Energy Convers. Mgmt Vol. 38, Suppl., pp.

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Pergamon PII: S0196-8904(96)00297-X

1997 ElsevierScienceLtd. All rights reserved Printed in Great Britain 0196-8904/97 $17.00+ 0.00

CARBON DIOXIDE UTILISATION IN THE CHEMICAL INDUSTRY. M. A ~ A and I. TOMMASI.

Centro MErEA e Dipartimento di Chimica, Universi~ di Bari, Campus Universitario, 70126, Italy.

ABSTRACT The m o u n t of carbon dioxide available for industrial utilisation may expand to unprecedented levels if the recovery of carbon dioxide from energy plants flue gases will be implemented. The potential of each of the three possible uses (technological, chemical, and biological) is far from being dearly defined. The chemical utilisation option, that has intrinsic thermodynamic and kinetic constraints, may rise controversial positions, depending on the criteria used for the analysis. The estimate of its real potential demands a thorough comparative analysis, using the Life Cycle Assessment methodology, of existing processes/products with the new ones based on CO2, in order to establish whether, or not, the latter avoid carbon dioxide (either directly or indirectly) and their economics. The rejection/consideration assessment methodology will produce reliable results only if an exhaustive number of parameters is used. The analysis cannot be limited to practiced industrial processes, but must be extended to an exhaustive inventory of cases. 1997ElsevierScienceLtd KEY WORDS Carbon Dioxide Utilisation. Thermodynamics. Economics. Life Cycle Assessment. INTRODUCTION Recovery of carbon dioxide from energy-plant flue gases may contribute to control its accumulation in the atmosphere. Large m o u n t s of carbon dioxide would be, thus, available either for disposal or for utilisation. This scenario has increased the interest to assess the extent to which the utilisation option (technological, biological and chemical), may be expanded. Such analysis is valuable for two main rea~ns: * recycling carbon dioxide may potentially contribute to both avoiding carbon dioxide and saving primary resources. * The utilisation may be economically more advantageous than disposal. As there is a general positive attitude towards the chemical utilisation of carbon dioxide, as a "clean synthetic methodology", the assessment study seems to be very timely. In this paper we present the current status of carbon dioxide utilisation in the chemical industry and discuss the complexity of the assessment methodology for the rejection/consideration of a given utilisation option finalized to the mitigation of carbon dioxide. PRESENT AND FUTURE OF CARBON DIOXIDE CHEMICAL UTILISATION Carbon dioxide, either recycled from industrial processes (reforming, fermentation, ammonia synthesis, water gas shift reaction, other sources) or extracted from natural wells, is presently used for two main industrial purposes: (i) technological application. (8) Fixation into chemicals. Case (i) includes the industrial uses that do not convert carbon dioxide into other chemicals:
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*Enhanced oil recovery (EOR) *Extraction/reaction solvent *Additive for drinks *Antibacterial and antifungi agent *Refrigerators *Food packaging *Fire estinguishers *Soldering *Moulding *Antidust *Water treatment (although carbon dioxide is converted into HCO3", this use is not considered a "conversion' technology). In several Countries, until recently, depending on the availability, a large amount of the carbon dioxide used for these purposes has been extracted from natural wells, that may supply quite pure CO2 (up to 99%): the use of recycled carbon dioxide would be recommended and appropriate. This consideration applies to EOR, in particular. If recycled carbon dioxide were used, part of it (ca. 50%) would remain in the oil reservoir, resulting in a "natural field" storage of carbon dioxide. Case (/l) includes all possible conversions of carbon dioxide, namely: a) Fixation of the entire molecule into organic products (synthesis of species in which the -COOmoiety is present: RCOOH, RCOOR', ROC(O)OR', RHCOOR', polycarbonates, polyurethans, etc. Urea, H2NCONH2, and its derivatives are also included in this list). b) Fixation into inorganic carbonates (synthesis of Group 1- and 2-element carbonates, that already find industrial application (see below), and interaction of carbon dioxide with natural basic silicates, mimicking the "silicate weathering' process, that produces carbonates). c) Reduction to other C1 molecules (HCOOH, CO, H2CO, CH3OH, CH4) or fixation of a reduced form (synthesis of Cn-alcohols and hydrocarbons, formamides, etc). This classification of the carbon dioxide chemical conversion (Aresta 1987, 1990, 1992, 1993), groups the reactions according to their energetics and other chemicals requirement. Noteworthy, cases (a) and (b) do not require hydrogen, while case (c) demands an external source of hydrogen for carbon dioxide conversion. This difference is of crucial importance, as the use of hydrogen may represent a limitation to the application of a process, standing the condition of scarce availability of hydrogen produced from water (or methane, as a second choice) at a low "carbon dioxide emission" rate (e.g., low energy process, use of solar energy). The industrial utilisation of carbon dioxide is limited today to a very few processes: * Synthesis of urea (ca 30 Mt y" 1). * Synthesis of salycilic acid (ca 20 kt y-1 ). * Synthesis of Group 1 and 2-element inorganic carbonates, such as Na2CO3, K2CO3, BaCO3 (a few tens Mt y-l). * Synthesis of polycarbonates from epoxides (only a few kt y-l, at present). * Additive in the synthesis of methanol (variable amounts, up to several Mt y-l). The first three processes, old one century or more, do not require any 'catalyst'. The last two, developed more recently, require a catalyst (either metal systems, or not). The engineering of catalystsfor carbon dioxide converslon was started after the firsttransition metal-carbon dioxide complex was discovered (Aresta 1975) and for long time remained a "scientificcuriosity'.Only recentlyithas reached the level of "interestfor industrialapplication'. However, the conversion of carbon dioxide is not an easy and straightforwardreaction,due to its molecular properties,thermodynamics (carbon dioxide lays in a potentialenergy well) and kinetics. Despite the enormous potential(Nature uses carbon dioxide as source of carbon in many different ways), the development of new catalyticreactionswas not too much encouraged in the recent past, as there was no urgent need to change the existingsynthetictechnologies,mostly based on cheap raw materials and intermediates. The concern of the environmental impact of some of these technologies, new regulationson carbon dioxide emission, and the expected availabilityof large masses of CO2, may dramaticallychange the scenario. The mitigationof carbon dioxide and the use of carbon dioxide for developing a "green chemistry" or 'clean syntheticmethodologies' are, indeed, complementary strategies.In fact,the reduction of the emission of carbon dioxide can be achieved in a direct(fixationof the molecule into chemicals) or indirectway (saving energy and reducing waste production).For thisreason, the estimation of the utilisationpotential may not be restrictedto the existing industrialapplications (only five processes!),nor limited by the exiguous number of catalyticreactionsand photochemical processes recently developed at the levelof "industrialapplication'.As we have reported above, thisapproach is very.young and there are stillmany unexplored areas.Therefore, the exclusion of possibilities should follow an exhaustive 'inventoryof cases': the contributionthe chemical fixationcan give to the utilisation option is the integralof all the "feasible'applications.Nature uses hundreds different systems (plants,algae, micro-organisms) to drive the "carbon cycle'! The assessment study must consider the implementation and exploitationof options not only in the short-,but also in the medium-, and long-term,as itisactuallydone for other technologies,such as

