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Catalytic Conversion of Glycerol to Value-added Chemical Products

Catalytic Conversion of Glycerol to Value-added Chemical Products
Author: Malaya Ranjan Nanda
Publisher:
Total Pages:
Release: 2015
Genre:
ISBN:

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Rapid expansion of biodiesel industry has generated a huge amount of crude glycerol. This thesis aimed to explore utilization of glycerol for the production of solketal as an oxygenated fuel additive and 1, 2-propanediol as a pre-polymer via catalytic conversion. The thesis work may be divided into two major parts. In the first part, the thermodynamics and kinetics of the glycerol ketalization for the synthesis of solketal were investigated in a batch reactor. From this information, a continuous-flow process was designed, developed and optimized using pure glycerol. Crude glycerol (13 wt% purity) was successfully upgraded into a purified crude glycerol product (> 96 wt% purity) and was used as feedstock in a modified reactor for the synthesis of solketal whose economical feasibility was demonstrated. In the second part, B2O3 promoted Cu/Al2O3 catalysts were used for selective hydrogenolysis of glycerol to 1, 2-propanediol in a flow reactor. Surface properties, acidity, crystallinity, and reducibility of the catalysts were measured using N2 adsorption, NH3-temperature programmed desorption (TPD), X-ray diffraction (XRD), and H2-temperature programmed reduction (TPR), respectively. The fuels/chemicals products obtained were analyzed by GC-MS/FID and Fourier-transformation infrared spectroscopy (FTIR). he ketalization reaction equilibrium constants were determined experimentally in the temperature range of 293-323 K. The activation energy of the overall reaction was determined to be 55.6 ± 3.1 kJ mol-1. Langmuir-Hinshelwood equation was used to model the rate law. The activity of all catalysts tested in the flow reactor follows the order: Amberlyst wet Zeolite Amberlyst dry > Zirconium Sulfate > Montmorillonite > Polymax. At optimum conditions (25 ̊C, 500 psi, acetone-to-glycerol molar ratio of 4 and 2 h-1 WHSV), the maximum solketal yield from pure glycerol was 94±2% over Amberlyst wet. Ketalization of purified crude glycerol over Amberlyst wet, led to 93± 3% glycerol conversion with 92 ±2% solketal yield at the optimum conditions. In the glycerol hydrogenolysis process with 10 wt% aqueous solution of glycerol as the feed, 5Cu-B/Al2O3 catalyst demonstrated a very high activity, yielding 98 ±1% glycerol conversion and 98±1% 1,2-propanediol selectivity at the optimum conditions (250 ̊C, 6 MPa H2, and 0.1h-1 WHSV).


Catalytic Conversion of Energy Resources into High Value-Added Products

Catalytic Conversion of Energy Resources into High Value-Added Products
Author: José Luis Pinilla
Publisher: MDPI
Total Pages: 134
Release: 2021-09-02
Genre: Technology & Engineering
ISBN: 3036510745

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Developing active, selective and energy-efficient heterogeneous catalysts is of paramount importance for the production of high value-added products from energy resources in a more sustainable manner. In this Special Issue of Energies, we provide a showcase of the latest progress in the development of cleaner, more efficient processes for the conversion of these feedstocks into valuable fuels, chemicals and energy. Most of the works collected are focused on the conversion of biomass which clearly reflects the paramount importance that the biorefinery concept will play in the years to come.


Biorefinery of Alternative Resources: Targeting Green Fuels and Platform Chemicals

Biorefinery of Alternative Resources: Targeting Green Fuels and Platform Chemicals
Author: Sonil Nanda
Publisher: Springer Nature
Total Pages: 503
Release: 2020-03-31
Genre: Medical
ISBN: 9811518041

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This book summarizes recent advances in the processing of waste biomass resources to produce biofuels and biochemicals. Worldwide interest in clean energy sources, environmental protection, and mitigating global warming is rapidly gaining momentum and spurring on the search for alternative energy sources, especially for the transportation and industrial sectors. This book reviews the opportunities presented by low-cost organic waste materials, discussing their suitability for alternative fuel and fine chemical production, physicochemical characterization, conversion technologies, feedstock and fuel chemistry, refining technologies, fuel upgrading, residue management, and the circular economy. In addition, it explores applied aspects of biomass conversion by highlighting several significant thermochemical, hydrothermal and biological technologies. In summary, the book offers comprehensive and representative descriptions of key fuel processing technologies, energy conversion and management, waste valorization, eco-friendly waste remediation, biomass supply chain, lifecycle assessment, techno-economic analysis and the circular bioeconomy.


