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.     

Synthesis, characterization of high Ti-containing Ti-MCM-41 catalysts and their activity evaluation in oxidation of cyclohexene and epoxidation of higher olefins

A series of titanium rich isomorphous substituted Ti MCM-41 and HMS materials have been synthesized with different Si/Ti ratios. The highest amount of Ti incorporated in synthesis gel is in TiMCM-41 (Si/Ti = 10). Whereas for TiHMS catalysts, Ti is incorporated up to Si/Ti = 50 successfully without forming any extra framework TiO₂. Cyclohexene epoxidation reaction with dry tert-butyl hydroperoxide (TBHP) as an oxidant has been studied to evaluate the catalytic properties of Ti substituted mesoporous catalysts. The effect of molar ratio of substrate:oxidant in this reaction has been studied and high conversion, high selectivity were achieved at 2: 1 molar ratio with TiMCM-41 (Si/Ti =25). Dry TBHP (in dichloromethane) and chloroform were found as good oxidant and solvent system for this reaction. Pure siliceous mesoporous silica and low `Ti' substituted mesoporous silicas were found to be efficient catalysts for oxidation of cyclohexene. An interesting variation of the selectivity from allylic oxidation to epoxidation during oxidation of cyclohexene was observed with an increase in the Ti amount in the mesoporous framework. The allylic oxidation of cyclohexene has been carried out using molecular oxygen as an oxidant and in the presence of a small amount of TBHP as initiator. Siliceous HMS materials gave better conversion compared to MCM-41 type of materials and other conventional silicas like silica gel, fumed silica etc. in allylic oxidation of cyclohexene. Epoxidation of higher cyclic olefins like cyclooctene, cyclododecene, cis-cyclododecene and linear olefins 1-Heptene, cis-2-hexene, 1-undecene was carried out over TiMCM-41 (Si/Ti = 25). Ti substituted mesoporous catalysts were characterized by elemental analysis, XRD, FTIR, UVDRS, ²⁹SiMASNMR, BET surface area and pore size distribution techniques.     

Comparison of polycarbonate precursors synthesized from catalytic reactions of bisphenol‐A with diphenyl carbonate,dimethyl carbonate,or carbon monoxide

Transesterification of bisphenol‐A with diphenyl carbonate or dimethyl carbonate, and direct oxidative carbonylation of bisphenol‐A were compared to obtain polycarbonate precursors for phosgene‐free polycarbonate synthesis. The melt‐transesterification of bisphenol‐A and diphenyl carbonate occurred readily to produce reactive precursors without a significant equilibrium constraint. On the other hand, the transesterification of bisphenol‐A and dimethyl carbonate showed a serious equilibrium limitation in obtaining reactive polycarbonate precursors leading to high molecular weight polymers, and coproduced a significant amount of methylated bisphenol‐A. The direct oxidative carbonylation of bisphenol‐A with CO produced diphenolic‐ended oligomers and a significant amount of by‐products, which are the least reactive in the subsequent polycondensation step of the phosgene‐free polycarbonate process. A novel method to synthesize the reactive polycarbonate precursors was proposed that employed the coupled oxidative carbonylation of both bisphenol‐A and phenol. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 937–947, 2002     

A new,nonphosgene route to poly(bisphenol a carbonate) by melt‐phase interchange reactions of alkylene diphenyl dicarbonates with bisphenol A

This article describes a new, nonphosgene method for the synthesis of poly(bisphenol A carbonate) (PC). The method involves three steps: the reaction of an aliphatic diol with phenyl chloroformate to form an alkylene diphenyl dicarbonate, the reaction of the alkylene diphenyl dicarbonate with bisphenol A to produce an aromatic–aliphatic polycarbonate, and the thermal treatment of the polycarbonate at 180–210°C under a stream of nitrogen with Ti(OBu)₄ to give PC and a cyclic alkylene carbonate. The method furnished low to moderate molecular masses of PC upon the complete elimination of the aliphatic moieties. The approach may be considered a new method, based on polycarbonate thermochemical degradation, for the synthesis of cyclic aliphatic carbonates. The obtained polymers were characterized by intrinsic viscosity and IR, ¹H‐NMR, and ¹³C‐NMR spectroscopy. The thermal treatment step was conducted in a glass reaction tube at 180–210°C under a stream of nitrogen, and the reaction was completed by heating to 250°C. In the thermal treatment step, semisolid effluents composed of cyclic alkylene carbonates were formed and subsequently eliminated from the reaction mixture. Heating to 250°C under nitrogen or under a dynamic vacuum furnished the pure aromatic PC residue. This intrachange reaction provides a flexible method for the synthesis of polycarbonates with alkylene diols containing two or three methylene groups, from which the pure PC homopolymer can be prepared. The potential of this approach was demonstrated by the successful synthesis of PC homopolymer from five different polycarbonates with a bisphenol A unit linked to 1,2‐propylene, 1,3‐propylene, 2‐methyl‐1,3‐propylene, 2,2‐dimethyl‐1,3‐propylene, and 1,3‐butylene as the alkane chains. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Methodologies for chemical utilization of CO2 to valuable compounds through molecular activation by efficient catalysts

