Mitigation of CO2 by Chemical Conversion

Energy & Fuels 1996, 10, 305-325
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Mitigation of CO2 by Chemical Conversion: Plausible Chemical Reactions and Promising Products
Xu Xiaoding and J. A. Moulijn*
Section of Industrial Catalysis, Faculty of Chemical Engineering and Materials Science, Delft University of Technology, Julianalaan 136, 2628 BL Delft, The Netherlands Received July 26, 1995. Revised Manuscript Received November 29, 1995X
A critical literature analysis was conducted on the viable usage of CO2 in the framework of the attempts to reduce the emissions of CO2 into the atmosphere from various processes or the rate of increase of the concentration of CO2 in the atmosphere. Applications based on the physical properties of CO2 are summarized first. Major examples are applications in supercritical extraction, enhanced oil recovery, and use as inert gas in fire extinguishing and safety application in industry. The various possibilities of use in chemical applications are systematically discussed. CO2 can react with several hydrocarbons and nitrogen-containing compounds (NH3, amines, imines). It can be used as a weak acid or as an oxidizing agent. It can be reduced electrochemically, photochemically, or chemically or by a syngas route. A variety of products can be manufactured from CO2, e.g., acids, alcohols, esters, lactones, carbamates, urethanes, urea derivatives, various copolymers, and polymers. In particular, polycarbonates are attractive products. Nevertheless, currently, less than 1% of the CO2 emitted is used in chemical reactions. To reduce the emission of CO2 substantially, only those reactions by which CO2 is used to produce bulk chemicals are relevant, whereas those useful in the manufacture of fine chemicals are not important in this respect. CO2 conversion to MeOH represents one of the most important options in CO2 mitigation. MeOH can be used as additive to fuels or as a substitute for motor fuels. An increasingly important application is in the production of MTBE (methyl tert-butyl ether), DMC (dimethyl carbonate), or DME (dimethyl ether) which are major components in modern gasoline to boost octane number. An interesting application of MeOH is the usage as fuel for cars via in situ decomposition into syngas; this results in enhancement of the energy efficiency. From MeOH several useful products can be made. Another reaction of importance that has been commercialized is the so-called dry reforming in which methane reacts with CO2, giving synthesis gas. Some processes are commercialized and the technology is mature. An example is a process in which a mixture of biomass and fossil fuels is converted into methanol and carbon which is stored. It is obvious that thermodynamically most processes using CO2 are not favorable for CO2 mitigation. This does not imply that processes are never feasible. Special situations do exist where the usage of CO2 in chemical applications is attractive. Examples are processes where CO2 is available at a high temperature, where an external heat source is present without a good outlet for the heat, processes where CO2 leads to the right stoichiometry or reaction environment. In these cases a high potential for an efficient process exists. An elegant example is chemical cooling of hot gases in the chemical process industry. A promising application is the direct substitution of certain chemicals by a reaction product of CO2; an example is the replacement of the hazardous phosgene by urea, which is produced from CO2, in the production of organic carbonates. A trivial case constitutes processes based on renewable energy sources; these processes, although perhaps inefficient, can lead to a reduction of CO2 emissions.
Contents Abstract 1. Introduction 1.1. Natural Carbon Sources 1.2. CO2 Emission Sources 1.3. Present Applications of CO2 1.4. Targets of CO2 Mitigation 2. Possible Strategies of Reducing CO2 Buildup in the Atmosphere 2.1. Increase of the Energy Efficiency or Shift of Primary Energy Source 1 2 3 3 4 4 4 4
2.2. Storage or Disposal of CO2 2.2.1. CO2 Separation 2.2.2. CO2 Storage in Aquifers 2.2.3. Underground CO2 Storage 2.3. Usage of CO2 3. Chemical Reactions of CO2 3.1. Introduction 3.1.1. Thermodynamics 3.1.2. CO2 Reactivity 3.2. Utilization as an Acid 3.3. Utilization as an Oxidizing Agent
1996 American Chemical Society
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3.3.1. Carbon Gasification 3.3.2. Oxidation of Alkyl Groups in Aromatic Compounds 3.3.3. Oxidative Dehydrogenation of Hydrocarbons 3.3.4. Oxidation or Combustion of Metals 3.4. Reduction of CO2 3.4.1. Electrochemical Reduction 3.4.2. Catalytic Reduction with H2 3.4.3. Photoreduction of CO2 3.5. Reactions with Compounds Having Activated Hydrogen Atoms 3.6. Reactions with Hydrocarbons without Activated Hydrogen Atoms 3.6.1. Saturated Hydrocarbons 3.6.2. Unsaturated Hydrocarbons 3.6.3. Reactions with Other Substituted Hydrocarbons 3.7. Production of Polycarbonates 3.8. Reaction with Epoxides 3.9. Reaction with Alcohols and Ethers 3.10. Reaction with Nitrogen Compounds 3.10.1. Reaction with NH3 3.10.2. Reactions with Amines and Imines 3.11. Reactions with Sulfur Compounds 3.12. Substitution for Other Chemicals 3.13. CO2 as a Carbon Source 4. Bioconversion 5. Concluding Remarks
9 9 9 10 10 10 10 12 12 13 13 13 15 15 15 16 17 17 17 18 18 19 19 19
Figure 1. Effect of increasing CO2 concentration on net photosynthesis of creosote bush at 301 K at high (2000), intermediate (1000), and low(500) photon flux densities (in einstein m-2 s-1).
1. Introduction CO2 is a major source for the so-called greenhouse effect (the effect of an increase in the absorption of radiation energy caused by the existence of gases in the atmosphere), leading possibly to changes in climate.1-7 CO2 content in the atmosphere is increasing at a rate of ca. 1% per year; from 250 ppm of the preindustrial period to a present level of ca. 400 ppm (315 ppm in 1958, 340 ppm in 1984). The enhancement of CO2 content is mainly caused by the combustion of fossil fuels and deforestation. The energy sector which is the largest source of CO2 emission per industrial sector is responsible for about 25% of the global CO2 emission. Moreover, deforestation of the tropic forests contributes up to 10-30% of enhancement of CO2 and volcanic gases also contribute significantly to the increasing CO2 level. CO2 is mainly emitted diluted in flue gases. Exhaled air contains ca. 4% CO2, while exhaust gases from petrol engines contain about 13%. It should be noted that also sources exist containing CO2 in much higher concentrations. Examples are exhaust gases of several chemical processes.7 In the sense of greenhouse effect, it is fair to point out, that CO2 is not the only gas contributing to the greenhouse effect. Other gases, in particular, chlorofluorohydrocarbons (CFC), NOx, and CH4, are also greenhouse gases. Due to their longer lifetimes and stronger greenhouse effect (shown as the relative radioactive forcing and global warming potential,
Tel.: 015-2784358. Fax: 015-2784452. E-mail: Xu.Xiaoding@ STM.TUDELFT. NL. X Abstract published in Advance ACS Abstracts, February 1, 1996.
GWP), some of them, e.g., N2O, CFCs, and CH4, per unit mass are much more harmful to the environment than CO2 (Table 1).8 Global warming potential defines the time-integrated warming effect due to the instantaneous release of unit mass of a given gas in todays atmosphere, relative to that of CO2. Therefore, the contribution of each greenhouse gas to global warming may be evaluated as the product of GWP and the amount of the gas emitted. Table 1 shows that CO2 is the least effective greenhouse gas per kilogram emitted, but its contribution to global warming (indicated by the total human contribution to radiative forcing) is the most significant due to the large amount released to the atmosphere.8 The increase of the CO2 content in the atmosphere is partly balanced by the photosynthesis of plants and organisms, estimated to be 100 Gt/y (1 Gt ) 109 tons), and the respiration processes of living animals. It is not surprising that at a higher atmospheric CO2 content photosynthesis is promoted. Figure 1 illustrates this for the photosynthesis of creosote bush for three different light intensities.1 Of course, this phenomenon opposes global warming. Furthermore, aquifers, lakes, rivers, oceans, and seas, are a large sink for CO2 (3.55.5 Gt of C as CO2 per year).9-12 CO2 can be taken up by the oceans as carbonates or dissolved CO2, as coral reefs in shallow sea banks, as clathrates (compounds with the formula of CO2nH2O, n ) 5.75), and as liquid at high depth. Figure 2 shows the worldwide mass balance of CO2.9 It appears that human activity contributes only a small fraction to the flow rate of CO2 into the atmosphere. Due to the balancing effect of photosynthesis, conversion, and accumulation in seas, oceans, etc., the increase of CO2 content in the atmosphere is actually much less than might be expected from the amount of CO2 emitted in the world. Figure 3 shows the CO2 sources and its cycle via fossil fuels, biomass, and production of chemicals.10 The total man-made carbon dioxide emission in the atmosphere has been estimated to be 6-8 Gt carbon, of which 5 Gt is from burning of fossil fuels and the rest from land use conversions and deforestation.3,7,9,11 Table
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Table 1. Potential of Selected Gases To Contribute to the Greenhouse Effect8 CO2 CH4 0.8 1.72 10 21 58 300 150 0.9 63 21 09 15 N2O 0.288 0.310 150 206 270 6 8 0.3 270 290 190 6 CFC-11 0 28 10-5 60 12400 4500 0.3 0.095 4 4500 3500 1500 CFC-12 0 4.84 10-6 130 15800 7100 0.4 0.17 4 7100 7300 4500 17
concentration (ppm) preindustrial (1750-1800) current (1990) lifetime in atmosphere (y) rel radiative forcing per mol per kg current human-made emission (Mt/y) rate of accumulation in the atmosphere 10-4 ppm/y %/y rel global warming potential t ) 20 y t ) 100 y t ) 500 y total human contribution to radiative forcing (%)
280 353 1 1 26000 18000 0.5 1 1 1 55
Figure 2. Inventories and flow rates of CO2.9 The numbers in rectangles represent the inventories and the other numbers the flow rate (net values, except the quasi equilibrium atmosphere T ocean).
Figure 4. Carbon sources in the nature.
Figure 3. The CO2 cycle.

