Pyrolysis kinetics behavior and pyrolysate compositions analysis of agriculture waste toward the production of sustainable renewable fuel and chemicals

This work deals with the characterization of feed, kinetic, and compositional study of sugarcane baggage (SCB) using a thermogravimetric analyzer (TGA), Py‐GC‐MS, and X‐ray fluorescence (XRF) analyzer. XRF analyzer was used to determine the mineral of ash content, and Py‐GC‐MS was employed to determine the hot vapor composition produced during fast pyrolysis. Cots‐Redfrem (CR) methods and master plots were utilized to determine the kinetic parameters. Studies on the physicochemical properties of SCB have demonstrated its potential for use as a bioenergy feedstock. The average activation energy was found to be 25.44 kJ mol−1 at (n = 1) and 31.21 kJ mol−1 at n ≠ 1 using the CR model. The master plot study suggested that pyrolysis occurred with various mechanisms, while kinetic results of SCB demonstrated that activation energy varied with conversion value. XRF examination revealed significant mineral materials that aided in the pyrolysis process. Finally, the introduction of ZSM‐5 at 20 wt % results increased hydrocarbons (~3 wt %), furfurelas (~4 wt %) and reduced the phenols (~15 wt %), acid (~9 wt %) and oxygnetaed compounds. The present study showed that introducing zeolite catalysts improved pyrolysis products' properties.