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the ocean disposal. Our attitude must be to evaluate if a tenfold expansion of the use of carbon dioxide, from the actual limit of ca. 100 Mt per year, is eventually possible. If we adopt a simplified approach we may possibly reach the conelasion that even 100 Mt is an impossible limit! The exact definition of the potential of the chemical utilisation technology, based on the inventory of feasible processes, must be completed with an economic study. The acceptance/rejection of new processes/products requires a comparative analysis with existing ones, through the "Life Cycle Assessment, LCA", that should consider: - Thermodynamics, Kynetics, Energy content of reagents, Yield, Selectivity, Energy requirements for processing main- and side-products and solvents, Waste treatment. This study should give the amount of: Recycled carbon dioxide, Primary resources saved, Avoided carbon dioxide per each process/product. The reaction rate, the life-time of the product, and the total market demand or amount used per year, will allow to calculate the specific fraction of recycled carbon dioxide per year. To complete the economic evaluation, the 'added value" of the product has to be considered. The useful datum is, indeed, the 'cost of avoided carbon dioxide'. Supposed that a process/product "avoids carbon dioxide', we have to decide if 'that particular utilisation has to be preferred to disposal'. In fact, if the 'availability of carbon dioxide" is set as the "zero point', the choise between 'disposal" and "utilisation" can be driven by the economic convenience: the disposal will always rise a 'cost' (both in terms of "avoided carbon dioxide" and "economics of the process') derived from the energy used for compressing, pumping, housing carbon dioxide, while the utilisation might result to be a "profit" (due to reduced amount of solvents and reagents used, lower processing costs, lower amount of wastes, etc. proper of the carbon dioxide based technology). The Scheme reported below summarizes a comparative analysis SCHEME DISPOSAL CO2 really disposed per t housed 1-X X = Y~ (ec, ep, ell .... ) UTILISATION CO2 fixed per t reacted
1 -Y+Z

Y = Y (er, eoc, epi, ewt,...)