Table 2. Sectional Use of Energy in Some European Countries in 1984 (%)13 buildings private Denmark France FRG Greece Ireland Italy UK Belgium Holland 23 22 25 20 33 25 25 29 28 commercial 9 13 11 10 12 10 13 transport 17 19 22 27 22 18 22 12 13 industry 31 31 34 43 33 42 35 53 41 rest 20 15 8 4 5 6 18
2 gives the sectional energy consumption in some West European countries in 1984.13 Major CO2 emission comes from private sources, in particular, heating of homes and transport. Also heating of public buildings and industrial transport are among the major CO2 emission sources. Further large
sources constitute power stations and industry, including oil refineries. 1.1. Natural Carbon Sources. Carbon is the precursor of CO2. Carbon and/or its compounds are present in all segments of the planet earth.9,10 Figure 4 shows the distribution. The amount of carbon present in the atmosphere is relatively very modest. By far the most part of carbon is present as terrestrial carbon. In fact calcite, CaCO3, is the most abundant carbon-containing mineral. Other important minerals containing carbon are dolomite (CaMg(CO3)2), magnesite (MgCO3), ankerite (Ca(Fe,Mg)(CO3)2), FeCO3, MnCO3, and ZnCO3. Even when the amount of fossil energy resources would be diminished significantly due to the consumption, it is clear that carbon present as CO2 in the atmosphere still will be a small fraction of the total carbon inventory. 1.2. CO2 Emission Sources. CO2 sources can be subdivided in concentrated and diluted streams.14,15 Examples of concentrated CO2 sources are natural CO2 reservoirs (they contain up to 97% of CO2) and exhaust gases from a wide variety of industrial plants. Examples of the latter are plants for processing of natural gas, production of ethanol by fermentation, and production of bulk chemicals such as ammonia and ethylene oxide. Also quantitatively important is the inorganic industry, notably for the production of cement. The major examples of dilute CO2 sources are flue gases from electric power generation and the blast furnace, and exhaust gases from cars, trucks, and buses. Electric power generation is the largest source of CO2 emission in industry. It contributes to around 25% of the global CO2 emission and is responsible for 14% of the estimated global warming in the 1980s. This figure could grow to 30% by the year 2030.
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Table 3. Present CO2 Sources Used in the US Industries15 industry ammonia production oil and gas refineries geological formations ethanol production chemicals manufacturing flue gases or cogeneration alcohol production others total contribution (%) 35 20 20 12 7 3 2 1 100
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The present CO2 sources used in the US industries are quantified in Table 3.15 Presently, many power stations in the world are using coal as the energy source; the exhaust gas contains 13 up to 27% CO2. This is rather low for a profitable process. Due to the high expenses in enrichment and separation, CO2 from flue gas of power stations has hardly been used as a source for CO2. To our knowledge, only one pilot plant (100 ton/day) was tested in USA for the separation of CO2 from flue gases of energy sector (Chapter 1, ref 14). Deforestation, especially burning of tropic forests, and respiration of living matters also lead to dilute CO2 sources which nevertheless contribute significantly to the global CO2 emission. 1.3. Present Applications of CO2. CO2 usage can be divided into two groups: those using the physical properties and those using the chemical properties.9,10,14-25 It should be borne in mind that on the one hand the former use does not contribute directly to the reduction of CO2 emission, but on the other hand, consumption of other materials might be decreased. The latter will, in fact, often lead indirectly to CO2 reduction. The first category, making use of its physical properties, includes the beverage industry (ca. 0.75 Mt/y), 14 enhanced oil recovery (EOR), and supercritical (SC) CO2 extraction and cleaning. Because CO2 is a safe gas, it is used as a protective gas (in chemical or steel industries, in food reservation, in welding, etc.) and even as fire extinguisher.9,10,14,15 Its favorable diffusion properties are the basis for application as blowing agent in polymer processing industries. It is also used as a pesticide to kill insects in fumigation.15 CO2 used in EOR (ca. 6-7 Mt/y)14 represents one of the largest potential applications of CO2. This application is expected to grow in the near future. It does not lead to a consumption of CO2 eventually, but due to the extra amount of oil produced, it is economically feasible in many cases.9,14-17 The benefits of using CO2 in EOR stems from the reduction of the viscosity due to mixing with CO2. Supercritical CO2 extraction is also a major use of CO2 at present.9,10,14,15 It is used in the production of decaffeinated coffee, in the extraction of soybeans and hops, in pharmaceutical industry to recover active substances, in the cosmetic industry to extract fats and ethereal oils, and in food industry to isolate spices, aromas and essences (Eisenbach, W. O., ref 9, pp 371388 and the references therein). In some cases, less energy is consumed if supercritical CO2 extraction is used, compared with other options. Moreover, supercritical CO2 may replace, e.g., in spray painting, solvents which contribute to global warming, e.g., volatile organ-
Figure 5. Major uses of CO2 in USA.9 The shaded area refers to the expected increase in usage.
ics or CFCs. In this sense, the use of supercritical CO2 is environmentally beneficial.9,20 Dry ice (solid CO2) is used in refrigeration (1.5 Mt/ y),14 especially in refrigerated railcars or trailers, to substitute CFCs.9,10,14,15 This replacement is important in combating the greenhouse effect as well as the ozone depletion problem. In the other category, CO2 is a reactant. In organic chemical industry, it is used in the synthesis of urea, methanol, salicylic acid, and cyclic organic carbonates.9,10,14,21 In inorganic chemical industry, it is used to manufacture Na2CO3 or NaHCO3 (e.g., the Solvay process), CaCO3, and other carbonates (e.g., lead or barium carbonates). Moreover, it is consumed in biomass production and in greenhouses to stimulate the growth of plants. It is also used as an acid in water purification or in neutralization processes.15 Figure 5 shows the major applications of CO2 in USA.9 Most applications are nonchemical. Totally, only 0.7-1.0% of the CO2 produced is used at present. The consumption in the production of chemicals is in the order of 0.1% (ca. 50 Mt/y). 1.4. Targets of CO2 Mitigation. According to the European Union, the CO2 emission should be brought back to the level of 1990 in the year 2000. Other countries, e.g., USA, Japan, and Canada, also aim at stabilization of CO2 emission at the level of 1990 in 2000. The long-term objective is to achieve a balanced CO2 production and uptake, energy saving, and the use of renewable energies. The Netherlands aims at stabilizing CO2 emission in 1994-1995 and at achieving a reduction of CO2 by 3-5% by the year 2000. 2. Possible Strategies of Reducing CO2 Buildup in the Atmosphere In principle, three strategies are possible, viz., reduction of the amount of CO2 produced, usage of CO2, and storage of CO2. 2.1. Increase of the Energy Efficiency or Shift of Primary Energy Source. In a sense, the CO2 problem is an energy problem. The increase of energy efficiency of the primary energy carrier is the most important in reducing CO2 emission. Also, the type of fossil fuel used is important. For example, the H values for the combustion of carbon (graphite), natural gas (CH4), and C2H4 to water and CO2 are respectively -393, -929.1, and -662.3 kJ/mol carbon, i.e., much less CO2 is produced when fossil fuels other than carbon are used. The replacement of C-rich energy carrier (coal) by other less C-rich fossil fuels (oil or natural gas) is an option that leads relatively easily to reduction of CO2
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emission. However, in practice, for obvious reasons, it is a wise policy to diversify the use of energy sources. Although combustion of fossil fuels is responsible for ca. two-thirds of the worlds CO2 production due to human activities, the usage of CO2 in these exhaust gases, however, due to its low concentration, often is economically less feasible.12 An exception might be those exhaust gases that are at a high temperature.26 Currently electricity is produced at 30-40% efficiency. If the best available technologies were used this would increase to about 60%. Thus, emission of CO2 would be halved.27 It can be estimated that replacement of oil by CH4 may result in 25% reduction of CO2 emission. It is important to point out that this is a route that leads to direct and efficient reduction of CO2 emission. Moreover, the fraction of CO2 emission reduction achievable is much larger than most other routes. However, as stated before, from a practical point of view, this option might be of limited value. In many countries, proposals have been formulated to reduce CO2 emission and economic evaluations have been made. Examples are the following. For USA, it has been estimated that carbon emission reduction of 10% is possible, provided an increased energy efficiency and some substitution of natural gas for coal in the electricity sector are achieved (with a net economic benefit of US $230/ton by the year 2000).28 It has been claimed that an increase of the end-use efficiency and the use of renewable energy sources in Swedens district heating and electricity sectors can result in 35% emission reductions and a net benefit of US $40/ton by the year 2010.28 Of course, the correctness of these predictions remains to be proven. 2.2. Storage or Disposal of CO2. 2.2.1. CO2 Separation. For any process aimed at reducing the emission to the atmosphere of CO2 produced, CO2 has to be captured and separated or at least the exhaust gases have to be enriched, which considerably adds to the cost of the process. The costs are of course dependent on the source. For instance, in the case of flue gas from coal-fired plants, due to the relatively low CO2 concentration, the separation will be expensive. Moreover, there are various sulfur and nitrogen compounds in the coal. During coal combustion, they will be converted into SOx and NOx compounds, which are usually catalyst poisons in downstream chemical processes. This generates additional costs. Several separation technologies are available:29 (i) gas/liquid scrubbing systems; (ii) gas/solid adsorption systems; (iii) cryogenic (fractionation) techniques; and (iv) membrane separation technology. Separation by solvent absorption systems (e.g., by using monoethanolamine, MEA) or by membrane technology appears to be the most viable technique.14 An interesting approach in power generation is combustion of fossil fuels in an atmosphere of pure oxygen (from prior air separation) and recycled CO2: in this way the CO2 produced is much more concentrated (>90%); the cost of such a process was estimated to be in the range of $15-100/t of CO2.5 The air separation/flue gas recycling process is reported to be the most energyefficient process analyzed, requiring 26-31% of the coal heating value, while the CO2 recovery is close to 100%. The other processes studied require over 50% of the coal heating value, and the resulting cost of electricity
production increases by over 80%.12 For practical applications, these numbers are obviously prohibitively high. Membrane technology is basically in the early stage of development. When a breakthrough occurs in the near future, membrane technology might well be the basis for feasible CO2 separation processes. 2.2.2. CO2 Storage in Aquifers. Aquifers, especially seas and oceans, constitute an important CO2 sink and buffer9,11-13 (cf. Figure 2); the amount of CO2 that can be stored additionally is in principle vast. It can be achieved by increasing microalgae biomass or by fixing CO2 as CaCO3-like coral reefs. It has even been suggested to add nutrients such as iron to ocean surface water for increasing the production of microorganisms. It was estimated that treatment of the Antarctic oceans with iron might allow the phytoplankton to convert all the available nutrients into new organic matter, this would amount to 0.3-1.7 Gt of carbon. It was estimated that the Antarctic Ocean, equatorial Pacific, and subarctic Pacific have a potential extra uptake of 2.8 Gt of C/y.30 CO2 can be injected into 700-1000 m, or even to 3000 m, deep ocean water (as liquid CO2). As to the formation of coral reefs, it was estimated that in the shallow sea banks near Japan, the CO2 consumed to form carbonates may amount to 3% of the CO2 emitted by that country. Of course, CO2 may also form (bi)carbonates or it may dissolve in water or it may form clathrates. According to some authors,7,11 storage in oceans is an important method to combat the CO2 problem, although the ecological impact of injecting large amount of CO2 into sea and ocean water is still uncertain. Moreover, it is not clear how the cations, e.g., iron or calcium, can be provided in a sensible way. 2.2.3. Underground CO2 Storage. Depleted oil or gas fields are often porous. It is possible to store a large amount of CO2 into those underground reservoirs6 (total capacity estimated to be ca. 80-300 Gt of C in exhausted gas wells and 40-200 Gt of C in exhausted oil wells).31 These quantities are very high. However, it remains to be seen if this storage can provide a longterm fixation of CO2. It was also suggested to use large quantities of natural underground brine deposits to store CO2. This approach appears less practical due to the lack of a large calcium source. Of course, lime can be obtained, from decomposition of CaCO3, which in turn can be used as a CO2 adsorbent or calcium source. It is needless to say that such a process does not lead to a reduced emission of CO2. 2.3. Usage of CO2. In principle, CO2 can be utilized in a large number of processes. In the above, applications were summarized based on the physical properties of CO2. In recent years the potential application of CO2 as a chemical feedstock has received a lot of attention. In the next chapter the potential application as a chemical feedstock is discussed systematically. 3. Chemical Reactions of CO2 3.1. Introduction. CO2 is one of the cheapest and most abundant carbon-containing raw materials in the world. Therefore, it is logical that it is considered as a potential building block for carbon-carbon chains or as a competitive carbon source in chemistry or in chemical industry.9,23 However, CO2 is rather inert and its
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Table 4. Enthalpy and Gibbs Free Energy Changesa in Some Exothermic Reactions Involving Carbon Dioxide21-23 eq 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19
a
reactions CO2(g) + H2(g) f HCOOH(l) CO2(g) + 2H2(g) f HCHO(g) + H2O(l) CO2(g) + 3H2(g) f CH3OH(l) + H2O(l) CO2(g) + 4H2(g) f CH4(g) + 2H2O(l) 2CO2(g) + H2(g) f (COOH)2(l) 2CO2(g) + 6H2(g) f CH3OCH3(g) + 3H2O(l) CO2(g) + H2(g) + CH3OH(l) f HCOOCH3(l) + H2O(l) CO2(g) + H2(g) + CH3OH(l) f CH3COOH (l) + H2O(l) CO2(g) + 3H2(g) + CH3OH(l) f C2H5OH(l) + 2H2O(l) CO2(g) + H2(g) + NH3(g) f HCONH2(l) + H2O(l) CO2(g) + CH4(g) f CH3COOH(l) CO2(g) + CH4(g) + H2(g) f CH3CHO(l) + H2O(l) CO2(g) + CH4(g) + 2H2(g) f (CH3)2CO(l) + H2O(l) CO2(g) + C2H2(g) + H2(g) f CH2dCHCOOH(l) CO2(g) + C2H4(g) f CH2dCHCOOH(l) CO2(g) + C2H4(g) + H2(g) f C2H5COOH(l) CO2(g) + C2H4(g) + 2H2(g) f C2H5CHO(l) + H2O(l) CO2(g) + C6H6(l) f C6H5COOH(l) CO2(g) + C6H5OH(l) f m-C6H4(OH)COOH(l)
H (kJ/mol) -31.0 -11.7 -137.8 -259.9 -39.3 -264.9 -31.8 -135.4 -221.6 -103.0 -13.3 -14.6 -70.5 -223.6 -49.1 -166.6 -171.1 -21.6 -6.6
G (kJ/mol) +34.3 +46.6 -10.7 -132.4 +85.3 -38.0 +25.8 -63.6 -88.9 +7.2 +58.1 +74.4 +51.2 -115.0 +26.2 -56.6 -44.4 +30.5 +46.9
Aspen was used in calculating the data. Table 5. Enthalpy and Gibbs Free Energy Changesa in Some Exothermic Reactions Involving CO22 eq 20 21 22 23 24 25 26 27 reactions CO(g) + 2H2(g) f CH3OH(l) CO(g) + H2O(l) f HCOOH(l) 2CO(g) + 2H2O(l) f (COOH)2(l) CO(g) + CH3OH(l) f HCOOCH3(l) CO(g) + CH3OH(l) f CH3COOH(l) CO(g) + NH3(g) f HCONH2(l) CO(g) + C2H2(g) + H2O(l) f CH2dCHCOOH(l) CO(g) + C2H4(g) + H2(g) f C2H5CHO(l) H (kJ/mol) -131.6 -24.8 -26.9 -25.6 -129.2 -96.8 -217.4 -164.9 G (kJ/mol) -29.9 +15.1 +46.9 +6.6 -82.8 -12.0 -134.2 -63.6
Aspen was used in calculating the data. Table 6. Enthalpy and Gibbs Free Energy Changesa in Some CO2-Involving Endothermic Reactions eq 28 29 30 31 32 33 34 reactions CO2(g) + CH2dCH2(g) f CH2CH2O(l) + CO(g) CO2(g) + C(s) f 2CO(g) 3CO2(g) + CH4(g) f 4CO (g) + 2H2O(l) CO2(g) + CH4(g) f 2CO(g) + 2H2(g) CO2(g) + 2CH4(g) f C2H6(g) + CO(g) + H2O(l) 2CO2(g) + 2CH4(g) f C2H4(g) + 2CO(g) + 2H2O(l) CO2(g) + C2H4(g) f C2H4O(g) + CO(g) H (kJ/mol) +152.9 +172.6 +235.1 +247.5 +58.8 +189.7 +178.0 G (kJ/mol) +177.3 +119.9 +209.2 +170.8 +88.0 +208.3 +176.0
Aspen was used in calculating the data.
reactions are energetically highly unfavorable. Of course, in principle the first problem can be solved by developing a good catalyst. The second point is of thermodynamic origin and not solvable by catalysis. In the following it will be shown that this is in general true, but when certain special conditions exist (high T or P, free energy available, need for CO2 for chemical reasons) a practical process might be feasible. 3.1.1. Thermodynamics. Table 4 shows the H and G values for several interesting exothermic CO2 reactions.21-23 At first sight it might be surprising that so many exothermic conversions exist in view of the high stability of CO2. However, when the Gibbs free energy G is considered it is clear that most of these reactions are associated with highly positive G values and, as a consequence, thermodynamically not favored. It is interesting to compare CO2 with CO because often CO2 is present mixed with CO or it is (partially) converted into CO. In Table 5, H and G values for some exothermic CO reactions are shown.22 Although many exothermic reactions of CO2 (and CO) do exist, it appears that for all the reactions in Tables 4 and 5, the Gibbs free energy values are less favor-
able: they are all more positive than the corresponding H values; only a few reactions have both negative G and H values. Upon closer examination of Table 4 it is apparent that all cases where G < 0, correspond to hydrogenations, or reactions leading to products containing C-O bonds. The reason for the relatively favorable values of G for hydrogenation reactions is that water is produced. As hydrogen has to be produced at the cost of energy input, in fact, none of these reactions is favorable for CO2 mitigation. So, these data might lead to a too optimistic view. In Table 5 also a few reactions with negative G are given which do not invlove hydrogenation. Inspection of the reaction equations reveals that no C-O bonds are broken and, as a consequence, the penalty for breaking of these bonds does not exist. Tables 4 and 5 refer to exothermic reactions. Of course also CO2 reactions with a positive H do exist. Table 6 gives some examples. It is no surprise that these reactions are associated with highly positive G values and are, as a consequence, not favorable. When producing a certain compound, it is interesting to compare CO and CO2 as potential feedstocks. In
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Table 7. Comparison of Enthalpy and Gibbs Free Energy Changesa in Some CO2 and CO Reactions
eq 1 21 3 20 8 24 14 26 7 23
a
reactions CO2(g) + H2(g) f HCOOH(l) CO(g) + H2O(l) f HCOOH(l) CO2(g) + 3H2(g) f CH3OH(l) + H2O(l) CO(g) + 2H2(g) f CH3OH(l) CO2(g) + H2(g) + CH3OH(l) f CH3COOH(l) + H2O(l) CO(g) + CH3OH(l) f CH3COOH(l) CO2(g) + C2H2(g) + H2(g) f CH2dCHCOOH(l) CO(g) + C2H2(g) + H2O(l) f CH2dCHCOOH(l) CO2(g) + H2(g) + CH3OH(l) f HCOOCH3(l) + H2O(l) CO(g) + CH3OH(l) f HCOOCH3(l)
H (kJ/mol) -31.0 -24.8 -137.8 -131.6 -135.4 -129.2 -223.6 -217.4 -31.8 -25.6
G (kJ/mol) +34.3 +15.1 -10.7 -29.9 -63.6 -82.8 -115.0 -134.2 +25.8 +6.6
Aspen was used in calculating the data.
Figure 6. Gibbs free energy for CO2 hydrogenation to methanol as a function of reaction pressure.
Figure 7. Gibbs free energy as a function of reaction temperature for (1) CO2(g) + CH4(g) ) 2CO(g) + 2H2(g), (2) 2CO2(g) + C2H6(g) ) 4CO(g) + 3H2(g).
Table 7 enthalpy and Gibbs free energy changes of some interesting and relatively favorable reactions starting from CO or CO2 are compared. It is obvious that the reaction enthalpies for the production of the same product from either CO or CO2 are comparable, although in most cases CO is favored compared to CO2. Coming back to the comparison of CO and CO2, it is appropriate to state that when the total production process is considered CO is much more favorable than CO2. For example, in the formic acid production in the former case H2O is consumed whereas in the latter case H2 is the reactant. The production of H2 requires energy, whereas H2O is free. It is obvious that the energy required is provided by the coreactant, be it H2 or a hydrocarbon. From the foregoing it should not be concluded that in all cases reactions based on CO2 or CO are only feasible in those cases where G has a reasonable value. In practice favorable conditions (T, pressure) can be chosen or, as is done in partial oxidation, reactions can be coupled. In the latter case, at favorable conditions, endothermic and exothermic reactions are carried out simultaneously and, the endothermic reaction occurs while the heat of reaction is produced by the exothermic oxidation. Figure 6 shows the G value for the reaction CO2(g) + 3H2(g) ) MeOH(l) + H2O(l) as a function of the total pressure. At all pressures G is negative and as pressure increases it becomes more negative; i.e., the reaction becomes more favorable, thermodynamically. A similar case is the reaction for formate from CO2 and H2 which has a positive G while an increase in CO2 or H2 pressure shifts the equilibrium favorably. Figure 7 shows the influence of temperature on the reaction of CH4 and C2H6 with CO2 to syngas. The former reaction is called dry reforming. It appears that as temperature increases the Gibbs free energies
for the respective reactions change from positive to negative. At 900 K the reaction between CO2 and CH4 giving synthesis gas is associated with a G value of zero. For the reaction between CO2 and C2H6 this applies at 800 K. So, when CO2 is available at high temperature (>800 K) a reaction with CH4 or C2H6 is possible, thermodynamically. As this will lead to cooling of the mixture the term chemical cooling has been used. Many process streams do exist where this principle might be used successfully. A second advantage in practice of the production of synthesis gas from CO2 and CH4 is the ratio of H2 and CO produced (1:1); in many practical applications steam reforming of CH4 gives the wrong ratio (3:1), i.e., too much H2. When CO2 instead of H2O is used, the ratio can be tuned without the necessity to carry out a separate water gas shift. A similar situation has been found for the reaction between CO2, H2, and amines producing formamides. In summary, although CO2 is the end product of energy-producing processes such as combustion, many chemical reactions using CO2 are thermodynamically feasible. However, in many reactions a coreactant is present, for instance hydrogen which reacts into water. The stability of water is the reason that overall G becomes negative for many hydrogenation reactions.3,23 Also, reactions do exist in which no C-O bonds are broken. This class contains reactions with favorable H and G values. From a thermodynamic point of view, it is clear that in general for a useful application of CO2 a special condition must exist. Examples are the following. CO2 can be present at very high temperature or pressure. Heat might be available without cost so that chemical cooling is feasible. There might be a surplus of hydrogen without an attractive outlet. The chemistry of a desired reaction might require CO2, for example, in methanol production.
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Figure 8. Possible routes of interaction between CO2 and a substrate (S) on a transition metal (M).
Figure 11. CO2 as an oxidant. Figure 9. Various modes of CO2 coordination to a metal center.
below 10-100 kt/y). They would never lead to substantial reduction of CO2 content in the atmosphere. Other features of CO2 chemistry make use of its acidity and oxidizing abilities.15,37 3.2. Utilization as an Acid. CO2 is an acidic oxide; when it is dissolved in water, either as bicarbonate or carbonate,14 it is slightly acidic. This weak acidity can be used in neutralization processes,15 e.g., in purification of water from swimming pools. Due to its weak acidity, the pH value it can reach is limited (from pH of 12-13 to 6-9). The use of CO2 in neutralization has its merits. It is a clean acid; it does not lead to environmental problems associated with strong acids, e.g., H2SO4 or HCl.15 Moreover, it is less harmful or even harmless to the enzymes used in processes involving microorganisms or enzymes.15 In this type of applications low cost technology is a must. In principle, a high concentration of CO2 is not needed and an application of CO2containing exhaust gas might be feasible without prior separation step. Indeed, it has been reported that flue gas from coal combustion can be used directly for neutralization purposes without purification or concentration.15 Of course, for most applications coal gas is too dirty to apply as acid and purification is absolutely necessary. The acid properties of CO2 can be improved by converting it in an organic acid, e.g., formic acid. CO2 is used to prepare various carbonates. Besides CaCO3, NaHCO3, and Na2CO3, it is used to prepare carbonates of La3+, Nd3+, Sm3+, Eu3+, Gd3+, Dy3+, and Ho3+ by reacting an aqueous solution of the corresponding oxide, M2O3, with supercritical CO2.38 At a temperature of 300-320 K and a pressure of 70-250 bar, the yield was reported to be >95%. 3.3. Utilization as an Oxidizing Agent. CO2 can be viewed as an oxygen carrier.37 Figure 11 shows some possibilities. CO2 can replace oxygen or air in oxidation processes. Compared with air or oxygen, CO2 is a mild oxidizing agent. Numerous reactions exist in which, in principle, CO2 can be used as an oxidizing agent. In some cases, this use may have beneficial results, e.g., a better selectivity to intermediate oxidation products in chemical industry. It is interesting to note that the NOx content in the flue gases from combustion of heating gas is reduced by injection of CO2 into the gas upstream of the burners.39 Although it might be thought that this is due to a different reaction kinetics, it is mainly caused by the lowering of the temperature. Examples of the use of CO2 as oxidizing agent are given later on.
Figure 10. Stoichiometric and catalytic reactions involving CO2 and alkanes or alkenes.10
3.1.2. CO2 Reactivity. Catalysis will play a crucial role in CO2 conversion reactions.10 Development of suitable catalysts represents a major challenge for the catalysis community. Possible interactions between CO2 and a substrate (S) on a transition metal (M) are schematically shown in the Figure 8.10 As shown in this figure, the formation of S-CO2, product between CO2 and a substrate S, can proceed either via S insertion, followed by CO2 insertion, or vice versa; due to the coordination to the active center (M), the activation energy might be lowered for the reaction. There are three possible bonding modes for CO2 (cf. Figure 9), namely, pure carbon coordination (I), pure oxygen coordination (II), and mixed oxygen-carbon coordination (III). Recent results indicate that, in general, the CO2 molecule prefers to adopt either a mixed carbon-oxygen coordination (III) or a pure oxygen coordination (II) to the metal center.14 Coordination to metal centers may lead to further chemical reactions.10,32-34 A large number of studies in literature describe the coordination chemistry of CO2.9,10,21,22,24,35,36 Figure 10 illustrates the wide variety of metal-mediated reactions in which CO2 can take part. However, many of the reactions are stoichiometrical, requiring expensive organometallic complexes, and often the reactions involve difficult conditions. Various useful products, fine chemicals, intermediates in pharmaceutical and food industries can be produced. However, these applications, if they may lead to industrial processes, only consume very small amounts of CO2 (typically
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3.3.1. Carbon Gasification. If carbon is reacted with CO2, CO is obtained in the reverse Boudouard reaction:
CO2 + C ) 2CO
H ) +172.6 kJ/mol CO2
(29)
This highly endothermic reaction is widely carried out. It is a crucial reaction in coal gasification, which is normally carried out autothermally; i.e. the heat required is produced by partial oxidation of the coal. This reaction is not limited to coal; in general, all carbonaceous materials can be gasified into CO which is a useful product. A modern example is gasification of waste material. Underground coal gasification is studied on a scale near to demonstration scale. It is sometimes defended that for coal utilization underground gasification is the technology of the future. Because of the large scale, the potential amounts of CO2 involved are enormous. Carbon gasification is also carried out in the manufacture of active carbon to obtain the desirable porosity. When the CO2 source is at high temperature, chemical cooling (use of its chemical potential) is possible. An example of using CO2 in chemical cooling is an advanced iron ore reduction process, where a large gas flow containing 15% CO2 and H2O has to be cooled from ca. 1900 K to 1100 K, because it is to be used in the reduction of iron ore, which gets sticky above 1100 K.40 It is considered to inject coal particles in this stream resulting in (i) an increased reducing power and (ii) a lowering of the temperature. Another example is already shown in Figure 7. If high-temperature CO2 is used in the oxidation of alkanes, the reactions are much more favorable. Although, at present, no technology is available to separate CO2 from the flue gas at high temperature, we think that in the near future membrane separation by inorganic membranes will probably provide the possible route to use high-temperature CO2, ceramic membranes have been developed which can be used for gas separations at much higher temperatures, e.g., 673-873 K, than the polymer membranes.41,42 3.3.2. Oxidation of Alkyl Groups in Aromatic Compounds. Alkylaromatic compounds can react with CO2 in the presence of catalysts containing Pd and oxides of La, Sm, Y, and Ce to give dealkylated derivatives and synthesis gas.43 For toluene and CO2 (1:1), the reaction proceeds at 673 K over a Pd-La2O3-Al2O3 catalyst to give benzene with 90% selectivity.
As complex radical chain reactions are involved, and the intermediates are much more reactive than the reactant, CH4, it is no surprise that selectivities in combination with high yields are disappointing up to the present. Total combustion occurs, to a significant extent. One may also think of using CO2. Indeed, it was reported that by using CO2/O2 mixtures instead of oxygen, the selectivity for ethane and ethylene in oxidative coupling of methane can be enhanced.44,45 Moreover, CO, a valuable product is produced. PbO/ MgO catalyst was considered to be the best system studied so far,45 although its activity is still too low for practical use.
CO2(g) + 2CH4(g) f C2H6(g) + CO(g) + H2O(g) H1098 K ) 196.7 kJ/mol CH4, G1098 K ) 70.0 kJ/mol CH4 (32)
The thermodynamic data show that the equilibrium is not favorable, not even at 1098 K. Another example is the oxidative dehydrogenation of propane into propylene:46,47
C3H8(g) + 1/2O2(g) f C3H6(g) + H2O(l) H ) -165.0 kJ/mol, G ) -151.0 kJ/mol (37)

