Hydrogen bond activation strategy for cyclic carbonates synthesis from epoxides and CO2: current state-of-the art of catalyst development and reaction analysis

Chemical fixation of CO₂ into useful organic compounds has been attracting much attention from the viewpoint of CO₂ emission reduction and energy structure reformation. A useful and widely investigated chemical utilization of CO₂ is the cycloaddition of CO₂ to epoxides for the synthesis of cyclic carbonates. Efforts have been paid to the design and preparation of various catalyst systems that are active and selective to the production of the desired products under mild conditions and in green processes. This article is to review the current state of the catalyst development and the experimental and theoretical analysis of reaction mechanism for the cyclic carbonate synthesis from epoxides, one of currently important reactions involving CO₂ as a reactant with 100% atom economy. Particular attention is given to the catalysis of multifunctional catalyst systems such as metal- and hydrogen-bond donor (HBD)-based catalysts.     

Direct conversion of CO2 with diols,aminoalcohols and diamines to cyclic carbonates,cyclic carbamates and cyclic ureas using heterogeneous catalysts

CO₂ has a large effect on global warming by greenhouse gases, and development of an effective technique for the reduction of CO₂ is a crucial and urgent issue. From the chemical viewpoint, CO₂ is regarded as a stable, safe and abundant C1 resource, and the transformation of CO₂ to valuable chemicals is promising not only for reduction of CO₂ but also for production of useful chemicals. This mini‐review focuses on the direct conversion of CO₂ with diols, aminoalcohols and diamines to cyclic compounds such as cyclic carbonates, cyclic carbamates and cyclic ureas, and in particular discusses the mechanisms for these reactions over heterogeneous catalysts. © 2013 Society of Chemical Industry     

Verwendung von Kohlendioxid bei technischorganischen Synthesen

Use of carbon dioxide in industrial organic syntheses . Although carbon dioxide is important as an abundant carbonaceous raw material, its utilization in chemical processes so far has been rather limited. This review covers the reactions of CO₂ employed in industry, such as the production of urea, the Kolbe-Schmitt reaction, the synthesis of cyclic organic carbonates, and the use of CO₂ in methanol synthesis. Interesting recent developments in CO₂ chemistry, especially the transition metal catalyzed reactions, are also elucidated. In addition to the synthesis of polymers and hydrocarbons, the production of oxygen-containing chemicals seems to be very profitable and attractive for future industrial applications. Not only can derivatives of formic acid and carbonic acid be formed but longer-chain carboxylic acids and their derivatives are also accessible by reactions of carbon dioxide with hydrocarbons such as alkynes, alkenes, and 1,3-dienes.     

Use of carbon dioxide in industrial organic syntheses

Although carbon dixoide is important as an abundant carbonaceous raw material, so far, its utilization in chemical processes has been rather limited. This review covers the reactions of CO₂ employed in industry, such as the production of urea, the Kolbe-Schmitt reaction, the synthesis of cyclic organic carbonates and the use of CO₂ in methanol synthesis. Interesting recent developments in CO₂ chemistry, such as the reactions catalyzed by transition metals, are also described. Apart from the synthesis of polymers and hydrocarbons, the production of oxygen-containing substances appears to be very profitable and attractive for future industrial applications. Not only can derivatives of formic and carbonic acids be produced but also longer-chain carboxylic acids and their derivatives by reactions of carbon dioxide with hydrocarbons such as alkynes, alkenes and 1,3-dienes.     

