Gas Yield Research Articles

Efficient Synthesis, Characterization, and DFT Calculation of 4,4’-Azo-1,2,4-triazole

ABSTRACT 4,4’-Azo-1,2,4-triazole (atrz) is a new high nitrogen energetic material with high energy density, high gas yield and wide application prospects, but the low synthesis temperature and long time are the main reasons limiting its application. To achieve efficient synthesis of atrz, the double drop synthesis method was designed to solve the problem of unstable concentration of oxidant (HClO) due to batch feeding. The reaction temperature, reaction time, and molar ratio of reactants of n(4-amino-1,2,4-triazole):n(ClO−) were studied and optimized using the single factor variable method; Characterization and analysis of atrz using theoretical calculations with elemental analysis, infrared spectroscopy, crystal morphology, and nuclear magnetic resonance; The thermal properties and stability of atrz were tested and analyzed using TG-DTA. The results showed that the reaction time of the double drop synthesis method was shortened from 5 hours to 1.5 hours under the conditions of similar yield, and the efficiency was increased by 2.3 times. The optimized process was a reaction temperature of 5°C-10°C, reaction time of 1.5 hours, n(4-amino-1,2,4-triazole):n(ClO−) of 1:2, and the yield reached 73%. The product was white, needle-like crystals, which were determined to be atrz by means of characterization and theoretical calculations. Atrz’s decomposition peak temperature is 309.0°C, and when the temperature is below 271.7°C, atrz is thermally stable. The activation energies of atrz calculated by Kissinger and Flynn-Wall-Ozawa methods were 195.0 kJ·mol−1 and 194.6 kJ·mol−1.

Experimental Study on Microwave Pyrolysis of Decommissioned Wind Turbine Blades Based on Silicon Carbide Absorbents

The rapid expansion of the scale of wind power has led to a wave of efforts to decommission wind turbine blades. The pyrolysis of decommissioned wind turbine blades (DWTBs) is a promising technological solution. Microwave pyrolysis offers the benefits of fast heating rates and uniform heat transfer, making it a widely used method in various heating applications. However, there are few studies on the microwave pyrolysis of DWTBs, and pyrolysis characteristics under different boundary conditions remain unclear. In this paper, we investigate the pyrolysis characteristics of DWTBs by utilizing silicon carbide (SiC) particles as a microwave absorbent. The results demonstrated that, when the microwave heating power increased from 400 W to 600 W, the heating rate and pyrolysis final temperature of the material increased, resulting in a reduction in pyrolysis residual solid yield from 88.30% to 84.40%. At 600 W, pyrolysis gas components included C2H4, CH4, and CO, while the tar components included phenol and toluene. The highest degree of pyrolysis was achieved under the condition of an SiC particle size of 0.85 mm, with better heating performance, and the calorific value of the pyrolysis gas generated was 36.95 MJ/Nm3. The DWTBs did not undergo pyrolysis when SiC was not added. However, when the mass ratio of SiC to DWTBs was 4, the tar yield was 4.7% and the pyrolysis gas yield was 17.0%, resulting in a faster heating rate and the highest degree of pyrolysis. Based on this, an optimal process for the microwave pyrolysis of DWTBs was proposed, providing a reference for its industrial application.

Component-based equilibrium modeling of biomass fixed-bed gasifier

In this paper, the process of gasification of rice husk directly with air in a fixed-bed gasifier was modeled using Aspen Plus. Unlike traditional models based on the elemental balance method, this study modeled the decomposition of rice husk into cellulose, lignin, and hemicellulose based on experimental data from the pyrolysis equipment, and the product yields were fitted to obtain the distribution of product yields in the pyrolysis stage of rice husk. In the redox stage, the thermodynamic equilibrium calculation model and the kinetic calculation model were used for the simulation, respectively, and compared and analyzed with the actual plant operation data. In the simulation of the thermodynamic equilibrium calculation model, the error of gas yield was about 5%. While in the kinetic calculation model, the errors of gas production rates of N2, H2 and CH4 were within 5%, the errors of CO and CO2 were larger, which were 13.73% and 17.09%, respectively. The error of the yield of Bio-char, an additional product of gasification, is about 2% in both models, which is close to the actual working conditions. Based on the model, the effects of gasification temperature, air equivalent ratio (ER) and air preheating temperature on the gasification reaction were discussed in this paper. The results concluded that the gasification temperature should be maintained at about 800 °C, the air equivalent ratio at about 0.3, and the air preheating temperature should be increased appropriately when performing rice husk gasification.