Essentially, the heat of reaction needed is provided by the formation of H2O. An alternative is the use of CO2 rather than O2:
C3H8(g) + CO2(g) f CO(g) + H2O(l) + C3H6(g) H ) 118.2 kJ/mol, G ) 105.5 kJ/mol (38)
In the reaction using K-Cr-Mn on silica catalysts, also ethylene, CO, and H2 are produced. This reaction, though rather highly endothermic, has potential merits. It is, in general, difficult to reach high selectivities in oxidative dehydrogenation. In fact, one of the undesired byproducts is CO2. When CO2 is used instead of air or oxygen, CO2 production is suppressed. It is not illogical to expect that use of CO2, which is a mild oxidant, may lead to higher selectivities in this type of reactions. Alkanes can be dehydrogenated (aromatized) into aromatics.46,47 Usually air is used, and water, CO and cracking products, lower alkanes, or alkenes are the products. It was reported46,47 that CO2 can be used in the dehydrogenation or aromatization of lower alkanes (e.g., of propane) over Ga- or Zn-doped H-ZSM-5 catalysts. It was interesting to find that the presence of CO2 suppresses cracking products and deactivation of the catalyst by coking. Ethane was reported to be active in the dehydrogenation by CO2 over the same catalysts.44
PhCH3(l) + CO2(g) f C6H6(l) + H2(g) + 2CO(g) H ) +210.1 kJ/mol, G ) +130.5 kJ/mol (35)
This reaction might be a good example for a process based on a membrane reactor. 3.3.3. Oxidative Dehydrogenation of Hydrocarbons. Hydrocarbons can be dehydrogenated in several ways.44-47 An often applied method is oxidative dehydrogenation. An example is the oxidative coupling of CH4 which has drawn a lot of attention.45 The desired reaction usually is
C2H6(g) + CO2(g) f C2H4(g) + CO(g) + H2O(l) H ) +842.2 kJ/mol, G ) +120.3 kJ/mol (39)
It is clear that all these CO2 based oxidative dehydrogenation reactions are thermodynamically unfavorable, in contrast to O2-based analogous processes. As the former are highly endothermic and the latter highly exothermic, a mixture of O2 and CO2 might lead to a feasible process. The alternative is to add heat from an external source or to start with a high-temperature reactant.
2CH4(g) + O2(g) f C2H4(g) + 2H2O(l) H ) -424.7 kJ/mol, G ) -306.3 kJ/mol (36)
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3.3.4. Oxidation or Combustion of Metals. Combustion of metals, e.g., Mg or Li, is used to generate energy under special conditions, e.g., in space ships.48 When using oxygen, these reactions are very fast and highly exothermic, and, as a consequence, favorable conditions are present for a runaway. The use of CO2, a mild oxygen carrier, is in this respect preferable over that of air.48 CO2 is used, in special cases, in catalyst calcination, to prevent the active phase from oxidation to too high an oxidation state or in special treatment, e.g., in the manufacture of uranium fuel particles. In all these examples, use is made of the mildly oxidizing capacity compared to oxygen and air. It is also successfully used in applications where the reducing capacity of a gas flow has to be decreased. An example is MeOH synthesis, where the catalyst is based on copper.49-54 The optimal oxidation state has been suggested to involve slightly oxidized Cu or Cu+,52,54 and synthesis gas without CO2 and H2O deactivates the catalyst by reducing copper essentially to Cu0. Therefore, CO2 is added to the reactant mixture in order to prevent the complete reduction of Cu oxide to metallic copper.50 3.4. Reduction of CO2. Although the previous paragraphs, which discuss CO2 as an oxidant, deal with reactions in which CO2 is reduced, reactions directly aimed toward CO2 reduction are treated separately. Reduction of CO2 can proceed electrochemically or chemically. 3.4.1. Electrochemical Reduction. Electrochemical reduction can be carried out catalytically or noncatalytically. Regardless of the route,9,14,22,55,56 in most cases, the major products obtained are hydrogen, oxygen, CO, formic acid, formaldehyde, methanol, and methane. In some cases, more complex molecules, such as oxalic, succinic, adipic, and suberic acids, i.e., dicarboxylic acid, HOOC-(CH2)n-COOH, with n ) 0, 2, 4, and 6, respectively, can be obtained.9,55,56 Some can be used as a building block in C1 chemistry. The selectivities reported are not high. Moreover, an overpotential is needed for the reaction to proceed. Electrocatalytic reduction deserves further study since it increases the efficiency of the process. There are reports of electroreduction processes which use solar energy as an energy source. These processes are promising since they use renewable energy. It should be pointed out that most products from electrochemical reduction can also be made by catalyzed chemical reduction routes. In many cases, the productivity of catalytic chemical reductions is much higher than that of the corresponding electroreduction. So, we conclude that only when cheap electricity is available, electrochemical processes can be attractive. 3.4.2. Catalytic Reduction with H2. With respect to catalytic reduction of CO2 or CO, hydrogen is the most commonly used reducing agent.32 The reactions, which belong to the class of so-called C1 chemistry, are well studied and technically viable and, in some cases, economically feasible.33,35,49-51 The economic feasibility of many processes depends strongly on fuel prices. Several routes can be proposed to use CO2 in hydrogen reduction: (1) conversion to products via synthesis gas, (2) direct hydrogenation into useful products, and (3) reactions to other products via MeOH.
3.4.2.1. Conversion to Products via Syngas Route. CO2 can be converted first to synthesis gas, CO/ H2, followed by reactions of the class of C1 chemistry, Fischer-Tropsch reaction, MeOH synthesis, methanation, etc. Synthesis gas can be produced via several reactions. The most important are steam reforming of CH4, CO2 reforming of CH4, partial oxidation of CH4 and partial oxidation of coal.
steam reforming of methane H2O(l) + CH4(g) ) CO(g) + 3H2(g) H ) +229.7 kJ/mol, G ) +161.5 kJ/mol (40) CO2 reforming of methane57,58 (dry reforming) CO2(g) + CH4(g) ) 2CO(g) + 2H2(g) H ) +223.5 kJ/mol, G ) +170.8 kJ/mol (31) partial oxidation of methane CH4(g) + 1/2O2(g) ) CO(g) + 2H2(g) H ) -59.7 kJ/mol, G ) -86.5 kJ/mol (41)
Actually, in the partial oxidation of methane, the reaction proceeds via two steps: the first step is methane oxidation which is usually a combination of two reactions in series (eqs 42 and 43), followed by methane reforming in the steam and CO2 produced (eqs 40 and 31):
2CH4(g) + O2(g) f 2CO(g) + 4H2O(l) H ) 638.5 kJ/mol CH4, G ) -562.7 kJ/mol CH4 (42) H ) 2CO(g) + O2(g) f 2CO2(g) 283.2 kJ/mol CO, G ) -257.3 kJ/mol CO (43)
So, methane reforming with CO2 is clearly a largely applied reaction in industry.
steam gasification of coal C(s) + H2O(l) ) CO(g) + H2(g) H ) +178.7 kJ/mol, G ) +100.7 kJ/mol (44)
It should be mentioned that in steam reforming of methane (eq 40), which is the most commonly used, a syngas mixture with a H2/CO ratio of 3 is produced, while the other two reactions produce syngas with a H2/ CO ratio of 1. For MeOH synthesis, the ratio should be ca. 2 which is usually achieved via the water-gas shift (WGS) reaction (45) or partial oxidation.
WGS reaction: CO(g) + H2O(l) f CO2(g) + H2(g) H ) +6.2 kJ/mol, G ) -19.2 kJ/mol (45)
The WGS reaction often plays a role in reactions involving CO and H2. It is interesting to analyze the reactions occurring in terms of the products obtained. The byproduct formed in oxidation reactions is either CO2 or water. The latter is not desired because in that case expensive hydrogen is converted into water. The WGS reaction is a crucial reaction in ammonia and MeOH synthesis, forming large amounts of CO2. Also in other syngas reactions, e.g., the synthesis of
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Figure 13. CARNOL process.