Synthesis of organic carbonates from alcoholysis of urea: A review

Organic carbonates are green compounds with a wide range of applications. They are widely used for the synthesis of important industrial compounds including monomers, polymers, surfactants, plasticizers, and also used as fuel additives. They can be divided into two main classes: cyclic and linear carbonates. Dimethyl carbonate (DMC) and diethyl carbonate (DEC) are the important linear carbonates. Carbonyl and alkyl groups present in DMC and DEC make them reactive and versatile for synthesizing various other important compounds. Ethylene carbonate (EC), glycerol carbonate (GC) and propylene carbonate (PC) are well-known cyclic organic carbonates. Phosgenation of alcohols was widely used for synthesis of organic carbonates; however, toxicity of raw materials restricted use of phosgenation method. A number of new non-phosgene methods including alcoholysis of urea, carbonylation of alcohols using CO₂, oxy-carbonylation of alcohols, and trans-esterfication of alcohols and carbonates have been developed for synthesizing organic carbonates. Carbonylation of alcohols is preferred as it helps in utilization and sequestration of CO₂, however, poor thermodynamics due to high stability of CO₂ is the major obstacle in its large scale commercialization. Oxy-carbonylation of alcohols offers high selectivity but presence of oxygen poisons the catalyst. Recently, alcoholysis of urea has received more attention because of its inexpensive abundant raw materials, favorable thermodynamics, and no water-alcohol azeotrope formation. Also, ammonia evolved in this synthesis route can be recycled back to urea by reacting it with CO₂. In other words, this method is a step towards utilization of CO₂ as well. This article reviews synthesis of DMC, DEC, GC, PC, and EC from urea by critically examining various catalysts used and their performances. Mechanisms have been reviewed in order to give an insight of the synthesis routes. Research challenges along with future perspectives have also been discussed.     

Carbon dioxide: a renewable feedstock for the synthesis of fine and bulk chemicals

The syntheses of carbon dioxide (CO₂) based industrially important chemicals have gained considerable interest in view of the sustainable chemistry and “green chemistry” concepts. In this review, recent developments in the chemical fixation of CO₂ to valuable chemicals are discussed. The synthesis of five-member cyclic carbonates via, cycloaddition of CO₂ to epoxides is one of the promising reactions replacing the existing poisonous phosgene-based synthetic route. This review focuses on the synthesis of cyclic carbonates, vinyl carbamates, and quinazoline-2,4(1H,3H)-diones via reaction of CO₂ and epoxide, amines/phenyl acetylene, 2-aminobenzinitrile and other chemicals. Direct synthesis of dimethyl carbonate, 1,3-disubstituted urea and 2-oxazolidinones/2-imidazolidinones have limitations at present because of the reaction equilibrium and chemical inertness of CO₂. The preferred alternatives for their synthesis like transesterification of ethylene carbonate with methanol, transamination of ethylene carbonate with primary amine and transamination reaction of ethylene carbonate with diamines/β-aminoalcohols are discussed. These methodologies offer marked improvements for greener chemical fixation of CO₂ in to industrially important chemicals.     

A fully bio-based monomer derived from undecylenic acid,glycerol, and CO2 useful for the synthesis of polyhydroxyurethanes

Undecylenic acid, glycerol, and CO₂ were used as building blocks for obtaining a fully bio-based carbonated monomer, useful for polyurethanes. The functionality of the monomer was close to 3 cyclic carbonates/mol, located in terminal positions. In a first stage, a synthetic triglyceride was obtained with 99% selectivity by esterification of glycerol and undecylenic acid at 160°C. The triglyceride was then epoxidized using H₂O₂ and Amberlyst 15 or Amberlite IR-120 acidic exchange resins at 57°C. The selectivity to epoxide was kept constant at 98% using Amberlite IR-120. Terminal cyclic carbonates were then inserted through epoxide moieties under mild conditions by the chemical fixation of CO₂ at 80°C and 6 MPa in 6 h. A complete conversion was obtained in 6 h reaction while the selectivity to carbonate groups was near to 99% during all the reaction time. An elastomeric polyhydroxyurethane was obtained by aminolysis of the carbonated monomer with ethylenediamine at 70°C, affording a Young's modulus of 22.6 MPa and T_g of −15.2°C. The material showed a good thermal stability below 240°C.     

