Study on the nitrogen transformation during the primary pyrolysis of sewage sludge by Py-GC/MS and Py-FTIR

The nitrogen transformation with attention to the intermediates and NO_x precursors has been investigated during the primary pyrolysis of sewage sludge by using Pyrolyzer-gas chromatography/mass spectrometry (Py-GC/MS) and Pyrolyzer-Fourier transform infrared spectrometry (Py-FTIR). A three-stage process of nitrogen transformation during the sewage sludge pyrolysis was suggested. The decomposition of labile protein and inorganic ammonium salt mainly occurred in the first stage (<300 °C), giving rise to a small amount of NH₃. In the second stage (300–600 °C), the macromolecular protein firstly cracked into small molecular amine compounds, and then went through deamination process, contributed to a large release of NH₃. In the third stage (600–900 °C), the amine compounds converted into nitriles, and generated a large amount of HCN, while the formation of NH₃ slowed down accordingly.     

Distribution of Nitrogen Species During Vitrinite Pyrolysis and Gasification

The formation of HCN and NH₃ during pyrolysis in Ar and gasification in CO₂ and steam/Ar was investigated. Vitrinites were separated and purified from different rank coal from lignite to anthracite. Pyrolysis and gasification were carried out in the drop-tube/fixed-bed reactor at temperatures of 600–900°C. Results showed that with increase of reaction temperature the yield of HCN increased significantly during pyrolysis and gasification. Decrease of coal rank also increased the yield of HCN. Vitrinite from lower rank of coal with high volatile content released more HCN. The yield of NH₃ was the highest at 800°C during pyrolysis and gasification. And the yield of NH₃ from gasification in steam/Ar was far higher than that from gasification in CO₂, where the hydrogen radicals play a key role. Nitrogen retained in char was also investigated. The yield of char-N decreased with an increase of pyrolysis temperature. Vitrinite from lower rank coal had lower yield of char-N than that from the high rank coal.     

Formation mechanism of HCN and NH3 during indole pyrolysis: A theoretical DFT study

Coal is a major contributor to the global emission of nitrogen oxides. The NO_x formation during coal utilisation typically derives from thermal decomposition of N-containing compounds pyrrole, which usually combines with an aromatic ring in the form of indole. NH₃ and HCN are common precursors of NO_x from the decomposition of N-containing compounds. In this study, possible pathways of indole pyrolysis to form HCN and NH₃ are investigated using the density functional theory (DFT) method. Calculation results indicate that indole pyrolysis has two type of possible initial reactions, which are internal hydrogen transfer and hydrogen homolysis reaction, respectively. The initial reaction mode of indole has a great impact on the subsequent pyrolysis pathway. Additionally, it is shown that indole can produce two nitrogen-containing products, i.e. HCN and NH₃. Five pathways will result in the formation of HCN (path-1, path-3, path-a, path-b, path-c), and another two pathways will lead to the NH₃ (path-2, path-4). Furthermore, among all the reaction mechanisms of indole pyrolysis, the path-1 is the optimal reaction pathway. During which, indole is converted to a diradical intermediate, then the intermediate undergoes a synergy ring-opening transition state to form a new intermediate. Afterwards, the new intermediate decomposes into CN by homolysis of the C–C bond.     

Mechanism study of nitric oxide reduction by light gases from typical Chinese coals

Coal devolatilization plays an important role in NO formation and reduction. In this study, the coal pyrolysis experiment was performed in an entrained flow reactor to obtain the light gas release characteristics. Six typical Chinese coals with volatile content ranged from 8.8% to 38.3% were studied. The pyrolysis temperature was in the range from 600 to 1200 °C. A significant rank dependence of HCN, CO and C₂H₂/C₂H₄/C₂H₆ was observed and their release for high volatile coals was higher than that for low volatile coals. The HCN–N/NH₃–N ratio ranged from 0.00 to 0.66 for anthracite coals and ranged from 1.63 to 3.90 for high volatile coals. Based on the experimental results, the effect of coal pyrolysis gas on NO reduction in a plug flow reactor at reducing atmosphere was kinetically calculated. The optimal excess air ratio(α_opt) corresponding to the maximum NO removal efficiency decreased with an increase in reduction temperature. For the light gas from the HL coal pyrolyzed at 800 °C, the α_opt decreased from 0.73 to 0.17 when the reduction temperature increased from 927 to 1327 °C. The rate of production analysis indicated that NO removal efficiency was determined by 3 competing reaction paths: NO reduction, NO formation and oxygen consumption by combustible species.     