Catalytic Co-conversion of Glycerol and Proton-donor Species to Gasoline-range Aromatics Over Alumina

Catalytic Co-conversion of Glycerol and Proton-donor Species to Gasoline-range Aromatics Over Alumina
Author: Arian Shahnazari
Publisher:
Total Pages: 0
Release: 2016
Genre: Aluminum oxide
ISBN:

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Glycerol is the main by-product of the biodiesel production process. Saturation of this by-product in the market would negatively affect the growth of biodiesel production industry. Due to complexities in the purification processes of crude-glycerol, less costly chemical conversion of glycerol to value-added products and feedstocks such as propenal and aromatics has gained more attention recently. In this work, the influence of co-feeding proton-donor and olefin-donor species on the catalytic conversion of glycerol over alumina catalyst to gasoline-range aromatics is studied. During the individual catalytic conversion of glycerol over alumina, because of the shortage of proton-donor intermediates in the process and high activity of glycerol on alumina at 470°C, glycerol mostly leads to form high carbon deposit content and aqueous phase stream, but less liquid organic production. Introducing methanol and ethanol as compound models of alcohols, and dodecane and hexadecane as compound models of long-chain alkanes next to glycerol remarkably decreases the formation of undesired stream, while selectivity to aromatics substantially increases. In terms of liquid aromatics generation and restricting the excessive carbonization on the catalyst surface, co-feeding 25 wt.% hexadecane with 75 wt.% glycerol has the highest efficiency among the selected compound models; with increasing the liquid aromatics selectivity from 17.7% to 42.5%. Additionally, Co-processing the latter compound model, noticeably shifts the distribution of produced aromatics from heavy undesired aromatics range to the gasoline-range aromatics such as xylenes and toluene. The potential influence of hexadecane on the glycerol to aromatics reaction pathway over alumina catalyst is also proposed, and the effective reactions between glycerol and hexadecane intermediates are discussed. It is also found that selecting a very high or low operational temperature would inversely affect the optimization of aromatics formation through the co-processing runs of glycerol and hexadecane.


Glycerine Production and Transformation

Glycerine Production and Transformation
Author: Marco Frediani
Publisher: BoD – Books on Demand
Total Pages: 138
Release: 2019-09-11
Genre: Technology & Engineering
ISBN: 1789846900

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The increase in the amount of glycerin in the market is a burden for all producers, especially those operating in the biodiesel sector: reuse options are in fact limited for the management of this by-product. Glycerol enhancement has therefore become a priority to improve the sustainability of the biodiesel industry. Nevertheless, the multifunctionality of glycerol makes it a promising precursor for different types of production (fuel/biofuel, chemical products). This conversion has therefore become a subject of multifaceted research that requires an exchange of knowledge across many sectors. In this book, different disciplines (chemistry, biology, engineering, etc.) have been taken into consideration to propose an interdisciplinary point of view on different aspects.


The Future of Glycerol

The Future of Glycerol
Author: Mario Pagliaro
Publisher: Royal Society of Chemistry
Total Pages: 145
Release: 2008
Genre: Science
ISBN: 0854041249

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By-products of global biodiesel manufacturing are a modern day global fact responsible for igniting a number of year's worldwide intense research activity into human chemical ingenuity. This highly anticipated 2nd Edition depicts how practical limitations posed by glycerol chemistry are solved based on the understanding of the fundamental chemistry of glycerol and by application of catalysis science and technology. The authors report and comment on employable, practical avenues applicable to convert glycerol into value added products of mass consumption. The best-selling reference book in the.