The reactions of CO₂ with oxirane to produce cyclic carbonate, and with aziridine to afford oxazolidine have been of interest as a useful method for its fixation by a chemical process. Highly efficient processes employing recyclable CO₂-phlilic homogeneous catalyst were devised for environmentally benign synthesis of cyclic carbonates and oxazolidinones under supercritical CO₂ without any organic solvent. These processes represent pathways for greener chemical fixations of CO₂ to afford industrial useful materials such as organic carbonates and oxazolidinones with great potential applications.     

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.     

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     

Aspects of carbon dioxide utilization

Carbon dioxide reacts with hydrogen, alcohols, acetals, epoxides, amines, carbon–carbon unsaturated compounds, etc. in supercritical carbon dioxide or in other solvents in the presence of metal compounds as catalysts. The products of these reactions are formic acid, formic acid esters, formamides, methanol, dimethyl carbonate, alkylene carbonates, carbamic acid esters, lactones, carboxylic acids, polycarbonate (bisphenol-based engineering polymer), aliphatic polycarbonates, etc. Especially, the productions of formic acid, formic acid methyl ester and dimethylformamide with a ruthenium catalyst; dimethyl carbonate and urethanes with a dialkyltin catalyst; 2-pyrone with a nickel-phosphine catalyst; diphenyl carbonate with a lead phenoxide catalyst; the alternating copolymerization of carbon dioxide and epoxides with a zinc catalyst has attracted attentions as the industrial utilizations of carbon dioxide. The further development of these production processes is expected.     

Synthesis and catalytic properties of TS-1 with mesoporous/microporous hierarchical structures obtained in the presence of amphiphilic organosilanes

Titanosilicates TS-1 with mesoporous/microporous hierarchical structures have been synthesized in the presence of an organosilane surfactant. Highly porous crystals, with regular pores of ca. 2.5–3.5 nm diameter, are obtained under hydrothermal conditions similar to those used for the preparation of conventional catalysts. The organosilane has a great influence on the textural properties of TS-1, but does not significantly affect the amount and coordination of Ti species in the framework. Mesoporous TS-1 have been used as catalysts in various oxidation reactions with an aqueous H₂O₂ and their activity has been compared with those of a conventional TS-1 and a mesoporous amorphous TiMCM-41. Data show that mesoporous TS-1 does not possess the expected properties for hierarchical catalysts, i.e. the properties of the conventional catalysts with advantages of mesoporous solids. In particular, the gain in diffusion due to intracrystalline mesopores is totally inhibited by the increase of the hydrophilic character of the zeolite, resulting from very high silanol group populations on the external surface.     

Sustainable Dimethyl Carbonate Production from Ethylene Oxide and Methanol

A large-scale dimethyl carbonate (DMC) production process from ethylene oxide (EO), CO₂, and methanol was simulated and optimized. Unlike most industrial processes of DMC production, the direct conversion of EO and CO₂ to ethylene carbonate (EC) and EC transesterification to DMC were performed in a single reactor. The reaction volume and the reactor operating pressure were selected as decision variables and evaluated. The key performance parameters, e.g., conversion per pass and CO₂ intensity, were compared with conventional commercialized routes or novel promising processes in the literature.     

