Comparative study of catalytic conversion of glycerol, a by-product of transesterification, to cyclic hydrocarbons using MCM-22, ZSM-5 and alumina

2021 ◽  
Vol 0 (0) ◽  
Author(s):  
Sandeep Kumar ◽  
Dinesh Kumar ◽  
Neeru Anand ◽  
Vinay Shah
Keyword(s):  
Rate Constant ◽  
Reaction Rate ◽  
Fixed Bed ◽  
Liquid Product ◽  
Value Added ◽  
Fixed Bed Reactor ◽  
High Yield ◽  
Esterification Reaction ◽  
Glycerol Conversion ◽  
Ms Analysis

Abstract Recently chemical consumption has increased due to the growth of human population and industrialization. Depleting fuel reserves and increase in chemicals rise has led and researcher to focus on alternative bio based chemicals. Glycerol which is produced as a major byproduct from the trans-esterification reaction of fatty acids for producing biodiesel has been used in this work for conversion to value added products. Conversion of glycerol in presence of alumina, MCM-22 (pure silica based mesoporous catalyst) and ZSM-5 (Si-Al based catalyst) is investigated at different temperature and catalyst weight in a fixed bed reactor. The conversion of glycerol was found to be maximum in presence of alumina whereas maximum liquid products were obtained with ZSM-5. GC/MS analysis confirmed the production of Furan compounds in higher fraction with both alumina as well as ZSM-5 showing the importance of acid sites for the glycerol conversion to higher hydrocarbons. The GC/MS analysis of liquid product obtained in presence of catalyst was also observed with high area% of unconverted glycerol. The order is as follow 54% (MCM-22) > 44% (ZSM-5) > 42.2% (Alumina). For the investigation of the conversion for varying catalyst weight (0–3 g with 0.5 g weight difference), reaction temperature were varied between 450 and 550 °C. Different values of n = 0, 1, 2 etc. were used for the fitting of the respective plot. A change in reaction rate and the rate constant indicated that with the change of temperature, reaction rate was increased. The rate constant value obtained between 0.09 and 0.12 h−1. In all cases 450 °C and catalyst weight of 2.5 g was obtained as optimum for higher liquid yield. TGA analysis of spent catalyst also showed that alumina give high yield (∼50% by weight) of coke as compared to ZSM-5 and MCM-22.

scholarly journals Toward the Sustainable Synthesis of Propanols from Renewable Glycerol over MoO3-Al2O3 Supported Palladium Catalysts

Catalysts ◽  
2018 ◽  
Vol 8 (9) ◽  
pp. 385 ◽  
Author(s):  
Shanthi Samudrala ◽  
Sankar Bhattacharya
Keyword(s):  
Catalytic Activity ◽  
Palladium Catalysts ◽  
Fixed Bed ◽  
Value Added ◽  
High Strength ◽  
Acid Sites ◽  
Fixed Bed Reactor ◽  
High Catalytic Activity ◽  
Impregnation Method ◽  
Glycerol Conversion

The catalytic conversion of glycerol to value-added propanols is a promising synthetic route that holds the potential to overcome the glycerol oversupply from the biodiesel industry. In this study, selective hydrogenolysis of 10 wt% aqueous bio-glycerol to 1-propanol and 2-propanol was performed in the vapor phase, fixed-bed reactor by using environmentally friendly bifunctional Pd/MoO3-Al2O3 catalysts prepared by wetness impregnation method. The physicochemical properties of these catalysts were derived from various techniques such as X-ray diffraction, NH3-temperature programmed desorption, scanning electron microscopy, 27Al NMR spectroscopy, surface area analysis, and thermogravimetric analysis. The catalytic activity results depicted that a high catalytic activity (>80%) with very high selectivity (>90%) to 1-propanol and 2-propanol was obtained over all the catalysts evaluated in a continuously fed, fixed-bed reactor. However, among all others, 2 wt% Pd/MoO3-Al2O3 catalyst was the most active and selective to propanols. The synergic interaction between the palladium and MoO3 on Al2O3 support and high strength weak to moderate acid sites of the catalyst were solely responsible for the high catalytic activity. The maximum glycerol conversion of 88.4% with 91.3% selectivity to propanols was achieved at an optimum reaction condition of 210 ∘ C and 1 bar pressure after 3 h of glycerol hydrogenolysis reaction.

scholarly journals Thermochemical Heat Storage in a Lab-Scale Indirectly Operated CaO/Ca(OH)2 Reactor—Numerical Modeling and Model Validation through Inverse Parameter Estimation

