Department of Chemical Engineering

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Author: search.filters.author.Srinivas, AppariSubject: search.filters.subject.Chemical Engineering

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Now showing 1 - 10 of 29
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    Effect of Calcination Time on the Catalytic Activity of Ni/γ-Al2O3 Cordierite Monolith for Dry Reforming of Biogas
    (Elsevier, 2021-02) Roy, Banasri; Srinivas, Appari
    Ni/γ-Al2O3 wash coated cordierite monolith catalysts are calcined in air at 800 °C for 4, 10, and 20 h in order to study the effect of calcination time on the activity of the catalysts for dry reforming of model biogas. Catalytic activity studies are performed at 800 °C with three different CH4/CO2 ratios of 1.0, 1.5, and 2.0. The catalyst calcined for the longest time (C-20) displays higher stability and activity in terms of CH4 and CO2 conversion compared to those calcined for 4 h (C-4) and 10 h (C-10). XRD data and TPR analysis detect the maximum amount of NiAl2O4/MgAl2O4 phases and strongest metal-support interaction, respectively, for the C-20 sample. FESEM reveals the particle size of the calcined and reduced C-20 sample to be smaller than that of the C-4 and C-10 samples. Whereas, H2 pulse-chemisorption characterization demonstrates the highest metal surface area, metal dispersion, and smallest Ni particle size for the C-20 catalyst. While, no carbon deposition on any catalyst occurs for the CH4/CO2 ratio of one, lowest amount of carbon nanotubes is formed on the C-20 sample for the CH4/CO2 ratio of 1.5 and 2.0, as observe by DTA-TGA. EDX reveals concentration variation of Mg and Si from the cordierite monolith wall along the thickness of the coating for all the samples. In addition, the maximum amount of these elements is observed for the calcined C-20 catalyst coating. These implies that the diffusion of Mg and Si from the cordierite monolith to the catalyst coating during calcination contribute significantly in controlling the physicochemical properties of the catalysts. As a result, the higher stability and activity of the C-20 could be attributed to the formation of higher amount of the Ni– Mg- alumina spinel complex in the catalyst coating during longer calcination time, which leads to the improved metal-support interaction and higher nickel dispersion over monolith.
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    A review on ethanol steam reforming for hydrogen production over Ni/Al2O3 and Ni/CeO2 based catalyst powders
    (Elsevier, 2022-02) Srinivas, Appari; Roy, Banasri
    Hydrogen is contemplated as an alternative clean fuel for the future. Ethanol steam reforming (ESR) is a carbon-neutral, sustainable, green hydrogen production method. Low cost Ni/Al2O3 and Ni/CeO2 powder catalysts demonstrate high ESR activity. However, acidic nature of Al2O3 and instability of CeO2 lead to deactivation of the catalysts easily. This article examines the research articles published on the modification of Ni by various noble and non-noble metals and on alteration of the supports by different metal oxides in detail and their effect on ESR all through 2000–2021. The ESR reaction mechanisms on Ni/Al2O3 and Ni/CeO2 powder catalysts and basic thermodynamics for different possible reactions and H2 yield are explored. Manipulation of catalyst morphology (surface area and particle size) via preparation method, selection of active metal promoter and support modifier are found to be significantly important for H2 production and minimizing carbon deposition on catalysts.
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    Recent advances and perspectives of perovskite-derived Ni-based catalysts for CO2reforming of biogas
    (Elsevier, 2022-11) Srinivas, Appari; Roy, Banasri
    CO2 reforming of biogas (CRBG) is a promising renewable energy source to tackle the global energy demands and environmental challenges. Biogas (BG) is reformed to produce syngas on numerous catalysts, including transitional (Ni, Co, Fe, and Mo) and precious (Pt, Pd, Rh, and Ru) metals over various supports. However, catalyst deactivation due to the carbon deposition and trace amounts of H2S in BG is a significant barrier to commercializing the CRBG. Recently, perovskite oxide catalysts have gained interest due to their unique structural characteristics and articulating properties that favor CRBG for carbon-free operation. This review discusses the perovskite oxide catalysts in CO2 reforming, emphasizing structural stability, activity, and carbon deposition. The exsolved perovskite catalysts are reviewed as potential alternatives to the conventional LaNiO3, which suffers the structure break-down during the dry reforming. The exsolution of the catalysts offers numerous benefits such as structural stability, strong metal support interaction, oxygen storage capacity, and active small particle size with good dispersion, thus leading to better catalyst stability without deactivation in CRBG. However, catalyst reduction conditions dictate the particle size and activity of the catalysts. This review extensively covers the studies on different Ni-derived perovskites, the effect of partial doping of various metals (Ni, Co, Fe, Pt, Pd, and Rh), and mechanisms and related mixed-oxide systems.
