Carbon dioxide and ethanol from sugarcane biorefinery as renewable feedstocks to environment-oriented integrated chemical plants.

Energy shortage and environmental problems are two dominant subjects. Dimethyl carbonate (DMC) is one of the oxygenated fuels with increasing interest as the alternative to diesel fuel or additive for conventional hydrocarbon fuels. In the last decade, comprehensive studies on DMC have been carried out in terms of synthesis, use, and oxidation and combustion mechanism. DMC synthesis from greenhouse gas such as carbon dioxide can achieve the carbon circulation between air and fuel. Ethylene carbonate route is one of the most promising ways to utilize carbon dioxide and synthesize DMC in terms of particle efficiency, energy consumption per one unit of product, and net carbon dioxide emission. In addition, the results show that pure DMC in compression ignition (CI) engines or DMC addition in diesel/gasoline could decrease emissions significantly. Moreover, DMC pyrolysis form carbon dioxide before carbon monoxide which is different from other oxygenated fuels. However, DMC can produce formaldehyde during oxidation process in high concentration, which is harmful to the environment and human health as well. The present DMC kinetic model needs to update the major reactions constant through recognizing the initial decomposition routes and low-temperature oxidation. In addition, further studies on the DMC/hydrocarbon fuels mixtures for the interaction chemistry are needed.

Synthesis of dimethyl carbonate and glycols from carbon dioxide, epoxides and methanol using heterogeneous Mg containing smectite catalysts: effect of reaction variables on activity and selectivity performance

Synthesis of dimethyl carbonate from methanol, propylene oxide and carbon dioxide over KOH/4A molecular sieve catalyst

The synthesis of dimethyl carbonate (DMC) from ethylene oxide (EO), methanol, and carbon dioxide was investigated. In the proposed one-pot synthesis of DMC, the reaction of EO with CO2 was coupled simultaneously with the reaction of ethylene carbonate with methanol under reaction conditions at which carbon dioxide was in supercritical state. The catalysts were experimentally screened at temperatures from 80 to 140 °C and pressures from 5.0 to 15.0 MPa. The mixture of KI and K2CO3 showed the highest catalytic activity for the one-pot DMC synthesis. The preferential weight ratio of KI to K2CO3 in the mixed catalyst ranges from 1:3 to 5:3. The effects of the reaction conditions, such as catalyst concentration, temperature, pressure, reaction time, and reactant compositions, were experimentally studied. High temperature favors the formation of the desired products, DMC and ethylene carbonate. The effect of pressure on the DMC yield is not significant. A high EO content in the feed is beneficial to increasing the selectivity of the desired products. Using the mixture of KI and K2CO3 (weight ratio of KI/K2CO3 = 1:1) as the catalyst with a molar ratio of catalyst to EO of 0.05, the DMC selectivity can reach above 73.0% at 100.0% EO conversion with less than 4.0% selectivity of the byproduct 2-methoxyethanol at the appropriate reaction conditions.

Potentials for CO2 Utilization: Diethyl Carbonate Synthesis from Propylene Oxide

Current research efforts in the field of poly(propylene carbonate) prepared from carbon dioxide and propylene oxide are reviewed. Interest in the polymer has been revived in light of the current discussion on sustainability and biodegradability. The progress in understanding and increasing the activity of heterogeneous zinc catalysts is steadily increasing, but without a quantum leap. The microstructure, the properties of the melt, and the solid material are given. The material property profile can be expanded through the synthesis of terpolymers based on propylene oxide, carbon dioxide and other epoxides, lactones or anhydrides etc. with the same catalyst; or the preparation of poly(propylene carbonate) blends with biodegradable or biocompatible components like calcium carbonate, wood flour, fibers, or other biodegradable polymers.

