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CaO modified with acetic acid solution or sodium hydroxide (H-CaO/OH-CaO) was used to explore the relationship between the physical and chemical properties of CaO and the components of bio-oil during the pyrolysis of rice straw (RS) and model compounds via experiment and density functional theory(DFT) simulation. The results showed that the modification changed the properties of CaO, and thus the catalytic performance on production of bio-oil components. H-CaO with the larger number of strong basic sites (1.10 ∼ 2 times than commercial CaO) and the longer Ca-O bond length showed the better selectivity and performance on formation of ketones (the maximum relative content in bio-oil reached 43 %). The conversion pathway of cellulose/hemicellulose was changed by H-CaO, which promoted the formation of ketones. The easier combining of H-CaO with the pyrolysis primary products due to the longer Ca-O bond was the key to its better performance., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Highly active biochar has great application potential in heterogeneous catalysis and adsorptive processes. The complexity of carbonization process makes it difficult to construct target active sites. This work put forward a reactive descriptor based on pyrolysis parameters and intrinsic composition of biomass. Results show that the model showed better predictive performance for C-C/C=C (R 2  = 0.85), C=O (R 2  = 0.85) and defect (R 2  = 0.91) sites. The SHapley Additive exPlanation analysis shows that the pyrolysis parameters and the higher heating values are equally important for the active sites. The predictive performance and guiding role of the descriptor were validated by experiments. The descriptors proposed in this study integrated significant advantages of simplicity and easy accessibility, which would break the bottleneck of accurate construction of active sites and provide a theoretical basis for high-value resource utilization of biomass., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Biochar produced from pyrolysis of biomass is a platform porous carbon material that have been widely used in many areas. Specific surface area (SSA) and total pore volume (TPV) are decisive to biochar application in hydrogen uptake, CO 2 adsorption, and organic pollutant removal, etc. Engineering biochar by traditional experimental methods is time-consuming and laborious. Machine learning (ML) was used to effectively aid the prediction and engineering of biochar properties. The prediction of biochar yield, SSA, and TPV was achieved via random forest (RF) and gradient boosting regression (GBR) with test R 2 of 0.89-0.94. ML model interpretation indicates pyrolysis temperature, biomass ash, and volatile matter were the most important features to the three targets. Pyrolysis parameters and biomass mixing ratios for biochar production were optimized via three-target GBR model, and the optimum schemes to obtain high SSA and TPV were experimentally verified, indicating the great potential of ML for biochar engineering., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

This study predicts pyrolytic product yields via machine learning algorithms from biomass physicochemical characteristics and pyrolysis conditions. Random forest (RF), gradient boosting decision tree (GBDT), eXtreme Gradient Boosting (XGBoost), and Adaptive Boost (Adaboost) algorithms are comparatively analyzed. Among these algorithms, the RF algorithm is the best modeling algorithm and performs best in predicting the bio-oil yield and performs well in predicting biochar and pyrolytic gas yields. The moisture content, carbon content, and final heating temperature are the most important factors in predicting pyrolysis product yields, and biomass characteristics are more important than pyrolysis conditions. Furthermore, the carbon content positively affects the bio-oil yield and negatively affects the biochar yield, and the final temperature positively affects the pyrolytic gas yield and negatively affects the biochar yield. This work provides new insight for controlling the yields of pyrolytic products via the RF algorithm, which can facilitate the process optimization in engineering applications., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

The effect of heat exchange area on the componential evolutions of biomass pyrolysis vapors was visualized through an innovative combining method of bio-oil composition inversion and function fitting. As the maximal diameter of condenser at 340 K increased from 35 mm to 55 mm, the fitted heat maps showed that the recovery of organics increased in the top of condenser and remained steady in the bottom, whereas the water recovery only increased in the top but decreased in the bottom. The recovery proportion of furfural and phenolic compounds increased by 20-40% with unvaried water recovery, and the content enrichment of high value-added components increased by 30-45% at 37 wt% of bio-oil yield. Heat exchange area exhibited a finer regulation effect on the condensation of pyrolysis vapors than traditional condensing adjustment methods, which first provided a remarkable promotion for the recovery and enrichment of organic components without improving water recovery., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