| INTRODUCTION
Fossil fuels account for almost all of the remarkable growth in contemporary human society.All nations are now searching for renewable and non-polluting options because of the limited reserves, territorial accessibility, and environmental problems (acid rain, global warming, climate change, etc.) brought on by the usage of fossil fuels. 1 Waste biomass from industrial and domestic sectors is regarded as a renewable, environmentally beneficial substitute for fossil fuels.The last few years have seen an unprecedented increase in research and development efforts to generate scientific knowledge for using readily accessible agricultural and non-agricultural waste as feedstock for creating energy and other finest products via biochemical, chemical, and thermochemical ways. 2 In the majority of industries, lignocellulosic feedstocks can substitute fossil fuels.Global activities are therefore being undertaken to utilize them as feed for creating clean energy and authentic materials, which are now produced from natural gas and petroleum. 3India, a nation with a large and overpopulated population, is hugely reliant on crude oil imports.India imported 189.24 million metric tonnes (MMT) of crude oil, costing Rs 864,875 crores between 2013 and 2015.Thus, India must strongly emphasize renewable energy sources, like biomass, to provide energy independence and meet its international norms to reduce its carbon footprint. 4garcane (Saccharum officinarum L.), a perennial monocotyledonous plant that originated in Asia and is a member of the Poaceae (Gramineae) group, is currently one of the fastest-growing cash crops in many tropical and subtropical countries.India is the second-largest supplier after Brazil, which produces 1/4 of the world's sugarcane. 4The average production in the top 10 countries is shown in Figure 1, together with the total area used for sugarcane farming globally from 1994 to 2019. 5 It is farmed on 4.95 million hectares of land in India, with a crop yield of 70.39 tonnes per hectare.The most plentiful agricultural in India is sugarcane leaves and tops, which typically account for 25%-30% of crop residues as waste. 5ermogravimetric analysis (TGA) is one of the most popular and successful methods for determining kinetic parameters when used in conjunction with iso-conversational models.For the determination of kinetic parameters, many authors employed TGA. 6,7The TGAdependent model, frequently used to estimate biomass's kinetic parameters, includes many models: a single model, two parallel reaction models, three pseudo components models, and distributed activation energy models.There are only two methods for pyrolyzing biomass in a TGA: isothermal and non-isothermal.Since the non-isothermal model differs little from the isothermal model in inaccuracy, it has gained widespread acceptance.The additional non-isothermal model was split into the model fitting and model-free major streams.
Due to its provision of kinetics parameters without making any assumptions and using dynamic or single heating rates, the model-free method was more tolerable.However, model-fitting techniques need various models to achieve the best statistical fit.The advantage of the iso-conversational model over alternatives is that there is no chance of choosing the incorrect kinetic model to achieve the best match of kinetic constraints. 8The coats-Redfern model (CR) is founded on isoconversational method and works on a single heating rate. 6 comprehend the pyrolysis characteristics of biomass, pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS) has been employed.Py-GC-MS is the most alluring analytical technique for determining pyrolysis behavior and accurately detecting pyrolytic end products by comparing the acquired chromatograph under various operating variables. 911]   12 studied the pyrolysis behavior of cynodon dactylon grass using Py-GC/MS analyzer.Py-GC-MS results confirmed that the formation of phenolic, aromatic hydrocarbons, and ketones rose between 450 and 650 C, whereas cyclopentanones, acids, esters, and other oxygenated compounds decreased.Li et al. 13 studied the catalytic pyrolysis of biomass over Fe-modified hierarchical ZSM-5 using Py-GC-MS.The findings showed that alkali treatment and Fe loading established the catalyst's hierarchical and porous structure, which also increased its acidity and produced attractive mono-aromatics and olefins selectivity.Huang et al. 14 studied the pyrolysis behavior of mushroom bran (MB) and corn straw (CS) using Py-GC-MS.The findings demonstrated that at greater heating rates, starch and hemicellulose breakdown overlapped, perhaps creating synergistic effects that would encourage the synthesis of furan and furfural.Additionally, pyrolysis studies demonstrated that lowering temperature decreased the synthesis of F I G U R E 1 World production of sugarcane countries from 1994 to 2020 (adapted from: FAOSTAT 56 ).
oxygen compounds, including acids and aldehydes.Most caneproducing nations have a rich history of using bagasse and sugar cane residue as fuel.During the preceding 10 years, several scientists have become interested in conducting systematic investigations to comprehend the thermal decomposition activity for generating real-worth products, including bio-oil, biochar, and biogas.The catalyst improves the properties of pyrolytic end products such as hot vapors.Using a catalyst increases the reaction rate, decreases the activation energy, and increases the desired products. 15It has been discovered that ZSM-5, a broadly used catalyst for biomass pyrolysis, significantly alters the configuration of bio-oil by generating more organic matter (bio-oil), which can be enhanced to gasoline and diesel, by significantly lowering oxygenated substances by deoxidization reactions, and by continuing to increase aromatic organisms. 16In order to study the improved properties of pyrolysis gases, ZSM-5 is used at 20 wt % in this study. 17The catalyst loading on SCB is optimized based on the available literature.Many authors also used the iso-conversational model to examine SCB kinetic modeling and thermal decay. 18,19However, very few researchers have attempted to examine the thermal degradation pattern and kinetics of SCB using the CR model.Furthermore, it is discovered that there is no literature at all on the study of reaction mechanisms employing master plots.Also, it is established that there is no literature on the one-stage thermos-catalytic pyrolysis of SCB utilizing Py-GC-MS.The kinetic study of SCB adds the information that can be used during designing a new pyrolyzer and optimizing the process parameters at the molecular level.Moreover, pyrolysis of SCB in Py-GC-MS helps to understand the pyrolysis behavior in a single stage.SCB is utilized in India as fuel for generating raw sugar and jaggery in simple furnaces and juice concentrators.However, there is little scientific research on combustion and thermal degradation behavior.
There has been much research on the kinetic exploration of various biomass, but no data is available to estimate the pyrolysis reaction for SCB using the CR model.In addition, the pyrolysis study of SCB is also found to be absent in the literature using a Py-GC-MS analyzer.
This study was conducted to ascertain the physiochemical outcomes, kinetic analysis, and pyrolysis characteristics of SCB.The kinetic parameters of SCB at 10 C min À1 were calculated using the iso-conversational model CR to understand the pyrolysis degradation process.Additionally, proximate, elemental analysis, TGA, and XRF analysis were performed to characterize the physiochemical properties of SCB, and Pyro-Gas chromatography-mass Spectrometry (Py-GC-MS) was employed to comprehend its pyrolysis properties.