Synthesis of Polycarbonate Precursors over Titanosilicate Molecular Sieves

A novel catalytic application of titanosilicate molecular sieves (TS-1 and TiMCM-41), in the synthesis of polycarbonate precursors like cyclic carbonates and dimethyl and diphenyl carbonates, avoiding toxic chemicals like phosgene or CO, is reported. Cyclic carbonates were prepared, over TS-1 and TiMCM-41, in high yields, by cycloaddition of CO₂ to epoxides, like epichlorohydrin, propylene oxide and styrene oxide, at low temperatures and pressures. Further, transesterification of the cyclic carbonates with methanol and phenol, over TiMCM-41, yielded other polycarbonate precursors like dimethyl carbonate (DMC) and diphenyl carbonate (DPC). The cyclic carbonates could also be synthesized from the olefins in the same reactor by reacting the olefins, in the presence of TiMCM-41, with a mixture of an epoxidizing agent (like H₂O₂ or tert-butyl hydroperoxide) and CO₂.     

Metal-carbonate formation from ammonia solution by addition of metal salts—An effective method for CO2 capture from landfill gas (LFG)

The absorption of CO₂ from LFG in different weight concentration ammonia solution and metal salts (Zinc and Barium) is investigated in this study. Addition of metal salts results in useful metal carbonates when LFG is passed through the solution. Barium salts show a better potential of removing CO₂ as compared to Zinc salts. Addition of Barium salts to ammonia solution results in a new absorbent as no study has been focused on it till date. Also metal salts are added to alkaline wastewater which not only decreases the pH of the wastewater but also useful metal carbonates are obtained from wastewater when LFG is passed through it. Different parameters like CO₂ loading, reaction rate and change in pH are investigated. Formation of carbonates is proved by using SEM and XRD analysis. Raman spectroscopy was performed on the discarded liquid after removal of carbonates to understand the formation of bicarbonates, carbonates and carbamates.     

Use of carbon dioxide as feedstock for chemicals and fuels: homogeneous and heterogeneous catalysis

CO₂ is considered to play a key role in an eventual climate change, due to its accumulation in the atmosphere. The control of its emission represents a challenging task that requires new ideas and new technologies. The use of perennial energy sources and renewable fuels instead of fossil fuels and the conversion of CO₂ into useful products are receiving increased attention. The utilization of CO₂ as a raw material for the synthesis of chemicals and fuels is an area in which scientists and industrialists are much involved: the implementation of such technology on a large scale would allow a change from a linear use of fossil carbon to its cyclic use, mimicking Nature. In this paper the use of CO₂ as building block is discussed. CO₂ can replace toxic species such as phosgene in low energy processes, or can be used as source of carbon for the synthesis of energy products. The reactions with dihydrogen, alcohols, epoxides, amines, olefins, dienes, and other unsaturated hydrocarbons are discussed, under various reaction conditions, using metal systems or enzymes as catalysts. The formation of products such as formic acid and its esters, formamides, methanol, dimethyl carbonate, alkylene carbonates, carbamic acid esters, lactones, carboxylic acids, and polycarbonates, is described . The factors that have limited so far the conversion of large volumes of CO₂ are analyzed and options for large‐scale CO₂ catalytic conversion into chemicals and fuels are discussed. Both homogeneous and heterogeneous catalysts are considered and the pros and cons of their use highlighted. © 2013 Society of Chemical Industry     

Synthesis of glycerol carbonate by direct carbonatation of glycerol in supercritical CO2 in the presence of zeolites and ion exchange resins

Glycerol carbonate is a key bifunctional compound employed as solvent, additive, monomer, and chemical intermediate. We have synthesized it on a pilot scale in the laboratory in cyclic or alicyclic organic carbonate medium. In this study, we examined the use of supercritical CO₂ as a reaction medium and as a source of carbonate for carbonatation of glycerol. Glycerol carbonate could be obtained by direct reaction of carbon dioxide with an organic carbonate in the presence of heterogeneous catalysts. Carbonatation of glycerol into glycerol carbonate went to equilibrium in supercritical CO₂ medium. This revised version was published online in July 2006 with corrections to the Cover Date.     

