Synthesis of dimethyl carbonate and glycols from carbon dioxide, epoxides, and methanol using heterogeneous basic metal oxide catalysts with high activity and selectivity
TL;DR: In this paper, a comprehensive report on a two-step synthesis of dimethyl carbonate (DMC) from epoxides, carbon dioxide and methanol using various basic metal oxide catalysts was given.
Abstract: This paper gives a comprehensive report on a two-step synthesis of dimethyl carbonate (DMC) from epoxides, carbon dioxide and methanol using various basic metal oxide catalysts. The first step is the reaction of ethylene oxide or propylene oxide with CO 2 to form the corresponding cyclic carbonates, and the second step is the transesterification reaction of the cyclic carbonates with methanol to DMC and glycols. Among the catalysts examined, MgO is the most active and selective for both these reactions. Other alcohols can be used for the second step, but the activity decreases as the carbon number of the alcohol increases. Although a one-pot synthesis of DMC, i.e. the sequential reaction of the epoxide, CO 2 and methanol, is also possible with MgO, the selectivity is low because of the alcoholysis of the epoxide. In contrast with the reactions of ethylene oxide and propylene oxide, when styrene oxide is used for the first reaction and for the one-pot synthesis, mandelic acid is produced. Basic properties of the metal oxide catalysts were measured by temperature programmed desorption of CO 2 . The relationship between the catalytic performance and the basic property is discussed.
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TL;DR: Reaction Mechanism, Synthesis of Urea and Urethane Derivatives, and Alcohol Homologation 2382 10.1.
Abstract: 4.3. Reaction Mechanism 2373 4.4. Asymmetric Synthesis 2374 4.5. Outlook 2374 5. Alternating Polymerization of Oxiranes and CO2 2374 5.1. Reaction Outlines 2374 5.2. Catalyst 2376 5.3. Asymmetric Polymerization 2377 5.4. Immobilized Catalysts 2377 6. Synthesis of Urea and Urethane Derivatives 2378 7. Synthesis of Carboxylic Acid 2379 8. Synthesis of Esters and Lactones 2380 9. Synthesis of Isocyanates 2382 10. Hydrogenation and Hydroformylation, and Alcohol Homologation 2382
3,203 citations
TL;DR: Hydrogenation of Alkenes and Arenes by Nanoparticles 2624 3.1.2.
Abstract: 2.5. Stabilization of IL Emulsions by Nanoparticles 2623 3. Hydrogenations in ILs 2623 3.1. Hydrogenation on IL-Stabilized Nanoparticles 2623 3.1.1. Hydrogenation of 1,3-Butadiene 2623 3.1.2. Hydrogenation of Alkenes and Arenes 2624 3.1.3. Hydrogenation of Ketones 2624 3.2. Homogeneous Catalytic Hydrogenation in ILs 2624 3.3. Hydrogenation of Functionalized ILs 2625 3.3.1. Selective Hydrogenation of Polymers 2625 3.4. Asymmetric Hydrogenations 2626 3.4.1. Enantioselective Hydrogenation 2626 3.5. Role of the ILs Purity in Hydrogenation Reactions 2628
1,996 citations
TL;DR: The motivation to develop CO2-based chemistry does not depend primarily on the absolute amount of CO2 emissions that can be remediated by a single technology and is stimulated by the significance of the relative improvement in carbon balance and other critical factors defining the environmental impact of chemical production in all relevant sectors in accord with the principles of green chemistry.
Abstract: CO2 conversion covers a wide range of possible application areas from fuels to bulk and commodity chemicals and even to specialty products with biological activity such as pharmaceuticals. In the present review, we discuss selected examples in these areas in a combined analysis of the state-of-the-art of synthetic methodologies and processes with their life cycle assessment. Thereby, we attempted to assess the potential to reduce the environmental footprint in these application fields relative to the current petrochemical value chain. This analysis and discussion differs significantly from a viewpoint on CO2 utilization as a measure for global CO2 mitigation. Whereas the latter focuses on reducing the end-of-pipe problem “CO2 emissions” from todays’ industries, the approach taken here tries to identify opportunities by exploiting a novel feedstock that avoids the utilization of fossil resource in transition toward more sustainable future production. Thus, the motivation to develop CO2-based chemistry does...
1,346 citations
TL;DR: The present article deals with the synthetic technologies leading to organic carbonates using CO(2) as a raw material.