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    Effects of metal loading and support modification on the low-temperature steam reforming of ethanol (LTSRE) over the Ni–Sn/CeO2 catalysts
    (Elsevier, 2023-05) Roy, Banasri; Srinivas, Appari
    This article presents the effect of metal loading and support modification with MgO on low-temperature steam reforming of ethanol (LTSRE) over Ni–Sn/CeO2 catalysts prepare by a single-pot solution combustion synthesis (SCS) method. Atmospheric pressure activity study of these catalysts (0.5 g) is performed at different temperatures (200–400 °C), H2O:EtOH = 12: 1 mol ratio, and feed flow rate 0.1 ml/min. After 10 h TOS at 400 °C, NiSn(5)/CM12 catalyst with 5 wt.% total metal loading, optimal Sn (Ni:Sn = 14:1), and Ce:Mg = 1:2 mol ratio shows EtOH conversion 100% and H2 selectivity 70% with low coke deposition. Physicochemical characterizations (XRD, Raman, FESEM, TEM, and N2 adsorption-desorption) reveal that addition of MgO in CeO2 and an optimal amount of Sn decrease both Ni and support particle sizes while oxygen storage capacity (OSC) of the support increases (by XPS). Alkaline characteristics of MgO reduces support's acidity and improves active metal-support interaction, as evaluated by NH3-TPD and H2-TPR.
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    Sustainable use of rice husk for the cleaner production of value-added products
    (Elsevier, 2022-02) Kuncharam, Bhanu Vardhan Reddy; Srinivas, Appari
    This paper covers a comprehensive review of the thermochemical conversion of rice husk (RH) into value-added products. RH is an organic residue and is produced in large quantities in China, India, Indonesia, and Bangladesh and appears to be a viable source for value-added products from thermochemical processes. The RH properties and operating conditions affect the quality and yield of the bio-oil, gaseous, and biochar products. The conversion techniques such as gasification, slow and fast pyrolysis, and product distribution are systematically reviewed. The literature shows that the Ni-based catalysts demonstrated high activity towards cracking of tar compounds and hydrocarbons, upgraded gas quality, and yielded high hydrogen production. Zeolite-based systems are promising catalysts for the upgradation of bio-oils. Due to the structured porosity and higher acidity, the metal-loaded zeolites catalysts have shown high removal efficiency towards the oxygenated compounds. RH ash is also used as an alternative cementitious material in the construction sector. The optimum level of cement replacement with RH ash in concrete is 15–20%, and higher compressive strength is witnessed for RH ash used concrete than conventional cement concrete. RH ash utilization for soil remediation and blended cement production are also discussed. A sustainable framework has been proposed for the utilization of RH in the chemical and construction sectors.
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    A mechanistic study on the reaction pathways leading to benzene and naphthalene in cellulose vapor phase cracking
    (Elsiever, 2014-10) Srinivas, Appari
    The reaction pathways leading to aromatic hydrocarbons such as benzene and naphthalene in gas-phase reactions of multi-component mixtures derived from cellulose fast pyrolysis were studied both experimentally and numerically. A two-stage tubular reactor was used for evaluating the reaction kinetics of secondary vapor phase cracking of the nascent pyrolysates at temperature ranging from 400 to 900 °C, residence time from 0.2 to 4.3 s, and at 241 kPa. The products of alkyne and diene were identified from the primary pyrolysis of cellulose even at low temperature range 500–600 °C. These products include acetylene, propyne, propadiene, vinylacetylene, and cyclopentadiene. Experiments were also numerically validated by a detailed chemical kinetic model consisting of more than 8000 elementary step-like reactions with over 500 chemical species. Acceptable capabilities of the kinetic model in predicting concentration profiles of the products enabled us to assess reaction pathways leading to benzene and naphthalene via the alkyne and diene from primary pyrolysates of cellulose. C3 alkyne and diene are primary precursors of benzene at 650 °C, while combination of ethylene and vinylacetylene produces benzene dominantly at 850 °C. Cyclopentadiene is a prominent precursor of naphthalene. Combination of acetylene with propyne or allyl radical leads to the formation of cyclopentadiene. Furan and acrolein are likely important alkyne precursors in cellulose pyrolysis at low temperature, whereas dehydrogenations of olefins are major route to alkyne at high temperatures.
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    Kinetic modeling of non-catalytic partial oxidation of nascent volatiles derived from fast pyrolysis of woody biomass with detailed chemistry
    (Elsiever, 2015-06) Srinivas, Appari
    The gas-phase partial oxidation (POx) of nascent volatiles (NV) derived from the fast pyrolysis of cedar sawdust at 700 and 800 °C was studied both numerically and experimentally. A detailed chemical kinetic model (DCKM) was applied to simulate the POx in a two-stage reactor: the first stage was designed for fast biomass pyrolysis and the second effected the POx of the NV. Analytical pyrolysis experiments were also conducted to approximate the molecular composition of the NV, which is required input for computations using DCKM. The DCKM was modified by an empirical kinetic model for the decomposition of an ill-defined portion of the NV. The kinetic model coupled with a plug-flow reactor model reproduced the observed trends in the product yields with respect to both temperature and oxygen-to-fuel ratio, for not only the major products, but also minor products such as aromatic hydrocarbons which are typically found in the refractory post-gasification tar.