Biocompatible and recyclable amino acid binary catalyst for efficient chemical fixation of CO2

In this work, the cycloaddition reactions of CO₂ with various epoxides to form five-membered cyclic carbonates catalyzed by an efficient amino acid based biocompatible catalyst were investigated. It was found that the activity of amino acid could be obviously enhanced in the presence of alkali metal salts, and the l-tryptophan catalytic system was the most efficient among the catalysts employed. Based on the result, a possible mechanism for the synergetic effect of catalyst was proposed. The process reported here represents a simple, ecologically safer, cost-effective route to cyclic carbonates with high product quality, as well as easy catalyst recycling.     

Nickel-catalysed electrochemical carboxylation of allylic acetates and carbonates

The electrochemical carboxylation of a series of allylic acetates and carbonates was carried out in the presence of CO₂ under atmospheric pressure, with a catalytic amount of nickel-bipyridine complex, to afford the corresponding β,γ-unsaturated carboxylic acids. In the absence of nickel catalyst, alcohols were obtained.     

2,2',2'-Terpyridine-Catalyzed Synthesis of Cyclic Carbonates from Epoxides and Carbon Dioxide under Solvent-Free Conditions

An efficient coupling reaction of epoxides with CO₂ affording cyclic carbonates with the use of 2,2'',2''''-terpyridine as catalyst under solvent-free conditions has been developed.     

Poly(4‐vinylphenol)/tetra‐n‐butylammonium iodide: Efficient organocatalytic system for synthesis of cyclic carbonates from CO2 and epoxides

An efficient polymer‐based catalytic system of poly(4‐vinylphenol) and tetra‐n‐butylammonium iodide was developed for the synthesis of cyclic carbonates from epoxides and CO₂. Owing to the synergistic effects of hydroxyl groups and iodide anions, this commercially available and metal‐free system was highly active for the reaction of various terminal epoxides under environmentally benign conditions, at 25 to 60 °C and atmospheric pressure of CO₂, without the use of any organic solvents. The catalyst system can be easily separated by adding ether, and its ability was recovered by treating it with 40% CH₃CO₂H aq. The recyclability was investigated in detail for three substrates, epichlorohydrin, 1,2‐epoxyhexane, and styrene oxide, using ¹H nuclear magnetic resonance analysis. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45189.     

Facile Construction of Carboxyl-Functionalized Ionic Polymer towards Synergistic Catalytic Cycloaddition of Carbon Dioxide into Cyclic Carbonates

The development of bifunctional ionic polymers as heterogeneous catalysts for effective, cocatalyst- and metal-free cycloaddition of carbon dioxide into cyclic carbonates has attracted increasing attention. However, facile fabrication of such polymers having high numbers of ionic active sites, suitable types of hydrogen bond donors (HBDs), and controlled spatial positions of dual active sites remains a challenging task. Herein, imidazolium-based ionic polymers with hydroxyl/carboxyl groups and high ionic density were facilely prepared by a one-pot quaternization reaction. Catalytic evaluation demonstrated that the presence of HBDs (hydroxyl or carboxyl) could enhance the catalytic activities of ionic polymers significantly toward the CO₂ cycloaddition reaction. Among the prepared catalysts, carboxyl-functionalized ionic polymer (PIMBr-COOH) displayed the highest catalytic activity (94% yield) in the benchmark cycloaddition reaction of CO₂ and epichlorohydrin, which was higher than hydroxyl-functionalized ionic polymer (PIMBr-OH, 76% yield), and far exceeded ionic polymer without HBDs groups (PIMBr, 54% yield). Furthermore, PIMBr-COOH demonstrated good recyclability and wide substrate tolerance. Under ambient CO₂ pressure, a number of epoxides were smoothly cycloadded into cyclic carbonates. Additionally, density functional theory (DFT) calculation verified the formation of strong hydrogen bonds between epoxide and the HBDs of ionic polymers. Furthermore, a possible mechanism was proposed based on the synergistic effect between carboxyl and Br⁻ functionalities. Thus, a facile, one-pot synthetic strategy for the construction of bifunctional ionic polymers was developed for CO₂ fixation.     

