Browsing by Author "Srinivas, Appari"

Now showing 1 - 20 of 32

A CFD study on the reacting flow of partially combusting hot coke oven gas in a bench-scale reformer
(Elsiever, 2015-11) Srinivas, Appari
A computational fluid dynamics (CFD) approach to simulate reacting flow in a hot coke oven gas (HCOG) reformer is presented. The HCOG was reformed by non-catalytic partial oxidation in a tubular reactor (0.6 m i.d. and ∼4.1 m long) with four oxygen nozzles (0.0427 m i.d.), which was installed on a platform of an operating coke oven. The reforming of HCOG, a multi-component mixture, in a turbulent flow was simulated numerically by considering both chemical reactions and fluid dynamics. The detailed chemical kinetic model, originally consisting of more than 2000 elementary reactions with 257 species, was reduced to 410 reactions with 47 species for realising a kinetic model of finite rate reactions with a k–ε turbulence model. The calculation was carried out using the eddy dissipation concept (EDC) coupled with the kinetic model, and accelerated using the in situ adaptive tabulation (ISAT) algorithm. Numerical simulations could reproduce the reformed gas compositions fairly well, such as H2, CO, CO2, and CH4, as well as the temperature profile in a HCOG reformer as measured by thermocouples.
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.
A circular framework for the valorisation of sugar industry wastes: Review on the industrial symbiosis between sugar, construction and energy industries
(Elsiever, 2018-12) Srinivas, Appari
This paper provides a comprehensive review of literature on the properties of sugar industry waste, their varied uses in energy and construction sector, performance and limitations. An efficient upcycling of sugar industry waste in energy production would help the energy sector to reduce its dependency on non-renewable fossil fuels. Literature demonstrates that in the recent years there has been an increased research interest in thermochemical conversion of sugarcane bagasse to produce cleaner energy, rather than its landfilling or combustion. On the other hand, utilisation of secondary by-products from sugar industry in the production of cement, bricks, paver blocks, activated binder and other construction products helps to cut down the carbon footprint of the construction industry, while improving the properties of the final products. From the perspective of the sugar industry, such an arrangement eliminates disposal problems and creates additional revenue. Although independent research studies investigating the use of sugar industry by-products exist, few studies consider these valorisation options together to minimise waste and to create an efficient material flow chain. This study identifies various material and energy recovery pathways from published literature and connects the materials and processes to form a continuous material supply chain with minimum wastage. From the findings, a symbiotic framework has been developed with primary and secondary by-products from the sugar industry serving as source materials for energy production and sustainable construction products.
Deactivation and regeneration of Ni catalyst during steam reforming of model biogas: An experimental investigation
(Elsiever, 2014-01) Srinivas, Appari
This paper presents detailed study of biogas reforming. Model biogas with different levels of H2S is subjected to reforming reaction over supported Ni catalyst in a fixed bed reactor at 700 °C and 800 °C. In order to understand the poisoning effects of H2S the reactions have been initially carried out without H2S in the feed stream. Three different H2S concentrations (20, 50 and 100 ppm) have been considered in the study. The H2O to CH4 ratio is maintained in such as way that CO2 also participates in the reforming reaction. After performing the poisoning studies, regeneration of the catalyst has been studied using three different techniques i) removal of H2S from the feed stream ii) temperature enhancement and iii) steam treatment. Poisoning at low temperature is not recoverable just by removal of H2S from the feed stream. However, poisoning at high temperature is easily reversed just by removal of H2S from the feed stream. Unlike some previous reports by Li et al. (2010) and Rostrup-nielsen (1971) [1,2], catalyst regeneration is achieved in shorter time frames for all the regeneration techniques attempted.
Detailed Chemical Kinetic Modeling of Vapor-Phase Reactions of Volatiles Derived from Fast Pyrolysis of Lignin
(ACS, 2015) Srinivas, Appari
The vapor-phase reactions of nascent volatiles derived from the fast pyrolysis of lignin were investigated both experimentally and numerically. Lignin residue after enzymatic hydrolysis was pyrolyzed in a two-stage tubular reactor at 773–1223 K. The nascent volatiles formed in the first stage underwent vapor-phase reactions in situ in the second stage. A detailed chemical kinetic model that consists of more than 500 species and 8000 elementary reactions was used to simulate the vapor-phase reactions of volatiles derived from fast pyrolysis of lignin. The contribution of tar in the vapor-phase reactions was considered in global reactions, which improves the predictive capability of the kinetic model. The experimental data and numerical predictions of 31 products were compared and analyzed to understand the mechanism of vapor-phase reactions of lignin. The model predictions were in good agreement with the experimental observations. Reaction pathway analysis for the formation of aromatic hydrocarbons was performed. Cyclopentadienyl radicals produced from phenol decomposition were suggested as important intermediates in the formation of aromatic hydrocarbons during lignin pyrolysis.
