Elsevier

Catalysis Today

Volume 115, Issues 1–4, 30 June 2006, Pages 33-52
Catalysis Today

Aspects of carbon dioxide utilization

https://doi.org/10.1016/j.cattod.2006.02.024Get rights and content

Abstract

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.

Introduction

Urea is manufactured about 100 million tons per year by using carbon dioxide [1], [1a], and consumed mainly as a chemical fertilizer, urea resins, urea-melamine resins, an animal feed additive, etc. The other organic chemicals such as alkylene carbonates (solvent), β-oxynaphthoic acid (raw materials of dyes), salicylic acid and its derivatives (pharmaceuticals, food preservatives, etc.) are also produced in small amounts. It is estimated that these organic chemicals obtained by utilizing carbon dioxide are produced only less than 0.2 billion tons per year in the world [1b].

Recently, the amounts of the carbon dioxide in the air have been changing as follows [1b], [2].

The amount of air is 5.3 × 1021 g (1 ppm = 5.3 billion tons) on the earth [3]. Carbon dioxide has increased by 90 ppm (480 billion tons) in about 200 years since 1800. Recently, it has increased by about 1.5 ppm (8 billion tons) per year [1b], [2]. Therefore, now, it is difficult to decrease the amounts of carbon dioxide in the air by consuming it by the production of these organic chemicals as shown in Table 1 [1], [2].

Nevertheless, chemists have to put more effort to increase the utilization of carbon dioxide by producing such organic chemicals. Unfortunately, carbon dioxide is a very stable compound, that is, a not very reactive compound, because carbon dioxide is a highly oxidized and thermodynamically stable compound, and its utilization in redox reactions requires high-energy substances or electro-reductive processes [4]. Therefore, it is required to find highly reactive metal catalysts. The investigations of the reaction between carbon dioxide and metal compounds, as transition elements, e.g., Ni [5], [6], [7], [8], [9], Pd [10], [11], Pt [22], Co [12], [55], Rh [13], [14], [22], [34], Ir [15], [16], [17], [18], Fe [19], [20], [21], [34], [53], Ru [22], [23], [24], [25], [26], [34], [53], Mn [27], [28], [29], Re [27], [30], [31], [32], [33], [34], Cr [35], Mo [35], [36], [37], [38], [39], W [35], [38], [39], [40], [41], V [42], Nb [43], [44], Ta [45], Ti [46], [47], [48], [49], Zr [50], [51], [52], [53] and U [54], and as non-transition elements, e.g., Mg [60], Zn [55], [56], Sn [57], [58], Cu [59] and Ag [59] have been carried out. The X-ray structures of these reaction products between carbon dioxide and the metal compounds such as Ni [8], Rh [14], Ir [16], [17], [18], Ru [24], [25], Mn [28], Re [31], Mo [37], [38], Ti [46], [48], [49], Zr [50], [51], Zn [55] and Mg [60], have been reported. The reviews of these reports have also been published [61], [62], [63], [64], [64a].

Carbon dioxide reacts with hydrogen, alcohols, acetals, epoxides, amines, carbon–carbon unsaturated compounds and oxetanes in the presence of metal compounds as catalysts. These reactions with carbon dioxide are carried out in two kinds of solvents, i.e., supercritical carbon dioxide and other solvents. Recently, the investigations of reactions in the former supercritical carbon dioxide have been increased [64b], [64c], [64d].

This review reports on formic acid, formic acid esters, formamides, other hydrogenation products, carbonic acid esters, carbamic acid esters (urethanes), lactones, carboxylic acids, polycarbonate (bisphenol-based engineering polymer) and aliphatic polycarbonates and other polymers, etc.

Section snippets

General considerations

The synthesis of formic acid and methyl alcohol by the hydrogenation of carbon dioxide, has been widely investigated for the utilization of carbon dioxide. Formic acid esters and formamides were also synthesized together with alcohols and amines, respectively, by the hydrogenation of carbon dioxide. These reactions were carried out with both homogeneous and heterogeneous catalysts. The heterogeneous catalysis can offer several technical advantages, which are linked with the stability,

Carbonic acid esters

Carbonic acid esters have come to occupy an important position as useful intermediates for a variety of industrial and synthetic applications [110]. Dimethyl carbonate (DMC) was reported as an environmentally benign compound. For example, the transesterification of DMC gives methyl phenyl carbonate (MPC), and diphenyl carbonate (DPC) is prepared by the disproportionation of MPC with phenol in the presence of a MoO3/SiO2 catalyst. The DPC is a raw material for a polycarbonate as shown in Section

Carbamic acid esters (urethanes)

Carbamic acid esters (urethanes) (NR2COOR′) obtained by reactions involving a CO2/amine system, have played an important role in industrial chemistry. Their derivatives are the important precursors of pharmaceuticals, herbicides, fungicides and pesticides in an agricultural field, and as the precursors of isocyanides, which in turn, are intermediates in the production of high-performance plastics, polyurethanes, elastomers and adhesives [130]. The isocyanates (RNCO) are synthesized by the

Lactones, carboxylic acids and others

Many transition metal complexes react with carbon dioxide. Carbon dioxide is activated by transition metals and forms complexes having bent bond structures and longer bond lengths, e.g. in Ni(CO2)(P(C6H11)3)2·Ph-CH3: Csingle bondOsingle bondC bond angle is changed from 180° to 133° and Csingle bondO bond lengths is changed from 1.16 to 1.22 Å and 1.17 Å as shown in Fig. 3 [8].

On the other hand, carbon–carbon unsaturated compounds such as monoolefins, dienes, allenes and acetylenes react also with transition metal complexes to

Polycarbonate (bisphenol-based engineering polymer)

Polymerization involving carbon dioxide is one of the most important utilizations of carbon dioxide. Polycarbonate formation without using phosgene, an alternating copolymerization with an epoxide, a condensation with benzenedimethanol and an alternating copolymerization with diynes, etc., can be exemplified. Especially, the polycarbonate formation without using phosgene, and the alternating copolymerization with the epoxide were already industrially applied.

Asahi Chemical Industry already

Conclusions

The utilization of carbon dioxide as a possible starting material for the synthesis of chemicals is expected to be useful for improving the global warming problem. Actually, carbon dioxide is utilized mostly for urea as fertilizers. The other utilizations are very small in amounts. Because carbon dioxide is a highly oxidized and thermodynamically stable compound, its utilization requires very active metal catalysts.

As promising industrial catalysts for carbon dioxide utilization reactions,

Acknowledgement

I should like to express my sincere appreciation to Dr. Sumio Chubachi for reading the full manuscript, which enhanced its accuracy and clarity, and for providing much valuable constructive criticism.

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