| Sample collection and preparations
Sugarcane baggage (SCB) was received from the local juice shop in Bangalore, Karnataka, India.The supplied sample was cleaned with fresh hot water to eradicate dirt and other impurities.After that, SCB was sundried for a week before being put in a hot air oven at 80 C overnight to eliminate moisture.The dried SCB was broken into smaller pieces (2-3 cm) and ground in a mixture grinder to 600-800 μm particle size.The powdered sample is then stored in an airtight plastic container to inhibit moisture absorption.ZSM-5 is used at 20 wt % loading in the pyrolysis of SCB.The catalyst loading is optimized based on the literature. 20

| Physicochemical characterization of biomass
The feasibility study can be used to estimate the prospective capabilities of organic matter or biomass.The physical and chemical evaluation of biomass was part of the feasibility analysis.The proximate investigation followed ASTM guidelines (E 872, D 1102, and E 871).
The difference was used to compute the quantity of fixed carbon.An elemental analyzer (Perkin-Elmer elemental analyzer, Thermo Scientific Flash 2000) is also used to evaluate the elemental analysis of SCB.In addition, the bulk density of SCB was estimated using a volumetric cylinder and a digital balance, while the higher heating value (HHV) was determined using an oxygen bomb calorimeter (Plain Jacket, Paar instrument, Model 1341).The extractive content was assessed using a Soxhlet extractor, and the biochemical analysis was determined using wet chemistry techniques.

| Thermal stability analysis
A thermogravimetric analyzer (NETZSCH, TG 209 F1 Libra) is used to investigate the sample thermal stability in an oxygen-deprived environment.To establish the thermal profile of SCB, 9 ± 0.001 mg of sample is employed.The sample is heated from 30 to 900 C at 10 C min À1 , while the inert gas flow rate is kept constant (50 mL min À1 ) during the test.

| Fourier Transform Infrared Spectroscopy (FTIR) analysis
Fourier Transform Infrared Spectroscopy is used to reconnoiter the company of functional groups in the feeds.FTIR study of the sample is achieved by Shimadzu (Model No.: IRAffinity-1).A hydraulic machine creates a film (approximately 1 mm) from the biomass and potassium bromide (KBr) in a 1:100 ratio.Further, biomass and KBr-based film are placed in the FTIR cabinet, and scanning is performed in the 400-4000 cm À1 region, with a step size of 4 cm À1 and a scanning rate of 40 scans.

| XRD study of biomass
The feedstock's X-ray diffraction (XRD) pattern was gained through a Rigaku TT Rax diffractometer coupled with a Cu-K radiation source and X-ray produced at 15 kW and 250 mA.At a speed of 0.03 min À1 , the scanning angle (2θ) was set to 10-60 for all biomass.The crystallinity index of the samples was calculated using Equation (1).
where the crystalline peak intensity was approximately 2θ = 22.25 for the crystalline section of the feedstock (i.e., cellulose) and the amorphous peak intensity was approximately 2θ = 16.12 for an amorphous portion (i.e., cellulose, hemicellulose, and lignin).

| X-ray fluorescence (XRF) analysis of residual
The ash content is rich in various inorganic components (primarily MgO) that act as efficient catalysts during pyrolysis. 21X-ray fluorescence spectroscopy (XRF, AMETEF SPECTRO XEPOS) examines the mineral components (oxides) involved in the ash composition.A slagging and fouling component exemplified ash accumulation characteristics.Slagging is described as molten or imperfectly fused deposits on the surface of a radiant-heated furnace.In contrast, fouling is described as developing fussy residues on a convective surface.Carpenter's equations (2-5) are used to calculate the deposition characteristics of inorganic residue. 22se to Acid Ratio

| Kinetic theory and parameters
Biomass is a heterogeneous mixture of diverse components, each with a specific disintegration temperature range.In addition, various intricate reactions occurred throughout pyrolysis, adding to its complexity.
One of the critical aspects controlling pyrolysis is the kinetic variables of the feedstock.Thus, a model-free approach such as the Cots-Redfern (CR) method is employed to explore kinetic characteristics such as activation energy (E), order of reaction (n), and preexponential factor (A). Tables 1 and 2 contains the model equations employed to figure out the kinetic constraints of SCB.Where β, R, T, A, n, and E are denoted as heating rate ( C min À1 ), gas constant (8.314J mol À1 K À1 ), absolute temperature (K), pre-exponential factor (min À1 ), reaction order, and activation energy (KJ mol À1 ), T m is peak decomposition temperature in (K), K B is Boltzmann constant.Here, x ¼ E RT and π x ð Þ is an approximation of the temperature integral that can be conveyed in a modest analytical form.