Assessing bioenergy prospects of algal biomass and yard waste using an integrated hydrothermal carbonization and pyrolysis (HTC–PY): A detailed emission–to–ash characterization via diverse hyphenated analytical techniques and modelling strategies

Hydrothermal carbonization (HTC) presents a promising method for converting carbonaceous waste into renewable fuels, facilitating energy recovery. This study focuses on the HTC pretreatment of microalgae (Chlorella sorokiniana) and yard waste, examining their physicochemical structural changes, component migration, and potential for valorization via integrated HTC and pyrolysis processes. HTC notably enhances the carbon content while reducing oxygen and nitrogen levels in these feedstocks, producing a clean solid fuel with high energy density. The study investigates the pyrolytic behavior of hydrochars and their blends using different analytical techniques, kinetic modeling, and fixed–bed reactor experiments. The blends with 90% and 70% of microalgae hydrochar (CSH) exhibited the most significant synergistic effects during co–pyrolysis, evident in its devolatilization behaviors and reduced activation energies. Integrating artificial neural networks and response surface methodology models facilitated optimization of pyrolysis parameters and accurate prediction of bio–oil, biochar, and gas yields. The analytical techniques enabled characterization of pyrolysis products, revealing notable changes in bio–oil and biochar compositions, suggesting potential enhancements. The study comprehensively evaluates the HTC–pyrolysis approach’s potential for converting microalgae and lignocellulosic biomass into eco–friendly biofuels for industrial applications.

Thermodynamic simulation of hydrogen production from the nano-CaO reactive sorption enhanced biomass steam reforming

Based on the principles of thermodynamic reaction equilibrium, a simulation method enhanced by the nano-CaO reactive sorption CO2 for hydrogen production from biomass steam reforming has been established. MATLAB R2022b software has been utilized to calculate the composition concentration of the product gas. Detailed simulations have been conducted to understand the changes in gas component concentration and yield under various reaction conditions, includes temperatures, steam to biomass (S/B) molar ratios, and CaO to carbon (CaO/C) molar ratios. The result demonstrated that temperature plays a significant role in both the concentration and yield of hydrogen. At an optimal reaction temperature of 650 °C, the concentration of H2 in the product reaches 77% (S/B = 2 and CaO/C = 0.5). S/B molar ratio over 2 is necessary to increase the H2 concentration. The study also reveals CaO/C molar ratio 0.5 enable successful removal of CO2 generated by reaction. The application of nano-CaO notably enhanced the efficiency of hydrogen production from biomass steam reforming, leading to a 25% increase in H2 concentration and a boost in H2 yield to 50 mL/gBiomass, and reaction temperature decrease 200 °C compared to the case without CaO.

Effect of reaction conditions on pyrolysis performance of waste plastics loaded with Ni/ZSM-5 catalyst

Ni/ZSM-5 catalysts were prepared by uniformly loading the active metal Ni to ZSM-5 zeolite using excessive wet impregnation method, and the characterization tests of XRD, SEM, H2-TPR, and NH3-TPD were carried out. For the prepared Ni/ZSM-5 catalyst, the pyrolysis–catalytic reforming of waste plastics for gas production performance was explored under different reaction temperatures, steam-carbon (S/C) ratio, catalyst addition amount, and plastic type. The results showed that the gas production volume and gas quality of pure pyrolysis of HDPE and catalytic pyrolysis of Ni/ZSM-5 were improved with the increase of temperature. Given the thermal economy, the optimal pyrolysis temperature was 700 °C, the catalytic gas production was 900 mL, and the hydrogen concentration was 64.4 %. S/C ratio of 1.5 and plastic: catalyst of 1 was the best reaction condition, under which the gas production was 1020 mL and the hydrogen concentration was 65.1 %, respectively. In addition, an appropriate increase in the amount of steam and the addition of catalysts would greatly optimize the final gas production performance. However, excess steam and catalysts was unfavorable to the gas production of plastic pyrolysis, resulting in a waste of resources. Finally, as for the gas production of four plastics, LDPE had the best pyrolysis gasification effect with gas yield of 1040 mL and hydrogen concentration of 65.7 %. The order of catalytic pyrolysis effect of different plastics was LDPE > HDPE > PP > PS.