Z = Y. (esc, er, eoc, epi, ewt,...) as C 0 2 equivalent as C02 equivalent Whea'e: e=energy; ~--compression;p=pumping;h=housing;r=reachon;oc=otherchemicalsinvolved into the reaction; s~-substituted chemicals; pi---p~uct isolation; wt=wastetreatment. However, a simplified study, based on a limited number of parameters, choosen among those listed above, may produce unclear results, as we discuss below. Major issues for the utilisation of carbon dioxide are the amount of fixed CO2 and the life of the product. The two operators (amount and life) c~,a operate simultaneously or indipendently. If we choose the former mode, we must take into consideration only those processes that fix large amounts (> 10 Mr/y) of anthropogenic CO2 (ca. 20 Gt y-l) in long-living products. Easily we reach the conclusion that the chemical utilisation could either be excluded a priori ('forget-it" position) as relevant to the mitigation option or, at best, only inorganic carbonates and polymers would be considered, that means to use a few tens Mt of carbon dioxide per year. If we decide to adopt the latter mode, we may greatly enlarge the number of products to take into consideration: fuels, organic carbonates, carbamates, isocyanates, urea, etc. These species have a market of several Mt per year, but are short-lived. As a further example, let us consider the energetics of reaction. For a preliminary consideration/ rejection of processes, thermodynamics is a useful tool. We may decide to consider, for example, only those processes characterized by a negative 'free energy' change (Free Energy, more than Enthalpy, should be used, as all reactions that use carbon dioxide have a high entropic content). All reactions using dihydrogen would have an "accepted' mark, as they have a negative free energy change. But dihydrogen availability is a limiting factor, as discussed above. Should we consider, or not, the fuel synthesis from carbon dioxide as a process worth to implement? Kinetics, yield and selectivity of a reaction may be choosen as consideration/rejection operators. In this ease, too, a careful analysis is necessary. Reactions that at a glance are judged to be of low or no practical interest, can be mastered to application. We discuss below the case of the use of carbon dioxide in the synthesis of carbamates, an apparently "unuseful' reaction because of the by-

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products, that has been driven towards high yield and excellent selectivity (Aresta and Quaranta 1992, 1993, 1996; McGhee et al 1995). An n-dimension matrix (or n-variable function) should be used in the assessment study, and the result optimized by varying the weight of each parameter. A point of great interest would be to attach to each studied option a list of "recommendations" or "must", for making the process of practical application. RECENT PROGRF~S IN CARBON DIOXIDE CONVERSION In this paragraph a short review of recent achievements for a selected number of reactions that convert carbon dioxide will be presented, with a comment on their status and perspectives. The selection is not exhaustive of possibilities. In general, chemicals with a market of the order of one Mt per year are taken into account. No attempt is made at this stage to use a "yes/not", "consideration/rejection" operator. Phosgene Substitution. Phosgene (COC12) is largely used in the chemical industry (6-8 Mt y-l) for the synthesis of urethans, polyurethans, isocyanates, carbonates, polycarbonates. Carbon dioxide is a good substitute in the reaction of synthesis of earbamic esters. (Aresta and Quaranta, 1996) Synthesis of earbamic esters and isocyanates. Phosgene based route Carbon Dioxide based route CO2 + 2R'R"NH = R'R"NCOOH2NR'R" CI-I4 + H20 = CO + 3H2 (1) R~R~NCOOH2NR'R"+ RX = R'R"NCOOR + C + H20=CO + H2 (2) CO + CI2 = COC12 ('3) R'R~rI2 X COC12 + ROll + Base = ROCOC1 + B~eHCI (4) Side reaction ROCOCI + 2 R'R~rI-I = R'R~IC(O)OR + R~R"NCOOH2NR'R"+ RX = CO2 + R'R"NH + RR'R~NHX R'R~-I2CI (5)

(6) (7) (8)