| Feasibility study of SCB
The practicality of SCB is determined by its physicochemical qualities and listed in Table 3.The obtained findings are also compared to other verified research, such as switchgrass, 11 corn stover, 23 and elephant grass. 24The proximate investigation determined a moisture of 5.12%, volatile matter content of 69.12%, ash content of 3.68%, and a fixed carbon content of 22.08%, respectively.The moisture content was determined to be lower than its acceptable limits (>10%), making SCB a more viable alternative for pyrolysis feedstock.Furthermore, the volatile matter is lower (69.12%)than the other recorded feedstock in Table 3, and the ash level is lower (3.68%)than corn stover and elephant grass.As SCB has a lower volatile matter and lower ash percentage, it is simpler to ignite throughout combustion. 25Furthermore, the lower ash content in biomass worked as a heat sink, lowering the fuel's heating value.In addition, the decreased ash level encouraged a T A B L E 1 Lists of the kinetic models used to calculate the kinetic parameters.

Model name Mathematical formula
significant reduction in fouling and slagging within the boiler or furnace. 26The fixed carbon content is 22.08%, somewhat greater than the other stated biomass in Table 3 owing to biochemical structural variances.SCB had 46.84% carbon, 6.50% hydrogen, 45.78% oxygen, 0.69% nitrogen, and 0.19% sulfur, which corresponded well with other published feedstock in Table 3.The presence of greater carbon content and lower hydrogen content in biomass verified the probability of a higher heating value of fuel and its prospective energy ability for energy generation. 11Furthermore, the sample's low oxygen concentration has the benefit of yielding a larger bio-oil yield with superior qualities, as the development of oxygen content reduces the heating value of the fuel.Furthermore, the reduced nitrogen and sulfur content of SCB resulted in a significant decline in SO x and NO x generation during combustion. 11The Van-Krevelen diagram (VKD) may be used to represent the energy density of feedstock.VKD is researching the atomic ratios of biomass.SCB has an atomic ratio that is extremely near to switchgrass, corn stover, elephant grass, coffee hulls, and bamboo leaves, and the VKD is shown in Figure 2. According to the elemental research findings, the hydrogen to carbon ratio (H/C) is 1.66, which is greater than switchgrass, corn stover, elephant grass, and lower than coffee hulls and bamboo leaves.The oxygen to carbon (O/C) ratio is also comparable to all of the materials indicated in Figure 2. The biochemical makeup of biomass caused the change in the atomic ratio of all biomass.The atomic ratio of carbonaceous fuel verifies the fuel's ignition efficiency. 27Furthermore, a greater atomic ratio (H/C) of fuel is required than an O/C ratio to attain an increased fuel grade. 27SCB's HHV was determined to be 18.68 MJ/kg, and its bulk density was 142.12 kg m À3 , indicating that transportation and storage of SCB would be simple. 11The HHV and bulk density of SCB values accord well with the other documented biomass in Table 3.
Using the Soxhlet apparatus, the extractive content of SCB was determined to be  the thermal decay temperature, activation energy, and depolymerization rate. 28As a result, before any pre-treatment, an XRD analysis of the material should be undertaken.The company of wax components, exceptionally high molecular weight hydrocarbons, and some fatty T A B L E 2 Algebraic expressions for f(α) and g(α) for the most frequently used mechanisms of solid-state processes. 41action mechanisms Symbols f(α) g ( α)

| XRD analysis
Order of reaction Limiting surface reaction between both phases One dimension R1 1 α Random nucleation and nuclei growth acids influence the crystallinity of feedstock.XRD spectra verified the lack of solid peaks, indicating that the biomass is amorphous.SCB has a crystallinity index of 33.95%, which is lower than the stated biomass crystallinity indexes of rice straw, rice husk, cotton stalk, wheat straw, corn stover, sorghum stalk, mustard stalk, corn cob, and Jatropha pruning (43%-61.90%). 29,30