Titania-silica aerogels with superior catalytic performance in olefin epoxidation compared to large pore Ti-molecular sieves

The paper provides a short overview on the various Ti- and Si-containing epoxidation catalysts, with a focus on the development and characterisation of titania-silica mixed oxides prepared by the sol-gel-aerogel method. Titania-silica aerogels, dried by semicontinuous extraction of the solvent with supercritical CO₂ at low temperature, possess high surface area, an amorphous mesoporous structure, and a rather even distribution of Ti in the silica matrix. The catalytic activities of mixed oxides, silica-supported titania and Ti-substituted molecular sieves (TS-1, Ti- and Ti-MCM-41) are compared in the epoxidation of 1-hexene, 1-octene, cyclohexene, cyclododecene and norbornene, based on literature data. The activities (i.e. the amount of converted olefin per unit time and catalyst weight) vary in a broad range of several orders of magnitude. It is shown that the low temperature aerogel containing 20 wt% TiO₂ is superior to any other Ti- and Si-containing catalyst for the epoxidation of cyclic olefins. In the epoxidation of linear alkenes TS-1 has outstanding activity. Ti-substituted large and ultra-large pore molecular sieves require further development concerning their catalytic performance.     

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.     

A new process for the synthesis of diphenyl carbonate from dimethyl carbonate and phenol over heterogeneous catalysts

The two-step synthesis of diphenyl carbonate (DPC) from dimethyl carbonate (DMC) and phenol has been compared in liquid phase and gas phase, both over heterogeneous catalysts. In the first step, equilibrium yields of methyl phenyl carbonate (MPC) in the transesterification of DMC and phenol were very low at low temperatures in the liquid phase although reaction rates were fast. This endothermic reaction was more favorable at high temperatures in the gas-phase reaction. Titanium oxide catalysts supported on SiO₂ or activated carbon were found to be effective in a continuous gas flow reactor. In case of the second step, the disproportionation of MPC, selective formation of DPC was not feasible in the gas-phase reaction due to extensive side reactions. However, there was no by-product in the liquid-phase reaction over the TiO₂/SiO₂ catalyst. Therefore, our proposed two-step synthesis process consists of the gas-phase transesterification of DMC and phenol followed by the liquid-phase disproportionation of MPC to DPC, both over the TiO₂/SiO₂ catalyst. This revised version was published online in July 2006 with corrections to the Cover Date.     

Selective production of hydrogen by partial oxidation of methanol over catalysts derived from CuZnAl‐layered double hydroxides

Hydrogen production by partial oxidation of methanol (POM) reaction (CH₃OH + (1/2)O₂ ⇌ ₂H₂ + CO₂) was investigated over a series of CuZnAl ternary oxide catalysts derived from CuZnAl hydroxycarbonate precursors containing hydrotalcite‐like layered double hydroxide as a major phase. These catalysts exhibited a good catalytic activity and high H₂ selectivity. A methanol conversion of about 40–60% was obtained at 200°C with high selectivity of H₂ and CO₂. The undesirable by‐product, CO was virtually not produced over most of the catalysts at this temperature. The catalytic activity was found to decrease with increasing (Cu + Zn)/Al atomic ratio in the precursor and, was correlated with Cu metal surface areas, Cu dispersion and Cu particle sizes, which were calculated by both XRD and TPR‐N₂O passivation methods. The catalyst with higher Cu surface areas and Cu dispersion displayed a higher catalytic activity. Lifetime experiments showed that these catalysts were stable over a period of 24 h of continuous operation. Catalyst precursors containing hydroxycarbonates other than LDH as a major phase offered considerable amount of dimethyl ether as a by‐product. This revised version was published online in July 2006 with corrections to the Cover Date.     

Supported imidazole as heterogeneous catalyst for the synthesis of cyclic carbonates from epoxides and CO2

Imidazole anchored onto a silica matrix, by means of a propyl linkage, is found to be an effective heterogeneous catalyst for the synthesis of cyclic carbonates from epoxides and CO₂ in near quantitative yield. The versatility of this catalyst is demonstrated by using different substrates (epichlorohydrin, propylene oxide, butylene oxide and styrene oxide) for this cycloaddition reaction. These CO₂ insertion reactions were typically carried out in the temperature range of 343 to 403 K at 0.6 MPa CO₂ pressure under solvent-free conditions. Several spectroscopic methods were used to characterize the catalyst and study the integrity of the fresh and spent 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     

Direct synthesis of dimethyl carbonate from methanol and carbon dioxide over Ga2O3-CeO2-ZrO2 catalysts prepared by a single-step sol-gel method: Effect of acidity and basicity of the catalysts

