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.     

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.     

Supercritical fluid extraction of cyclic oligomers from depolymerizing PBT

Cyclic oligomers of polyester show great potential for a reaction‐injection‐molding process, because of their initial low viscosity and rapid ring‐opening polymerization at low temperatures (180°C) without exothermic reaction or condensates. In this work, we report the synthesis of cyclic oligo(butylene terephthalate) (COBT) from linear poly(butylene terephthalate) by a formation–extraction process employing supercritical fluids (SCF) CO₂ and pentane at T = 230°C and P = 250 bar. Following this, depressurization of SCF leads to easy recovery of the COBTs. When compared with SCF CO₂, SCF pentane is found to be an attractive solvent because of its higher solubilizing capacity (0.8 mg COBT dimer/g pentane) for the COBTs. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 4487–4492, 2006     

Reactions of cyanamide, dicyandiamide and related cyclic azines in high temperature water

Cyanamide, dicyandiamide, and the related cyclic azines (melamine, ammeline, ammelide, and cyanuric acid) were reacted in water at 100–300 °C in a sealed 316 SS tube (275 bar) for the purpose of characterizing the hydrothermolysis chemistry of cyanamide. The conversion of cyanamide to dicyandiamide dominates at 100–175 °C. At 175–250 °C, when the reaction times are shorter than 15 min, the major pathway is hydrolysis of the cyanamide-dicyandiamide mixture to CO₂ and NH₃. A minor pathway is cyclization to higher azines (melamine, ammeline, ammelide and cyanuric acid). Above about 225 °C, hydrolysis of these cyclic azines to aqueous NH₃ and CO₂ occurs in a relative ratio which depends on the particular cyclic azine, and, to an extent, which increases with temperature. At 300 °C the conversion of all compounds to CO₂ and NH₃ is complete in 10 min. The hydrothermolysis chemistry of cyanamide and urea are compared.     

CO2载体CaO循环煅烧/碳酸化反应的分形特征

捕捉煤燃烧释放出的CO₂时,作为CO₂载体的CaO微观结构特性对其循环碳酸化性能具有显著影响。采用分形维数作为表征CaO微观结构的特征参数,研究在循环煅烧/碳酸化反应过程中CaO的分形特征及其对CO₂捕捉性能的影响规律。结果表明,随着循环次数的增加CaO分形维数逐渐下降,CaO孔道也由粗糙和不规则变得越来越平滑和有规则性。煅烧温度升高则CaO分形维数下降。分形维数较大的CaO具有较高的碳酸化速率。在碳酸化过程的前10 min内CaO的分形维数迅速减小,此后随时间变化缓慢。在分形维数D≤2.61的实验范围内,CaO分形维数与其循环碳酸化转化率呈线性正相关;当D＞2.61时,可能存在临界分形维数D_cr,当D＞D_cr时随着分形维数的进一步增大CaO转化率反而减小。     

Recent advances on the reduction of CO2 to important C2 + oxygenated chemicals and fuels

The chemical utilization of CO₂ is a crucial step for the recycling of carbon resource. In recent years, the study on the conversion of CO₂ into a wide variety of C_2 + important chemicals and fuels has received considerable attention as an emerging technology. Since CO₂ is thermodynamically stable and kinetically inert, the effective activation of CO₂ molecule for the selective transformation to target products still remains a challenge. The well-designed CO₂ reduction route and efficient catalyst system has imposed the feasibility of CO₂ conversion into C_2 + chemicals and fuels. In this paper, we have reviewed the recent advances on chemical conversion of CO₂ into C_2 + chemicals and fuels with wide practical applications, including important alcohols, acetic acid, dimethyl ether, olefins and gasoline. In particular, the synthetic routes for CC coupling and carbon chain growth, multifunctional catalyst design and reaction mechanisms are exclusively emphasized.     

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.     

Sustainable synthesis of cyclic carbonates from bio‐based polyether polyol: the structure characterization,rheological behaviour and thermal properties

The cycloaddition of CO₂ to epoxides represents a green efficient method to form bis(cyclic carbonate)s. The main purpose of the work reported in this paper was to examine the effect of the gas flow rate (20, 40, 60 and 100 mL min^–1) during carbonation on the conversion yield, chemical structure, rheological behaviour and thermal properties of the prepared compounds. A series of new bis(cyclic carbonate)s was obtained from bio‐based polyether polyol. The syntheses were performed in the absence of toxic solvents and the process did not require the use of elevated pressure. The progressive structural changes and the presence of characteristic chemical groups were monitored by attenuated total reflection Fourier transform infrared spectroscopy. The characterization of the structure by ¹H NMR and ¹³C NMR also confirmed the formation of cyclic carbonate moieties. The non‐Newtonian behaviour and the optimal mathematical model (Herschel–Bulkley) were verified by rheological measurements. The materials obtained could be used as a chemical intermediate to synthesize advanced materials based upon polyurethanes without using isocyanates. © 2019 Society of Chemical Industry     

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.     