| FTIR analysis
Fourier Transform Infrared Spectroscopy spectra of SCB revealed a complex relationship with water, ester, ether, phenols, acid, alkane, aliphatic, and aromatic products.A spectrum has been plotted wavenumber against transmittance and listed in Figure 3b.The -OH deformation was assigned an absorption band in 3000-3634 cm À1 , establishing the company of water, acid, phenols, proteins, and aromatic components. 31Furthermore, the absorption band 2850-3000 cm À1 identified to C-H stretching established the occurrence of alkane and carbonyl/carboxylic acid. 32Furthermore, the adsorption band 1590 cm À1 assigned to C=C stretching vibration impeded the viability of aromatics and alkene.In contrast, peaks in the range 1232-1455 cm À1 related to C-C deformation vibration confirmed the presence of alkyne. 31,32The adsorption band at 1054 cm À1 was related to C=O stretching and deformation vibration, indicating the incidence of esters and ether.In contrast, the peak range between 716 and 430 cm À1 was accredited to O-H bending, indicating the incidence of mono and polycyclic substituted aromatics constituents. 32nalysis SCB Switchgrass 11 Corn stover 23 Elephant grass 24 Proximate study (wt %) (dry basis) Moisture 5.12 ± 0.02 6. 25    34 The current investigation likewise finds a near breakdown profile, with minor variations driven by differences in chemical constitution.In the lower and transitional periods, the elements of biomass were dispersed.Furthermore, hemicellulose has more moisture than lignin, which leads to higher moisture content. 35lan, the final component of hemicellulose breakdown, has decreased thermal stability due to pentosan hydrolysis and dehydration. 35Unlike hemicellulose, cellulose degrades in three stages.

| Thermal profile study
The very first step was being at lower temperatures (280 C).It incorporates reactions that contribute to cellulose depolymerization via bond cleavage, dehydration, the formation of oxidants (carbonyls, carboxyl groups, and peroxides), the growth of free radicals, the emergence of CO and CO 2 , and eventually biochar growth. 35The next stage befalls between 280 and 550 C, produc- particles and aromatic ring cleave. 35Biochar is found based on the breakdown of comparatively weaker bonds (alkyl-aryl ether) in moderate reaction conditions. 35At the finish of the experiment, the solid residue stays as char, which may be used for a variety of purposes, such as bio-adsorbents, the production of carbon nanotubes (CNT), fertilizers, cosmetic goods, etc., 36 DTG thermographs of SCB displayed in Figure 3 reveal that the opening peak (68 C) formed in the initial phase was caused by removing chemically bound moisture and poor hot volatiles. 33Furthermore, the peaks that formed in the second stage at 218, 285, and 343 C were caused by the degradation of hemicellulose and cellulose due to an interrupted heat supply.Lastly, lignin degradation happened at a high temp (>550 C) and a slow rate, with no abrupt peaks. 33The lignin proportion was smaller than that of hemicellulose and cellulose, and the slower breakdown rate of lignin precludes the creation of prominent peaks. 37The thermal Study of SCB exposed that 7.37% of the biomass degraded in the 1st stage, 72.52% in the 2nd stage, and 7.58% in the 3rd stage, respectively.
The results aligned well with the nearby proximate of SCB research (Tables 1 and 2).  4 is very comparable to other biomass that has been reported, including rice straw and husk, cotton stalk, wheat straw, bagasse, corn stover, sorghum stalk, corn cob, jatropha pruning, Jatropha, coal, and oak wood. 21,30,31Results acquired from the empirical equations of slagging and fouling indices are found to be 0.528 Acid to the Base ratio (A/B), 13.10 Silica to Alumina ratio (S/A), 0.992 Iron to Calcium ratio (I/C), and 17.34 Total Alkali.Slagging and fouling indices were premised on XRF study findings.However, the deposition propensity is sensitive to various restrictions and situations.According to these projections, using SCB in the boiler will cause ash-related issues since it contains more alkali, creating molten salts via vaporization, condensation, secondary reactions, and a high acid-to-base ratio. 38Furthermore, alkali metals abundant in biomass, mainly Na, K, Mg, P, and Ca, aid in heating.The interaction between silica and alkali metal in ash aids in creating a sticky liquid mobile phase, resulting in the clogging of boiler and furnace airways. 39

