolet photoionization mass spectrometry

Pyrolysis is one of the most important methods to convert biomass into biofuel, which is a potential substitute for fossil fuel. The pyrolysis process of poplar biomass, a potential biofuel feedstock, has been studied with tunable synchrotron vacuum ultraviolet (SVUV) photoionization mass spectrometry (PIMS). The mass spectra at different photon energies, temperatures, and time-evolved profiles of selected species during poplar pyrolysis process were measured. Our results reveal that poplar is typical of hardwood according to its relative contents of three lignin monomeric precursors. As temperature increases from 300 to 700 °C, the overall intensities of pyrolysis products decrease due to the gas-phase cracking. Observed intensities of syringyl and guaiacyl subunits of lignin in poplar at low temperature present different trends: the intensities of syringyl subunits of lignin undergo an increase firstly and then a decrease, whereas those of guaiacyl subunits of lignin show decrease continuously. Time-dependent data demonstrate that hemicellulose pyrolysis is faster than lignin in poplar. This work reports a new application of SVUV PIMS in biomass pyrolysis, which performs very well in products analysis.     

CARS diagnostics of a CO2-laser pyrolytic experiment for the production of nanosized ceramic powders

Spatial distributions of rotational temperatures and molecular number densities of C₂H₂ and H₂ were measured with CARS during the production of ultrafine SiC powders in a laser pyrolytic process flame. By means of a CO₂ laser, the reaction gases SiH₄ and C₂H₂ (or alternatively C₂H₄) are converted into SiC and H₂. From the CARS measurements temperature gradients are determined between 8.8 × 10⁵ K/m and 1.6 × 10⁶ K/m with corresponding heating rates of 1.8 × 106 K/s and 1.3 × 10⁶ K/s. The CARS data also allow an estimation of the gas expansion behaviour in the reaction zone. Moreover, they show that diffusive velocity components of the hydrogen in the hot reaction zone do not exceed 0.4 m/s.     

Importance of flue gas cooling conditions in particulate matter formation during biomass combustion under conditions pertinent to pulverized fuel applications

Laboratory-scale experiments pertinent to pulverised fuel (PF) combustion are often carried out in drop-tube furnaces (DTFs) at air-fuel equivalence ratios and cooling rate for quenching flue gas that are much higher than those in PF boilers. This paper reports the effect of flue gas cooling conditions on the properties of PM with aerodynamic diameter of <10 µm (PM₁₀) from biomass combustion. This study considers four cooling rates (1000, 2000, 6000 and 20,000 °C/s) and two biomass feeding rates (0.05 and 0.25 g/min) that represents flue gases with significantly-different concentrations of inorganic vapours. The PSDs of PM₁₀ have a bimodal distribution with a fine mode within PM with aerodynamic diameter of <1 µm (PM₁) and a coarse mode within PM with aerodynamic diameter of 1–10 µm (PM_1–10). All experimental conditions produce PM₁₀ with similar PM₁ and PM_1–10 yields (～0.8 and ～1.6 mg/g_biomass, respectively) and similar coarse mode diameters (i.e. 6.863 µm). However, at a biomass feeding rate of 0.05 g/min, the fine mode diameter shifts from 0.022 to 0.077 µm when the cooling rate decreases from 20,000 to 1000 °C/s, indicating more profound heterogeneous condensation at a lower cooling rate. As the biomass feeding rate increases to 0.25 g/min, the fine mode diameter further shifts to 0.043 µm and at 20,000 °C/s but remained at 0.077 µm at 1000 °C/s though a clear shift of PSD to larger diameters is evident. These are attributed to enhanced heterogeneous condensation and coagulation of small particulates resulting from increased particle population density in hot flue gas. Chemical analyses show PM₁ contains dominantly volatile elements (i.e. Na, K and Cl) while PM_1–10 consists of mainly Ca. Similar trends are also observed for elemental PSDs and yields. It is also observed that slow cooling of hot flue gas leads to an increased yield of Cl in PM_1–10 due to enhanced chlorination of Ca species.     