Utilizing Formate as an Energy Carrier by Coupling CO2 Electrolysis with Fuel Cell Devices

Electrochemical reduction of CO₂ to useful chemicals can change the role of CO₂ from harmful waste to a valuable feedstock. Despite a lot of progress in the alkaline electrochemical conversion of CO₂ to formate, there is still a lack of potential applications for the generated aqueous formate solution. Here, the general ability of formate to be used as an energy or hydrogen carrier is discussed and compared to well‐known energy storage chemicals. Concepts to employ formate solution as an energy carrier by combining CO₂ electrolysis with the reconversion of formate into electricity via a direct formate fuel cell or catalytic decomposition to H₂ combined with a proton exchange membrane fuel cell are demonstrated.     

Tungsten oxides supported on nano-size zirconia for cyclic production of syngas and hydrogen by redox operations

For cyclic production of syngas and H₂ by redox (methane reforming-water splitting) operations, samples of tungsten oxides supported on nano-size zirconia (WO₃/n-ZrO₂) were investigated at 1,223 and 1,273 K and compared with those on micron-size zirconia (WO₃/µ-ZrO₂). The reduction characteristics of WO₃/n-ZrO₂ observed in this study were consistent with those of WO₃/µ-ZrO₂ reported in the literature. Specifically, the reduction process comprised three stages, the syngas production rate decreased as WO₃ content increased, and the overall degree of reduction gradually decreased with repeated cycles. However, there were differences due to the smaller particle size, namely, WO₃/n-ZrO₂ yielded a higher syngas production rate and a lower H₂/(CO+CO₂) ratio. In addition, the hydrogen yield by water splitting was significantly lower than the amount expected based on the overall degree of WO₃ reduction. The H₂/(CO+CO₂) ratio also gradually decreased with repeated cycles. These results were mainly attributed to rapid sintering of WO₃/n-ZrO₂, which gradually began to resemble WO₃/µ-ZrO₂.     

Investigations of Two Bidirectional Carbon Monoxide Dehydrogenases from Carboxydothermus hydrogenoformans by Protein Film Electrochemistry

Carbon monoxide dehydrogenases (CODHs) catalyse the reversible conversion between CO and CO₂. Several small molecules or ions are inhibitors and probes for different oxidation states of the unusual [Ni‐4 Fe‐4 S] cluster that forms the active site. The actions of these small probes on two enzymes—CODH I_Ch and CODH II_Ch—produced by Carboxydothermus hydrogenoformans have been studied by protein film voltammetry to compare their behaviour and to establish general characteristics. Whereas CODH I_Ch is, so far, the better studied of the two isozymes in terms of its electrocatalytic properties, it is CODH II_Ch that has been characterised by X‐ray crystallography. The two isozymes, which share 58.3 % sequence identity and 73.9 % sequence similarity, show similar patterns of behaviour with regard to selective inhibition of CO₂ reduction by CO (product) and cyanate, potent and selective inhibition of CO oxidation by cyanide, and the action of sulfide, which promotes oxidative inactivation of the enzyme. For both isozymes, rates of binding of substrate analogues CN^? (for CO) and NCO^? (for CO₂) are orders of magnitude lower than turnover, a feature that is clearly revealed through hysteresis of cyclic voltammetry. Inhibition by CN^? and CO is much stronger for CODH II_Ch than for CODH I_Ch, a property that has relevance for applying these enzymes as model catalysts in solar‐driven CO₂ reduction.     

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     

Adsorptive cyclic purification process for CO2 mixtures captured from coal power plants

CO₂ capture technology combined with bulk separation and purification processes has become an attractive alternative to reduce capture costs. Furthermore, the required purity in the application for CO₂ conversion and utilization is more stringent than that required from a captured CO₂ mixture for geological storage. In this study, an adsorptive cyclic purification process was developed to upgrade a CO₂/N₂ mixture captured from greenhouse gas emission plants as a feasibility study for a second capture unit or captured CO₂ purifier. To purify 90% CO₂ with balance N₂ as a captured gas mixture, two‐bed pressure swing adsorption and pressure vacuum swing adsorption (PVSA) processes using activated carbon were experimentally and theoretically studied at adsorption pressures of 250–650 kPa and a fixed vacuum pressure of 50 kPa. CO₂ with higher than 95% purity was produced with more than 89% recovery. However, a four‐bed PVSA process could successfully produce CO₂ with greater than 98% purity and 90% recovery. © 2016 American Institute of Chemical Engineers AIChE J, 63: 1051–1063, 2017     

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.     

Effect of bed height on the carbon dioxide capture by carbonation/regeneration cyclic operations using dry potassium-based sorbents

The effect of bed height on CO₂ capture was investigated by carbonation/regeneration cyclic operations using a bubbling fluidized bed reactor. We used a potassium-based solid sorbent, SorbKX35T5 which was manufactured by the Korea Electric Power Research Institute. The sorbent consists of 35% K₂CO₃ for absorption and 65% supporters for mechanical strength. We used a fluidized bed reactor with an inner diameter of 0.05 m and a height of 0.8 m which was made of quartz and placed inside of a furnace. The operating temperatures were fixed at 70 °C and 150 °C for carbonation and regeneration, respectively. The carbonation/regeneration cyclic operations were performed three times at four different L/D (length vs diameter) ratios such as one, two, three, and four. The amount of CO₂ captured was the most when L/D ratio was one, while the period of maintaining 100% CO₂ removal was the longest as 6 minutes when L/D ratio was three. At each cycle, CO₂ sorption capacity (g CO₂/g sorbent) was decreased as L/D ratio was increased. The results obtained in this study can be applied to design and operate a large scale CO₂ capture process composed of two fluidized bed reactors. This work was presented at the 7 ^th China-Korea Workshop on Clean Energy Technology held at Taiyuan, Shanxi, China, June 26–28, 2008.     