Catalytic Conversion of Glycerol and Sugar Alcohols to Value-added Products

Catalytic Conversion of Glycerol and Sugar Alcohols to Value-added Products
Author: Mohanprasad A. Dasari
Publisher:
Total Pages:
Release: 2006
Genre: Chemical reactions
ISBN:

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The current research is based on developing an improved and fundamental understanding of technology that will allow the conversion of this crude glycerin to a propylene glycol based antifreeze product. Hydrogenolysis of glycerol to propylene glycol was performed using copper chromite catalyst. At temperatures above 200°C and hydrogen pressure of 200 psi, the selectivity to propylene glycol decreased due to excessive hydrogenolysis of the propylene glycol. The yield of propylene glycol increased with decreasing water content. The main causes for the deactivation were reduction of the cuprous chromium active species into metallic copper species, metal leaching, and blocking of sites by strongly adsorbed inorganic and organic species present in the feed or generated during the reaction. A new reaction pathway for converting glycerol to propylene glycol via an intermediate was validated by isolating the acetol intermediate. In the first step involves dehydration of glycerol to acetol with subsequent hydrogenation of acetol to propylene glycol. High acetol selectivities ([greater than] 90%) were achieved using copper-chromite catalyst and operating in semi-batch reactive distillation mode. The acetol from this reaction readily hydrogenates to from propylene glycol with selectivities exceeding 95%.


Catalysis for Clean Energy and Environmental Sustainability

Catalysis for Clean Energy and Environmental Sustainability
Author: K. K. Pant
Publisher: Springer Nature
Total Pages: 933
Release: 2021-05-13
Genre: Technology & Engineering
ISBN: 3030650170

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This book is part of a two-volume work that offers a unique blend of information on realistic evaluations of catalyst-based synthesis processes using green chemistry principles and the environmental sustainability applications of such processes for biomass conversion, refining, and petrochemical production. The volumes provide a comprehensive resource of state-of-the-art technologies and green chemistry methodologies from researchers, academics, and chemical and manufacturing industrial scientists. The work will be of interest to professors, researchers, and practitioners in clean energy catalysis, green chemistry, chemical engineering and manufacturing, and environmental sustainability. This volume focuses on the potentials, recent advances, and future prospects of catalysis for biomass conversion and value-added chemicals production via green catalytic routes. Readers are presented with a mechanistic framework assessing the development of product selective catalytic processes for biomass and biomass-derived feedstock conversion. The book offers a unique combination of contributions from experts working on both lab-scale and industrial catalytic processes and provides insight into the use of various catalytic materials (e.g., mineral acids, heteropolyacid, metal catalysts, zeolites, metal oxides) for clean energy production and environmental sustainability.


Glycerol

Glycerol
Author: Claudio J. A. Mota
Publisher: Springer
Total Pages: 116
Release: 2017-06-15
Genre: Science
ISBN: 3319593757

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This book is aimed at providing a concise discussion on the use of glycerol as a renewable raw material for the chemical industry. With the increasing use of biodiesel produced from oils and fats, there is a surplus of glycerol in the world. This abundant and rather cheap raw material can be transformed in commodities and specialty chemicals, as well as in fuels. The book describes the main processes of chemical transformation of glycerol, highlighting those that are currently in commercial use and pointing out potential processes to be used in the future. The first chapter introduces the concept of biofuel and briefly describes the production of biodiesel. It also highlights glycerol as the main byproduct of biodiesel synthesis and presents some numbers regarding the world production of glycerol. The second chapter shows the common uses of glycerol and addresses the point whether or not they can drain the large amounts of glycerol produced from biodiesel. The chapter addresses pros and cons of each use. The third chapter covers the main biotechnological processes of glycerol transformation. The fourth chapter thoroughly describes the main thermochemical processes to transform glycerol into commodities, products that will be further used in the chemical industry to produce polymers, for instance. The fifth chapter covers the production of glycerol derivatives of high added-value. The sixth chapter addresses the use of glycerol in the context of a biorefinery. The main idea is to show that many of the processes described in the previous chapters could be entirely green, using exclusively renewable raw materials.