This study aimed to utilize machine learning algorithems combined with feature reduction for predicting pyrolytic gas yield and compositions based on pyrolysis conditions and biomass characteristics. To this end, random forest (RF) and support vector machine (SVM) was introduced and compared. The results suggested that six features were adequate to accurately forecast (R 2  > 0.85, RMSE < 5.7%) the yield while the compositions only required three. Moreover, the profound information behind the models was extracted. The relative contribution of pyrolysis conditions was higher than that of biomass characteristics for yield (55%), CO 2 (73%), and H 2 (81%), which was inverse for CO (12%) and CH 4 (38%). Furthermore, partial dependence analysis quantified the effects of both reduced features and their interactions exerted on pyrolysis process. This study provided references for pyrolytic gas production and upgrading in a more convenient manner with fewer features and extended the knowledge into the biomass pyrolysis process., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

A novel experimental method based on the combination of bio-oil composition inversion and function fitting was purposed and verified for describing the componential evolution curves during the liquefaction of biomass pyrolysis vapors. The evolution curves of representative condensable components were fitted by linear and Slogistic function in the short, middle and long three condensing fields. Linear function exhibited a significant effectiveness for the description and prediction of low-boiling water and furfural and the relative deviations were no more than 5% between actual values in long condenser and predictive values from the elongation of curves in short and middle condensers. For high-boiling phenolic compounds, linear function failed to fit their evolutions in long condenser but Slogistic fitting remained effective despite the relative deviation increasing to about 10%. This investigation provided a unique and effective prediction method for the vapor evolution in industrial shell and tube heat exchanger according to laboratory-scale experiment., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

This study was devoted to proposing an effective experimental method based on bio-oil composition inversion for understanding biomass pyrolysis vapor evolution in four-staged condensers. The effective length of each condenser was 200 mm. The evolution curves and heat maps of condensable vapors in the whole multi-staged condensing field were provided by Logistics model fitting. With changing condition from "365-345-325-305" to "345-325-305-285", the condensing efficiency of the first condenser increased by 100% but that of the third condenser decreased by 80%. Under condition "365-345-325-305", the largest recovery rate of water was observed at 400 mm away from multi-staged condensing field entrance while that of eugenol was observed at 50 mm away from the entrance, which explained that water was primarily recovered by the second and third condensers whereas eugenol was recovered by the first condenser, and verified the remarkable effect of fractional condensation on the separation of water and high-boiling phenols., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

This study investigated the interactions between volatile and char during biomass pyrolysis at 400 °C, employing a β-5 lignin dimer and amino-modified graphitized carbon nanotube (CNT-NH 2 ) as their models, respectively. The results demonstrated that both -NH 2 and its carrier (CNT) facilitated the conversion of the β-5 dimer, which significantly increased from 9.7% (blank run), to 61.6% (with CNT), and to 96.6% (with CNT-NH 2 ). CNT mainly favored the breakage of C-O bond in the feedstock to produce dimers with a yield of 55.5%, while CNT-NH 2 promoted the cleavage of both C-O and C-C bonds to yield monomers with a yield up to 63.4%. Such significant changes in the pyrolysis behaviors of the β-5 lignin dimer after the introduction of CNT-NH 2 were considered to be mainly caused by hydrogen-bond formations between -NH 2 and the dimeric feedstock/products, in addition to the π-π stacking between CNT and aromatic rings., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

The experiments on bio-oil recovery in a vertical tubular condenser with two flumes were conducted for speculating the componential distribution of walnut shell pyrolysis vapors during condensation. Bio-oil elements and functional groups from different locations of condenser were compared with each other. Aromatic H and H in phenolic OH were concentrated in the top and middle bio-oil and their percentage were improved with increasing water bath temperature. Ten representative compounds in bio-oil were chosen for quantitative analysis. As water bath temperature increased from 273 K to 353 K, the recovered water decreased by 85% whereas the guaiacol and its derivatives (guaiacols) merely decreased by 40%. Vapor distributions of water, acetic acid, furfural and guaiacols were simulated by the back analysis of bio-oil components. According to the simulated results, tubular condenser can be properly lengthened for promoting the recovery of specific components at high water bath temperatures., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