| Kinetic and master plots study
The kinetic parameters of SCB were computed using the integral technique (Cots-Redfern method) at 10 C min À1 heating rate and the results are shown in Table 5.These parameters include apparent activation energy (AAE) (E, kJ mol À1 ), order of reaction (n), and frequency factor (A, min À1 ).The CR technique is an integral approach that operates at a single heating rate.It was generally known that a solid matrix's first breakdown includes several intricate processes.In contrast, a greater decomposition range might be allied with inadequate solid remains and unfavorable experimental errors. 40The assessed activation energy of SCB was established to be 25.44 kJ mol À1 for n = 1 and 31.21kJ mol À1 for n ≠ 1, respectively.Additionally, it was revealed that the correlation coefficient (R 2 ) was higher than 0.90, indicating the absolute best model-data fitting.Our findings are comparable to pine, sal, and areca nut husks. 7e master plot approach is used to anticipate the reaction mechanisms using the activation energy obtained from the CR model at n ≠ 1.The master plot is achieved at a 10 C min À1 heating rate.
Figure 5 evaluated and depicted the theoretical Z (α) versus conversion value.The data in Figure 5 illustrates the theoretical and experimental Z (α) plots employed to estimate the mechanisms underlying the pyrolysis reaction.Theoretical curves are widely recognized as related to experimental data to determine how well the solid reaction mechanism degrades. 41The four stems of the algebraic equations mentioned are Fn, Dn, Rn, and An, respectively.The growth of nuclei to remove thermal deficiency, the diffusion method connected to heat transfer capability, the estimation of reaction mechanism by the material's surface, and the random disintegration of nuclei are not reaction mechanisms. 42The experimental data plotted in Figure 5 showed that the sample was taken into account for conversion values between 10% and 80%.The D1, D2, and D3 curves overlapped, indicating that the SCB was degraded via corresponding diffusion techniques in the 1D, 2D, and 2D dimensions. 41The SCB's diffusion process matched the other instances that had been examined really well. 32,43Also, diffusion was the major driving phenomenon at lower conversion value (CV).The experimental z-curve is enclosed between the D1 and D2 master plots, corresponding to one-dimensional (1D) and twodimensional (2D) diffusion, with CV ranging from 0.1 to 0.2.The experimental z (α) curve is near D1, associated with 1D diffusion when CV drops between 0.2 and 0.5.Finally, the experimental Z (α) plot overlaps the plot for D3, which is susceptible to the diffusion phenomenon in three dimensions, where CV ranges from 0.6 to 0.8. 32,42ditionally, direct random nucleation happened at greater conversion values (above 0.5). 41The foundation of growth for the decomposition reactions is the decay of the reaction mechanism delivered from random locations.Furthermore, pyrolysis included the breakdown of biomass and promoted the disintegration of cellulose chains above