Table 8. Comparison of Various MeOH Production Processes from Methane63
Figure 12. HYDROCARB process.

process
higher alcohols, syngas with a H2/CO ratio of less than 2 is preferred and the WGS reaction can be applied to tune the syngas composition.49 It is not necessary to apply the WGS reaction in order to arrive at the desired ratio. Syngas of the right composition can be produced from methane directly by combining CO2 and H2O reforming. In such a way large amounts of CO2 are consumed while at the same time the WGS reaction is avoided, which reduces process cost. In CO2 conversion processes, as mentioned above, thermodynamics are in general not favorable and process schemes leading to a net CO2 consumption are only possible in special cases. It is not surprising that several processes based on renewable energy carriers have been suggested. Methane can be produced in a hydropyrolyzer in which a carbonaceous feedstock (e.g., biomass) can be converted to methane.59-63 The reactions for hydrogenolysis of biomass, coal (bituminous) and oil, respectively, are as follows:62
CH4 efficiency CO2 emission (mol MeOH/ (mol CO2/ mol MeOH) mol CH4) 0.95 1.039 1.01 0.845 1.05 0.962 0.99 0.684
steam reforming (eq 50) H2O + CH4 f CH3OH + H2 CO2 reforming (eq 51) CO2 + CH4 + 0.33H2 f 1.33CH3OH steam + CO2 reforming (eq 52) 1.5CH4 + H2O + 0.5CO2 f 2CH3OH CARNOL process (eq 53) 0.5CO2 + CH4 f 0.5C + CH3OH
CH1.44O0.66 + 1.94H2 ) CH4 + 0.66H2O CH0.8O0.08 + 1.68H2 f CH4 + 0.08H2O CH1.7 + 1.15H2 f CH4
(46) (47) (48)
fossil fuels, and instead of hydrogasification, CO2 gasification is applied. 50% of the carbon produced is stored and, as a consequence, prevented from entering the atmosphere.63 Table 8 shows the methane efficiency and CO2 emission per mol MeOH produced for the four processes.63 From the viewpoint of CO2 emission, the CARNOL process is superior to steam reforming, CO2 reforming, or a combination of steam/CO2 reforming.63 Of course, its CH4 efficiency is lower than the other processes, since carbon is produced and stored. The separation of the carbon produced is less difficult as compared to other processes. Carbon can be sold as a natural commodity. 3.4.2.2. Direct CO2 Hydrogenation. CO2 can be directly hydrogenated into several products.32,49,64,65 An interesting example is methanol synthesis.
CO2(g) + 3H2(g) f CH3OH(l) + H2O(l) H ) -137.8 kJ/mol, G ) -10.7 kJ/mol (3)