To understand the synergetic effect of magnesium citrate (MC) and temperature on biomass pyrolysis, co-pyrolysis of lotus seedpod (LS) and MC was carried out in a fixed bed reactor. With the addition of MC, CO 2 become the dominate composition in gas (55.83-90.75 vol%). And with temperature increasing, the main components in bio-oil converted from carboxylic acid to phenols and aromatics. Meanwhile, the mesoporous carbon was formed, with the BET specific surface area up to 514.66 m 2 /g, and pore diameter mainly focused at 3-8 nm. For the catalytic effect, the secondary cracking of pyrolytic volatiles (acetic acid and anhydrosugar) was inhibited, therefore the gas releasing was inhibited below 550 °C. However, at higher temperature, MgO catalysts favored the reduction of acids and deoxygenation via ketonization and aldol condensation reactions. The formed MgO as a template and the catalysis of MgO during co-pyrolysis contributed to the mesoporous structure of solid char., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Exploring the dielectric properties of mineral-biomass mixtures is fundamental to the coupled application with biomass pyrolysis and microwave technology to mineral reduction. In this work, the microwave dielectric properties of five pyrolusite-biomass mixtures were measured by resonant cavity perturbation technique and the pyrolysis reduction characteristics were systematically investigated, including poplar, pine, ageratina adenophora, rapeseed shell and walnut shell. Results indicated that the dielectric properties commonalities of five mixtures with temperature represented by increasing firstly, dropping intensely and finally rising slightly, with excellent responsiveness to microwaves; which the change trend was mainly attributed to the crystal transformation of amorphous MnO 2 and pyrolusite reduction reactions by biomass pyrolysis. Meanwhile, the heating characteristics successfully matched the dielectric properties of the mixtures, and the pyrolusite reduction process by biomass can be divided into two stages: biomass pyrolysis and pyrolusite reduction. The work highlights the universal feasibility of the novel coupled method for mineral reduction., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Replacing fossil energy by utilizing biomass as carbon source to convert metal oxides has meaning for reduction of minerals. Microwave pyrolysis of walnut shell for reduction process of low-grade pyrolusite was proposed. Thermogravimetric analysis indicated biomass pyrolysis process for reduction of pyrolusite was divided into four phases identified by temperatures: dehydration stage (<150 °C), pre-pyrolysis stage (150 °C-290 °C), curing decomposition stage (290 °C-480 °C) and carbonization stage (>480 °C), and manganese recovery reached 92.01% at 650 °C for 30 min with 18% walnut shell. The strongest preferential orientation of MnO was appeared, with good crystalline structure and no MnO 2 and FeO peaks detected. The product surface became loose and porous with numerous cracks, pits and holes, and molten granules were interconnected and stacked with regular shape. The methods propose new idea of selective reduction of pyrolusite based on biomass pyrolysis by microwave heating., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

This paper examines the effect of microwave drying on biomass characteristics and subsequent dry pyrolysis and characteristics of produced biochar from rice straw, sugarcane bagasse, rice husk and cotton stalk compared to oven drying at 105 °C. Dried samples from both methods are torrefied at 250 and 300 °C with 30-minutes residence time. Drying time reached 60 times faster with microwave. The fast and violent microwave drying ruptured the biomasses' surface, releasing more volatiles and having lower crystallinity; these lowered the heating value, energy yield and elemental carbon compared to oven drying except for cotton stalk only due to its woody nature which reduced devolatilization. Sugarcane, rice husk and cotton stalk have the most promising values of elemental carbon, energy yield and heating value reaching that of the bituminous coal. Torrefied rice straw showed high crystallinity of 50.7% while sugarcane and rice husk were completely amorphous., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

The effect of condensing temperature on composition of bio-oil obtained via fractional condensation was investigated by pyrolysis-condensation experiments of walnut shells at condensing temperatures from 290 K to 370 K. The condensing efficiency of the first stage condenser decreased from 0.59 to 0.12 with increasing temperature. Moisture of bio-oil decreased from 40% to 5%, but the C/O ratio increased from 0.50 to 1.50. Compared with contents observed at the lowest condensation temperature, the maximum content of each component increased by 50%-500%. Combined with variations in condensing efficiency and composition content, the optimum condensing temperature range for declining water in bio-oil was 340-350 K. The condensing temperature associated with the enrichment of acetic acid and furfural was 345 K. The 355 K optimum condensing temperature could be selected to achieve the maximum enrichment of guaiacol and its derivatives., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