Accurate Prediction of Two-Phase Behavior of the Mixtures of Carbon Dioxide and Different Perfluoroalkane Compounds: Comparison of the Presented Neuro-Fuzzy Model with Advanced Soft-SAFT Molecular Model

An advanced adaptive neuro-fuzzy inference system (ANFIS) has been proposed for accurate prediction of the two-phase behavior of CO₂/perfluoroalkane mixtures regarding the design of CO₂ sequestration and recovery systems. The most important fluoroalkane solvents such as linear (perfluoro-n-octane), cyclic (perfluorodecalin and perfluoromethylcyclohexane), and aromatic compounds (perfluorobenzene and perfluorotoluene) are considered in this study. The proposed ANFIS model can be used for accurate predictions of CO₂/perfluoroalkane phase behavior over wide ranges of temperatures and pressures and is a useful tool for the design of environmental friendly CO₂ recovery processes. The proposed neuro-fuzzy model outperforms the soft-SAFT (Statistical Associating Fluid Theory) and polar soft-SAFT molecular models both in accuracy and in generality.     

Carbon capture and utilization via chemical looping dry reforming

Chemical looping combustion (CLC) is a clean energy technology for CO₂ capture that uses periodic oxidation and reduction of an oxygen carrier with air and a fuel, respectively, to achieve flameless combustion and yield sequestration-ready CO₂ streams. While CLC allows for highly efficient CO₂ capture, it does not, however, provide a solution for CO₂ sequestration.Here, we propose chemical looping dry reforming (CLDR) as an alternative to CLC by replacing air with CO₂ as the oxidant. CLDR extends the chemical looping principle to achieve CO₂ reduction to CO, which opens a pathway to CO₂ utilization as an alternative to sequestration. The feasibility of CLDR is studied through thermodynamic screening calculations for oxygen carrier selection, synthesis and kinetic experiments of nanostructured carriers using cyclic thermogravimetric analysis (TGA) and fixed-bed reactor studies, and a brief model-based analysis of the thermal aspects of a fixed-bed CLDR process.Overall, our results indicate that it is indeed possible to reduce CO₂ to CO with high reaction rates through the use of appropriately designed nanostructured carriers, and to integrate this reaction into a cyclic redox (“looping”) process.     

Investigation of the pH effect of a typical host rock and buffer solution on CO2 sequestration in synthetic brines

Carbon dioxide sequestration in deep saline aquifers is a critical component of long-term storage options. It is suggested that the precipitation of mineral carbonates is mostly dependent on brine pH and is favoured above a basic pH of 9.0. However, brine pH will drop to acidic values once CO₂ is injected into the brine. Therefore, there is a need to raise brine pH and maintain it stable. Synthetic brines were used here instead of natural brines because of the difficulty in obtaining and storing natural brines. Therefore, experiments were conducted to prepare a series of synthetic brines and to compare their suitability to natural brines for carbon sequestration firstly. A typical host rock (Oriskany rock) and a buffer solution (NaCl/NaHCO₃) were selected to buffer brine pH. In a subsequent step, studies were conducted to correlate how brine samples respond in the presence of the host rock or the buffer solution at realistic reservoir temperatures (40 and 100 °C) and pressures (1160 and 1500 psi) for CO₂ storage. The results show that synthetic brines prepared can be used as analogues as natural brines for carbon sequestration studies in terms of chemical composition and pH response. Both XRD and SEM/EDS analyses confirmed the presence of mineral carbonates in the CO₂-rock-brine and the CO₂-buffer-brine experiments. However, the amount of carbonates precipitated from the CO₂-buffer-brine reactions is nearly 18 times larger than that formed from the CO₂-rock-brine experiments. ICP-MS studies also verified that there was only 4% reduction in Ca concentration in solution after the CO₂-rock-brine studies, while the concentrations of Ca and Sr decreased by 90% during the CO₂-buffer-brine experiments.