NOx formation and reduction mechanisms in staged O2/CO2 combustion

The purpose of this study was to investigate the NO_x formation and reduction mechanisms in staged O₂/CO₂ combustion and in air combustion. A flat CH₄ flame doped with NH₃ for fuel-N was formed over the honeycomb, and NO_x formation characteristics were investigated. In addition, chemiluminescence of OH^* distribution was measured, and CHEMKIN-PRO was used to investigate the detailed NO_x reduction mechanism. In general, the NO_x conversion ratio decreases with decreasing primary O₂/CH₄ ratio, whereas NH₃ and HCN, which are easily converted to NO_x in the presence of O₂, increases rapidly. Therefore, a suitable primary O₂/CH₄ ratio exists in the staged combustion. Our experiments showed the primary O₂/CH₄ ratio, which gave the minimum fixed nitrogen compounds in O₂/CO₂ combustion, was lower than in air combustion. The NO_x conversion ratio in O₂/CO₂ combustion was lower than in air combustion by 40% in suitable staged combustion. This could be explained by high CO₂ concentrations in the O₂/CO₂ combustion. It was shown that abundant OH radicals were formed in O₂/CO₂ combustion through the CO₂ + H → CO + OH, experimentally and numerically. OH radicals produced H and O radicals through H₂ + OH → H + H₂O and O₂ + H → OH + O, because a mass of hydrogen source exists in the CH₄ flame. O and OH radicals formed in the fuel-rich region enhanced the oxidation of NH₃ and HCN. NO_x formed by the oxidation of NH₃ and HCN was converted to N₂ because the oxidation occurred in the fuel-rich region where the NO_x reduction effect was high. In fact, the oxidation of NH₃ and HCN in the fuel-rich region was preferable to remaining NH₃ and HCN before secondary O₂ injection in the staged combustion. A significant reduction in NO_x emission could be achieved by staged combustion in O₂/CO₂ combustion.     

Effects of Fe2O3 on pyrolysis characteristics of soybean protein and release of NOx precursors

The effects of ferric oxide (Fe₂O₃) on the pyrolysis characteristics of soybean protein and the release of precursors to nitrogen oxides (NOx) were studied using thermogravimetry and mass spectrometry. The results show that, as the content of Fe₂O₃ increases, there is no major difference between initial and peak temperatures of protein pyrolysis samples. Moreover, between the temperature range of 204 and 550°C where weight loss mainly occurs, total weight-loss rate decreases before increasing, with obvious weight loss occurring around the temperature of 650°C. Fe₂O₃ displays both inhibiting and promoting effects on the precipitation of nitrogen-containing gases such as ammonia (NH₃), hydrogen cyanide (HCN), isocyanic acid (HNCO), and acetonitrile (CH₃CN), with the inhibition effect prevailing over promotion effect on the whole.     

Fuel gas production from dusty tar pyrolysis

Dusty tar is an undesired product obtained from a coal pyrolysis/combustion system. Thermal conversion of dusty tar into fuel gas was studied with a fixed-bed reactor. It is found that C₂-C₅ hydrocarbons are mainly derived from the cracking of long-chain aliphatics, while CH₄ from the decomposition of long-chain aliphatics and alkyl-substituted aromatic chemicals. The yield of the gas product increases monotonously, but the heating value of gas gradually decreases as temperature increases from 400 to 950°C. Decomposition of chemicals with a boiling point over 360°C contributes to 50–90% C₁-C₅ hydrocarbons and CO_x when pyrolysis temperature is lower than 600°C.     