941 citations
TL;DR: A broad spectrum of properties of EG and significant advances in the prevalent synthesis and applications of EG are described, with emphases on the catalytic reactivity and reaction mechanisms of the main synthetic methodologies and applied strategies.
Abstract: Ethylene glycol (EG) is an important organic compound and chemical intermediate used in a large number of industrial processes (e.g. energy, plastics, automobiles, and chemicals). Indeed, owing to its unique properties and versatile commercial applications, a variety of chemical systems (e.g., catalytic and non-catalytic) have been explored for the synthesis of EG, particularly via reaction processes derived from fossil fuels (e.g., petroleum, natural gas, and coal) and biomass-based resources. This critical review describes a broad spectrum of properties of EG and significant advances in the prevalent synthesis and applications of EG, with emphases on the catalytic reactivity and reaction mechanisms of the main synthetic methodologies and applied strategies. We also provide an overview regarding the challenges and opportunities for future research associated with EG.
746 citations
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TL;DR: Dimethyl carbonate (DMC) is considered an option for meeting the oxygenate specifications on gasoline and as a means of converting natural gas to a liquid transportation fuel as discussed by the authors, and the fuel characteristics and known chemical synthesis schemes for DMC are reviewed.
Abstract: Dimethyl carbonate (DMC) is considered an option for meeting the oxygenate specifications on gasoline and as a means of converting natural gas to a liquid transportation fuel. In this report, the fuel characteristics and known chemical synthesis schemes for DMC are reviewed. Three production schemes have a commercial track record, while others are still under development. The older of the three commercially proven schemes is undesirable because it employs phosgene. The other two commercially proven schemes have a complex mixture of advantages and disadvantages with regard to the synthesis chemistry and are reviewed in greater detail. One other commercially viable production scheme that involves coproduction of either ethylene or propylene glycol is also reviewed. This scheme is still in the development stage and would require a commitment to coproduce the glycol from ethylene or propylene. The authors are not aware of any refiner that either has blended or is blending DMC into gasoline for commercial use.
782 citations
TL;DR: Homogeneous molecular catalysts, which have far greater control over selectivity than heterogeneous solid catalysts are now being tested in SCFs, and early results show that high rates, improved selectivity, and elimination of masstransfer problems can be achieved.
Abstract: Supercritical fluids (SCFs), compounds heated and pressurized beyond the critical point, have many unusual properties. Homogeneous molecular catalysts, which have far greater control over selectivity than heterogeneous solid catalysts, are now being tested in SCFs, and early results show that high rates, improved selectivity, and elimination of masstransfer problems can be achieved. As industry moves away from toxic or environmentally damaging solvents, supercritical carbon dioxide may be an ideal replacement medium for nonpolar or weakly polar chemical processes. More than simply substitutes for nonpolar solvents, SCFs can radically change the observed chemistry. Supercritical carbon dioxide is also an excellent medium for its own fixation, as demonstrated by studies of its hydrogenation.
732 citations
TL;DR: A comprehensive review of catalysts for CO2/epoxide coupling can be found in this article, where the authors compile the different catalysts into their general groups of similarity, with the hopes of shedding light on some of the important differences in reaction pathways.
709 citations
Book•
01 Jan 1999
TL;DR: In this article, the authors introduce SCF, history, recent trends basic physical properties, phase behaviour and solubility physical properties as related to chemical reactions, reaction equipment design and safety extraction using SCFs precipitation and crystallization techniques surfactants for SCFs.
Abstract: Introduction: introduction to SCF, history, recent trends basic physical properties, phase behaviour and solubility physical properties as related to chemical reactions. Experimental techniques - reaction equipment design and safety extraction using SCFs precipitation and crystallization techniques surfactants for SCFs. Spectroscopy of SCF solutions: 3.1 IR and Raman spectroscopy in SCF 3.2 NMR spectroscopy in SCF 3.3 other spectroscopic techniques (UV, ESR) 4 reactions in SCF: 4.1 stoichiometric organic synthesis 4.2 stoichiometric inorganic synthesis 4.3 photochemistry 4.4 polymerization in scCO2 4.5 free-radical polymerization in reactive supercritical fluids 4.6 homogeneous catalysis 4.7 heterogeneous catalyis 4.8 enzymatic catalysis 4.9 phase transfer catalysis.
664 citations
650 citations