Pyrolysis oil (PO) derived from biomass has the potential to serve as a renewable feedstock for future carbon black (CB) production. However, its composition is significantly different from the fossil feedstocks currently used for CB manufacturing, as it contains higher concentrations of oxygen and water that might influence the yield and nanostructure of CB. In this article, we examine how the water content in PO affects the production of CB at high-temperature pyrolysis (1400-1600 °C) in an electrically heated entrained flow reactor. The main objective was to investigate the influence of water content on the yield and quality of the CB produced from upgraded PO with varying inherent water contents (0-20 wt %). The experiments in this work were performed with model compounds to simulate an upgraded PO. The produced CB was characterized by using several analytical techniques, including elemental composition, powder X-ray diffraction, transmission electron microscopy, and nitrogen physisorption. The results show a clear correlation between the water content in the PO feedstock and the output of CB, showing a reduced yield of CB as the water content increases. These results highlight the crucial role of feedstock composition in making PO a viable renewable feedstock for CB production.

Oxy-fuel biomass combustion can facilitate carbon capture in heat and power plants and enable negative carbon dioxide (CO2) emissions. We demonstrate oxy-fuel combustion (OFC) of softwood powder in a 100-kW atmospheric down-fired pulverized combustor run at a global oxidizer-fuel equivalence ratio of around 1.25. The simulated oxidizer was varied between oxygen (O2)/CO2 mixtures of 23/77, 30/70, 40/60 and 54/46, and artificial air. The concentrations of the main gaseous potassium (K) species: atomic K, potassium hydroxide (KOH) and potassium chloride (KCl), were measured at two positions in the reactor core using photofragmentation tunable diode laser absorption spectroscopy (PF-TDLAS). Major species were quantified by TDLAS in the reactor core and with Fourier transform infrared spectroscopy and mass spectrometry at the exhaust. Flue gas particles were collected at the exhaust employing a low-pressure impactor and analyzed by X-ray powder diffraction and scanning electron microscopy. The measured individual K species concentrations in the reactor core agreed with predictions by thermodynamic equilibrium calculations (TEC) within one order of magnitude and the sum of K in the gas phase agreed within a factor of three for all cases. Atomic K was underpredicted, while the dominating KOH and KCl were slightly overpredicted. The ratios of measured to predicted total K were similar in artificial air and OFC, but the distributions of the individual species differed at the upper reactor position. The gaseous K species and fine particle concentrations in the flue gas were directly proportional to the O2 content in the oxidizer. The crystalline phase compositions of the coarse mode particles were rich in K- and calcium-containing species. The fine mode particles, which contained most of the K, consisted mainly of K2SO4 (94%) and K3Na(SO4)2, which is in excellent agreement with TECs of gas phase condensation. As supported by the solid phase analysis, complete sulfation of K species was achieved for all studied cases. A CO2 purity (dry) of up to 94% was achieved for OFC. 

The grate-kiln process for iron-ore pellet induration utilizes pulverized coal fired burners. In a developed infrastructure for H2, it might be desirable to heat the existing rotary kilns with renewably produced H2. Technical challenges of H2 heating of grate-kilns include high emissions of NOX and maintaining sufficient heat transfer to the pellet bed. This article examined cofiring (70% coal/30% H2) in 130 kW experiments using two different integrated burner concepts. Compared to pure coal combustion, cofiring creates a more intense, smaller flame with earlier ignition and less fluctuations. The process temperature and heat transfer are enhanced in the beginning of the kiln. The co-fired flames emit 32% and 78% less NOX emissions compared to pure coal and H2 combustion, respectively. We can affect the combustion behavior and NOX emissions by the burner design. H2/coal cofiring using integrated burners is probably an attractive solution for emission minimization in rotary kilns.