Tunable electronic properties and carrier mobility in binary pnictogen nanosheets,PX (X = As,Sb, and Bi)

Catalytic graphitization of kraft lignin to nano-materials was investigated over four transitional metal catalysts (Ni, Cu, Fe, and Mo) through a thermal treatment process under an argon flow at 1000 °C. The catalytic thermal process was examined using thermal gravimetric analysis (TGA) and temperature-programmed decomposition (TPD) experiments. The crystal structure and morphology of the thermal-treated metal-lignin samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), and Raman spectroscopy. Catalytic graphitization of kraft lignin to nano-materials was investigated over four transitional metal catalysts (Ni, Cu, Fe, and Mo) through a catalytic thermal treatment process. It was observed that multi-layer graphene-encapsulated metal nanoparticles were the main products, beside along with some graphene sheets/flakes. The particle sizes and graphene shell layers were significantly affected by the promoted metals. BET surface areas of samples obtained from different metal precursors were in the range of 88–115 m²/g within the order of Ni-?>?Fe-?>?Mo-?>?Cu-. Thermal gravimetric analysis (TGA) and temperature-programmed decomposition (TPD) experimental results showed that adding transitional metals could promote the decomposition and carbonization of kraft lignin. The catalytic activity increased with an order of Mo?Cu?<?Ni?Fe. XRD results show that face-centered cubic (fcc) Cu crystals is formed in the thermal-treated Cu-lignin sample, fcc nickel phase for the Ni-lignin sample, β-Mo₂C hexagonal phase for the Mo-lignin sample and α-Fe, γ-iron, and cementite(Fe₃C) for the Fe-lignin sample. Average particle sizes of these crystal phases calculated using the Scherrer formula are 52.4 nm, 56.2 nm, 21.0 nm, 23.3 nm, 11.3 nm, and 32.8 nm for Ni, Cu, β-Mo₂C, α-Fe, γ-iron, and Fe₃C, respectively. Raman results prove that the graphitization activity of these four metals is in the order of Cu?<?Mo?<?Ni?<?Fe. Metal properties such as catalytic activity, carbon solubility, and tendency of metal carbide formation were related to the graphene-based structure formation during catalytic graphitization of kraft lignin process.

     

On the primary thermal decomposition pathways of hydroxycinnamic acids

Valorization of pyrolytic lignin to fuels and chemicals is still poorly understood due to its ill-defined structure and the complexity of the decomposition chemistry. To shed some light on the dominant reaction pathways of lignin thermolysis, novel experimental and first-principles based calculations of its building blocks have been carried out. Pyrolysis chemistry of hydroxycinnamic acids is investigated in this work using a unique Py-GC × GC-FID/TOF-MS coupled with a customized GC to detect water and gases, to gain an understanding of the role of the branching ratios in lignin and its linkages with hemicellulose. Mean residence times of cinnamic and ferulic acids were estimated to be 12 and 21 s at 573 K, based on time-resolved experiments. Cinnamic acid undergoes a CO₂ elimination reaction at temperatures higher than 873 K without an intermediate liquid phase. At temperatures as low as 573 K, –OH and –OCH₃ substituted cinnamic acids underwent decarboxylation despite bearing similar BDEs for Cβ–Cγ scission. At these temperatures, p-coumaric and ferulic acids were converted into 4-vinylphenol and 4-vinylguaiacol by 40 wt% and 30 wt%, respectively. On the other hand, sinapinic acid converted nearly by 80 wt% at temperatures below its boiling point of 676 K. In conjunction with novel quantum chemical calculations, it could be ruled out that decarboxylation was not occurring via concerted unimolecular reactions at low temperatures. Instead, water-catalyzed reactions of hydroxycinnamic acids seem to be the primary cause for the CO₂ elimination in the intermediate liquid phase via a 6-centered transition state.     

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.     