2021 ◽  
Vol 11 (2) ◽  
pp. 682
Author(s):  
Gabriele Seitz ◽  
Farid Mohammadi ◽  
Holger Class
Keyword(s):  
Numerical Model ◽  
Gas Flow ◽  
Reaction Rate ◽  
Heat Storage ◽  
Bulk Material ◽  
Fixed Bed ◽  
Experimental Results ◽  
Fixed Bed Reactor ◽  
Thermochemical Heat Storage ◽  
Speed Up

Calcium oxide/Calcium hydroxide can be utilized as a reaction system for thermochemical heat storage. It features a high storage capacity, is cheap, and does not involve major environmental concerns. Operationally, different fixed-bed reactor concepts can be distinguished; direct reactor are characterized by gas flow through the reactive bulk material, while in indirect reactors, the heat-carrying gas flow is separated from the bulk material. This study puts a focus on the indirectly operated fixed-bed reactor setup. The fluxes of the reaction fluid and the heat-carrying flow are decoupled in order to overcome limitations due to heat conduction in the reactive bulk material. The fixed bed represents a porous medium where Darcy-type flow conditions can be assumed. Here, a numerical model for such a reactor concept is presented, which has been implemented in the software DuMux. An attempt to calibrate and validate it with experimental results from the literature is discussed in detail. This allows for the identification of a deficient insulation of the experimental setup. Accordingly, heat-loss mechanisms are included in the model. However, it can be shown that heat losses alone are not sufficient to explain the experimental results. It is evident that another effect plays a role here. Using Bayesian inference, this effect is identified as the reaction rate decreasing with progressing conversion of reactive material. The calibrated model reveals that more heat is lost over the reactor surface than transported in the heat transfer channel, which causes a considerable speed-up of the discharge reaction. An observed deceleration of the reaction rate at progressed conversion is attributed to the presence of agglomerates of the bulk material in the fixed bed. This retardation is represented phenomenologically by mofifying the reaction kinetics. After the calibration, the model is validated with a second set of experimental results. To speed up the calculations for the calibration, the numerical model is replaced by a surrogate model based on Polynomial Chaos Expansion and Principal Component Analysis.

scholarly journals Valuable Chemicals Derived from Pyrolysis Liquid Products of Spirulina platensis Residue

2019 ◽  
Vol 19 (3) ◽  
pp. 703 ◽  
Author(s):  
Siti Jamilatun ◽  
Budhijanto Budhijanto ◽  
Rochmadi Rochmadi ◽  
Avido Yuliestyan ◽  
Arief Budiman
Keyword(s):  
Polyaromatic Hydrocarbons ◽  
Food Additives ◽  
Fixed Bed ◽  
Liquid Product ◽  
Fixed Bed Reactor ◽  
Water Phase ◽  
Gas Chromatography Mass Spectrometry ◽  
Human Needs ◽  
Liquid Products ◽  
Interesting Alternative

With a motto of preserving nature, the use of renewable resources for the fulfillment of human needs has been seen echoing these days. In response, microalgae, a water-living microorganism, is perceived as an interesting alternative due to its easy-to-cultivate nature. One of the microalgae, which possess the potential for being the future source of energy, food, and health, is Spirulina plantesis. Aiming to identify valuable chemicals possibly derived from it, catalytic and non-catalytic pyrolysis process of the residue of S. plantesis microalgae has been firstly carried out in a fixed-bed reactor over the various temperature of 300, 400, 500, 550 and 600 °C. The resulting vapor was condensed so that the liquid product consisting of the top product (oil phase) and the bottom product (water phase) can be separated. The composition of each product was then analyzed by Gas Chromatography-Mass Spectrometry (GC-MS). In the oil phase yield, the increase of aliphatic and polyaromatic hydrocarbons (PAHs) and the decrease of the oxygenated have been observed along with the increase of pyrolysis temperature, which might be useful for fuel application. Interestingly, their water phase composition also presents some potential chemicals, able to be used as antioxidants, vitamins and food additives.

scholarly journals Simulation of CO2 Conversion into Methanol in Fixed-bed Reactors: Comparison of Isothermal and Adiabatic Configurations

REAKTOR ◽  
2019 ◽  
Vol 19 (3) ◽  
pp. 131-135
Author(s):  
Fadilla Noor Rahma
Keyword(s):  
Fixed Bed ◽  
Value Added ◽  
Fixed Bed Reactor ◽  
Inlet Temperature ◽  
Methanol Production ◽  
Greenhouse Gases Emissions ◽  
Fixed Bed Reactors ◽  
Adiabatic Reactor ◽  
Co2 Conversion Into Methanol ◽  
Feed Inlet