Actually, in practice CO2 (ca. 5%) is mixed with syngas in the synthesis of methanol.9 By the reverse reaction of MeOH synthesis, viz., methanol decomposition,66 syngas can be obtained in situ. For small-scale applications of syngas this often is a convenient route.67 Another interesting application of methanol decomposition is the following. If syngas from MeOH decomposition is injected into a diesel or gasoline engine, the combustion efficiency can be greatly enhanced.66 The energy needed for MeOH decomposition can be provided by heat exchanging with the hot exhaust gas from the engines. MeOH, either pure or mixed with other fuels, can be used as fuel for engines.66-71 It was reported that using MeOH as a fuel less environmentally harmful gases, e.g., hydrocarbons, SOx, and NOx are produced, although formaldehyde emission is increased.67,68,71 Note that most of the engines used in testing the environmental effect of fuels were designed for using fuels other than methanol.68,71 Engines designed specially for using methanol will show even better performance. Methanol as fuel has also disadvantages. Due to its lower heat capacity (compared with gasoline) a larger tank is needed. Methanol is more corrosive than gasoline and as a consequence, measures to prevent
Hydrogen can be produced by catalytic decomposition of methane at 1273-1373 K:62,63
CH4 f C + 2H2
(49)
After separation, the hydrogen can be used in the hydrogenation processes, whereas the carbon can be used as a fuel or stored permanently or for future use.62,63 The combination of these reactions with methane reforming in CO2 and syngas reactions can lead to low or zero CO2 emission processes for electricity generation and production of chemicals, e.g., fuel methanol.59 Promising processes are the HYDROCARB and CARNOL processes.62,63 In the former process biomass and fossil fuels are converted simultaneously producing methanol and carbon black, which is stored.62 Figure 12 illustrates the HYDROCARB process. In this process, an essentially zero emission of CO2 is realized by removing carbon from the cycle. When the carbon is stored, of course, an energy penalty exists.62,63 Figure 13 shows the CARNOL process.63 The CARNOL process is similar to the HYDROCARB process in that they both contain processes of methane pyrolysis and methanol synthesis. The feedstock in CARNOL process is methane instead of biomass and
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corrosion should be taken.66-68,71 The methanol consumption is increasing tremendously, mainly because of changes in the composition of the gasoline pool. It should be stressed that MeOH used as fuel or fuel additive is one of the most important potential chemical usage of CO2 by volume.26,68 MeOH can be produced from hydrocarbons for which there is no outlet. For example, it provides a means to use the hydrocarbons in remote oil production sites or refineries. In many cases, natural gas is a byproduct of oil winning and for convenience the natural gas is flared, leading to CO2 emission.67 An elegant solution is to convert the useless hydrocarbons via synthesis gas into methane which can be easily and safely stored and shipped.67 The simplest example of direct hydrogenation of CO2 is the production of methane.
Figure 14. Scope of production of chemicals via MeOH-based routes.
CO2(g) + 4H2(g) f CH4(g) + 2H2O(l) H ) -259.9 kJ/mol, G ) -132.4 kJ/mol (4)

Of course, economically, this reaction is not attractive: hydrogen is more expensive than methane. Fischer-Tropsch reactions are also possible:49,72
nCO2 + (3n + 1)H2 f CnH2n+2 + 2nH2O nCO2 + 3nH2 f CnH2n + 2nH2O
(54) (55)
Besides these products, other products, such as aldehydes, ethers, acids, and esters, can be synthesized.9,33,34,72 In the production of oxygenates compared to hydrocarbons, less hydrogen is consumed and the thermodynamics is more favorable. This is illustrated for formic acid and formaldehyde:
Higher alcohols can be manufactured by reaction with syngas.49 This reaction can be viewed as a combination with Fischer-Tropsch reactions.72 With the phase-out of the tetraalkyllead-type antiknocking agents in petrol, the octane pool needs to be modified by the addition of either alcohols or esters, e.g., MTBE. Both additions need a large amount of MeOH because either methanol is used as such or it is a reactant in the production of the additive.67-71 In some countries, e.g., in Germany, 3-5% MeOH is added to the gasoline to enhance the octane number.49 Using the Mobil MTG (methanol-to-gasoline) process, MeOH can be converted to gasoline. This is a route which can produce gasoline from nonoil sources.49,66,72,73 Via dehydrogenation, formaldehyde can be produced:73
CH3OH f HCHO + H2
(58)
CO2(g) + H2(g) f HCOOH(l) H ) -31.0 kJ/mol, G ) +34.3 kJ/mol (1) CO2(g) + 2H2(g) f HCHO(g) + H2O(l) H ) -11.7 kJ/mol, G ) +46.6 kJ/mol (2)
In the presence of H2 and HX (X ) OH, OM, OR, NR2), CO2 can be converted to HCOX, derivatives of formic acid: 9,10,33
H2 + CO2 + HX f HCOX + H2O
(56)
Some of these products are quite useful, e.g., esters or amides of formic acid. 3.4.2.3. Reactions to Other Products via MeOH. Synthesis gas to MeOH is the only alcohol synthesis reaction with both a high selectivity (>99%) and a high productivity (>1 g MeOH/g catalysth).49,50,72 All the other alcohol products suffer from a lack of productivity and/or selectivity.49 MeOH is a bulk product which is widely used in chemical industry.73 Many useful products can be produced from methanol.73 Figure 14 summarizes the major possible reactions into useful products from MeOH. The carbonylation of methanol is currently the most important synthetic route to acetic acid. The reaction of MeOH and formic acid may lead to methyl formate:
It is clear that methanol is a building block in chemical industry with a lot of potential.73 MeOH is the first choice in the recent Japanese national program for CO2 conversion.74 3.4.3. Photoreduction of CO2. The energy needed for photoreduction of CO29,75-78 is solar energy or another form of light. It is too early to assess the potential of photoreduction. Only a few publications have appeared. Kisch et al.75 reported the heterogeneous photocatalysis of CO2 to formate by irradiation of light with g 290 nm. Osaka et al.76 described photocatalytic fixation of CO2 in oxoglutaric acid to isocitric acid. Matsuoka et al.77 reported the photoreduction of CO2 to formic acid at irradiation of light with g 290 nm. Since renewable energy79,80 is used for the CO2 conversion, they certainly lead to CO2 mitigation. The problem, however, is the selectivity of the reactions and in particular, the limited efficiency. 3.5. Reactions with Compounds Having Activated Hydrogen Atoms. Compounds with activated hydrogen in the molecule can react with CO2 by insertion of CO2 into the C-H bond.10,22 For example, acetophenone reacts with CO2 in the presence of phenolates to yield carboxylic acid (DMK ) dimethyl ketone):10
O PhCCH3 + CO2
PhOK DMK
O PhCCH2COOK
O PhCCH2COOH (59)
CH3OH(l) + HCOOH(l) f HCOOCH3(l) + H2O(l) H ) -309.5 kJ/mol, G ) -8.5 kJ/mol (57)
This reaction is interesting due to its mild reaction conditions and wide applications. For example, citric
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3.6.1. Saturated Hydrocarbons. CO2 methane reforming is probably the most interesting reaction with saturated hydrocarbons.13,57,58
CO2(g) + CH4(g) f 2CO(g) + 2H2(g) H ) +247.5 kJ/mol, G ) +170.8 kJ/mol (31)

It has been commercialized under the name SPARG process. Levy et al.81 described a 20 kW reforming/ methanation installation based on a solar furnace, for providing the energy for heating the CO2 and for the enthalpy of the endothermic reforming reaction. CO2 reforming is not restricted to methane; higher hydrocarbons may also be converted:
nCO2 + CnH2n+2 f 2nCO + (n + 1)H2
(62)
Moreover, as stated before, in principle, other products may be produced:
CO2(g) + CH4(g) f CH3COOH(l) H ) -13.3 kJ/mol, G ) +58.1 kJ/mol (11)

In view of the low reactivity of both CO2 and CH4, a high temperature is called for and an acceptable selectivity can probably not be reached. Moreover, thermodynamics is not favorable. It has been suggested to carry out cracking of hydrocarbons in the presence of CO2.9,10,22 The process takes place at elevated temperatures, typically at 800-900 K. Radicals are formed and in this reactive environment CO2 might show reactivity and interesting products could be formed, e.g., various lower carboxylic acids.9,10,22
Figure 15. Some compounds with active hydrogen and their carboxylation products.22
acid can be made via three stages from acetone (DMF ) dimethylfuran):9
O CH3 C CH3 O + CO2
PhONa DMF
CnH2n+2 + CO2 f CmH2m+1COOH (m , n)
(63)
NaOOCCH2CCH2COONa
HCN
(60) CH2COOH
[H+]
OH NaOOCCH2CCH2COONa CN
HOCCOOH CH2COOH
The reaction of sodium phenolate with CO2, the socalled Kolbe-Schmitt process, has been used in the industrial synthesis of salicylic acid since 1874:9,22
COONa CO2 +
[H+]
COOH OH (61)
ONa
OH
The product is mainly used in the production of aspirin, the most popular drug of all. In 1980 in USA, the production of salicylic acid amounted to 25 kt/y. Carboxylation of hydrocarbons with activated hydrogen has received a lot of attention. Figure 15 shows that a wide variety of products can be made.22 3.6. Reactions with Hydrocarbons without Activated Hydrogen Atoms. In contrast to activatedhydrogen-containing hydrocarbons, paraffins which do not contain activated hydrogen can be carboxylated only under drastic conditions. Of course, unsaturated hydrocarbons are more reactive than saturated ones.
An original suggestion is to use underground reservoirs as reactor. Under such conditions temperatures of say 333 K and pressures up to 130 bar exist, allowing the synthesis of oxygenates. In principle, it is possible to use supercritical liquid CO2 to extract the oxygenates formed and to bring them to the surface for further concentration.9 Due to the large reactor volume and, as a consequence, the long residence time, the conversion might be acceptable. However, the costs for product extraction and purification may not be favorable. To the same category belongs microbiologically enhanced oil recovery.82 3.6.2. Unsaturated Hydrocarbons. The reactions of CO2 with unsaturated hydrocarbons can be subdivided into9,10,22,83 reactions with monoalkenes, dienes, cycloalkenes, alkynes, and other substituted hydrocarbons. 3.6.2.1. Monoalkenes. CO2 can react with monoalkenes, e.g., ethylene and propylene, at 743-753 K catalyzed by triethylamine and calcium chloride, leading to, respectively, ethylene carbonate and propylene carbonates:9,22
CO2(g) + C2H4(g) f CH2dCHCOOH(l) CH3CHdCH2 + CO2 f CH2(COOH)CHdCH2
(15) (64)
Both products are very useful. For example, propylene carbonate is a tonnage petrochemical solvent; ethylene carbonate has also an excellent potential.10
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Other organic carbonates also may have applications as solvents or additives. Lapidus et al.84 reported a Ru-catalyzed reaction of ethylene and CO2; ethanol, propionic acid, and its ethyl ester were formed in yields of up to 38% at 450 K and 700 atm.
CH2dCH2 + CO2 9 CH3CH2CO2CH2CH3 + 8 CH3CH2OH + CH3CH2COOH (65)

Ethylene, propylene, 1-butene, 2-butene, and 1-pentene can react similarly.85 However, many of these reactions cannot be carried out catalytically, but only stoichiometrically. A challenging goal in CO2 chemistry is the development of catalysts for these conversions. 3.6.2.2. Dienes. In a great number of stoichiometric reactions, 1,3-dienes proved to be more reactive than monoenes. Reactions with dienes are illustrated by that of isoprene:
[Ru]
Figure 16. Linkage modes of isoprene and piperylene with butadiene and CO2.
of the reactions between butadiene and CO2 (lactones), and the octadienyl esters.9,10
H2CdCHsCMedCH2 + CO2 f Me2CdC(CO2H)CH2CHdCMeCHdCH2 + Me2CdC(CO2H)CH2CHdCHCMedCH2 (66)

Apparently, CO2 insertion into the dimer occurs.86 Two esters and a pyrone are formed from allene in the presence of a Pd catalyst as shown below.10
O CH2 C CH2 + CO2
[cat]
OH
+ CO2
[cat]
OH
(68)
+
O
O O O (67)
OH
Ni and Ru compounds catalyze the formation of -lactones, though only in low yield (ca. 6%).10 The large variety of new lactones presented in this section may become of interest as fine chemicals which may be useful, e.g., in the production of fragrances. A great number of natural compounds are known which have a similar lactone structure.10 Both in plants, for instance, the aromatic components of black tea, strawberries, or coconuts, and in animal products, for example, in beef, pork, and butter fat, comparable lactones are found. After alcoholic fermentation, numerous lactones act as flavorings in whiskey, rum, beer, and wine. The application of lactones as herbicides or pharmaceuticals is also under investigation.10 Many attempts of reacting dienes, other than butadiene, with CO2 failed. However, copolymerization of butadiene and CO2 with isoprene or piperylene yielded novel lactones,10 as shown in Figure 16, though the yields were low (around 5%). These products, substituted -valerolactone (lactones of substituted 5-hydroxypentanoic acid) might be interesting chemicals in pharmaceutical industry. Butadiene can also react with CO2 and an epoxide catalytically. The reactions with ethylene or propylene epoxide are shown below. The byproducts are products
Copolymer of styrene and a conjugated diene, hydrogenated in the presence of CO2, is used to introduce a carboxylic groups, predominantly on the diene units (carboxylated polymers). 3.6.2.3. Cycloalkenes. Cyclic methylenecyclopropanes are more reactive than linear alkenes, leading to -lactones by using Pd catalysts.10
[A] CO2 [B]
(69)
[A] CO2 [B]
(70)
CO2 [B,C]
O (71)
O [A] = Pd(dba)2/PPh3 [B] = Pd(dppe)2 [C] = Pd(PPh3)4
(dba = dibenzylidineacetone) (dppe = 1,2-bis(diphenylphosphino)ethane)
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The reaction of unsubstituted methylenecyclopropane with CO2 leads to 3-methyl-2-buten-4-olide in yields up to 80%.10
+ CO2
diols by the promotion of crown ethers; polycarbonates with the structure shown below are the products: 22
nXCH2
CH2X + nKOROK OCOCH2
CO2 crown ethers
CH2OCOOR CH2,
(1)
[Pd]
+ 2nKX
(75)
R= X = Cl, Br
(1)
CH2
C(CH3)2
O O codimer
[Pd]
[1]
(1) O O O O
copentamers (72)
cotrimers O cotetramers O
A number of crown ethers can be used; those having an 18-membered ring were found to give the best results.22 Synthesis of polycarbonates represents, in principle, a method for long-term CO2 fixation as organic polymers.83 Of great interest is the polymerization of propylene carbonate to yield high molecular weight polymers. These should be long lasting and finally biodegradable and should have very large markets.83 These polymers can also be strengthened by inorganic carbonates. It is also possible to synthesize polycarbonates by CO2 reaction with epoxides, which will be described in the following section. Polycarbonates are appealing in the sense that they constitute a type of chemical change of CO2 molecules. The best compound in this respect would be the polycarbonate,
C( O) O
n
3.6.2.4. Alkynes. CO2 can react with alkynes (e.g., 1-butyne, propyne), producing unsaturated organic carbonates. Thus, 1-hexyne reacts with CO2 producing 4,6dibutyl-2-pyrone.10
n-Bu
CO2+ 2n-BuC CH
[Ni]
n-Bu
O O (73)
With other substituted alkynes, substituted pyrones are obtained. Alkynes with internal triple bonds, such as 3-hexyne or 4-octyne, can react similarly, while phenyl and diphenyl acetylene did not react, possibly for steric reasons. Derien et al.87 reported that the incorporation of CO2 into nonactivated alkynes gives R,-unsaturated acids. 3.6.3. Reactions with Other Substituted Hydrocarbons. CO2 is able to react with many other substituted hydrocarbons.9,10,22 For example, reactions with polymers giving carboxy-terminated polymers (functionalization of polymers) were reviewed by Quirk et al.88 The products of CO2 with hydrocarbons may lead to polymers with special properties, carboxylic acids, esters, lactones, etc. Amatore et al.89 reported the electrochemical reaction between CO2 and bromobenzene, catalyzed by NiII(dppe)Cl2 (dppe ) 1,2-bis(diphenylphosphino)ethane), which after hydrolysis leads to benzoic acid nearly quantitatively.
. A higher density of CO2 is not conceivable. We, however, expect that this polymer will not be stable enough under ambient conditions. 3.8. Reaction with Epoxides. CO2 can form copolymers with epoxides9,22,83 under mild conditions catalyzed by organometallic catalyst systems. The product is a high molecular weight aliphatic polycarbonate. The reactions are given below.
[cat]
+ CO2
O O
(76)
+ nCO2
[cat]
OCO O
n
(77)
CH2CHR + CO2 O
(CH2CHROCO)n O
(78)
CO2 + C6H5Br + 2e f C6H5COO- + Br- (74)