The thermodynamics and kinetics of both reaction routes are quite favourable. The alkylation of the amine (eq. 8) is a side-reaction that until now prevented the practical application of the carbon dioxide process. Quite recent studies have shown that this reaction can be prevented (Aresta and Quaranta 1992, 1993, MeGhee et al. 1995) and a new interest in this synthetic methodology for the synthesis of carhamic esters at the industrial level grew up. By the way, the carbon dioxide route would allow to avoid chlorine (that is an important goal, for the ebemieal industry). Alkylating agents other than halogenated species can be also employed. Primary amine (R'NH2) carbamates can be easily converted into isocyanates: R'HNCOOR ....... > R'NCO + ROH. (9) Single-, or multi-step procedures have been developed, characterized by high yield and selectivity (dose to 100%) that deserve consideration for full exploitation. Polyearbonates and polyurethanes can be prepared by this way. The co-polymerization of unsaturated amines with carbon dioxide in mild conditions is a new process (Tsuda 1995). The market of these products is sizeable at several tens Mt per year. Methanol The synthesis of methanol from carbon dioxide, instead of carbon monoxide, implies the use of one extra mole of hydrogen: C O + 2 H2 = CH3OH (10) CO2 + 3 H 2 = CH3OH +I-I20 (11) The yield and selectivity of the reaction based on carbon dioxide have been quite improved (Saito el al. 1995) and the reaction conditions are getting milder with new catalysts. A fact of interest would be the development of catalysts for the direct conversion of carbon dioxide into methanol, avoiding the preliminary conversion into carbon monoxide. Methanol can be used for the synthesis of hydrocarbons (Inui et al. 1996, Lee et al. 1996). Hydrogen could be provided, in the future, by biological systems that produce dihydrogen from

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water (Miura 1996), or developing the methane reforming with carbon dioxide (Inui et al. 1996). The synthesis of methanol from biomasses (Steinberg 1996) is a process of great interest. The market of methanol, used as a chemical or energy product, may be of hundreds Mt per year. Dimeth1carbonate and Homologues, Diphenylcarbonate. These compounds find a large industrial application as monomers for polymers, solvents, additives for fuels, alkylating-(arylating) (supplanting alkyl halides) or acylating-(aroylating) agents (substituting phosgene and other reagents, to afford earbamic esters and isocyanates of industrial interest) (Aresta et al. 1995, Aresta and Quaranta, 1996). The thermodynamics strongly depend on the nature of the group R. 2ROH + CO2 = (RO)2CO + H20 (12) The free energy change is negative when R=methyl or higher alkyl, but is positive when R=phenyl (+19.6 kcal tool-1, with the reagents in their stardard state). Despite the favourable thermodynamics, up to date the synthesis of dimethylcarbonate, DMC, and its higher homologues, has found an obstacle in the very low yield and selectivity (Ko et al. 1995, Wagner at al. 1995). Diphenylearbonate, that has a large industrial application, is prepared from DMC and phenol through a transesterification reaction. On the other hand, the unfavourable thermodynamics of the direct synthesis from phenol and carbon dioxide can be almost circumvented by combining two reactions, i.e. using a third species (olefin) that is converted into marketable products. A new synthetic methodology produces cyclic carbonates (that are used as monomers for the synthesis of polymers) from olefins, carbon dioxide and dioxygen (Aresta et al. 1996). RHC=CHR' + CO2 + 0.502 = RHC- CHR'OC(O)O (13) This reaction is of great interest as the starting materials are easily accessible. The potential market of carbonates is of tens Mt per year. Urea Urea, (H2N)2CO, is produced at a rate of a few tens Mt per year and finds a large use as agrochemieal and intermediate in the chemical industry. It reacts with alcohols to afford carbamates and carbonates. The strict control of the reaction conditions and a catalyst are required in order to avoid the conversion into ammonia and the formation of the trimer of isocyanic acid (eq. 16). (H2N)2CO + ROH = NH3 + H2NCOOR (14) H2NCOOR + ROH = NH3 + (RO)2CO (15) H2NCOOR = 1/3 (HNCO)3 + ROH (16) The utilisation of urea as intermediate has not been fully explored yet; the chemistry of urea and that of carbonates can be combined to give an interesting network of reactions (Aresta and Quaranta, 1996). The market is already of 30 Mt per year and could be expanded. Polymers These materials have a long-life and a large potential market. Up to date, only polycarbonates and polyurethanes have been synthesized from carbon dioxide, in low amount. The synthesis of propylene poly-carbonate, a co-polymer of carbon dioxide and propyleneoxide, is an example of industrial exploitation. New reactions have been developed that eo-polymerize carbon dioxide with unsaturated amines under very mild conditions. (Tsuda, 1995) The potential of this reaction and the application of the new polymers are unknown (Saito et al. 1995). Inorganic Carbonates These are very long-lasting species. A few tens Mt per year of carbonates of Group 1 and 2elements (Na, K, Ba, other) are currently synthesized often using natural calcium carbonate, as