Nitrogen oxides reduction by liquid petroleum gas over Co–Ce–Ti catalysts in a simulated rotary reactor

Hydrocarbons could be used as the reductant for elimination of NO_x emissions. Liquid petroleum gas, with higher carbon hydrocarbons and cheaper costs, may be of practical value as reducing agents. Due to the consumption of hydrocarbons by oxygen, the NO_x reduction efficiency is significantly inhibited by oxygen in the flue gas. In this research, a novel rotary reactor, realizing the alternating cycle of adsorption zone and reduction zone, was proposed to overcome this negative effect. Co–Ce–Ti mixed oxide catalysts synthesized by a sol–gel method were tested in a simulated rotary reactor for NO_x removal by liquid petroleum gas and characterized by SEM, BET, XRD and XPS. The results showed that catalysts exhibited better NO conversion efficiency at higher temperature but were highly susceptible to oxygen. Catalysts achieved nearly full removal of NO_x from flue gas at 300 °C in a simulated rotary reactor, and 300 °C is considered to be the most optimum temperature with lower energy consumption and excellent flue gas purification performance.     

Hydrogen-rich syngas produced from the co-pyrolysis of municipal solid waste and wheat straw

The co-thermochemical conversion of Municipal Solid Waste (MSW) and biomass is a new environmental technology and can produce hydrogen-rich syngas. This study investigated the co-pyrolysis of MSW and wheat straw, using a drop-tube furnace experiment. Using a temperature range of 500 °C–1000 °C, the study assessed pyrolysis gas yield, product distribution, gas low heating value, and carbon conversion of co-pyrolysis MSW with different amounts of wheat straw. Adding wheat straw only slightly increases the gas yield and carbon conversion, but improved the carbon monoxide and carbon dioxide in the syngas. At an experimental temperature below 700 °C, adding wheat straw promoted the cracking reaction of hydrocarbon gas, generated by the pyrolysis of MSW. At a temperature of 600 °C, adding 25% wheat straw improved carbon conversion in the blended sample. This study provides a basis for the application of MSW and WS thermo-chemical conversion.     

Theoretical study of the effect of hydrogen radicals on the formation of HCN from pyrrole pyrolysis

As a typical fossil fuel, coal is a major contributor to nitrogen oxide (NO_x) pollution. The detailed mechanism of NO_x generation from coal pyrolysis need to be clarified. Within this research, we used density functional theory (DFT) to investigate the formation mechanism of HCN as a NO_x precursor during pyrolysis of pyrrole in the presence of hydrogen (H) radicals. Firstly, three different reaction positions for hydrogen radical attacking were compared. It was identified that hydrogen radical initially reacts with pyrrole at the location adjacent to N through a single elementary reaction step with an activation energy of 77.12 kJ/mol. Additionally, to examine the role of hydrogen radical in the pyrrole pyrolysis to form HCN, 12 subsequent reaction pathways were theoretically investigated. It was found that one of the pathway (Pathway a-4) involving hydrogen transfer followed by carbon-carbon cleavage processes is the route with the lowest energy barrier of all of the mechanisms reported, thus it plays an important role in the formation of HCN from the pyrrolic components of coal. These results further indicated that the hydrogen radicals significantly reduce the energy barrier of the pyrrole pyrolysis.     

Influence of pyrolysis conditions on nitrogen speciation in a biochar ‘preparation-application’ process

To investigate biochar nitrogen conversion in a ‘preparation-application’ system and the response of its transportation in plants, biochar samples were produced from rice straw at different pyrolysis temperatures (400 °C and 800 °C) and atmospheres (N₂ and CO₂). Subsequently, biochar was synthesized under CO₂ atmosphere to explore its nitrogen nutrient characteristics and further improve the chemical and physical properties of soil. Nitrogen speciation of the biochar and plant root samples were evaluated by X-ray photoelectron spectroscopy. Research has shown that organic nitrogen such as protein-N, free amino acid-N, and alkaloid-N in rice straw is converted into organic (nitrile-N, pyridine-N, amino-N, and pyrrole-N) and inorganic (NH₄⁺-N, NO₂^?-N, and NO₃^?-N) species in biochar during the biomass pyrolysis process. In turn, biochar nitrogen is transported to plants as protein-N, free amino acid-N, alkaloid-N, NH₄⁺-N, NO₂^?-N, and NO₃^?-N. Comprehensive consideration of the biochar quality and preparation cost indicated the lower pyrolysis temperature (400 °C) under CO₂ atmosphere as the best conditions for biochar preparation.     