3.7. Production of Polycarbonates. CO2 can react with R,-dibromo compounds and the potassium salt of
Many epoxides are copolymerizable. Figure 17 shows some of them.22 Many catalyst systems can catalyze this reaction. It was reported that using aluminum porphyrin catalyst or diethylzinc-water catalyst, the copolymer has a very narrow molecular weight.22 The synthesis of macromolecules with controlled molecular weight is of importance for molecular design of polymeric materials. This reaction has been claimed to be the first example of the synthesis of an alternative copolymer with a narrow molecular weight distribution.9 High molecular weight alternating copolymer of CO2 and propylene oxide or ethylene oxide may be molded to sheets or film by pressing it at 413-423 K.9,83 Low permeability of oxygen is one of the characteristics of this material. Because of the high oxygen content they
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Figure 17. Cyclic ethers for copolymerization with CO2 by an organozinc catalyst system.22
Figure 18. Chemistry based on carbonates.
possess a low heat of combustion and decompose at a relatively low temperature.9 Their highly regular structure is reflected in the fact that decomposition takes place within a narrow temperature range and a simple product spectrum is observed.9,83 The product of the thermal decomposition of CO2-propylene oxide copolymer, for example, at 453 K is exclusively propylene carbonate. The aliphatic polycopolymer was confirmed to be biodegradable, which makes it applicable in controlled release drug systems.9 Those long-lasting biodegradable polymers should have large markets. CO2 can also react with epoxides to form cyclic organic carbonates:10
R CH2CHR + CO2 O
[cat]
Other examples of epoxides that can form cyclic carbonates with CO2 are styrene epoxide and epichlorohydrin (1-chloro-2,3-epoxypropane). The diepoxide of butadiene leads to erythritol (HOCH2[CH(OH)]2CH2OH) dicarbonate. Vinylethylene carbonate is formed from the monoepoxide in the presence of KOH:10
CH2 CH O CH CH2 O C O CH2 + CO2 CH O
[cat]
CH
CH2 polymers (82)
O O
O (R = H, CH ) 3
(79)
Chemische Werke Huls adopted this reaction for an industrial process, and plants using the Huls process were built in Germany and Romania.10 At room temperature ethylene carbonate is a solid which melts at 310 K and boils at 520 K. Propylene carbonate has also an exceptionally high boiling point (516 K).10 These two cyclic carbonates are used as high-boiling solvents for natural and synthetic polymers such as lignin, cellulose ester, nylon, and PVC. The ability of these solvents to dissolve a wide range of substances has led to their extensive use in the production of polyacrylic fibers and paints.10 It is possible to produce vinylene carbonate via chlorinating and subsequently dehydrochlorinating.10
Cl O O O
+ Cl2 HCl
The major applications of cyclic carbonates are illustrated in Figure 18.9 Many useful products, which are otherwise difficult to prepare, can be made from cyclic carbonates. 3.9. Reaction with Alcohols and Ethers. Alcohols can react with CO2 in the presence of a metal alkoxide; the general reaction equation is22
O ROH + CO2
ROM
ROCOH
(83)
Alkyl formates can be produced, catalyzed by several transition metal complexes and tertiary amines under 25 atm of CO2 and H2 at 413 K:22,33
ROH + CO2 + H2 f HCOOR + H2O
R) Me, Et, Pr (84)
O O
HCl
O O
(80)
The reaction for linear carbonates is illustrated by the synthesis of 1,2-propanediol formates from CO2, H2, and propylene oxide.33
CH3 CO2 + H2 + H2C CH3 H 2C HCO O CH + H2C OH CH O CH3 CH + H2C HCO O CH3 CH + H2C OCH O O CH3 CH + H2C O HO CH3 CH OH (81)
Typical catalysts are Pd(diphos)2 and RuH2(PPh3)4, while Et3N is a representative amine cocatalyst.33 Epoxides can be considered as a type of cyclic ethers, whose reactions with CO2 have already been described. Other ethers can also react with CO2. CO2 and ethyl vinyl ether yield a polymeric product containing 23% ester linkage when heated at 340 K with aluminum acetylacetonate or aluminum alkoxide as a catalyst. Vinyl methyl ether gives a copolymer with CO2 when heated at 350 K without any added catalyst.22
CH2 CH + CO2 OCH3 CH CH2
x
C O
CH2
CH
CH
CH2 (85)
y
HO HCO O
CH2
OCH3
OCH3
OCH3
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Table 9. Symmetrical Ureas from CO2 and Amines22 aminea aniline o-toluidine isopropylamine cyclohexylamine N-methylaniline diphenylamine diethylamine
a

Table 10. Yields of Polycondensation of CO2 and Various Diamines22 diamine
NH2 CH2 NH2
yield of symmetrical ureas 85 74 23 27 0 0 0
(%)b
yield (%) 100 100
NH2
NH2
100
NH2 O
2
HOP(OC6H5)2 ) amine ) 50 mmol in 40 mL of pyridine; T ) 313 K; time ) 4 h. b Based on the amine used.
(CH3)2
86
NH2 SO2 NH2
This type of copolymers might be used in the production of blends of poly(vinyl methyl ether) (PVME) and polycarbonates. 3.10. Reaction with Nitrogen Compounds. 3.10.1. Reaction with NH3. CO2 can react with various nitrogen-containing compounds, e.g., ammonia and amines.9,10,22 The best known example is urea production:
100
NH2 NH2
46
NH2CH2 CH2NH2
Using diphenyl phosphate in pyridine at 20 atm CO2 at 673 K for 4 h. Table 11. Examples of the Synthesis of Carbamates22
2NH3 + CO2 f H2O + NH2CONH2
(86)
In fact, this process belongs to bulk chemical production (1985: 42 Mt/y).10 Urea or (alkyl-) substituted ureas can be further reacted to produce derivatives.22 3.10.2. Reactions with Amines and Imines. Aliphatic amines can be carboxylated by CO2; R-amino acids are obtained.22
RCH2NH2 + CO2
H2O2 (30%) 283323 K, HCl D,L-RCHCOOH
(87)
NH2
Ureas can be synthesized from CO2 and various amines with a number of phosphorous compounds in the presence of tertiary amines under mild conditions.
CO2 + RNH2 + HOP(OC6H5)2 O RNHCNHR + C6H5OH + (OH)2POC6H5 (88)
Pyr 313 K
Many symmetrical ureas can be similarly synthesized (cf. Table 9).22 The reaction is influenced by the basicity of the amine and the steric hindrance at the nitrogen atom of the amine; the latter may explain the failure of similar reactions with dialkylamines. Diamine can react further with CO2 with various N-phosphonium salts of pyridine, giving polyurea:9
NH2(CH2)nNH2 + CO2
(PhO)2POH
Ternary copolymerization is also possible such as that of CO2, cyclic phosphonite and acrylic compounds (e.g., acrylonitrile), yielding a 1:1:1 copolymer with molecular weight of ca. 20000.22
O
NH(CH2)nNHCO
(89)
C6H5
P O
+ CH2
CH + CO2 CN O O CH C CN O
n
Table 10 shows some of the diamines that can react in polycondensation reaction.22 Some diamines may form copolymers with CO2 and acrylonitrile (CH2dCHsCN). Thus when heated at 393-433 K in the presence of triethylenediamine, N(C2H4)3N, CO2, and acrylonitrile form a copolymer with the following structure:22
O CH2 CH2 CH2 O CN CH2 CH2 O CN
x
CH2
CH2 O P CH2 C6H5
(91)
CH2
N C O
CH2
CH
CH2 CH CN
1x
(90)
It was reported that various carbamates, compounds with an -O-C(O)-N- bond, can be obtained from the CO2 reaction with amines. Table 11 gives some examples of the cyclic carbamates.22 Reactions may take place between CO2, an epoxide, and an amine, with carbamate and amino alcohol (the decarboxylation product of the former) as the products.22 Table 12 shows some examples.
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Table 12. Examples of Products Formed by the Reaction of CO2, Epoxide, and Amine22 epoxide
O
aminea Me2NH Et2NH n-PrNH2 Ph2NH Me2NH Et2NH n-PrNH2 Ph2NH Me2NH Et2NH n-PrNH2 Ph2NH
carbamate (%) 6 21 15 0 16 24 20 0 42 62 54 0
amino alcohol (%) 15 15 6 0 2 42 21 0 40 5 5 0
a CO , 50 bar, amine and epoxide, 0.2 mol each; 353 K; 22 h. 2 Oligomer of ethylene oxide was formed.
Figure 19. Direct substitution opportunities for CO2 (after Lipinsky).25
Carbamate esters can be prepared from CO2, vinyl ether and amines (dimethyl or diethyl).22
R2NH + CO2 + H2C CHOCH2CH3 R2NC(O)OCH CH3
308373 K 70 h
OCH2CH3
(92)
The extremely high positive values of H and G do not need further comment. Nevertheless, also in this case a process might be feasible by using a combination of O2 and CO2 in a multifunctional reactor such as a membrane reactor. Direct oxidation processes exist in which H2S is oxidized to elemental sulfur: CO2 can substitute also in this case air:92
The reaction products of epoxide and CO2, organic cyclic carbonates, can be used in chemical synthesis; they react with ammonia and several amines, even at low temperatures, to form carbamates:10
R O O O + NH3 R O (93)
2H2S + CO2 f CS2 + 2H2O CS2 + CO2 f S(g) + CO T > 800 K
(96) (97)
CO2 can also be used in the manufacture of COS.93
CH2CHOCNH2 OH
CS2 + CO2 f 2COS
(98)
In the reaction with diamines, di(hydroxyethyl) carbamates are formed which, for example, can react further with urea to form polyurethanes. CO2 can also react with aziridines to form products which possess urethane (H2NCO2C2H5) linkages. The ring-opening reaction is facilitated only by acidic reagents, in contrast to that of epoxides which is facilitated by both acidic and basic reagents.10 The reaction is as follows:
CH2 CO2 + N R CH2 CH2CH2N R
n
CO2 is added to an aqueous solution of thioantimonate in NH4Cl to manufacture antimony pentasulfide.94 3.12. Substitution for Other Chemicals. Many chemicals can be made from CO2, which can substitute other chemicals, that are harmful to the environment. This substitution can be either direct or indirect. The idea of direct substitution is illustrated in Figure 19.25 Urea, a product from CO2, can in many cases directly replace phosgene (COCl2, with an annual market of 8 Mt) in the production of organic carbonates, e.g., dimethyl carbonates, diethyl carbonates, diphenyl carbonates.9,25
O H2NCNH2 + 2ROH O ROCOR + 2NH3 (99)
CH2CH2NCO RO
m
(94)
Ethylen- and propylenimines also react with CO2 to form soluble polymers.22 This type of reactions is undesired, leading to deterioration of the aziridines.90 Aziridines are useful chemicals in paper making industry, textile industry, and waste water treatment. The reaction is often very exothermic which may lead to explosion.90 Sodium hydroxide is often used to inhibit the reaction by neutralizing carbon dioxide in the air. 3.11. Reactions with Sulfur Compounds. Many processes exist for the conversion of H2S in waste streams in a useful product. The most prominent process is the Claus process. Here, part of the H2S is combusted in air giving SO2. CO2 can be used to substitute air:91
The old process using phosgene may result in Clcontaining byproducts.25