A detailed kinetic model for biogas steam reforming on Ni and catalyst deactivation due to sulfur poisoning
(Elsiever, 2014-02) Srinivas, Appari
This paper deals with the development and validation of a detailed kinetic model for steam reforming of biogas with and without H2S. The model has 68 reactions among 8 gasphase species and 18 surface adsorbed species including the catalytic surface. The activation energies for various reactions are calculated based on unity bond index-quadratic exponential potential (UBI-QEP) method. The whole mechanism is made thermodynamically consistent by using a previously published algorithm. Sensitivity analysis is carried out to understand the influence of reaction parameters on surface coverage of sulfur. The parameters describing sticking and desorption reactions of H2S are the most sensitive ones for the formation of adsorbed sulfur. The mechanism is validated in the temperature range of 873–1200 K for biogas free from H2S and 973–1173 K for biogas containing 20–108 ppm H2S. The model predicts that during the initial stages of poisoning sulfur coverages are high near the reactor inlet; however, as the reaction proceeds further sulfur coverages increase towards the reactor exit. In the absence of sulfur, CO and elemental hydrogen are the dominant surface adsorbed species. High temperature operation can significantly mitigate sulfur adsorption and hence the saturation sulfur coverages are lower compared to low temperature operation. Low temperature operation can lead to full deactivation of the catalyst. The model predicts saturation coverages that are comparable to experimental observation.
The Distinctive Effects of Glucose-Derived Carbon on the Performance of Ni-Based Catalysts in Methane Dry Reforming
(MDPI, 2020) Srinivas, Appari
This study aimed to investigate the effect of carbon derived from glucose (C) on the physicochemical characteristics and catalytic activity of Ni, supported over SiO2, ZSM-5, and TiO2 in methane dry reforming. Among the Ni catalysts without C, Ni/SiO2 exhibited the highest CH4-CO2 conversion and stability at all experimented temperatures. On the other hand, the C-incorporated catalysts prepared by glucose impregnation, followed by pyrolysis, showed dissimilar performances. C improved the stability of Ni/SiO2 in the reforming at 650 °C and 750 °C and increased the CH4 and CO2 conversion to the level close to the thermodynamic equilibrium at 850 °C. However, this element did not substantially affect the activity of Ni/ZSM-5 and exerted a retarding effect on Ni/TiO2. Characterizations with H2-TPD, XRD, EXAFS, and STEM-EDS revealed that the different influences of C by the supports were attributed to the extent of metal dispersion and metal-support interaction
Dual reforming of model biogas for syngas production on Ni/γ-Al2O3 and Ni-C/ZSM-5 cordierite monolith catalysts
(Elsevier, 2023) Roy, Banasri; Srinivas, Appari
This work attempts to convert the model biogas on Ni/γ-Al2O3 and Ni-C/ZSM-5 into syngas using a dual-bed catalytic monolith reactor. The monolith is wash-coated with alumina and ZSM-5, respectively, followed by Ni and glucose-assisted Ni (Ni-C) loading using the wet impregnation technique. These two monoliths are loaded in an Inconel reactor and placed in a two-zone heating furnace. In dual reforming, either Ni/γ-Al2O3 or Ni-C/ZSM-5 monolith is used for dry reforming, and then Ni/γ-Al2O3 is used for steam reforming. A distance of ∼ 10 cm is maintained between these two monoliths. The exhaust gases from the first monolith are combined with steam before passing to the second monolith. The biogas reforming is carried out for a feed ratio (CH4:CO2) 1.5, GHSV of 1440 h−1 and 2880 h−1, at 800℃ and 1 atm pressure. The steam to CH4 ratio (S/C) is optimized to maximize the conversions (greater than80 %) of both CH4 and CO2. It was observed that the CH4 conversions increase with an increased S/C ratio due to the steam reforming in the second monolith. The TGA results show 7.6 % carbon formation on Ni-C/ZSM-5 and 35 % on Ni/γ-Al2O3 in dry reforming on the first monolith bed.
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.
Effect of Calcination Time on the Catalytic Activity of Ni/γ-Al2O3 Cordierite Monolith for Dry Reforming of Biogas
(Elsiever, 2020) Srinivas, Appari; Roy, Banasri
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.