The pyrolysis kinetics of extractive tobacco stem and pretreated samples with different KCl impregnation ratios were investigated by the thermogravimetric experiment and an optimized three-parallel distributed activation energy model (DAEM). The significant fitting deviation for the cellulose pyrolysis and the unrealistic partial fitting curve for the hemicellulose pyrolysis were mitigated during the optimization process by applying the Avrami-Erofeev-DAEM and reducing the latent interferences. The optimized parameters with good fitting qualities (about 2%) were obtained. Furthermore, based on the experimental results (changes in reaction intensity and temperature), model calculations (differences in reaction order, activation energy, volatiles fraction, etc.), and the maximum residual error analysis (with a high catalytic reaction rate) regarding different KCl-to-biomass ratios, it was found that KCl kinetically promoted the hemicellulose pyrolysis, which can be utilized as the theoretical support for the industrial application., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

The kinetic compensation effect in the logistic distributed activation energy model (DAEM) for lignocellulosic biomass pyrolysis was investigated. The sum of square error (SSE) surface tool was used to analyze two theoretically simulated logistic DAEM processes for cellulose and xylan pyrolysis. The logistic DAEM coupled with the pattern search method for parameter estimation was used to analyze the experimental data of cellulose pyrolysis. The results showed that many parameter sets of the logistic DAEM could fit the data at different heating rates very well for both simulated and experimental processes, and a perfect linear relationship between the logarithm of the frequency factor and the mean value of the activation energy distribution was found. The parameters of the logistic DAEM can be estimated by coupling the optimization method and isoconversional kinetic methods. The results would be helpful for chemical kinetic analysis using DAEM., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

The effect of ammonium dihydrogen phosphate (NH4H2PO4) on rice straw (RS) carbonization was evaluated at temperatures of 350-650°C. The carbonized products of RS with NH4H2PO4 show higher solid and energy yields, but lower higher heating values than the carbonized RS at every carbonization temperature. The optimum carbonization operation of RS with NH4H2PO4 which has a higher energy yield at a lower solid volume may be determined between 350 and 450°C, and RS with NH4H2PO4 carbonized at 450°C presents better pore properties than carbonized RS. The carbonized products of RS with NH4H2PO4 all have lower gaseous potassium release ratios than those of RS carbonized at the same temperature at combustion temperatures of 700-1000°C by retaining potassium in non-volatile phosphorus compounds with high melting points. It is an effective method for inhibiting the gaseous potassium release during combustion of the carbonized products., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

A predictive model was satisfactorily developed to describe the general trends of product distribution in fluidized beds of lignocellulosic biomass pyrolysis. The model was made of mass balance based on proximate analysis and an empirical relationship with operating parameters including fluidization hydrodynamics. The empirical relationships between product yields and fluidization conditions in fluidized bed pyrolyzers were derived from the data of this study and literature. The gas and char yields showed strong functions of temperature and vapor residence time in the pyrolyzer. The yields showed a good correlation with fluidization variables related with hydrodynamics and bed mixing. The predicted product yields based on the model well accorded well with the experimental data., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

Lignin pyrolysis was studied in a bubbling fluidized bed reactor equipped with a fractional condensation train, using nitrogen as the fluidization gas. The effect of different bed materials (silica sand, lignin char, activated lignin char, birch bark char, and foamed glass beads) on bio-oil yield and quality was investigated for a pyrolysis temperature of 550 °C. Results how that a bed of activated lignin char is preferable to the commonly used silica sand: pyrolysis of Kraft lignin with a bed of activated lignin char not only provides a pure char product, but also a higher dry bio-oil yield (with a relative increase of 43%), lower pyrolytic water production, and better bio-oil quality. The bio-oil obtained from Kraft lignin pyrolysis with a bed of activated lignin char has a lower average molecular weight, less tar, more phenolics, and less acidity than when sand is used as bed material., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