Steam gasification of lime dried sewage sludge: Effects of temperature and addition of lime

Gasification shows great potential as an alternative method for energy utilization from sewage sludge. Lime (CaO) is a cheap and commonly used dewatering conditioner for sewage sludge. The calcium hydroxide (Ca(OH)2) generated during the drying process with lime can enhance the pH level of the sludge, thereby providing disinfection properties. This paper investigated enhancement mechanism of Ca(OH)2 on hydrogen gas generation and the effect on gas product yield during the steam gasification process of lime-dried sludge. The experiments were conducted in an electrically heated reactor at 500–800 °C. The forms of calcium present in the gasified sludge char samples were analyzed using X-ray diffraction (XRD) analysis to investigate their transformation process. Fourier transform infrared spectroscopy (FTIR) was utilized to obtain information regarding the chemical structure in the gasified sludge char samples, with the aim of exploring the mechanism behind hydrogen production from lime-dried sludge. The results indicate that the CaO generated from Ca(OH)2 dehydration acts both CO2 adsorbent and catalyst during the gasification process. The addition of Ca(OH)2 during the sewage sludge gasification process leads to a reduction in the aromatic CH content in the organic matter, while significantly increasing the content of reactive CH3-chains. It also promotes the ring-opening and rearrangement reactions of aromatic hydrocarbons and nitrogen-containing heterocycles and steam reforming reaction of tar. The combined effects of these factors contribute to an overall increase in hydrogen gas yield.

Prediction of Individual Gas Yields of Supercritical Water Gasification of Lignocellulosic Biomass by Machine Learning Models.

Supercritical water gasification (SCWG) of lignocellulosic biomass is a promising pathway for the production of hydrogen. However, SCWG is a complex thermochemical process, the modeling of which is challenging via conventional methodologies. Therefore, eight machine learning models (linear regression (LR), Gaussian process regression (GPR), artificial neural network (ANN), support vector machine (SVM), decision tree (DT), random forest (RF), extreme gradient boosting (XGB), and categorical boosting regressor (CatBoost)) with particle swarm optimization (PSO) and a genetic algorithm (GA) optimizer were developed and evaluated for prediction of H2, CO, CO2, and CH4 gas yields from SCWG of lignocellulosic biomass. A total of 12 input features of SCWG process conditions (temperature, time, concentration, pressure) and biomass properties (C, H, N, S, VM, moisture, ash, real feed) were utilized for the prediction of gas yields using 166 data points. Among machine learning models, boosting ensemble tree models such as XGB and CatBoost demonstrated the highest power for the prediction of gas yields. PSO-optimized XGB was the best performing model for H2 yield with a test R2 of 0.84 and PSO-optimized CatBoost was best for prediction of yields of CH4, CO, and CO2, with test R2 values of 0.83, 0.94, and 0.92, respectively. The effectiveness of the PSO optimizer in improving the prediction ability of the unoptimized machine learning model was higher compared to the GA optimizer for all gas yields. Feature analysis using Shapley additive explanation (SHAP) based on best performing models showed that (21.93%) temperature, (24.85%) C, (16.93%) ash, and (29.73%) C were the most dominant features for the prediction of H2, CH4, CO, and CO2 gas yields, respectively. Even though temperature was the most dominant feature, the cumulative feature importance of biomass characteristics variables (C, H, N, S, VM, moisture, ash, real feed) as a group was higher than that of the SCWG process condition variables (temperature, time, concentration, pressure) for the prediction of all gas yields. SHAP two-way analysis confirmed the strong interactive behavior of input features on the prediction of gas yields.