水热法碱活化生物质乙醇木质素的化学结构变化

为了提高生物质乙醇木质素的反应活性,采用水热法在四种不同碱性条件下对生物质乙醇木质素进行催化活化处理。运用傅里叶变换红外光谱(FTIR)、核磁共振氢谱(1H-NMR)、凝胶色谱(GPC)和有机元素分析手段研究了生物质乙醇木质素被四种碱(NaOH, KOH, K₂CO₃和Na₂CO₃)催化活化前后木质素的化学结构以及组分变化。FTIR结果表明生物质乙醇木质素碱经处理后,木质素的酚羟基特征吸收峰1 375 cm-1都有明显增大趋势,醚键振动吸收峰1 116 cm-1减弱,1 597和1 511 cm-1处苯环骨架振动吸收峰强度变化很小;1H-NMR分析结果表明酚羟基含量都有增大趋势,增加顺序为：KOH>NaOH>K₂CO₃>Na₂CO₃,其中KOH处理后的木质素酚羟基含量增加量为原木素的170%。这由于离子半径大的钾离子更容易与木质素β—O—4醚键上的氧形成加和物,进而发生醚键断裂反应,生成新的酚结构衍生物。GPC 表明生物质乙醇木质素碱处理后分子量分布向低分子区域扩展, 数均和重均分子量减小。元素分析结果显示木质素经过水热反应处理后,C含量都有所增加,而H和O含量则降低了,表明木质素经水热反应处理过程中有脱羧基作用,同时蛋白质的含量也有所降低,提高了木质素的纯度。这都有利于直接将木质素用于制备酚醛树脂胶黏剂。     

Sonocatalytic–Fenton reaction for enhanced OH radical generation and its application to lignin degradation

The present study demonstrated that the combined use of the sonocatalytic reaction (using ultrasound and titanium dioxide) and the Fenton reaction exhibited synergistically enhanced hydroxyl (OH) radical generation. Dihydroxybenzoic acid (DHBA) concentration as index of OH radical generation was 13 and 115 μM at 10 min in the sonocatalytic reaction and Fenton reaction, respectively. On the other hand, the DHBA concentration was 378 μM at 10 min in the sonocatalytic–Fenton reaction. The sonocatalytic–Fenton reaction was used for degradation of lignin. The lignin degradation ratio was 1.8%, 49.9%, and 60.0% at 180 min in the sonocatalytic reaction, Fenton reaction, and sonocatalytic–Fenton reaction, respectively. Moreover, the sonocatalytic–Fenton reaction was applied to pretreatment of lignocellulosic biomass to enhance subsequent enzymatic saccharification. The cellulose saccharification ratio was 11%, 14%, 16% and 25% at 360 min of pretreatment by control reaction, the sonocatalytic reaction, Fenton reaction, and sonocatalytic–Fenton reaction, respectively.     

水-四氢呋喃混合溶剂中硫酸氢钠催化生物质转化制备5-羟甲基糠醛及糠醛

报道了在水-四氢呋喃组成的混合溶剂中,采用硫酸氢钠催化各种生物质原料(玉米芯、玉米秸秆、麦秆、稻秆和甘蔗渣)制备重要的生物质基平台化学品5-羟甲基糠醛和糠醛的研究. 考察了反应温度(160～200 oC)、反应时间(30～120 min)、水与四氢呋喃的溶剂比例(1:1～1:10)和原料质量分数(2.4wt%～11.1wt%)等反应工艺的影响.在优化的工艺条件下(190 oC, 90 min, 10:1 THF:H₂O),转化玉米芯得到了47mol%的HMF和56mol%的糠醛. 此外,原料中的木质素也被有效地转化为有机溶木质素.     

Rapid initiation of reactions in Al/Ni multilayers with nanoscale layering

Research into nanoenergetic materials is enabling new capabilities for controlling exothermic reaction rates and energy output, as well as new methods for integrating these materials with conventional electronics fabrication techniques. Many reactions produce primarily heat, and in some cases it is desirable to increase the rate of heat release beyond what is typically observed. Here we investigate the Al-Ni intermetallic reaction, which normally propagates across films or foils at rates lower than 10 m/s. However, models and experiments indicate that local heating rates can be very high (10⁷ K/s), and uniform heating of such a multilayer film can lead to a rapid, thermally explosive type of reaction. With the hopes of using a device to transduce electrical energy to kinetic energy of a flyer plate in the timescale of 100's of nanoseconds, we have incorporated a Ni/Al nanolayer film that locally heats upon application of a large electrical current. We observed flyer plate velocities in the 2-6 km/s range, corresponding to 4-36 kJ/g in terms of specific kinetic energy. Several samples containing Ni/Al films with different bilayer thicknesses were tested, and many produced additional kinetic energy in the 1.1-2.3 kJ/g range, as would be expected from the Ni-Al intermetallic reaction. These results provide evidence that nanoscale Ni/Al layers reacted in the timescale necessary to contribute to device output.     