A machine vision driven sensor for estimating the instantaneous feeding rate of pelletized fuels was developed and tested experimentally in combustion and gasification processes. The feeding rate was determined from images of the pellets sliding on a transfer chute into the reactor. From the images the apparent area and velocity of the pellets were extracted. Area was determined by a segmentation model created using a machine learning framework and velocities by image registration of two subsequent images. The measured weight of the pelletized fuel passed through the feeding system was in good agreement with the weight estimated by the sensor. The observed variations in the fuel feeding correlated with the variations in the gaseous species concentrations measured in the reactor core and in the exhaust. Since the developed sensor measures the ingoing fuel feeding rate prior to the reactor, its signal could therefore help improve process control. 

The efficiency of the gasification process and product quality largely depend on the degree of fuel conversion. We present the real-time in-situ tunable diode laser measurements of main carbon and oxygen-containing species in the hot reactor core of a pilot-scale entrained flow biomass gasifier (EFG). The concentrations of CO, CO2, CH4, C2H2, H2O, soot, and gas temperature were measured during the air and oxygen-enriched gasification of stem wood at varying equivalence ratios. The experiments were made at the upper and lower optical ports inside a 4 m long, ceramic-lined, atmospheric EFG, allowing to access the degree of the fuel conversion inside the reactor. The exhaust composition was measured by micro-GC, FTIR, and low-pressure impactor. There was a good agreement between the data measured inside the reactor and at the exhaust for oxygen-enriched gasification implying that the chemical reactions are practically frozen downstream the optical ports. For air, the data indicated that the gasification reactions are still active at the measurement locations. Significant concentrations of C2H2, up to 5000 ppm, were found inside the reactor. 

Changed utilization of black liquor in the pulp and paper industry has the potential to offer simplified carbon capture and, thus, negative net emissions from these large point sources. This can be achieved either by adapting existing recovery boilers to oxyfuel combustion or by replacing them with black liquor gasification technology. In this work, the chemistry during black liquor conversion was therefore studied in detail under different atmospheres relevant for pyrolysis, gasification, and oxyfuel combustion. Experiments were performed using environmental scanning transmission electron microscopy (ESTEM) and thermogravimetric analysis (TGA), supported with thermodynamic equilibrium calculations (TECs) to understand and interpret the results. Black liquor conversion was found to be generally similar in air and oxyfuel atmospheres containing approximately 20-25 mol % oxygen. The results however indicated that there was a higher probability of forming carbonates in the melt at higher carbon dioxide (CO2) partial pressures, which in addition was found to be associated with potentially higher sulfur loss during black liquor conversion. Both of these characteristics can negatively affect the chemical recycling at the pulp mill by increasing the need for lime and makeup chemicals.

This work describes the morphological and material changes in the iron powder during four regeneration-combustion cycles. The regeneration in H2 and combustion in air experiments were made in a fluidized bed (FB) and an entrained flow reactor (EFR), respectively. The average size of the iron oxide particles more than doubled between the first and fourth combustion cycles, and many of the particles were hollow. The regeneration step did not change the size of the particles but increased their porosity. A mechanism is proposed that describes the formation of large-diameter hollow particles which increases as a function of the regeneration-combustion cycles. The observed increase in particle size and the change in particle morphology complicates the iron fuel concept, as it leads to a degradation of the structural stability of the particle with time.