Oxy-hydrogen, solar and wind assisted hydrogen ([formula omitted]) recovery from municipal plastic waste (MPW) and saltwater electrolysis for better environmental systems and ocean cleanup

The pyrolysis of plastic waste and the electrolysis of saltwater is a promising route to carbon neutrality in ocean cleanup and plastic waste management. Therefore, a solar and wind assisted H2-fuelled fast pyrolysis of MPW (municipal plastic waste) and electrolysis of desalinated saline were developed. The combined system uses an oxy-hydrogen furnace for thermal decomposition of MPW feed, CO2 as an inert reaction medium and both solar and wind energy systems to operate the electrical units. The deionised H2O feed to the electrolyser cell was produced from saltwater using the recovered heat from the fast pyrolyser unit. The process CO2 was captured and reused for soil improvement as current waste-to-energy routes of MPW recycling emit 695,850 tonnes of CO2. 2.65 kg/hrH2 fuel in an O2 environment was utilised to meet the decomposer operating temperature and heat duty which is approximately 29 % of the produced H2. Instability associated with bio-oil was prevented by using fast pyrolysis which release more volatiles. Compared to the related studies, this investigated work achieved the highest gas and carbon yields. Thermal NO < 0.1 ppm was recorded. The developed system is expected to reach ≥70 % energy efficiency and a sales price of < $3.89/kgH2.

H2-enriched gaseous fuel production via steam-gasification of biomass by using lime-based sorbents

The main objective of the present study was to compare the catalytic activity of selected limestones (Göynük, Dikmen, Polatlı Yolu, Kınık Tüneli and Köserelik) in terms of H2-rich syngas production from biomass gasification. In order to achieve this goal, an ASPEN plus-based model for biomass gasification integrated with carbonation reaction was developed. Tar formation was also considered and the gasification process was carried out based on Gibbs free energy minimization. A combined effect of temperature (600-710 °C), steam/biomass ratio, S/B (0.58-1.58), and limestone/biomass ratio, L/B (0-2.0) on gas composition, H2 yield (HY) and gas yield (GY) was also studied. An increase in both S/B and L/B was beneficial for H2 enrichment. The CO2 content declined sharply from 16.83 vol% to 10.28 vol% with increasing L/B from 0 to 1.5; however, a marginal reduction in CO2 content was observed with further increase in L/B. The highest HY (51.01 g/kg) was produced with Dikmen followed by Göynük, Polatlı Yolu, Kınık Tüneli and Köserelik. The results also showed that the limestone samples with high CaO content in general exhibits a better H2 production capacity than limestones with low CaO content. To the best of our knowledge, no simulation study has been presented to compare the catalytic activity of different limestones in terms of H2 production.

Plasma Processing of Rubber Powder from End-of-Life Tires: Numerical Analysis and Experiment

Tire recycling is becoming an increasingly important problem due to the growing number of end-of-life tires (ELTs). World-wide, ELTs account for more than 80 million tons. ELTs contribute to environmental pollution in the long term. They are flammable, toxic and non-biodegradable. At the same time, ELTs contain rubber, metal and textile cord, which are valuable raw materials. ELTs are buried in landfills, burned, crushed and restored. Most of these methods have a negative impact on the environment. From an environmental point of view, the most preferred ways to recycle tires are retreading and shredding. Rubber powder (RP) or crumb is mainly used for rubber pavers production, waterproofing, curbs, road slabs and various surfaces. An alternative method for RP processing, eliminating the disadvantages of the above approaches, is plasma gasification and pyrolysis. The paper presents a thermodynamic and kinetic analysis and an experiment on plasma processing of RP from worn tires to produce flammable gas. At a mass-average temperature of 1750 K, the yield of synthesis gas from plasma-air gasification of RP was 44.6% (hydrogen—19.1, carbon monoxide—25.5), and 95.6% of carbon was gasified. The experimental and calculated results satisfactorily agreed. It was found that plasma products from RP did not contain harmful impurities, either in calculations or experiments. Plasma gasification allows for recycling ELTs in an environmentally friendly way while also generating flammable gases that are valuable commodities. In this research, plasma technology was demonstrated to be effective for gasifying RP to produce flammable gas.

Co-pyrolysis of coal and biomass blends: Impact of pyrolysis temperature and biomass blending on thermal stability of coal, and composition of pyrolysis products