XGa₂O₃-CeO₂-ZrO₂ (X=0, 1, 3, 5, 7, and 9) catalysts were prepared by a single-step sol-gel method with a variation of Ga₂O₃ content (X, wt%) for use in the direct synthesis of dimethyl carbonate from methanol and carbon dioxide. The ratio of cerium oxide:zirconium oxide in the XGa₂O₃-CeO₂-ZrO₂ catalysts was fixed to be Ce_0.6Zr_0.4O₂. Effect of acidity and basicity of XGa₂O₃-CeO₂-ZrO₂ on the catalytic performance in the direct synthesis of dimethyl carbonate from methanol and carbon dioxide was investigated using NH₃-TPD and CO₂-TPD experiments, respectively. Experimental results revealed that both acidity and basicity of the catalysts played important roles in determining the catalytic performance in the reaction. The amount of dimethyl carbonate increased with increasing both acidity and basicity of the catalyst. Among the catalysts tested, 3Ga₂O₃-CeO₂-ZrO₂, which retained the largest acidity and basicity, exhibited the best catalytic performance in the direct synthesis of dimethyl carbonate from methanol and carbon dioxide.     

Synthesis of TS-1 by microwave heating of template-impregnated SiO2–TiO2 xerogels

TS-1 was prepared by microwave heating of a SiO₂–TiO₂ xerogel dry-impregnated with the template, TPAOH. A highly crystalline product was obtained within 30 min after microwave irradiation with yields over 90%. These are significant advantages over the TS-1 obtained by conventional oven heating using alkoxide precursors in liquid phase, which requires 1–2 day crystallization time with low product yields. Characterization of the TS-1 obtained was carried out using XRD, SEM, FT-IR, and UV-vis spectroscopy, and catalytic activity was examined for 1-hexene epoxidation using H₂O₂ as oxidant. These studies revealed that the material obtained by microwave heating of the mixed oxide gel shows essentially identical physicochemical properties to those prepared by conventional means.     

Epoxidation of Linear Olefins over Stacked TS-1 Zeolite Catalysts

Stacked TS-1 [NSTS-1(MW)] has been prepared by microwave synthesis and applied to the epoxidation of linear olefins with H₂O₂ under mild conditions, and the epoxidation activities were compared with the non-stacked TS-1 and the conventional TS-1, which were also synthesized by microwave and by typical hydrothermal method, respectively. Stacking of TS-1 crystals was accomplished by using microwave which facilitated the dehydration of hydroxyl groups on the external surface of crystallites through the selective absorption of microwave onto Ti species. The stacked crystallites seemed to allow the running pore structure in the b-axis orientation through the crystallites in the stacked morphology. Besides this unique pore structure, the stacked TS-1 showed peculiar features like higher hydrophobicity and enhanced catalytic property than typical TS-1. Moreover, the NSTS-1(MW) showed the highest activity in the epoxidation of linear olefins among three catalysts, and also coincided with the differences in the adsorption of linear aliphatics due to strong interaction with the straight channel in the stacked morphology, which gave larger Henry’s constants, obtained by the tracer chromatographic analysis, as the increase in the carbon chain length.     

One-pot terpolymerization of CO2, cyclohexene oxide and maleic anhydride using a highly active heterogeneous double metal cyanide complex catalyst

This paper describes a convenient one-pot terpolymerization of CO₂, cyclohexene oxide (CHO) and maleic anhydride (MAH) to afford a poly (ester-carbonate) with a low content of ether units (2.9-4.3 mol%) using a highly active Zn-Co(III) double metal cyanide complex (DMCC) catalyst. Terpolymerization was carried out in tetrahydrofuran (THF) at 75-90 °C and 1.0-4.0 MPa and no cyclic carbonate was observed in NMR spectra. The number-average molecular weight (M_n) of the terpolymer was up to 14.1 kg/mol with a narrow molecular weight distribution of 1.4-1.7. The apparent efficiency of the catalyst was up to 12.7 kg polymer/g Zn, representing the highest catalytic activity for terpolymerization of CO₂, epoxides and cyclic anhydrides to date. THF dramatically inhibited polyether formation in this terpolymerization owing to its nucleophilicity towards the Zn²⁺ center of Zn-Co (III) DMCC. This presents the first example of solvent-assisted selectivity for inhibiting ether units in CO₂ polymerization catalyzed by a heterogeneous system. Kinetic analyses of MAH/CHO/CO₂ terpolymerization (MAH/CHO 0.2) suggested that polyester production was slightly faster than polycarbonate production in the early stage. A mechanism for this terpolymerization catalyzed by Zn-Co (III) DMCC catalyst was proposed. Moreover, addition of small amounts of MAH (MAH/CHO molar ratio ≤0.2) during CO₂/CHO copolymerization can improve the thermal properties of the resultant terpolymers.