CO2 capture and utilization (CCU) has been widely considered as a potential solution to overcome global warming. Conversion of CO2 into methanol is an interesting option to transform waste into value-added chemical while also reducing greenhouse gases emissions in the atmosphere. In this paper, utilization of CO2 into methanol was simulated using Aspen Plus software. The reaction between CO2 and H2 to produce methanol and water was carried out in a simulated fixed-bed reactor with Cu/ZnO/Al2O3 commercial catalyst, following LHHW (Langmuir – Hinshelwood – Hougen – Watson) kinetic model. Isothermal and adiabatic reactor configurations were compared under similar feed conditions and the concentration profile along the reactor was observed. The result showed that isothermal configuration converted 3.23% more CO2 and provided 16.34% higher methanol yield compared to the adiabatic reactor. Feed inlet temperature variation was applied and the effect to methanol production on both configurations was studied. The highest methanol yield for adiabatic and isothermal reactor was obtained at 200 oC and 240 oC respectively.

scholarly journals Effect of Temperature on Plasma-Assisted Catalytic Cracking of Palm Oil into Biofuels

2020 ◽  
Vol 9 (1) ◽  
pp. 107-112 ◽  
Author(s):  
I. Istadi ◽  
Teguh Riyanto ◽  
Luqman Buchori ◽  
Didi Dwi Anggoro ◽  
Roni Ade Saputra ◽  
...  
Keyword(s):  
Palm Oil ◽  
Catalytic Cracking ◽  
Plasma Reactor ◽  
Fixed Bed ◽  
Liquid Product ◽  
Fixed Bed Reactor ◽  
Effect Of Temperature ◽  
Catalytic Reactor ◽  
Catalytic Role ◽  
Reactor Temperature

Plasma-assisted catalytic cracking is an attractive method for producing biofuels from vegetable oil. This paper studied the effect of reactor temperature on the performance of plasma-assisted catalytic cracking of palm oil into biofuels. The cracking process was conducted in a Dielectric Barrier Discharge (DBD)-type plasma reactor with the presence of spent RFCC catalyst. The reactor temperature was varied at 400, 450, and 500 ºC. The liquid fuel product was analyzed using a gas chromatography-mass spectrometry (GC-MS) to determine the compositions. Result showed that the presenceof plasma and catalytic role can enhance the reactor performance so that the selectivity of the short-chain hydrocarbon produced increases. The selectivity of gasoline, kerosene, and diesel range fuels over the plasma-catalytic reactor were 16.43%, 52.74% and 21.25%, respectively, while the selectivity of gasoline, kerosene and diesel range fuels over a conventional fixed bed reactor was 12.07%, 39.07%, and 45.11%, respectively. The increasing reactor temperature led to enhanced catalytic role of cracking reaction,particularly directing the reaction to the shorter hydrocarbon range. The reactor temperature dependence on the liquid product components distribution over the plasma-catalytic reactor was also studied. The aromatic and oxygenated compounds increased with the reactor temperature.©2020. CBIORE-IJRED. All rights reserved

scholarly journals Solution Combustion Synthesis of Fe2O3-Based Catalyst for Ammonia Synthesis

Catalysts ◽  
2020 ◽  
Vol 10 (9) ◽  
pp. 1027
Author(s):  
Binxiang Cai ◽  
Huazhang Liu ◽  
Wenfeng Han
Keyword(s):  
Combustion Synthesis ◽  
Reaction Rate ◽  
Ammonia Synthesis ◽  
Fixed Bed ◽  
Solution Combustion Synthesis ◽  
Fixed Bed Reactor ◽  
High Dispersion ◽  
Synthesis Reaction ◽  
Solution Combustion ◽  
Metal Nitrates

Fe2O3-based catalysts were prepared by solution combustion synthesis (SCS) with metal nitrates (Fe, K, Al, Ca) as the precursors and glycine as the fuel. The activities of catalysts were evaluated in terms of ammonia synthesis reaction rate in a fixed bed reactor similar to the industrial reactors. The results indicate that the precursor of catalyst prepared by SCS is Fe2O3 which facilitates the high dispersion of promoters to provide high activity. The catalysts exhibit higher activity for ammonia synthesis than that of traditional catalysts, and the reaction rate reaches 138.5 mmol g−1 h−1. Fe2O3 prepared by SCS could be favorable precursor for ammonia synthesis catalyst. The present study provides a pathway to prepare catalyst for ammonia synthesis.

scholarly journals Production of value-added chemicals from esterification of waste glycerol over MCM-41 supported catalysts