Industrial thermal plasma torches can heat a gas up to 5000–20,000 K, i.e., well above the temperature needed to replace the heat generated from the combustion of traditional fossil fuels (e.g., coal, oil, and natural gas) in large-scale process industry furnaces producing construction materials (e.g., iron, steel, lime, and cement). However, there is a risk for significant NOx emissions when air or N2 are used as plasma-forming gas since the temperature somewhere in the furnace always will be higher compared to the threshold NOx formation temperature of ∼1800 K. Torch NOx forms inside the high temperature region of the plasma torch (>5000 K) when air is used as gas. Process NOx forms instead when the hot gas (when air or nitrogen is used as plasma forming gas) from the plasma torch mixes with process air downstream the torch. By analysing the complex chemistry of both the torch- and process NOx formation with thermodynamic equilibrium and one-dimensional chemical kinetic calculations it was shown that adding H2 to the plasma-forming N2 gas significantly reduces the NOx emissions with more than 90 %. Verifying experiments with air, pure N2, and mixtures of H2 and N2 as plasma-forming gas were performed in a laboratory scale insulated laboratory furnace with different pre-heating temperatures of process air (293, 673, and 1073 K) which the plasma gas mixes with downstream the torch. Depending on the pre-heating temperature the NOx emissions were between 12,000–14,000 mg NO2/MJfuel when air was used as plasma forming gas. Substantial NOx emission reduction occurs both when N2 replaces air, where the NOx emissions was in the span of 8000–11,500 mg NO2/MJfuel and furthermore when H2 was mixed into the N2 gas stream. For the highest degree of H2 mixing (28.6 vol-%), the NOx emissions were between 450–1700 mg NO2/MJfuel depending on the pre-heat temperature of the process air, i.e., a reduction of 88–96 % and 85–94 %, respectively when air or N2 was used as plasma forming gas. The measured NOx emissions are then of the same order of magnitude as would be expected from the combustion of traditional fuels (coal, oil, biomass and pure H2). Finally, by analysing the aerodynamics in an axisymmetric furnace with an experimentally validated computational fluid dynamics (CFD) model using reduced chemistry for the NOx formation (19 species and 70 reactions), further guidelines into the process of NOx reduction from thermal plasma torches are given. 

Environmental transmission electron microscopy (ETEM) can provide unique insights into nanocarbon oxidation processes through atomic resolution and real time imaging of materials at high temperatures in reactive atmospheres. However, the electron beam can also influence the reaction rates, and even alter the processes entirely, complicating the interpretation of the in situ observations. Many mechanisms have been proposed to account for the impact of the electron beam, predominantly involving ionization of the oxidative gases to form more reactive species. However, these mechanisms have not been critically evaluated and compared to predictions from theory. Here, we evaluate the impact of the electron beam both qualitatively (oxidation mode and spatial extent) and quantitatively (oxidation rates), using high resolution imaging and electron energy loss spectroscopy, at different electron energies and dose rates. We demonstrate that transient defects generated by elastic scattering, forming highly active sites for carbon abstraction by oxygen, is the main mechanism for the enhanced oxidation rates observed in situ. This is evident from an insensitivity to electron energy and saturation of the effects at high electron dose rates. To avoid undue influence of the electron beam in future ETEM studies, we therefore recommend conditions where the intrinsic oxidation dominates over the beam-enhanced oxidation (note that no conditions are completely “safe”) and extensive comparisons with other methods. © 2023 The Author(s)

The development of a model of carbon oxidation has engaged researchers for decades. Yet many outstanding questions remain due to the inability to experimentally study the details of the oxidation. Today, novel techniques such as environmental transmission electron microscopy (ETEM), allowing for in-situ nanoscale observations of the oxidation process, can help illuminate some of these questions. In this study of few layer graphene (FLG), multi-walled carbon nanotubes (MWCNTs), buckminsterfullerene (C60), and nanodiamonds (NDs) oxidizing in temperatures up to 1100 °C and we analyze the importance of nanostructure for the thermal stability of nanocarbons. The study was complemented with thermogravimetric analysis (TGA) and the experiments were in good agreement with oxidation rates increasing sharply with temperature and the thermal stability of the materials MWCNTs, FLG, C60 and NDs in descending order. Based on the direct nanoscale visualization obtained in the ETEM the materials can be divided into two overall categories: materials with low strain sp2-bonds (FLG and MWCNT); and materials with high strain sp2-bonds (C60) or sp3-bonds (NDs). For materials in the first category, it is possible to identify several different phenomena as their oxidation rate increases as a function of temperatures whereas materials in the second category appear to be more influenced by extrinsic factors such as the electron beam and by structural transformation upon heating. This study clearly shows the value of adding ETEM results to traditional TGA investigations since it gives both a complementary and more detailed information about the dynamic oxidation process.