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    Predicting the temperature and reactant concentration profiles of reacting flow in the partial oxidation of hot coke oven gas using detailed chemistry and a one-dimensional flow model
    (Elsiever, 2015-04) Srinivas, Appari
    A numerical approach is presented for predicting the species concentrations and temperature profiles of chemically reacting flow in the non-catalytic partial oxidation of hot coke oven gas (HCOG) in a pilot-scale reformer installed on an operating coke oven. A detailed chemical kinetic model consisting of 2216 reactions with 257 species ranging in size from the hydrogen radical to coronene was used to predict the chemistries of HCOG reforming and was coupled with a plug model and one-dimensional (1D) flow with axial diffusion model. The HCOG was a multi-component gas mixture derived from coal dry distillation, and was approximated with more than 40 compounds: H2, CO, CO2, CH4, C2 hydrocarbons, H2O, aromatic hydrocarbons such as benzene and toluene, and polycyclic aromatic hydrocarbons up to coronene. The measured gas temperature profiles were reproduced successfully by solving the energy balance equation accounting for the heat change induced by chemical reactions and heat losses to the surroundings. The approach was evaluated critically by comparing the computed results with experimental data for exit products such as H2, CO, CO2, and CH4, in addition to the total exit gas flow rate. The axial diffusion model slightly improves the predictions of H2, CO, and CO2, but significantly improves those of CH4 and total exit flow rate. The improvements in the model predictions were due primarily to the improved temperature predictions by accounting for axial diffusion in the flow model.
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    Chemical structures and primary pyrolysis characteristics of lignins obtained from different preparation methods
    (J-Stage, 2014) Srinivas, Appari
    This work aims at investigating correlations between primary pyrolysis characteristics of lignin and chemical structure of lignin feedstock. Three different types of lignin samples were prepared through enzymatic hydrolysis, organosolv extraction, and Klason procedure. Analysis by FT-IR and solid state 13C-NMR revealed that the lignin samples exhibited different contents of aromatic carbons, connection carbons, methoxyl carbons, and aliphatic side chains. The three lignin samples were pyrolyzed in a two-stage-tubular reactor at 650 ℃, and pyrolysis products were analyzed with gas chromatographs on-line. More than fifty compounds including inorganic gases, light hydrocarbons (LHs), aromatic hydrocarbons (AHs), phenol derivatives and light non-phenolic oxy-compounds (NPOCs) were gaschromatographically separable and quantified. The influence of the lignin structures on the pyrolysis characteristics was studied, and the correlation of product distribution and lignin chemical structures was examined. The total carbon selectivity into char and tar was increased with increasing lignin aromaticity. Methoxyl group and aliphatic substituents likely contributed for enhancing char formation, while hydrogen in lignin enhanced tar formation. Yields of LHs and NPOCs were increased with increasing aliphatic carbons of the lignin samples. AHs were formed from gas-phase recombination of LHs such as olefins, diolefines and alkynes, rather than directly from aromatic structures in the original lignin likely because of high energy required to cleavage carbon-oxygen bond existed in major structural units such as syringols or guaiacols.
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    In-situ reforming of the volatiles from fast pyrolysis of ligno-cellulosic biomass over zeolite catalysts for aromatic compound production
    (Elsiever, 2014-11) Srinivas, Appari
    Characteristics of in-situ catalytic reforming of the products derived from fast pyrolysis of biomass were studied with an originally designed analytical pyrolysis technique. The volatile products derived from ligno-cellulosic biomass as well as cellulose, xylan, and lignin were converted using a two-stage tubular reactor at 550 °C over various zeolite catalysts with different acidities and pore structures. HZSM-5 exhibited the best performance for converting the cedar derived volatiles to arenes, which mainly composed of benzene, toluene, and naphthalene with a selectivity of 26% on carbon basis. The HZSM-5 had a little effect in increasing the yields of the arenes for xylan and lignin, while it had a significant effect for cellulose, showing that more than 30% of carbon in cellulose was converted into arenes. A reaction pathway analysis for reforming of volatiles suggested that alkyne and diene such as acetylene, propyne, and cyclopentadiene are the important precursors of the major aromatic hydrocarbon products such as benzene, toluene, and naphthalene. The formations of those intermediates were also confirmed experimentally in an early stage of the in-situ reforming.