O COCl2 + 2ROH ROCOR + 2HCl (100)
2H2S(g) + 4CO2(g) f 2SO2(g) + 4CO(g) + 2H2(g) H ) 578.9 kJ/mol, G ) 494.8 kJ/mol (95)
By using urea, not only is the use of poisonous phosgene prevented but also the production cost is reduced.25 There is a market for dialkyl carbonates as solvents and as chemical intermediates for the production of plastics; e.g., that for dimethyl carbonate is estimated to be about 105 tons per year.31 The synthesis of isocyanates, useful intermediates in the chemical industry, from primary amine carbonates obtained from CO2 (dialkylcarbonates) deserves specific attention. Another example is the use of CO2 in fumigation to replace chemical pesticides traditionally used.15 CO2 is registered at the US Environmental Protection Agency
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Table 13. Reactants and Their Products in CO2 Reactions reactants alkane cycloalkane active-H compd monoalkene dienea cycloalkene substituted hydrocarbonc alkyne epoxide NH3 and amine diamine imines products with CO2 syngas, acids, esters, lactones acids, esters, lactones acids, esters, lactones acids, esters, lactones acids, esters, lactonesb acids, esters, lactones, (co)polymers acids, esters, lactones, polycarbonates lactones, unsaturated organic carbonates carbonates, (co)polymers (polycarbonates) symmetrical ureas, aminoacids, (co)polymers ureas, carbamates, (co)polymers (polyureas) carbamates, (co)polymers (urethane)
as a nonrestricted pesticide. Even an atmosphere of 60% CO2 is sufficient to kill 100% of all insects via desiccation caused by hyperventilation.15 Moreover, insects cannot develop a resistance to it. This application of CO2 is environmentally beneficial. An example of indirect substitution is the replacement of CFCs. When solid CO2 is used to replace CFCs in the in-transit refrigeration,15 not only are the CFCs replaced by the harmless CO2, but also the harmful effect of CFCs on the depletion of ozone layer is reduced. Another example is the replacement of relatively expensive TiO2 ($2000/ton) by cheap CaCO3 ($200-500/ ton) in paint, paper, rubber, and ink industries.25 CaCO3 is one of the most stable carbon compounds, which can be easily made from lime and CO2. This replacement leads to cost savings. Currently, almost half (ca. 0.5 Mt/y) of the TiO2, used in the past in industry, has been replaced by CaCO3.25 This is an example of indirect substitution. Unfortunately, since energy is needed for the decomposition of CaCO3, and this decomposition itself produces CO2, the whole process of CaCO3 production cannot contribute to the reduction of CO2. In fact, one may think of numerous cases, in which products from CO2 may substitute one or another chemicals, directly or indirectly, which make the processes safer, cheaper, or environmentally better. 3.13. CO2 as a Carbon Source. After splitting into carbon and oxygen or after reduction, CO2 can be used as a carbon source in CVD (chemical vapor deposition) synthesis of diamond and carbon fibers95 and in the manufacture of additives for lubricants (by carbonation).96,97 Walker98 reported the synthesis of tar- and ash-free carbon from CO via the Boudouard reaction (reverse reaction of eq 29). 4. Bioconversion CO2 can be converted biochemically or biologically; of course, the most important reaction is photosynthesis:
10
a Allenes and 1,3-dienes. b With longer C-C chain than the original monomer. c Dihalogen substituted.
nCO2 + nH2O f (CH2O)n + nO2
(101)
It was estimated that glucose is formed at a rate of 1 g per hour per square meter of leaf surface and ca. 200 Gt/y of glucose are produced by this process.10 One should realize that this reaction uses atmospheric CO2 with a very low concentration (ca. 0.4%) and solar energy to produce organic fuel substituent with a high selectivity and a high rate at ambient temperature. Until now, none of the man-made catalysts could compete with this catalyst made by mother nature. It was estimated13 that in The Netherlands, each year 475 000 hectares of agricultural land will become free. Taking the capacity of photosynthesis as 3000 kg carbon/ha annually, ca. 3% CO2 emitted can be used in photosynthesis. This example shows that due to the large area of land needed, the capacity of CO2 mitigation via bioconversion is very limited. Of course, efficient agricultural technology might result in the sequestration of larger amounts of CO2.99 5. Concluding Remarks CO2 emission is mainly caused by the combustion of fossil fuels, and the energy sector is the major contribu-
tor to CO2 emission. In a certain sense, the CO2 problem is an energy problem. Saving energy is a direct method of reducing CO2 emission. The increase of the energy efficiency in the energy sector is extremely important in reducing CO2 emissions. The CO2 production from various fossil fuels is per unit of energy quite different. Therefore, an option is to use a higher fraction of natural gas (methane) which produces the lowest amount of CO2. It is not surprising that thermodynamically the conversion of CO2 is unfavorable. Only in special situations CO2 conversion is favorable in CO2 mitigation. In fine chemistry several reactions with a negative Gibbs free energy exist. However, the volumes involved are too modest. In bulk chemistry not so many favorable reactions exist, but here the volumes involved are much higher. The equilibria change when the reaction conditions are changed. CO2-containing gases at severe conditions (high temperature or high pressure) can lead to an attractive process. An example is chemical cooling of hot gases in the chemical process industry. In general, there is an energy penalty with CO2 reactions: energy input is needed for the reaction or for the production of a reactant, for example hydrogen, or electricity. The most ideal energy source is of course a renewable energy, such as solar, wind, tidal, hydro, geothermal energy, and biomasses. An example is using CO2 in methane reforming, coupled with solar energy input.100 Carbon dioxide can react in different ways with a large variety of compounds. The products that may be obtained are, e.g., organic carbonates, (amino-) acids, esters, lactones, amino alcohols, carbamates, urea derivatives, and various polymers or copolymers. The limited number of publications in this research area show that this new territory is still to be exploited. Some of these products are of great technical interest. The major reactions and their products are listed in Table 13. CO2 may be utilized directly or indirectly; the latter refers to the use of reaction products of CO2 as described above. Considering the potential amounts of CO2 to be utilized chemically, the production of bulk products is relevant whereas fine chemicals are not very interesting, because of the low volumes involved. MeOH and other gasoline or diesel substitutes are potential candidates. Moreover, MeOH as engine fuel leads to environmental advantages over gasoline at equivalent
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(28) Mills, E.; Wilson, D.; Johannson, T. In Climate Change: Science, Impacts and Policy; Proc. 2nd World Climate Conf., 1990; Jaeger, J., Ferguson, H. L., Eds.; Cambridge University Press: London, 1991; pp 311-328. (29) Greenhouse Issues 1992, Feb. (30) Takeda, S. Reduction of atmospheric CO2 by enhancing marine phytoplankton productivity: (1) preliminary evaluation of ocean fertilization with iron and other micronutrients, Report no. CRIEPI-U-91049; 1992. (31) IEA Greenhouse Gas R & D Prog.: Annu. Rep. 1993, 6. (32) Behr, A. In Activation of carbon dioxide via coordination to transition metal complexes; Keim, W., Ed.; Catalysis in C1 Chemistry; D. Reidel: Dordrecht, 1983; pp 169-217. (33) Eisenberg, R.; Hendriksen, D. E. Adv. Catal. 1979, 28, 79172. (34) Ibers, J. A. Chem. Soc. Rev. 1982, 11, 57-73. (35) Volpin, M. E. Pure Appl. Chem. 1972, 30(3-4), 607-626. (36) Volpin, M. E.; Kolomnikov, I. S. Pure Appl. Chem. 1973, 33(4), 567-581. (37) Denise, B.; Sneeden, R. P. A. CHEMTECH 1982, Feb, 108112. (38) Yanagihara, N.; Vemulapalli, K.; Fernado, Q. Kidorui 1991, 18, 136-137 (in Japanese). (39) Meyrahn, H. DE 384383; 1990. (40) Weeda, M.; Tromp, P. J. J.; van der Linden, B.; Moulijn, J. A. Fuel 1990, 69, 846-850. (41) Uhlhorn, R. J. Ceramic Membranes for Gas separation, synthesis and transport properties, Ph.D. Thesis, Twente University, The Netherlands, 1990. (42) Geus, E. R. Preparation and characterization of composite inorganic zeolite membranes with molecular sieve properties. Ph.D. Thesis, Delft University of Technology, The Netherlands, 1993. (43) Ichikawa, M.; Oonishi, R.; Musukumaru, B. JP 0418038; 1992. (44) Mamedov, A. Kh.; Mirzabekova, S. R.; Nuriev, Sh. A.; Aliev, V. S. Neftekhimiya 1991, 31(5), 630-636 (in Russian). (45) Aika, K. Use of CO2 in the manufacture of chemicals; The Chemical Society of Japan: Tokyo, 1993; pp 20-32 (prepared for British Coal Corp.). (46) Hattori, T.; Matsumoto, M. Use of CO2, in the Manufacture of Chemicals; The Chemical Society of Japan: Tokyo, 1993; pp 8-19 (prepared for British Coal Corp.). (47) Hattori, T.; Yamauchi, S.; Endo, M.; Komai, S.; Satsuma, A.; Murakami, Y. Catalytic Reduction of Carbon Dioxide by Lower Alkanes. Proc. Int. Symp. CO2 Chem., Hemavan, Sweden 1993. (48) Yuasa, S.; Isoda, H. Proc. 22nd Int. Symp. Combust. (1988) 1989, 1635-1641. (49) Xu, Xiaoding; Doesburg, E. B. M.; Scholten, J. J. F. Catal. Today 1987, 2, 125-170. (50) Bart, J. C. J.; Sneeden, R. P. A. Catal. Today 1987, 2, 1-124. (51) Chinchen, G. C.; Denny, P. J.; Jennings, J. R.; Spencer, M. S.; Waugh, K. C. Appl. Catal. 1988, 36, 1-65. (52) Campbell, C. T. Appl. Catal. 1987, 32, 367-369. (53) Chinchen, G. C.; Spencer, M. S.; Waugh, K. C.; Whan, D. A. Appl. Catal. 1987, 32, 371-372. (54) Klier, K. Adv. Catal. 1982, 31, 243. (55) Ulman, M.; Aurian-Blajeni, B.; Halmann, M. CHEMTECH 1984, April, 235-239. (56) Sullivan, B. P.; Krist, K.; Guard, H. E. Electrochemical and Electrocatalytic Reactions of Carbon Dioxide; Elsevier: Amsterdam, 1993. (57) Ashcroft, A. T.; Cheetham, A. K.; Foord, J. S.; Green, M. L. H.; Grey, C. P.; Murrel, A. J.; Vernon, P. D. F. Nature 1990, 344, 319-321. (58) Vermon, P. D. F.; Green, M. L. H.; Cheetham, A. K.; Ashcroft, A. T. Catal. Today 1992, 13, 417-426. (59) Steinberg, M. The coprocessing of fossil fuels and biomass for carbon dioxide emission reduction in the transportation sector. Prepr. Pap.sAm. Chem. Soc., Div. Fuel Chem. 1993, 38(3), 893-894. (60) Steinberg, M. Energy Convers. Mgmt. 1992, 33(5-8), 3111315. (61) Steinberg, M. The World & I. 1992, Oct, 218-225. (62) Steinberg, M.; Dong, Yuanji; Borgwardt, R. H. The coprocessing of fossil fuels and biomass for CO2 emission reduction in the transportation sector. In Carbon Dioxide Chemistry: Environmental Issues; Paul, J., Pradier, C.-M., Eds.; The Royal Society of Chemistry: Cambridge, UK, 1994; pp 189-199. (63) Steinberg, M.; Dong, Yuanji. An Analysis of Methanol Production and Utilization with Reduced CO2 Emission. Proc. Int. Conf. CO2 Utilization, Sept. 26-30, 1993, Bari, Italy 1993, 127-134.
temperature and average speed (except for formaldehyde emission).68,71,101 Although the knowledge of mankind in biochemistry and catalysis has improved tremendously, photosynthesis is still the most efficient method for CO2 conversion. The development in imitating photosynthesis catalysts will certainly contribute to the reduction of CO2 emission. Using CO2 as a reactant, many useful products can be made. The economy of these processes, besides the price of products and reactants, depends on the source of energy and/or hydrogen and on the development of new active catalysts. Many of the potential technologies are already used. In countries with a (high) carbon tax, the relevant technologies could be implemented earlier. The environmental impact of many of the proposed technologies is unanswered. Possibly, depleted oil and gas fields are attractive options for CO2 disposal though these have their own unique problems and limited applicability. Acknowledgment. We thank NOVEM (Netherlands Agency for Energy and the Environment) for financial support and Braun Consultants in Technology and Management in Hengelo, The Netherlands, for subcontracting us in the NOVEM project. References and Notes
(1) Clark, W. C., Ed. Carbon Dioxide Review: 1982; Clarendon Press: Oxford, U.K., 1982; p 303.
(2) Oman, H. CHEMTECH 1988, Feb, 116-119. (3) Gushee, D. E. CHEMTECH 1989, Aug, 470-479. (4) Xu, Xiaoding; Moulijn, J. A. Shell Venster. 1993, March, 2425. (5) Greenhouse Issues 1992, April. (6) Greenhouse Gases Bull. 1992, 1, May and July issues. (7) Goudriaan, J. Energiespectrum. 1991, Nov, 268-274. (8) Wojtowicz, M. A.; Pels, J. R.; J. A. Moulijn, J. A. Fuel Process. Technol. 1993, 34, 1-71. (9) Aresta, M., Forti, G., Eds. Carbon Dioxide as a Source of Carbon; NATO ASI Series, D; Reidel: Dordrecht, The Netherlands, 1987. (10) Behr, A. Carbon Dioxide Activated by Metal Complexes; VCH: Weinheim, Germany, 1988. (11) de Baar, H. J. W. Chem. Mag. 1990, Nov, 570-574. (12) Herzog, H.; Golomb, D.; Zemba, S. Environ. Prog. 1991, Feb, 64-74. (13) Braun, A. R. Mogelijkheden tot beperking van CO2 in de atmosfeer; VROM-opdracht no.: 661.065-01, 1991 (in Dutch). (14) Ayers, W. M., Ed. Catalytic Activation of Carbon Dioxide; ACS Symposium Series 363; American Chemical Society: New York, 1988. (15) Steiner, R. W. Chem. Eng. 1993, 100(3), 114-119. (16) Shankland, R. V. CHEMTECH 1982, Nov, 684-688. (17) Orr, F. M., Jr.; Heller, J. P.; Taber, J. J.; Card, R. J. CHEMTECH 1983, Aug, 482-487. (18) Shimshick, E. J. CHEMTECH 1983, June, 374-375. (19) Basta, N.; Ondrey, G.; Moore, S. Chem. Eng. 1992, Aug, 3033. (20) Aaltonen, O.; Rantakyla, M. CHEMTECH 1991, April, 240 248. (21) Behn, A. Bull. Soc. Chim. Belg. 1985, 94(9), 671-683. (22) Inoue, S., Yamazaki, Y., Eds. Organic and Bio-organic Chemistry of Carbon Dioxide; Kodansha: Tokyo, 1982. (23) Darensbourg, D. J.; Ovalles, C. CHEMTECH 1985, Oct, 636-640. (24) Sneeden, R. P. A. J. Mol. Catal. 1982, 17, 349-357. (25) Lipinsky, E. S. Utilizing CO2: Complex-molecules from simple waste. Battelle 1992, Jan. 31. (26) Xu, X. D.; Moulijn, J. A. Chemical usage of CO2. Proc. Int. Symp. CO2 Chem., Hemavan, Sweden 1993. (27) Kram, T.; Okken, P. A. Kansen voor alternatieve brandstoffen in het wegverkeer in Nederland tot 2020 onder invloed van de olieprijs, NOx en CO2-plafonds; ESC Report, No. 52; Petten, The Netherlands, Nov. 1989 (in Dutch).
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(64) Loktev, S. M. J. Mol. Catal. 1982, 17, 225-230. (65) Sie, S. T.; Sender, M. M. G.; Wechem, H. M. H. Catal. Today 1990, 8(1), 371-394.). (66) Pettersson, L.; Sjostrom, K. Combust. Sci. Technol. 1991, 80, 265-303. (67) von der Decken, C. B.; Dotsch, H.; Hohlein, B.; Fedders, H.; Riensche, E.; Brockerhoff, P.; Pischinger, F.; Hilger, U.; Barnert, H.; Niesen, H.; Walbeck, M. Energy Alcohols, Production and Application of a Synthetic Liquid Energy Carrier. Institut fur Reaktorbauelemente, Kernforschung sanlage: Julich, Germany, 1987 (ISSN 0343-7639). (68) Sperling, D. New Transportation Fuels: A Strategic Approach to Technological Change; University of California Press: Berkeley, CA, 1989. (69) Haggin, J. Chem. Eng. News 1989, Aug. 14, 25-27. (70) Ember, L. R. Chem. Eng. News 1989, Oct. 30, 17-18. (71) Gray, C. L., Jr.; Alson, J. A. Sci. Am. 1989, Nov, 108-114. (72) Henrici-Olive, G.; Olive, S. Catalyzed Hydrogenation of Carbon Monoxide; Springer-Verlag: Berlin, 1984. (73) King, D. L.; Grate, J. H. CHEMTECH 1985, April, 244251. (74) Greenhouse Issues 1992, July. (75) Kisch, H.; Twardzik, G. Chem. Ber. 1991, 124(5), 11611162. (76) Osaka, H.; Kubo, Y.; Yoneyama, H. J. Chem. Soc., Faraday Trans. 1991, 87(4), 553-557. (77) Matsuoka, S.; Kohzuki, T.; Pac, C.; Yanagida, S. Chem. Lett. 1990, 11, 2047-2048. (78) Dzhabiev, T. S.; Tarasov, B. B.; Uskov, A. M. Catal. Today 1992, 13, 695-696. (79) Klass, D. L. CHEMTECH 1984, Aug, 486-491. (80) Klass, D. L. CHEMTECH 1984, Oct, 610-615. (81) Levy, M.; Lvitan, R.; Rubin, R.; Rosin, H. Energy Res. Abstr. 1990, 15(6), abstr. no. 13042.