The study investigates the thermal pyrolysis of coal and co-pyrolysis of the coal-sawdust blend (100% blend) in a fixed-bed reactor. The pyrolysis od coal and sawdust was performed at 773 K, 823 K, and 873 K temperature and 30 K min−1 heating rate under nitrogen purge gas (300 mL min−1). Co-pyrolysis coal and biomass was performed at 50%, 100%, and 200% blends at 873 K temperature. The pyrolysis and co-pyrolysis products such as liquid and gas was analysed and compared. Coal pyrolysis resulted higher coal char generation with negligible yield of liquid and gas compared to sawdust. However, 100% co-pyrolyzed blend resulted in higher oil yield % with the increase in temperature from 773 to 873 K with conversion % at 37.35% at 873 K temperature. It was confirmed that the increase in biomass blending percentage with coal, the conversion % increased to 92.8% for the 200% blend. GC/MS characterization of oil from 100% and 200% blended samples revealed that alkane is the main component along with a remarkable Cp value of 1.094 kJ kg−1 K−1 and 0.271 kJ kg−1 K−1 obtained at 823 K and 873 K reaction temperatures respectively. The pyrolysis oil obtained at 873 K at higher biomass to coal blended condition contained higher aromatic compounds. Certain rare comp compounds such as 1-Methyl cyclopropane methanol, 3, 3’- Thiodipropanol, 3- Trans-(1,1-Dimethylethyl)-4, Cis, Methoxycyclohexane-1-ol, 1, 1 -Dimethyl-1-Sinacyclobutane, Octadecane, 2,2,4,15,17,17-Hexamethyl-7, 12-Bis (3, 5,5-Trimethylhexyl), 1,4:3,6-Dianhydro-Alpha-D-Glucopyranose, Hexacosyl acetate and 1,2-Benzenediol, 4-Methyl- present in the copyrolysis oil was also a significant observation in this study.

Effect of recycled polyethylene catalyst for Mediterranean pine seed shell biomass pyrolysis on hydrogen and methane production

ABSTRACT The present study exhibits the potential of hydrogen and methane gases production from the Mediterranean pine tree seed shell biomass over recycled polyethylene wastes as catalyst. In the study, firstly, the viscosity and density of polyethylene materials and degassing point were determined. The pyrolysis was carried out at a rate of 50 °C/min at 600°C temperature. The obtained gases were analyzed with gas chromatography device. At the last step of the experiments, solid residues were observed under an optical microscope, and their microstructures were also examined. The results showed that Mediterranean pine seed shell biomass and its mixture with low-density polyethylene may produce methane and hydrogen gases. M8 catalyst, which has one of the lowest viscosity values (0.45 gr/10 min.) and highest density values (0.950 gr/cm3) produced the highest methane and hydrogen gas yields. In the pyrolysis experiments, 38.44% CH4, 19.50% CO2 and 42.06% H2 gases were obtained from Mediterranean pine seed shell biomass. Moreover, CO2 emission values of biomass were calculated and compared with DEFRA values. The study demonstrated that, since hydrogen and methane can be obtained through the pyrolysis process, Mediterranean pine tree seed shell can be classified as a new biomass source and has potential to alternative fuel to fossil-based fuels for internal combustion engines.

The Influence of Solid Heat Carrier Load of Char on Pyrolysis Characteristics of Pulverized Coal in a Fluidized Bed Reactor

Pulverized coal pyrolysis based on solid heat carrier has a huge advantage in high tar yield. In this study, pyrolysis experiments on pulverized coal were conducted in a lab-scale fluidized bed reactor at 650 °C, utilizing char as the solid heat carrier. The influence of mass ratio of char to coal (RATIO) was investigated. Results show that the incorporation of solid heat carrier of char significantly enhanced the primary pyrolysis reaction in coal pyrolysis, resulting in increasing yields of tar and gas but reducing one of char. The yield of tar maximally reached 148.80–262.22% of the Gray–King analysis value at the RATIO of 14.52 g/g. As the RATIO increased, the tar contained more light component content, indicating that incorporating solid heat carriers improved the tar quality. These findings offer significant insights for the design of fluidized bed pyrolysis unit utilizing char as solid heat carrier.

Investigation on the thermochemical characteristics, kinetics and evolved gases for typical kitchen waste pyrolysis