Intensification of delignification of Tectona grandis saw dust as sustainable biomass using acoustic cavitational devices

Delignification of sawdust was studied using ultrasound assisted alkali peroxide approach using longitudinal horn for the first time and the efficacy compared with more commonly used configurations of ultrasonic reactors. Comparison with the conventional approach based on stirring has also been presented to establish the process intensification benefits. Effect of different operating parameters such as sodium carbonate concentration (0.1, 0.15, 0.2, 0.25 M), hydrogen peroxide concentration (0.2, 0.4, 0.6, 0.8, 1 M) and biomass loading (2, 4, 6, 8, 10 wt%), on the efficacy of lignin extraction has been investigated for different ultrasonic reactors. The optimum conditions for probe type ultrasonic horn were established as 150 W, 50% duty cycle and 80% amplitude with optimum process conditions as Na₂CO₃ concentration as 0.2 M, H₂O₂ concentration as 1 M, biomass loading of 10 wt% and operating time of 70 min. Longitudinal horn resulted in best efficacy (both in terms of yield and energy requirements) followed by ultrasonic horn and ultrasonic bath whereas the conventional approach was least effective. The obtained lignin was also analyzed using different characterization techniques. The presence of peaks at wavelength range of 875–817, 1123–1110, and at 1599 cm⁻¹ for the extracted sample confirmed the presence of lignin. Increase in the crystallinity index of the processed sample (maximum for longitudinal horn) also confirmed the lignin removal as lignin is amorphous in nature. Overall it has been concluded that ultrasound can be effectively used for delignification with longitudinal horn as best configuration.     

Effect on thermoluminescence parameters of biotite mineral due to thermal quenching

The Thermally Stimulated Luminescence (TSL) at room temperature X-ray irradiated natural biotite in form of micro-grain powder was studied under various heating rates. TSL peaks showed at temperatures 393 K, 399.6 K, 403.5 K, 404.5 K, 406.9 K at their respective heating rates 2 K/s, 4 K/s, 6 K/s, 8 K/s and 10 K/s. The effect of thermal quenching on thermoluminescence parameters such as peak maximum temperature, peak area, FWHM, geometrical symmetry factor, the activation energy were investigated. From the symmetry factor it is clear that the TL glow curve follows the first order kinetics for the lowest heating rate, but as the heating rate increases it defers from the first order. The activation energies for each heating rates were calculated by using Chen peak shape methods for general order kinetics and found to be decreased for higher heating rates. When activation energy is calculated by variable heating rate method it is observed that the method overestimated the value of activation energy and pre-exponential frequency factor significantly due to thermal quenching.     

Role of Structural Stresses in the Thermodestruction of Supercoiled Cellulose Macromolecules after Nitration

Thermogravimetry is used to study the thermodestruction of nitrocellulose (NC) with various nitrogen contents at various heating rates. At high degrees of nitration and high heating rates of the sample, the reaction occurs in an explosion mode with a threshold of its weight loss depending on the temperature. To explain this behavior, it is assumed that the nitration of cellulose gives rise to structural stresses, which weaken the covalent bonds in it by ～37 kJ/mol (at a nitrogen content of ～13%). This process apparently involves two different mechanisms of weight loss during heating: (a) conventional thermal destruction of NC macromolecules through the rupture of covalent bonds (with k₀ = 10¹³ s^?1, E = 150.2 kJ/mol, and n = 1) at heating rates of up to 10 K/min and nitrogen content in NC of up to 9%; (b) Zhurkov’s thermofluctuational mechanism of the destruction of strained macromolecules, characterized by a sharp (threshold) dependence of the weight loss on the heating rate, which is operative at heating rates above ～4 K/min and high (>13%) nitrogen contents and at 20 K/min and a low (～9%) nitrogen content. Under conditions of rapid heating, ～10–20 K/min, the work done by stressed states to overcome the potential barrier to the rupture of covalent bonds causes an increase in the decomposition rate by a factor of 2000. The observed threshold pattern of weight loss during the thermodestruction of NC explains the long-known critical dependence of the properties of NC used to manufacture propellants on small changes in the nitrogen content.     