(82) Simpson, T. B. Environ. Prog. 1991, 10(4), 248-250. (83) Inoue, S. CHEMTECH 1976, Sept, 588-595. (84) Lapidus, A.; Pirozhkov,S. D.; Koryakin, A. A. Izv. Akad. Nauk. USSR, Ser. Khim. 1978, 12, 2814-2816. (85) Besecke, S.; Schroder, G. DOS 2948888; 1981. (86) Hoberg, H.; Minato, M. J. Organomet. Chem. 1991, 406, C25-28. (87) Derien, S.; Dunach, E.; Perichon, J. J. Am. Chem. Soc. 1991, 113, 8447-8454. (88) Quirk, R. P.; Yin, J.; Guo, S. H.; Hu, X. W.; Summers, G.; Ki, J.; Zhu, L. F.; Schock, L. E. Makromol. Chem., Makromol. Symp. 1990, 32, 47-59. (89) Amatore, C.; Jutand, A. J. Am. Chem. Soc. 1991, 113, 28192825. (90) Kirk-Othmer. Encyclopedia of Chemical Technology, 3rd ed.; John Wiley & Sons: New York, 1981; Vol. 13, pp 142-166. (91) Potapkin, B. V.; Strelkova, M. I.; Fridman, A. A. Khim. Vys. Energ. 1992, 26(1), 63-68 (in Russian). (92) Brown, M. G. Greenhouse Gases Bull. 1992, 1(3), 173. (93) Denisov, E. N.; Globin, V. A.; Imashev, U. B. Khim. Promst. 1991, 9, 543-545 (in Russian). (94) Abdurakhmanov, S.; Artykbaev, T.; Baev, S. A.; Umarova, I. K.; Valiev, Kh. R.; Shuklin, A. M. SU 1623960; 1990. (95) Murata, K.; Sato, K.; Matsumoto, M. JP 0185320; 1989. (96) Chang, Yuehsiung. US 4865754; 1989. (97) Jao, Tze Chi; Powers, W. J. US 4810396; 1989. (98) Walker, D. G. Prepr. Pap.sAm. Chem. Soc., Div. Fuel Chem. 1991, 36(3), 1129-1136. (99) Benemann, J. R. J. Plant Nutr. 1992, 15(10), 2277-2313. (100) Buck, R.; Muir, J. F.; Hogan, R. E.; Skocypec, R. D. Sol. Energy Mater. (Sol. Cells) 1991, 24(1-4), 449-463. (101) Greenhouse Gases Bull. 1992, 1(3), 173.
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Mitigation of CO2 by Chemical Conversion

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Energy & Fuels 1996, 10, 305-325

Energy & Fuels, Vol. 10, No. 2, 1996

Energy & Fuels, Vol. 10, No. 2, 1996 307

280 353 1 1 26000 18000 0.5 1 1 1 55

Figure 4. Carbon sources in the nature.

Figure 3. The CO2 cycle.

Energy & Fuels, Vol. 10, No. 2, 1996

Energy & Fuels, Vol. 10, No. 2, 1996 309

Energy & Fuels, Vol. 10, No. 2, 1996

Aspen was used in calculating the data.

Energy & Fuels, Vol. 10, No. 2, 1996 311

Aspen was used in calculating the data.

Energy & Fuels, Vol. 10, No. 2, 1996

Energy & Fuels, Vol. 10, No. 2, 1996 313

H ) +172.6 kJ/mol CO2

C3H8(g) + 1/2O2(g) f C3H6(g) + H2O(l) H ) -165.0 kJ/mol, G ) -151.0 kJ/mol (37)

2CH4(g) + O2(g) f C2H4(g) + 2H2O(l) H ) -424.7 kJ/mol, G ) -306.3 kJ/mol (36)

Energy & Fuels, Vol. 10, No. 2, 1996

Energy & Fuels, Vol. 10, No. 2, 1996 315

Figure 13. CARNOL process.

Figure 12. HYDROCARB process.

(46) (47) (48)

CO2(g) + 3H2(g) f CH3OH(l) + H2O(l) H ) -137.8 kJ/mol, G ) -10.7 kJ/mol (3)

Hydrogen can be produced by catalytic decomposition of methane at 1273-1373 K:62,63

Energy & Fuels, Vol. 10, No. 2, 1996

Figure 14. Scope of production of chemicals via MeOH-based routes.

CO2(g) + 4H2(g) f CH4(g) + 2H2O(l) H ) -259.9 kJ/mol, G ) -132.4 kJ/mol (4)

nCO2 + (3n + 1)H2 f CnH2n+2 + 2nH2O nCO2 + 3nH2 f CnH2n + 2nH2O

H2 + CO2 + HX f HCOX + H2O

CH3OH(l) + HCOOH(l) f HCOOCH3(l) + H2O(l) H ) -309.5 kJ/mol, G ) -8.5 kJ/mol (57)

Energy & Fuels, Vol. 10, No. 2, 1996 317

CO2(g) + CH4(g) f 2CO(g) + 2H2(g) H ) +247.5 kJ/mol, G ) +170.8 kJ/mol (31)

nCO2 + CnH2n+2 f 2nCO + (n + 1)H2

Moreover, as stated before, in principle, other products may be produced:

CO2(g) + CH4(g) f CH3COOH(l) H ) -13.3 kJ/mol, G ) +58.1 kJ/mol (11)

CnH2n+2 + CO2 f CmH2m+1COOH (m , n)

CO2(g) + C2H4(g) f CH2dCHCOOH(l) CH3CHdCH2 + CO2 f CH2(COOH)CHdCH2

Energy & Fuels, Vol. 10, No. 2, 1996

CH2dCH2 + CO2 9 CH3CH2CO2CH2CH3 + 8 CH3CH2OH + CH3CH2COOH (65)

H2CdCHsCMedCH2 + CO2 f Me2CdC(CO2H)CH2CHdCMeCHdCH2 + Me2CdC(CO2H)CH2CHdCHCMedCH2 (66)

[A] CO2 [B]

O [A] = Pd(dba)2/PPh3 [B] = Pd(dppe)2 [C] = Pd(PPh3)4

(dba = dibenzylidineacetone) (dppe = 1,2-bis(diphenylphosphino)ethane)

Energy & Fuels, Vol. 10, No. 2, 1996 319

CO2 + C6H5Br + 2e f C6H5COO- + Br- (74)

Energy & Fuels, Vol. 10, No. 2, 1996

Figure 18. Chemistry based on carbonates.

CH2 polymers (82)

ROH + CO2 + H2 f HCOOR + H2O

R) Me, Et, Pr (84)

Energy & Fuels, Vol. 10, No. 2, 1996 321

yield of symmetrical ureas 85 74 23 27 0 0 0

yield (%) 100 100

2NH3 + CO2 f H2O + NH2CONH2

CH2 O P CH2 C6H5

Energy & Fuels, Vol. 10, No. 2, 1996

amino alcohol (%) 15 15 6 0 2 42 21 0 40 5 5 0

Figure 19. Direct substitution opportunities for CO2 (after Lipinsky).25

2H2S + CO2 f CS2 + 2H2O CS2 + CO2 f S(g) + CO T > 800 K

CO2 can also be used in the manufacture of COS.93

CS2 + CO2 f 2COS

The old process using phosgene may result in Clcontaining byproducts.25

Energy & Fuels, Vol. 10, No. 2, 1996 323