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.
Experimental studies of catalyst deactivation due to carbon and sulphur during CO2 reforming of CH4 over Ni washcoated monolith in the presence of H2S
(Wiley, 2021-07-18) Srinivas, Appari
This study presents the CO2 reforming of CH4 over Ni coated monolith catalyst at 800°C and 101.325 kPa. The high CH4 to CO2 ratio employed in this study is similar to the CH4:CO2 ratio of >1 found in biogas. Cordierite monolith samples (0.258 channels per m2) washcoated with alumina are used for the experimental purpose. The study considers the combined deactivation effect due to sulphur poisoning and fouling due to carbon deposition. Four different cases with respect to the introduction and removal of H2S are considered. The rate of deactivation due to simultaneous carbon deposition and sulphur poisoning is much faster than the individual poisoning processes. The catalyst shows almost stable operation for 6 h without the presence of urn:x-wiley:00084034:media:cjce24266:cjce24266-math-0001 in the feed stream. From the conversion studies, it appears that the pre-treatment of catalyst samples with H2S leads to negligible sulphur coverage. The sulphur poisoning effect is also found to be reversible.
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.
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.
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.
Micro-kinetic modeling of NH3 decomposition on Ni and its application to solid oxide fuel cells
(Elsiever, 2011-11) Srinivas, Appari
This paper presents a detailed surface reaction mechanism for the decomposition of NH3 to H2 and N2 on a Ni surface. The mechanism is validated for temperatures ranging from 700 to 1500 K and pressures from 5.3 Pa to 100 kPa. The activation energies for various elementary steps are calculated using the unity bond index-quadratic exponential potential (UBI-QEP) method. Sensitivity analysis is carried out to study the influence of various kinetic parameters on reaction rates. The NH3 decomposition mechanism is used to simulate SOFC button cell operating on NH3 fuel.
Modeling of gas/particle flow in coal conversion with a drop tube reactor using a lumped kinetic model accounting volatiles–char interaction
(INFOFNA, 2015) Srinivas, Appari
Steam reforming (SR) and partial oxidation (POx) of nascent volatiles (NV) generated from fast pyrolysis of cedar wood chips in a two-stage reactor were studied numerically. A detailed chemical kinetic model (DCKM) consisting of more than 8000 elementary step-like reactions and more than 500 chemical species was used to simulate pyrolysis at 750 °C and reforming of the NV at 9 00 °C in the first and second stages, respectively. The molecular composition of the NV, which is one of the required boundary conditions for computations using the DCKM, was approximated based on analytical pyrolysis experiments. Global reactions accounting for the decomposition of t he ill-defined portion of t he NV and soot reforming were also tested to improve t he model capabilities. The DCKM with the global reaction coupled with a plug-flow reactor model could fairly reproduce the experimentally observed trends for the effects of oxygen and steam partial pressures on the yields of major products such as hydrogen, carbon monoxide, and tar residual rate.
Numerical study of on-board fuel reforming in a catalytic plate reactor for solid-oxide fuel cells
(Elsiever, 2011-02) Srinivas, Appari
A pseudo-transient numerical model is used for the simulation of a multi-functional catalytic plate reactor (CPR). The work mainly addresses the problems associated with on-board reforming for solid-oxide fuel cells. Heat management is achieved by indirectly coupling partial oxidation with reforming. Water management is achieved by partially recycling the anode stream from a solid-oxide fuel cell. The model uses detailed heterogeneous chemistry for reforming and oxidation reactions occurring on the catalyst beds.
Numerical study on the steam reforming of biomass tar using a detailed chemical kinetic model
(JIE, 2015) Srinivas, Appari
Steam reforming (SR) and partial oxidation (POx) of nascent volatiles (NV) generated from fast pyrolysis of cedar wood chips in a two-stage reactor were studied numerically. A detailed chemical kinetic model (DCKM) consisting of more than 8000 elementary step-like reactions and more than 500 chemical species was used to simulate pyrolysis at 750 °C and reforming of the NV at 9 00 °C in the first and second stages, respectively. The molecular composition of the NV, which is one of the required boundary conditions for computations using the DCKM, was approximated based on analytical pyrolysis experiments. Global reactions accounting for the decomposition of t he ill-defined portion of t he NV and soot reforming were also tested to improve t he model capabilities. The DCKM with the global reaction coupled with a plug-flow reactor model could fairly reproduce the experimentally observed trends for the effects of oxygen and steam partial pressures on the yields of major products such as hydrogen, carbon monoxide, and tar residual rate.
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.