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source of carbon dioxide, that is converted into calcium chloride. Instead, it would be of great interest to substitute recovered carbon dioxide to calcium carbonate. Another interesting reaction is the fixation of carbon dioxide by some natural silicates, mimicking the natural weathering process, that affords silicates (Aresta, Quaranta and Tommasi 1992) and a carbonate. We report below a few examples of reactions that would be interesting to exploit. 2Mg2SiO4 + 2 H20 + CO2 === H4Mg3Si209 + MgCO3 (17) olivine serpentine 3 KAISi308 + H20 + CO2 ~ orthoclase KH2A13SiO12 + K2CO3 + 6 SiO2 muscovite

(IS)
(19)

2 KAISi308 + 2 H20 + CO2 === H4AI2Si209 + K2CO3 + 4 SiO2 orthoclasc kaolin

3 MgCa(SiO3)2 + 2 H20 + 3 CO2 === H4Mg3Si209 + 3 CaCO3 + 4 SiO2 (20) diopside The kynetics of these processes are very slow in Nature and should be modified for practical application. The investigation of these systems is giving promising results. (Kojima, 1996) C(~CIMSICIqS Carbon dioxide is used by the chemical industry at the rate of 100 Mt per year. This limit must be expanded for the utilisation would be a technology significant for the mitigation of carbon dioxide. The assessment of the real potential of this technology, requires an inventory of feasible processes and the defintion of the conditions for exploitation. A comprehensive analysis is necessary in order to avoid trivial errors in comparing the utilisation option with disposal. REFERENCES Aresta M, C.F. Nobile, V.G. Albano, E. Forni and M. Manassero (1975), J.CS. Clx~CcJiim.,t536 Aresta M. (1987) in "Carbon Dioxide as a Source of Carbon: Chemical and Biochemical Uses", M. Aresta and G. Forti eds., Reidel Publ., pp. 1-20. Aresta M. (1990) In : "Enzymatic and Model Reactions for Carboxylation and Reduction Reactions", M. Aresta and J. V. Schloss eds., Elsevier Publ., pp. 1-25. Aresta M, E. Quaranta and I. Tommasi (1992), In : Energy Convers. Mgmt, Elsevier Science Ltd., Vol. 33, No. 5-8, pp. 495-504. Aresta M. and E. Quaranta (1992), Tetrahedron, 48, p. 1515. Aresta M. (1993), In : Energy Conv. Mgmt, Elsevier Science Ltd., Vol.34, Na 9-11, pp745-752. Aresta M. and E. Quaranta (1993), Ital. Pat. 1237208. Aresta M., E. Quaranta and I. Tommasi (1994), New. J. Chem., 18, 133-142. Aresta M., C. Berloco, E. Qnaranta (1995), Tetrahedron, 51, pp. 8073 - 8088. Aresta M., I. Tommasi, E. Quaranta, C. Fragale, J. Mascetti, M. Tranquille, F. Galan, M. Fouassier (1996), Inorg. Chem., 35, p. 4254 - 4260 and references therein. Aresta M. and E. Quaranta (1996), Chem. Tech., in the press. Inui T., H. Hara, T. Takeguchi, J.B. Kim, S. Iwamoto (1996), In : ICCDR-III, Cambridge (USA), 9-11 September 1996. Ko K., F. Ogata, (Chem. Abstr. 1995), Jim.KdciTekk~Ko~JP0)33715arflreferences therein. Kojima T., A. Nagamine, N. Ueno, S. Uemina (1996), In : ICCDR-III, Cambridge (USA), 9-11 September 1996. Lee K.-W., P.H. Choi, K.W. Jun, S.J. Lee and i . J . Choi (1996), In : ICCDR-III, Cambridge (USA), 9-11 September 1996. McGhee W., C. Riley, K. Christ, Y. Pan, B. Parnas (1995), Org. Chem., ~ p. 2820. Miura Y. (1996), In : ICCDR-III, Cambridge (USA), 9-11 September 1996. Saito M., T. Fujitani, I. Takahara, T. Watanabe, M. Takeuchi, Y. Kanai, K. Moriya, T. Kakumoto (1995), In : Energy Convers. Mgmt., Elsevier Science Ltd., Vol. 36, p. 577. Steinberg M. (1996), In: ICCDR-III, Cambridge (USA), 9-11 September 1996. Tsuda T. (1995), Gazz. Chim. Ital., 125, p. 101. Wagner A., W. Loeffer, B. Haas, (Chem. Abstr. 1995), Ga'. EE,4310 109and references therein.