Chemical looping ammonia synthesis at atmospheric pressure benefiting from synergistic effect of Mn- and Fe-based nitrogen carriers

Chemical looping ammonia synthesis (CLAS) based on the synergistic effect of Mn- and Fe-based nitrogen carriers, is proposed as an environmental-friendly NH₃ production alternative. This approach has superiority of intermittent and simplified operation, especially in locations where implementing sophisticated Haber-Bosch process is challenging. This work revealed that nitrogen carriers could yield up to 166.3 μmol NH₃ per gram of Mn after conversion with H₂ at 600 °C. NH₃ production capacity was deteriorated by sintering and ammonia decomposition at high temperature. Pores resulting from the elimination of molecular nitrogen by bursting out of the surface were found at 700 °C, which could be explained by the parasitic conversion of N to N₂ rather than NH_3. N-carrier with 50% Al₂O₃ was the most interesting candidate with outstanding conversion ratio of lattice nitrogen. Generally, simple design, operational security and low cost make CLAS possible to scale up for industrial usage in the future.     

Optimization of the operating conditions for steam reforming of slow pyrolysis oil over an activated biochar-supported Ni–Co catalyst

Highly performing activated biochar-based catalysts were produced for steam reforming of slow pyrolysis oil. The raw biochar obtained from the slow pyrolysis step was physically activated with CO₂ at 700 °C and 1.0 MPa and then employed as support. Preliminary tests on steam reforming of acetic acid at 600 °C showed that using activated biochar-supported catalysts containing 10 wt % Ni and 7 wt % Co led to a conversion above 90% with a relatively slow deactivation rate. When a representative organic model compounds mixture was used as feed, relatively fast deactivation of the catalyst was observed, probably due to the adsorption of heavy organic compounds, which could subsequently react to form not easily desorbable reaction intermediates. However, the dual Ni–Co catalysts exhibited a good performance during the steam reforming of a real slow pyrolysis oil at 750 °C, showing long stability and a constant carbon conversion of 65%.     

Cobalt metal–organic framework derived cobalt–nitrogen–carbon material for overall water splitting and supercapacitor

Metal-organic frameworks (MOFs) have been the subject of intensive structural tuning via methods like pyrolysis for superior performance in electrocatalytic oxygen and hydrogen evolution processes (OER and HER) and supercapacitors. Here, a Co-MOF based on 2-methylimidazole was synthesized using a precipitation approach, and its electrochemical characteristics were tuned via pyrolysis at different temperatures, including 600, 700, and 800 °C. Characterization findings corroborated the formation of Co–N–C moieties from Co-MOF, and XPS analyses indicated that 700 °C was the optimal temperature for achieving a high density of Co–N–C moieties. The optimized Co-MOF-700 sample displayed remarkable HER and OER performance in terms of lower overpotentials of 75 mV and 370 mV as well as small Tafel slopes of 118 mV/dec and 79 mV/dec, respectively. Furthermore, at a current density of 1 A/g, the Co-MOF-700 sample had a specific capacitance of 210 F/g. The enhanced electrochemical properties of Co-MOF-700C as compared to other samples can be attributed to the availability of a high density of Co–N–C sites for catalytic reaction and its porous architecture. This study will expand the knowledge of how compositional and morphological changes in MOFs affect their utility in energy conversion and storage applications.     

HCl emission and capture characteristics during PVC and food waste combustion in CO2/O2 atmosphere

The emission and capture characteristics of HCl during PVC and food waste combustion in CO₂/O₂ atmospheres were studied. Replacement of N₂ by CO₂ decreased the dechlorination rate of limestone at 600–700 °C but increased dechlorination rate at 800–900 °C. The chlorine species and temperature highly influenced the HCl emission and capture efficiency of limestone for HCl in CO₂/O₂ atmospheres. Compared with inorganic chloride in food waste, organic chlorine in PVC had much greater Cl–HCl conversion percent (75.0–93.9%), and higher dechlorination rate (20.4–44.9%) with 10% limestone in 80CO₂/20O₂ atmosphere. The increment of O₂ partial pressure in CO₂/O₂ atmospheres promoted Cl–HCl conversion. Sulphur in the fuel suppressed the formation of HCl but decreased the dechlorination rate at 700–1000 °C in CO₂/O₂ atmospheres. The dechlorination efficiency of limestone was better than magnesium based additive and could be improved by modification with NaOH. This research helps control HCl and manages MSW oxy-fuel incineration.     