In this work, the role of Brønsted acid for furfural production in biomass pyrolysis on supported sulfates catalysts was investigated. The introduction of Brønsted acid was shown to improve the degradation of polysaccharides to intermediates for furfural, which did not work well when only Lewis acids were used in the process. Experimental results showed that CuSO4/HZSM-5 catalyst exhibited the best performance for furfural (28% yield), which was much higher than individual HZSM-5 (5%) and CuSO4 (6%). The optimum reaction conditions called for the mass ratio of CuSO4/HZSM-5 to be 0.4 and the catalyst/biomass mass ratio to be 0.5. The recycled catalyst exhibited low productivity (9%). Analysis of the catalysts by Py-IR revealed that the CuSO4/HZSM-5 owned a stronger Brønsted acid intensity than HZSM-5 or the recycled CuSO4/HZSM-5. Therefore, the existence of Brønsted acid is necessary to achieve a more productive degradation of biomass for furfural., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

A conical spouted bed reactor was designed and tested for fast catalytic pyrolysis of miscanthus × giganteus over Zeolite Socony Mobil-5 (ZSM-5) catalyst, in the temperature range of 400-600 °C and catalyst to biomass ratios 1:1-5:1. The effect of operating conditions on the lumped product distribution, bio-oil selectivity and gas composition was investigated. In particular, it was shown that higher temperature favors the production of gas and bio-oil aromatics and results in lower solid and liquid yields. Higher catalyst to biomass ratios increased the gas yield, at the expense of liquid and solid products, while enhancing aromatic selectivity. The separate catalytic effects of ZSM-5 catalyst and its Al2O3 support were studied. The support contributes to increased coke/char formation, due to the uncontrolled spatial distribution and activity of its alumina sites. The presence of ZSM-5 zeolite in the catalyst enhanced the production of aromatics due to its proper pore size distribution and activity., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

The removal of CO2 and tar in fuel gas produced by biomass thermal conversion has aroused more attention due to their adverse effects on the subsequent fuel gas application. High quality fuel gas production from sawdust pyrolysis with CaO was studied in this paper. The results of pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) experiments indicate that the mass ratio of CaO to sawdust (Ca/S) remarkably affects the behavior of sawdust pyrolysis. On the basis of Py-GC/MS results, one system of a moving bed pyrolyzer coupled with a fluid bed combustor has been developed to produce high quality fuel gas. The lower heating value (LHV) of the fuel gas was above 16MJ/Nm(3) and the content of tar was under 50mg/Nm(3), which is suitable for gas turbine application to generate electricity and heat. Therefore, this technology may be a promising route to achieve high quality fuel gas for biomass utilization., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

To improve chemicals selectivity under low temperature, a new method that involves the injection of additives into biomass pyrolysis is introduced. This method allows biomass pyrolysis to achieve high selectivity to chemicals under low temperature (300°C), while nothing was obtained in typical pyrolysis under 300°C. However, by using the new method, the first liquid drop emerged at the interval between 140°C and 240°C. Adding methanol to mushroom scrap pyrolysis obtained high selectivity to acetic acid (98.33%), while adding ethyl acetate gained selectivity to methanol (65.77%) in bagasse pyrolysis and to acetone (72.51%) in corncob pyrolysis. Apart from basic chemicals, one high value-added chemical (2,3-dihydrobenzofuran) was also detected, which obtained the highest selectivity (10.33%) in corncob pyrolysis through the addition of ethyl acetate. Comparison of HZSM-5 and CaCO3 catalysis showed that benzene emerged in the liquid because of the larger degree of cracking and hydrodeoxygenation over HZSM-5., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

In this work, density functional theory (DFT) was employed to investigate the reaction pathways of β-D-glucopyranose for better understanding the pyrolysis mechanism of cellulose in hydrogen plasma. Many possible reactions were considered, and the reaction enthalpies and activation energies of these reactions were calculated using density functional theory (DFT) with a Gaussian method of B3LYP and basic set of 6-31G(d,p). A most possible reaction pathway was brought up. According to this reaction pathway, the main products of cellulose pyrolysis in hydrogen plasma would be syngas, and few light hydrocarbons. CO mainly comes from the decomposition of aldehyde group, while H2 mainly comes from dehydrogenation processes. Active H in plasma are found to play a very important role in many reactions, and they can remarkably lower the energies needed for reactions., (Copyright © 2013 Elsevier Ltd. All rights reserved.)