2019 ◽  
Vol 8 (1) ◽  
pp. 128-134 ◽  
Author(s):  
Emine Kaya Ekinci ◽  
Nuray Oktar
Keyword(s):  
Acetic Acid ◽  
High Selectivity ◽  
Supported Catalysts ◽  
Value Added ◽  
Mass Spectrometry Analysis ◽  
Molar Ratio ◽  
Esterification Reaction ◽  
Glycerol Conversion ◽  
Spectrometry Analysis ◽  
Mcm 41

Abstract A series of active and selective MCM-41 supported catalysts have been successfully prepared and used for bioderived glycerol esterification with acetic acid to produce fuel additives. In the synthesis of MCM-41, an acidic hydrothermal synthesis route was used, and silicotungstic acid (STA) and zirconia (ZrO2) were added to the catalyst structure by wet impregnation. X-ray diffraction, nitrogen adsorption-desorption methods, scanning electron microscopy with energy-dispersive spectroscopy, and inductively coupled plasma-mass spectrometry analysis were used for characterizations of the catalysts. Diffuse reflectance infrared Fourier transform spectroscopy analyses of pyridine-adsorbed catalysts owns Lewis and Brønsted acidity hosting in one, which promotes the esterification reaction of glycerol into glycerol esters with high selectivity. Esterification of glycerol reactions were performed at temperature intervals of 105°C–200°C, with an amount of catalyst equal to 0.5 g, and glycerol/acetic acid molar ratio of 1:6 in a stirred autoclave reactor operated batchwise. STA and ZrO2-impregnated MCM-41 catalysts showed better performance with a complete glycerol conversion and high selectivity to triacetin.

TLC-FID and GC-MS Analysis of Tars Generated by Oil Sand Pyrolysis at Different Temperature

2015 ◽  
Vol 737 ◽  
pp. 128-131 ◽  
Author(s):  
De Min He ◽  
Fan Nie ◽  
Jun Guan ◽  
Hao Quan Hu ◽  
Qiu Min Zhang
Keyword(s):  
Fixed Bed ◽  
Product Yield ◽  
Fixed Bed Reactor ◽  
Oil Sand ◽  
Condensation Reactions ◽  
Ms Analysis ◽  
Higher Temperature

Tars generated by oil sand pyrolysis at different temperature in a fixed bed reactor were studied through TLC-FID and GC-MS. Compared to the raw oil sand extracts, pyrolysis could reduce the asphaltenes of oil which is benefit for storage, transport and further utilization. The temperature of pyrolysis affects not only product yield but also its composition. Analyzed together by TLC-FID and GC-MS, groups of tars at different temperature were identified. It was found higher temperature would strengthen the condensation reactions revealing increasing of cycloalkanes, indenes and PAHs increased with raising temperature. There was also a great amount of benzothiophenes which may generated by the decomposition of oil sand bitumen or aromatization of ring sulfides. That mainly contributed to the high content of resin in the tars.

scholarly journals Reactive Chromatography Applied to Ethyl Levulinate Synthesis: A Proof of Concept

Processes ◽  
2021 ◽  
Vol 9 (9) ◽  
pp. 1684
Author(s):  
Carmelina Rossano ◽  
Claudio Luigi Pizzo ◽  
Riccardo Tesser ◽  
Martino Di Serio ◽  
Vincenzo Russo
Keyword(s):  
Levulinic Acid ◽  
Separation Efficiency ◽  
Fixed Bed ◽  
Value Added ◽  
Low Flow ◽  
Esterification Reaction ◽  
Flow Rates ◽  
Ethyl Levulinate ◽  
Wide Range ◽  
Chromatographic Reactor

Levulinic acid (LA) has been highlighted as one of the most promising platform chemicals, providing a wide range of possible derivatizations to value-added chemicals as the ethyl levulinate obtained through an acid catalyzed esterification reaction with ethanol that has found application in the bio-fuel market. Being a reversible reaction, the main drawback is the production of water that does not allow full conversion of levulinic acid. The aim of this work was to prove that the chromatographic reactor technology, in which the solid material of the packed bed acts both as stationary phase and catalyst, is surely a valid option to overcome such an issue by overcoming the thermodynamic equilibrium. The experiments were conducted in a fixed-bed chromatographic reactor, packed with Dowex 50WX-8 as ion exchange resin. Different operational conditions were varied (e.g., temperature and flow rate), pulsing levulinic acid to the ethanol stream, to investigate the main effects on the final conversion and separation efficiency of the system. The effects were described qualitatively, demonstrating that working at sufficiently low flow rates, LA was completely converted, while at moderate flow rates, only a partial conversion was achieved. The system worked properly even at room temperature (303 K), where LA was completely converted, an encouraging result as esterification reactions are normally performed at higher temperatures.

Sign in / Sign up

Export Citation Format

Share Document