Kitchen waste is a complex biomass waste, whose composition and properties vary with factors such as source, season and region. It is challenging to classify and characterize it. A thermogravimetric and kinetic study was performed to estimate pyrolysis characteristics and gas emissions of starch, peel, nut shell, and vegetables. Samples underwent pyrolysis in the Simultaneous Thermal Analysis from room temperature to 1200 K at different heating rates of 10, 20, 30 and 50 K/min. The starch had the narrowest pyrolysis temperature range, while nut shell exhibited the highest residual rate. The average activation energy for pyrolysis process calculated using Coats–Redfern method was in order of starch > vegetable ≈ nut shell > peel. The gaseous products and typical functional groups of the released volatiles were identified using specific information from Fourier Transform Infrared Spectroscopy (FTIR) and Mass Spectrometry (MS). These primarily included small inorganic molecules, aldehydes, aromatics, ethers, furans, ketones, organic acids, and phenols. Aliphatic hydrocarbons significantly contributed to the total gas yield and were the most abundant for all samples. The characteristic ion fragment with m/z = 60 was only observed in peel and nut shell, while m/z = 58 ion fragments were exclusive to starch and vegetables. The practical research can provide theoretical basis for the resource utilization and environmental management of kitchen waste.

Enhancing biomethanation performance through co-digestion of diverse organic wastes: a comprehensive study on substrate optimization, inoculum selection, and microbial community analysis.

A blend of organic municipal solid waste, slaughterhouse waste, fecal sludge, and landfill leachate was selected in different mixing ratios to formulate the best substrate mixture for biomethanation. Individual substrates were characterized, and the mixing ratio was optimized with the help of a response surface methodology tool to a value of 1:1:1:1 (with a C/N ratio of 28±0.769 and total volatile fatty acid (VFA) concentration of 2500±10.53 mg/L) to improve the overall biomethanation. The optimized blend (C/N ratio: 28.6, VFA: 2538 mg/L) was characterized for physicochemical, biological, and microbial properties and subjected to anaerobic digestion in lab-scale reactors of 1000 mL capacity with and without the addition of inoculum. The biogas yield of individual substrates and blends was ascertained separately. The observed cumulative biogas yield over 21 days from the non-inoculated substrates varied between 142±1.95 mL (24.6±0.3 ml/gVS) and 1974.5±21.72 mL (270.4±3.1 ml/gVS). In comparison, the addition of external inoculation at a 5% rate (w/w) of the substrate uplifted the minimum and maximum cumulative gas yield values to 203±9.9 mL (35.0±1.6 mL/gVS) and 3394±13.4 mL (315.3±1.2 mL/gVS), respectively. The inoculum procured from the Defence Research and Development Organisation (DRDO) was screened in advance, considering factors such as maximizing VFA production and consumption rate, biogas yield, and digestate quality. A similar outcome regarding biogas yield and digestate quality was observed for the equivalent blend. The cumulative gas yield increased from 2673±14.5 mL (373.7±2.2 mL/gVS) to 4284±111.02 mL (391.47±20.02 mL/gVS) over 21 days post-application of a similar dosage of DRDO inoculum. The 16S rRNA genomic analysis revealed that the predominant bacterial population belonged to the phylum Firmicutes, with the majority falling within the orders Clostridiales and Lactobacillales. Ultimately, the study advocates the potential of the blend mentioned above for biomethanation and concomitant enrichment of both biogas yield and digestate quality.

A Study on the Hydro-Liquefaction Kinetics of Shengli Lignite during the Heating-Up and Isothermal Stages under Mild Conditions

Studying the hydro-liquefaction kinetics of lignite contributes to optimizing the mild liquefaction process for lignite. In this paper, the direct liquefaction performance of Shengli lignite (SL) was investigated using a H2/THN system with 4 MPa of initial pressure, and reaction kinetic models were established for the heating-up stage and the isothermal stage. The result showed that the liquefaction performance of the SL was excellent, with a conversion of 62.18% and an oil and gas (O + G) yield of 29.88% at 698.15 K. After one hour of reaction, the conversion and O + G yield were 94.61% and 76.78%, respectively. During the heating-up stage, the easily reactive part of the SL was 50.07%, and it was converted directly into oil, gas, asphaltene (AS), and preasphaltene (PA) simultaneously. There was no significant secondary hydrogenation conversion of the AS and PA products. During the isothermal stage, the hard-to-react part was predominantly converted into AS and PA, while the remaining easily reactive part continue to react completely. The conversion of AS and PA into oil and gas was a rate-controlling step during this stage. The amount of unreacted coal estimated using the model calculated in the isothermal stage was 2.98%, which was significantly consistent with the experimental value of 2.81%.