Formation of HNCO, HCN, and NH3 from the pyrolysis of bark and nitrogen-containing model compounds

Bark pellets have been pyrolyzed in a fluidized bed reactor at temperatures between 700 and 1000 °C. Identified nitrogen-containing species were hydrogen cyanide (HCN), ammonia (NH₃), and isocyanic acid (HNCO). Quantification of HCN and to some extent of NH₃ was unreliable at 700 and 800 °C due to low concentrations. HNCO could not be quantified with any accuracy at any temperature for bark, due to the low concentrations found. Since most of the nitrogen in biomass is bound in proteins, various protein-rich model compounds were pyrolyzed with the aim of finding features that are protein-specific, making conclusions regarding the model compounds applicable for biomass fuels in general. The model compounds used were a whey protein isolate, soya beans, yellow peas, and shea nut meal. The split between HCN and NH₃ depends on the compound and temperature. It was found that the HCN/NH₃ ratio is very sensitive to temperature and increases with increasing temperature for all compounds, including bark. Comparing the ratio for the different compounds at a fixed temperature, the ratio was found to decrease with decreasing release of volatile nitrogen. The temperature dependence implies that heating rate and thereby particle size affect the split between HCN and NH₃. For whey, soya beans, and yellow peas, HNCO was also quantified. It is suggested that most HCN and HNCO are produced from cracking of cyclic amides formed as primary pyrolysis products. The dependence of the HNCO/HCN ratio on the compound is fairly small, but the temperature dependence of the ratio is substantial, decreasing with increasing temperature. The release of nitrogen-containing species does not seem to be greatly affected by the other constituents of the fuel, and proteins appear to be suitable model compounds for the nitrogen in biomass.     

Catalytic performance of modified kaolinite in pyrolysis of benzyl phenyl ether: A model compound of low rank coal

A serials of modified kaolinites were prepared by calcination and further acid treatment and characterized by in-situ XRD, N₂ adsorption, NH₃-TPD, Py-IR and ²⁷Al MAS-NMR. And their catalytic performance in pyrolysis of methanol/benzyl phenyl ether (MeOH-BPE), a model compound of low-rank coal, were investigated at 400 °C in a fixed-bed reactor to explore the correlation between the structure of modified samples and their catalytic performances. The results show that calcination temperature above 500 °C causes the collapse of kaolinite structure. Further acid leaching facilitates the formation of micropores and mesopores. The calcination of kaolinite leads to the transformation of six-coordinate Al atoms (Al^VI) into four and five coordinate species (Al^IV and Al^V), while the subsequent acid treatment increases the contents of Al^IV and Al^VI and removes Al^V. Total acid sites exhibit a first increase and then decrease tendency with the raising calcination temperature. In the presence of the modified kaolinites, BPE conversion significantly enhances and reaches the highest value of 91.41% over K-A-700 prepared by calcination at 700 °C of kaolinite and further acid leaching. Besides, the maximum content of phenol and toluene is also achieved due to the highest acid sites and Al^IV content of K-A-700, which favors the generation of ·H, thus resulting in an obvious inhibition of bibenzyl formation but a significant increase of 2-benzylphenol. In-situ pyrolysis by time-of-flight mass spectrometry suggests that the cleavage of C_al-O bond of BPE to form phenol radicals and benzyl radicals is the primary way, while insufficient ·H results in the formation of dominant product of 2-benzylphenol.     