Solar Light Photocatalytic CO2 Reduction: General Considerations and Selected Bench-Mark Photocatalysts

The reduction of carbon dioxide to useful chemicals has received a great deal of attention as an alternative to the depletion of fossil resources without altering the atmospheric CO₂ balance. As the chemical reduction of CO₂ is energetically uphill due to its remarkable thermodynamic stability, this process requires a significant transfer of energy. Achievements in the fields of photocatalysis during the last decade sparked increased interest in the possibility of using sunlight to reduce CO₂. In this review we discuss some general features associated with the photocatalytic reduction of CO₂ for the production of solar fuels, with considerations to be taken into account of the photocatalyst design, of the limitations arising from the lack of visible light response of titania, of the use of co-catalysts to overcome this shortcoming, together with several strategies that have been applied to enhance the photocatalytic efficiency of CO₂ reduction. The aim is not to provide an exhaustive review of the area, but to present general aspects to be considered, and then to outline which are currently the most efficient photocatalytic systems.     

Dipole moments and statistical conformations of cyclic and linear dimethylsiloxane oligomers

The statistical conformations of cyclic dimethylsiloxane oligomers [(CH₃)₂SiO]_x with x in the range 4–10 have been studied by using rotational isomeric state models to describe the ‘cyclic’ conformations of the open chain molecules. Stringent criteria were used to select ‘cyclic’ conformations of the equivalent open chains based on the relative orientations and rotational states of their terminal skeletal bonds. The root-mean-square electric dipole moments $\text{〈μ}{}^2\text{〉}{}_0{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ and the temperature coefficients d $\text{ln}\text{〈μ}{}^2\text{〉}{}_0\text{dT}$ were calculated using a modified form of the rotational isomeric state model of Flory, Crescenzi and Mark. The calculated dipole moments are compared with some experimental values measured for cyclic oligomers in the undiluted state at 298 K. For the ‘cyclic’ conformations of the open chains the magnitude of the calculated temperature coefficients for x = 5–9 were found to be very nearly inversely proportional to the fraction of rotatable skeletal bonds occupying trans rotational states; a functional dependence opposite to that found for the open chains.     

Prediction of phase equilibrium of CO2/cyclic compound binary mixtures using a rigorous modeling approach

Vapor liquid equilibrium (VLE) data has significant role in designing processes which include vapor and liquid in equilibrium. Since it is impractical to measure equilibrium data at any desired temperature and pressure, particularly near critical region, thermodynamic models based on equation of state (EOS) are usually used for VLE estimating. In recent years due to the development of numerical tools like artificial intelligence methods, VLE prediction has been find new alternatives.In the present study a novel method called Least-Squares Support Vector Machine (LSSVM) used for predicting bubble/dew point pressures of binary mixtures containing carbon dioxide (CO₂) + cyclic compounds as function of reduced temperature of the system, critical pressure, acentric factor of the cyclic compound, and CO₂ composition. A 333 binary equilibrium data points of CO₂ and six cyclic compounds within temperature and pressure ranges of 308.15–473.15 K and 0.5–27.71 MPa were used to develop the model. Results show that the proposed model is able to predict VLE data for binary systems containing supercritical or near-critical CO₂/cyclic compounds with an acceptable average absolute relative deviation percent (AARD%) of 3.9381% and the coefficient of determination (R²) value of 0.9980. For detection of the probable doubtful experimental data, and applicability of the model, the Leverage statistical approach performed on the data sets. This algorithm showed that the proposed LSSVM model is statistically valid for VLE prediction and the whole phase equilibrium data points are in applicability domain of the model.     

Application of the random pore model to the carbonation cyclic reaction

Calcium oxide has been proved to be a suitable sorbent for high temperature CO₂ capture processes based on the cyclic carbonation‐calcination reaction. It is important to have reaction rate models that are able to describe the behavior of CaO particles with respect to the carbonation reaction. Fresh calcined lime is known to be a reactive solid toward carbonation, but the average sorbent particle in a CaO‐based CO₂ capture system experiences many carbonation‐calcination cycles and the reactivity changes with the number of cycles. This study applies the random pore model (RPM) to estimate the intrinsic rate parameters for the carbonation reaction and develops a simple model to calculate particle conversion with time as a function of the number of cycles, partial pressure of CO₂, and temperature. This version of the RPM model integrates knowledge obtained in earlier works on intrinsic carbonation rates, critical product layer thickness, and pore structure evolution in highly cycled particles. © 2009 American Institute of Chemical Engineers AIChE J, 2009