The multi‐stage gasification process of low‐rank coal samples from gravity separation process

AbstractThe separation process is a well‐established method for beneficiation technologies of low‐rank coal, especially in the case of utilization in the thermochemical processes. In this study, three coal samples, including the original low‐rank coal sample and two coal samples (C1 and C2) from the gravity separation process of the original coal sample, were gasified in a multi‐stage gasification process at the gasification temperature of 900°C and the steam‐to‐carbon (S/C) ratio of 1.00 and 1.25. The separation process led to a significant improvement in the quality of coal samples. This improvement is particularly characterized by a higher carbon and volatile fractions and a lower ash content compared with the original coal. This could be the main reason for the higher gasification performance in the case of the experiment of C1 and C2 coal samples. The volume of syngas obtained from gasification experiments of C1 and C2 samples increased between 1.3 and 1.5 times that of the original coal sample. At all S/C ratios and 900°C, the gasification experiment of the C2 sample produced the highest produced gas yield followed by the gasification experiment of the C1 sample. From the chemical point of view, the produced gas had an H2/CO ratio close to the desired ratio of 2.00, which is suitable for chemical synthesis processes. In the case of C1 sample experiments, the H2/CO ratios were 2.11 and 2.18 at S/C ratios of 1.00 and 1.25, respectively. For the experiments of the C2 sample, the H2/CO ratio reached 1.88 and 2.00 at S/C ratios of 1.00 and 1.25, respectively.

Catalytic upgrading of Naomaohu coal pyrolysis volatiles over NiAl and NiLiAl oxides

Catalytic upgrading of volatiles is an essential technology to improve the product distribution of pyrolysis for the clean and efficient utilization of low-rank coals. In this work, novel acid-base bifunctional catalysts composed of Ni/Li/Al oxides were designed and prepared using LDH precursors with tunable chemical composition and structural properties. The catalysts were systematically characterized by X-ray diffraction (XRD), thermogravimetric analysis (TGA), physisorption, NH3-temperature programmed desorption (NH3-TPD), CO2-temperature programmed desorption (CO2-TPD), H2-temperature programmed reduction (H2-TPR), and scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDS). A two-stage fixed bed reactor was employed to evaluate the performance of the catalysts. Characterization results suggest that the crystal size of NiO and the surface area of the catalyst decreased with increasing Li content and decreasing Ni content in the catalyst, while the pore volume and pore diameter were positively correlated with Li content. Moreover, the addition of Li reduced the amount of weak acid sites and raised the amount of total basic sites. Consequently, the bifunctional catalysts boosted the yield of light tar and the contents of aromatics and phenols in tar. Specifically, with the highest total acid sites (569 μmol/g) promoting the cracking of heavy pitch components, Ni2.5Li0.5Al1 decreased the content of pitch in tar to 23.8 wt%, representing a 42.7 % drop from the corresponding non-catalytic pyrolysis. Accordingly, it improved the light tar yield to 7.2 wt%, which was 18 % higher than non-catalytic pyrolysis. 450 °C is identified as a suitable temperature for the catalytic upgrading of volatiles from Naomaohu coal; higher catalysis temperatures at 500 °C and 550 °C led to lower tar yield and lower phenols content, along with higher gas yield and more carbon deposition.

Influence of red mud as a catalyst in the thermocatalytic reforming process

AbstractThis work studies red mud, a residue from the processing of bauxite, as a support catalyst in the thermocatalytic reforming (TCR) process, using wood, digestate, and straw as case studies. Thermocatalytic reforming is a thermochemical process for the conversion of biomass into biofuels, combining intermediate pyrolysis and catalytic reforming and resulting in high‐quality biofuels. The quantity and quality of the catalyst in the postreformer is vital as it influences the reactions taking place in it. Normally, nonreactive components of the char produced in the process act as the catalyst in the postreformer but adding a support catalyst may improve the products. In this work, red mud is introduced in the process by mixing it with the feedstock in a ratio of 1:3. The results, in comparison with normal TCR experiments on the same feedstock materials, show that the introduction of red mud into the process generally reduces the biochar yield and generally increases the biogas and product water yields, and the bio‐oil yield remains constant. Its introduction also increases the hydrogen fraction of the gas and tends to reduce the nitrogen and sulfur content of the products, thus improving their quality. These observations are consistent across feedstock materials and postreformer temperatures. The results therefore suggest that red mud is a good support catalyst for increasing the gas yield, increasing the hydrogen fraction of the gas, and improving the quality of the products from the TCR process.