| Py-GC-MS analysis
Sugarcane baggage is pyrolyzed in a Py-GC-MS analyzer and the obtained spectra were compared to the NIST library and earlier reported works.The peak areas of the substances linked to mass spectra are depicted in Figure 6, and Table 6 summarizes the mass component of the substances.The findings of the pyrolysis showed that the hydrocarbons, phenols, ketones, acids, oxygenated compounds, and furfurals used to make SCB are more suitable for pyrolysis. 44In general, bio-oil is a multifarious blend of several chemicals.However, it should be emphasized that the biochemical structure of the feed, pyrolysis types, and primary operating parameters all have a significant impact on the composition of bio-oil.Most of the products produced by the thermal breakdown of hemicellulose and cellulose include aromatic hydrocarbons, cycloalkane, furanic compounds, acids, kenotic products, and other hydrocarbons. 45The prevalence of these substances has also increased due to recent studies.
The conclusion also shows that temperature has the main role in changing the product's constitution.Dehydration, primary, and secondary decay are the three main processes in biomass pyrolysis. 46ile secondary decomposition occurred in more than a second, initial decomposition occurred in less than a second. 46The dehydration reaction primarily removes water content.were primarily produced by the breakdown of lignin and in small quantities by the aromatization of cellulose and hemicelluloses. 47The structure of the phenylbenzofuran was typical for lignin, and around 30% of benzene derivate comes from benzofuran. 48The secondary pyrolysis of intermediate phenylbenzofuran was crucial in forming benzofuran. 49It is found that using ZSM-5 at 20 wt %, hydrocarbon percentage slightly augmented from 11.13% to 13.34% due to the cyclization reaction to produce benzene. 50,51A sequence of alkylation reactions would occur to create substituted benzene derivatives (aromatic hydrocarbons). 50Phenol percentage is found to be decreased from 30.1% to 16.71% at 20 wt % ZSM-5 due to deoxygenation reactions (revolution of phenols into aromatic hydrocarbons). 52The reduced phenols can be observed in the augmented hydrocarbon percentage.Furfurals were assumed to be the end products of the cyclization of the cellulose unit after dehydration, and they had a stable structure. 53Further, it was found that the use of ZSM-5 at 20 wt %,  furfurals percentage increased by 3.5% due to possibly furfural turned into valued aromatics by continuous catalytic fast pyrolysis. 54As carboxylic acids are reduced more quickly at higher temperatures, the proportion of acids was discovered to be decreased by 9.21%.It is generally known that the acetic acids are produced by the eradication of acetyl groups attached to the xylose unit on the C-2 position, followed by the ring-fission of uronic acid that is left over after the removal of carbonyl and O-methyl groups. 55Additionally, it was shown that ketones were less abundant at 20 wt % ZSM-5 due to the evaporation of water.The interaction between the molecules of oxygen and hydrogen during pyrolysis results in the creation of water.
Also, the amount of alcohol was found to be decreased from 3.76% to 1.83% due to the formation of increased hydrocarbons.Combining the entire Py-GC-MS data, it is reasonable to conclude that ZSM-5 at 20 wt %, changed the composition of hot vapors which added the fuel properties.

| CONCLUSIONS
Thermogravimetric analyzer and Py-GC-MS analyzer were used to evaluate SCB pyrolysis behavior and kinetics analysis.Characterization results highlighted its bioenergy potential for generating fuel and chemicals.XRF study confirmed the presence of various useful compounds that act as a catalyst during biomass pyrolysis.The functional group study of SCB confirmed the attendance of phenol, aromatics, acids, and other oxygenated compounds.The kinetic analysis showed that different reaction mechanisms are used during pyrolysis.However, the activation energy changes against the conversion value.
Finally, Py-GC-MS confirmed that at 20 wt % ZSM-5 loading, there was a considerable increase in hydrocarbon production and a reduction in oxygenated and acidic products.

2. 8 |
Py-GC-MS studyPy-GC-MS analyzer (CDS Pyroprobe 5250) is intended to investigate the precise distribution of organic compounds.Py-GC-MS analyzer is an exploratory pyrolyzer that provides materials predicted pyrolysis products in one step.To avoid sample loss, a sample container (quartz tube in cylindrical shape) was covered at both extremities with quartz wool.A predetermined sample (0.30 mg) of SCB was loaded into the quartz tube and weighed on a digital scale with a reading of 0.01 mg.The pyrolysis test was carried out at 650 C and 20 C ms À1 heating rate for 20 s.The pyrolysis vapor was examined in a GC-MS (Agilent, 7890B/5977A) with a DB-5MS capillary column (30 m 0.25 mm i.d., 0.25 m film thickness).The injector temperature was kept steady at 280 C. Helium gas of high purity (99.99%) was used as a carrier gas with a constant flow rate of 1 mL min À1 and a split ratio of 1:80.The GC oven temperature was designed to range from 40 to 200 C with a heating rate of 5 C min À1 , then to 280 C (kept for 2 min) with a heating rate of 10 C min À1 .The GC/MS interface temperature was constant at 280 C, and the mass spectrometer operated in EI mode at 70 eV.The mass spectra were collected in the total ion current (TIC) mode from m/z 30 to 400.The chromatographic peaks were distinguished using the NIST library and existing publications.