The fate of char-N at pulverized coal conditions

The fate of char-N (nitrogen removed from the coal matrix during char oxidation) has been widely studied at fluidized bed conditions. This work extends the study of char-N to pulverized coal conditions. Coal chars from five parent coals were prepared and burned in a laboratory-scale pulverized coal combustor in experiments designed to identify the parameters controlling the fate of char-N. The chars were burned with natural gas (to simulate volatiles combustion) in both air and in a nitrogen-free oxidant composed of Ar, CO₂, and O₂. In some experiments, the char flames were doped with various levels of NO or NH₃ to simulate formation of NO_x from volatile-N (nitrogen removed during coal devolatilization). The conversion of char-N to NO_x in chars burned in the nitrogen-free oxidant was 50-60% for lignites and 40-50% for bituminous coals. In char flames doped with NO_x, the apparent conversion of char-N to NO_x (computed using the NO_x measurements made before and after the addition of char to the system) decreased significantly as the level of NO_x doping increased. With 900 ppm NO_x present before the addition of char, apparent conversion of char-N to NO_x was close to 0% for most chars. While there is no clear correlation between nitrogen content of the char and char-N to NO_x conversion at any level of NO_x in the flame, the degree of char burnout within a given family of chars does play a role. Increasing the concentration of O₂ in the system in both air and nitrogen-free oxidant experiments increased the conversion of char-N to NO_x. The effects of temperature on NO_x emissions were different at low (0 ppm) and high (900 ppm) levels of NO_x present in the flame before char addition.     

The effect of powder preparation method on the artificial photosynthesis activities of neodymium doped titania powders

The effects of nanostructure on the artificial photosynthesis activities of undoped and Nd doped titania (TiO₂) powders prepared by three different chemical co-precipitation methods were investigated. Substitutional/interstitial N and S doping was observed in powders due to the presence of high concentrations of HNO₃ (NP) and H₂SO₄ (SP) in the powder preparation media, respectively. Nd, N and S doping caused anatase/rutile phase transformation inhibition and crystallite size reduction in the nanostructure. Light absorption was significantly enhanced by Nd doping and the residual SO₄^2?/NO_x species in the nanostructure. Photocatalytic hydrogen production activity of Nd doped NP powder was 4 times greater than undoped NP powder at 700 °C and had a high purity (CO:H₂ ratio～0.00). CO was determined to be the main product in photocatalytic CO₂ reduction. NP powders had the highest CO yields and Nd doping enhanced CO production. The powders with high crystallite sizes and rutile weight fractions had the highest artificial photosynthesis activities.     

NOx formation and selective non-catalytic reduction (SNCR) in a fluidized bed combustor of biomass

Caledonian Paper (CaPa) is a major paper mill, located in Ayr, Scotland. For its steam supply, it previously relied on the use of a Circulating Fluidized Bed Combustor (CFBC) of 58 MW_th, burning coal, wood bark and wastewater treatment sludge.It currently uses a bubbling fluidized bed combustor (BFBC) of 102 MW_th to generate steam at 99 bar, superheated to 465 °C. The boiler is followed by steam turbines and a 15 kg/s steam circuit into the mill. Whereas previously coal, wood bark and wastewater treatment sludge were used as fuel, currently only plantation wood (mainly spruce), demolition wood, wood bark and sludge are used.Since these biosolids contain nitrogen, fuel NO_x is formed at the combustion temperature of 850–900 °C. NO_x emissions (NO + NO₂) vary on average between 300 and 600 mg/Nm³ (dry gas). The current emission standard is 350 mg/Nm³ but will be reduced in the future to a maximum of 233 mg/Nm³ for stand-alone biomass combustors of capacity between 50 and 300 MW_th according to the EU LCP standards. NO_x abatement is therefore necessary.In the present paper we firstly review the NO_x formation mechanisms, proving that for applications of fluidized bed combustion, fuel NO_x is the main consideration, and the contribution of thermal NO_x to the emissions insignificant.We then assess the deNO_x techniques presented in the literature, with an updated review and special focus upon the techniques that are applicable at CaPa. From these techniques, Selective Non-catalytic Reduction (SNCR) using ammonia or urea emerges as the most appropriate NO_x abatement solution.Although SNCR deNO_x is a selective reduction, the reactions of NO_x reduction by NH₃ in the presence of oxygen, and the oxidation of NH₃ proceed competitively.Both reactions were therefore studied in a lab-scale reactor and the results were transformed into design equations starting from the respective reaction kinetics. An overall deNO_x yield can then be predicted for any operating temperature and NH₃/NO_x ratio.We then present data from large-scale SNCR-experiments at the CFBC of CaPa and compare results with the lab-scale model predictions, leading to recommendations for design and operation. Finally the economic impact is assessed of implementing SNCR-technology when applying an NH₃ SNCR or urea SNCR to the CFBC at CaPa.