Polycyclic aromatic hydrocarbons from the co-pyrolysis of catechol and 1,3-butadiene

In order to better understand the reactions responsible for the formation and growth of polycyclic aromatic hydrocarbons (PAH) from solid fuels, we have performed pyrolysis experiments in an isothermal laminar-flow reactor (at temperatures of 600-1000 °C and a fixed residence time of 0.3 s) with catechol, a model fuel representative of the aromatic moieties in coal and biomass fuels; 1,3-butadiene, a major product of biomass pyrolysis; and with catechol and 1,3-butadiene together (in a catechol-to-1,3-butadiene molar ratio of 0.83). No PAH of ?3 rings are produced at temperatures <700 °C, but PAH production becomes significant at temperatures ?800 °C. Analysis of the higher-temperature reaction products by high-pressure liquid chromatography with diode-array ultraviolet-visible absorbance detection has led to the identification of over 100 PAH (ranging in size to 10 fused aromatic rings) - 47 of which have never before been reported as products of any phenol-type fuel. Quantification of the product yields shows that a much higher percentage of fed carbon is converted to PAH in the catechol-only pyrolysis experiments than in the 1,3-butadiene-only pyrolysis experiments - a result attributable to catechol’s relatively labile O-H bond and capacity for generating oxygen-containing radicals, which accelerate both fuel conversion and the pyrolysis reactions leading to 1- and 2-ring aromatics and PAH. When the two fuels are co-pyrolyzed, the percentage of the total fed carbon converting to PAH is more than two times higher than the amount calculated for the hypothetical case of the two fuels together behaving as a linear combination of the two fuels individually. This elevated production of PAH from the co-pyrolysis experiments reflects not only the reaction-accelerating role of the oxygen-containing radicals but also the efficacy, as growth agents, of the C₂ - and especially the C₄ - species abundantly present in the catechol/1,3-butadiene co-pyrolysis environment.     

Thermally stimulated luminescence of polycrystalline CdWO4 at low temperatures

CdWO₄ scintillator powders were produced via solid state reaction and investigated by thermally stimulated luminescence technique after UV irradiation. Under a heating rate of 0.1 K/s, the glow curve presented a superposition of peaks at low temperatures. Four peaks were identified below 80 K by partial heating method and their kinetic parameters were evaluated from the initial rise analysis. Measurements were also performed for heating rates of 0.05 and 0.2 K/s and allowed the kinetic study by peak position method. Surface effects due to the polycrystalline feature of the sample were investigated by comparing the results with those reported for CdWO₄ single crystals.     

Acetaldehyde adsorption and catalytic decomposition on Pd(1 1 0) and the dissolution of carbon

The reaction of acetaldehyde with the Pd(1 1 0) surface has been studied using a molecular beam reactor, TPD and LEED. Below 270 K acetaldehyde sticks to the surface with a high initial probability (∼0.8), but no gas phase products evolve. When the reaction is run at >270 K, hydrogen evolves into the gas phase early in the reaction together with methane in a non-steady-state fashion, but above 300 K there is a very efficient steady-state catalytic reaction at the surface; this reaction is the decarbonylation of acetaldehyde to produce methane and carbon monoxide in the gas phase. This behaviour continues up to about 400 K. However, when acetaldehyde is dosed at 423 K, the reaction rate slowly evolves through a maximum to a very low catalytic rate. Upon carrying out reactor experiments at 473 K and above, the reaction mechanism changes to total dehydrogenation, and CO and H₂ are produced at high steady-state rate, not withstanding the fact that carbon is continually being deposited onto the surface. This carbon does not appear to affect the reaction, which takes place on a surface with a c(2 × 2)-C layer present, since the extra carbon is lost from the reaction zone by diffusion into the bulk of the crystal.