The homogeneous dinuclear zinc catalyst going back to the work of Williams et al. is to date the most active catalyst for the copolymerisation of cyclohexene oxide and CO(2) at one atmosphere of carbon dioxide. However, this catalyst shows no copolymer formation in the copolymerisation reaction of propylene oxide and carbon dioxide, instead only cyclic carbonate is found. This behaviour is known for many zinc-based catalysts, although the reasons are still unidentified. Within our studies, we focus on the parameters that are responsible for this typical behaviour. A deactivation of the catalyst due to a reaction with propylene oxide turns out to be negligible. Furthermore, the catalyst still shows poly(cyclohexene carbonate) formation in the presence of cyclic propylene carbonate, but the catalyst activity is dramatically reduced. In terpolymerisation reactions of CO(2) with different ratios of cyclohexene oxide to propylene oxide, no incorporation of propylene oxide can be detected, which can only be explained by a very fast back-biting reaction. Kinetic investigations indicate a complex reaction network, which can be manifested by theoretical investigations. DFT calculations show that the ring strains of both epoxides are comparable and the kinetic barriers for the chain propagation even favour the poly(propylene carbonate) over the poly(cyclohexene carbonate) formation. Therefore, the crucial step in the copolymerisation of propylene oxide and carbon dioxide is the back-biting reaction in the case of the studied zinc catalyst. The depolymerisation is several orders of magnitude faster for poly(propylene carbonate) than for poly(cyclohexene carbonate).

Behaviour of highly crystalline graphitic materials in lithium-ion cells with propylene carbonate containing electrolytes: An in situ Raman and SEM study

Low pressure carbon dioxide solubility in pure electrolyte solvents for lithium-ion batteries as a function of temperature. Measurement and prediction

It is widely understood that industrial chemistry is based on fossil raw materials. However, this view ignores the fact that renewable raw materials have also experienced a boom since the 1970s as alternative feedstocks for industrial chemistry and nutrients for industrial fermentation and industrial biotechnology in general. During growth, renewable resources absorb carbon dioxide. Whilst these resources are kept in the technical material system, they act as carbon storage. When they are ultimately managed as waste, e.g. incinerated, or composted, they will not contribute to net emissions of carbon dioxide into the atmosphere, as opposed to fossil-based products. However, nearly 30 years after the United Nations Conference on Sustainable Development in Rio de Janeiro, insufficient progress has been made on almost all global environmental problems, especially emissions of climate-relevant gases such as CO2, deforestation, soil degradation, and mass extinction of species, calling for a change of mindset away from an “ego-centric” worldview towards an “eco-centric” worldview. In this sense, renewable raw materials and resources used in the technical cycle link the concepts of bioeconomy and circular economy.

Freezing and crystallization of commercial ethylene carbonate-based binary electrolytes, leading to irreversible damage to lithium-ion batteries (LIBs), remain a significant challenge for the survi...

Anodic oxidation of propylene carbonate and ethylene carbonate on graphite electrodes

Low pressure methane solubility in lithium-ion batteries based solvents and electrolytes as a function of temperature. Measurement and prediction

The solubility of carbon dioxide in γ-butyrolactone (BL), caprolactone (CL), propylene carbonate (PC), ethylene carbonate (EC), dimethylcarbonate (DMC), diethylcarbonate (DEC), and mixtures of these components has been determined at temperatures from 275 to 333 K at atmospheric pressure. The Henry's law constant (kH) for the dissolution of CO2 in these solvents has been deduced from the solubility data. The value of kH increases in the following order: DEC < DMC < PC < CL < BL < EC, which is identical to the order of the Hildebrand parameters (δ) of the corresponding solvents. The accuracy of classical theories for predicting gas solubilities in liquids has been examined. The best results are given by the Vilcu–Perisamu equation, which is derived from the Scatchard–Hildebrand theory but takes into account the polarizability of the solute and the permittivity of the solvent. A modified form of the Prausnitz and Shair equation is proposed to estimate the solubility of nonpolar molecules in strongly dipolar solvents. This equation fits the experimental data with improved precision.Key words: alkylcarbonate, lactone, carbon dioxide, liquid–gas equilibrium, Henry's law, Hildebrand parameter.

Solubility of CO2 and H2S in carbonates solvent: Experiment and quantum chemistry calculation