Figure 3a displays
Figure 3a displays the XRD spectra plotted between two theta degrees and intensity.Assessing cellulose crystallinity in the feedstock is a challenging task.By modifying the cellulose inter-hydrogen bond, the crystalline phase of cellulose may be altered.The development of liquid mediators and the temperature of thermal dilapidation are generally disturbed by cellulose crystallinity.Lower crystallinity abridged

Figure 4
Figure 4 depicts the temperature-dependent breakdown curve of SCB.TGA and DTG profiles revealed that SCB decayed in three main

F I G U R E 2
Van-Krevelen diagram of biomass and biochar.stages: dehydration (up to 150 C), devolatilization (150-550 C), and char development (>550 C).A similar breakdown profile for grape marc has also been described by Khiari and Jeguirim. 33During the initial stage, primarily chemically assured humidity and very mild hot volatiles were emitted.However, the highest breakdown profile of SCB was observed in the temperature range of 150 to 550 C. Due to the constant input of heat, the primary elements of biomass (hemicellulose and cellulose) degrade into lower molecular weight molecules in the second stage.It is known that biomass splitting begins around 170 C, with tarry fumes, and remains reaching 400 C.
ing tar-rich pyrolysates (anhydrosugars, levoglucosan, oligosaccharides) and minor quantities of glucose from glycosidic bond depolymerization.Then, at a temperature over 550 C, the last detonation stage drives the direct conversion of cellulose into smaller units and hot volatiles by fission, dehydration, disproportionation, and decarboxylation processes. 35As a result of its increased thermal resilience, lignin fragments at somewhat extremely high temperatures (>550 C).The lignin disintegration is attributed to the breakage of C-O bonds, which results in compounds with a single oxygen atom.Following that, at 327-380 C, the methoxy cleavage C-O bonds provide products containing two oxygen atoms; ultimately, the chain length C-C bonds between carbon

F 3 . 5 |
I G U R E 3 (a) X-ray diffraction of sugarcane bagasse (SCB), and (b) Functional group study of SCB using FTIR analyzer.F I G U R E 4 Thermal profile study of sugarcane bagasse at 10 C min À1 .Slagging and fouling indices and ash deposition tendencies of residual biomass Ash offers inorganic elements that have beneficial effects during pyrolysis.The inclusion of ash either increases pyrolytic liquid yield or improves fuel characteristics.There are some standards for deposition inclinations, including low (B/A < 0.5), medium (0.5 < B/A < 1), and high deposition tendencies (B/A > 1).Additionally, deposition tendency is high for values between 0.3 and 3 of the silica-alumina and iron-calcium ratios, whereas it is low for values between 0.31 and 3. Further, S < 0.6 indicates low deposition propensity, 0.6 < S < 2 indicates medium deposition tendency, and S > 2 indicates high deposition tendency.In conclusion, the fouling propensity is low when TA < 0.3, medium when 0.3 < TA < 0.4, and high when TA > 0.4.The XRF (X-ray fluorescence) analysis shown in Table

0. 5
CV at a higher temperature (350 C), leading biomass toward random nucleation (F1 corresponds to unplanned nucleation with one nucleus in the separate particle).42Lower-weight molecules are predicted to be a hub for the decomposition reaction's random nucleation and growth.This decomposition-related reaction mechanism is introduced from random sites and serves as a center of expansion for breakdown reactions.According to the findings, at a conversion value of 0.5, a higher temperature (350 C) causes biomass to fragment and encourages the breakdown of cellulose chains (Fn-related decomposition).According to expectations, smaller molecular mass chains may serve as random nucleation and development hubs for the breakdown process.Z (α) values correspond to the 3D diffusion since they lie over the D3 reactions.This typically happened when hemicellulose and extractives are degraded at a lower temperature.Moreover, both diffusion in solids and diffusion of hot gases could be attributed to speeding up the breakdown of cellulose in this process.A similar study was also reported on Lagerstroemia speciosa seeds hull and Saccharum officinarum L.32,42

F I G U R E 6
Compositional analysis of sugarcane bagasse (SCB) biomass using Py-GC-MS at 650 C. F I G U R E 5 Theoretical and experimental plots for predicting solidstate reaction mechanism via master plot.T A B L E 6 Compositional study of SCB in Py-GC-MS.
Chen et al. investigated the torrefaction of rubber wood sawdust (RWS) at 200, 250, and 300 C and pyrolysis at 450, 500, and 550 C.They found that torrefaction at temperatures of 200 and 250 C results in the development of ester (diethyl phthalate), likely due to the establishment of hemicellulose.Mishra et al.
T A B L E 4 XRF analysis of sugarcane bagasse (SCB) ash content.