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Energy & Fuels 1996, 10, 305-325


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


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

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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 µeinstein 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 today’s 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 CO2‚nH2O, 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

3 270 290 190 6 CFC-11 0 28 × 10-5 60 12400 4500 0. Further large sources constitute power stations and industry.4 0. CaCO3.15 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. 1. production of ethanol by fermentation. Carbon is the precursor of CO2. and production of bulk chemicals such as ammonia and ethylene oxide.10 Figure 4 shows the distribution. in particular. heating of homes and transport. is the most abundant carbon-containing mineral. Carbon and/or its compounds are present in all segments of the planet earth. 1996 307 Table 1. Also quantitatively important is the inorganic industry. Figure 4. ankerite (Ca(Fe.9 63 21 09 15 N2O 0. it is clear that carbon present as CO2 in the atmosphere still will be a small fraction of the total carbon inventory.3 0.5 1 1 1 55 Figure 2. Electric power generation is the largest source of CO2 emission in industry. Carbon sources in the nature. No. Natural Carbon Sources. It contributes to around 25% of the global CO2 emission and is responsible for 14% of the estimated global warming in the 1980s.1. Inventories and flow rates of CO2. The amount of carbon present in the atmosphere is relatively very modest. notably for the production of cement. Potential of Selected Gases To Contribute to the Greenhouse Effect8 CO2 CH4 0. CO2 Emission Sources. 10.310 150 206 270 6 8 0. MnCO3. By far the most part of carbon is present as terrestrial carbon.Mg)(CO3)2).288 0. and exhaust gases from cars. . The major examples of dilute CO2 sources are flue gases from electric power generation and the blast furnace. Vol.13 Major CO2 emission comes from private sources. magnesite (MgCO3).095 4 4500 3500 1500 CFC-12 0 4. Other important minerals containing carbon are dolomite (CaMg(CO3)2). Table 2.2. Also heating of public buildings and industrial transport are among the major CO2 emission sources.8 1.9 The numbers in rectangles represent the inventories and the other numbers the flow rate (net values. The CO2 cycle. FeCO3.9. including oil refineries. trucks.Reviews Energy & Fuels. Even when the amount of fossil energy resources would be diminished significantly due to the consumption. Examples of the latter are plants for processing of natural gas. except the quasi equilibrium atmosphere T ocean). In fact calcite. CO2 sources can be subdivided in concentrated and diluted streams.14.72 10 21 58 300 150 0. This figure could grow to 30% by the year 2030. and ZnCO3.84 × 10-6 130 15800 7100 0. 2. 1.17 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. and buses. Figure 3. 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.

1% (ca. aromas and essences (Eisenbach. Supercritical CO2 extraction is also a major use of CO2 at present.10. the exhaust gas contains 13 up to 27% CO2.g. Due to the high expenses in enrichment and separation.10. and Canada. 1996 Table 3. salicylic acid. CO2 from flue gas of power stations has hardly been used as a source for CO2. According to the European Union.g.. USA. Vol. in the cosmetic industry to extract fats and ethereal oils. the use of supercritical CO2 is environmentally beneficial..3. Also. 0.10. less energy is consumed if supercritical CO2 extraction is used. and the use of renewable energies.14.9 The shaded area refers to the expected increase in usage. in food reservation.7-1. 2. the CO2 emission should be brought back to the level of 1990 in the year 2000. pp 371388 and the references therein). To our knowledge. reduction of the amount of CO2 produced. in the extraction of soybeans and hops. and in food industry to isolate spices. The increase of energy efficiency of the primary energy carrier is the most important in reducing CO2 emission. supercritical CO2 may replace. only one pilot plant (100 ton/day) was tested in USA for the separation of CO2 from flue gases of energy sector (Chapter 1.14-25 It should be borne in mind that on the one hand the former use does not contribute directly to the reduction of CO2 emission.5 Mt/ y). lead or barium carbonates). No. etc. especially burning of tropic forests. It is also used as an acid in water purification or in neutralization processes.308 Energy & Fuels. compared with other options.4. viz. the Solvay process). Moreover. 1. solvents which contribute to global warming. ref 14). W. in fact. The long-term objective is to achieve a balanced CO2 production and uptake.15 This replacement is important in combating the greenhouse effect as well as the ozone depletion problem. Increase of the Energy Efficiency or Shift of Primary Energy Source.1. CO2 is a reactant.9. natural gas (CH4). O. 14 enhanced oil recovery (EOR). it is used as a protective gas (in chemical or steel industries.9. 10.15 It is used in the production of decaffeinated coffee..15 CO2 used in EOR (ca. it is used in the synthesis of urea. In the other category. in pharmaceutical industry to recover active substances. and supercritical (SC) CO2 extraction and cleaning. In a sense.9. to substitute CFCs.14. also aim at stabilization of CO2 emission at the level of 1990 in 2000. Deforestation.0% of the CO2 produced is used at present.. only 0. Present Applications of CO2. Moreover.14 especially in refrigerated railcars or trailers. and -662. in welding. Totally. Major uses of CO2 in USA. e.g.) and even as fire extinguisher.20 Dry ice (solid CO2) is used in refrigeration (1. ics or CFCs. it is consumed in biomass production and in greenhouses to stimulate the growth of plants. The Netherlands aims at stabilizing CO2 emission in 1994-1995 and at achieving a reduction of CO2 by 3-5% by the year 2000. and storage of CO2.21 In inorganic chemical industry.e. but on the other hand. e. the ∆H values for the combustion of carbon (graphite). The first category. 2. 2. This is rather low for a profitable process.g.15 Presently. and C2H4 to water and CO2 are respectively -393.3 kJ/mol carbon. the CO2 problem is an energy problem. Other countries. Targets of CO2 Mitigation. the type of fossil fuel used is important. it is used to manufacture Na2CO3 or NaHCO3 (e. The consumption in the production of chemicals is in the order of 0.10. often lead indirectly to CO2 reduction. it is economically feasible in many cases. 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 .9...10.9 Most applications are nonchemical. much less CO2 is produced when fossil fuels other than carbon are used. i. The latter will. 50 Mt/y). and cyclic organic carbonates. For example.15 Figure 5 shows the major applications of CO2 in USA. volatile organ- Figure 5. CaCO3. This application is expected to grow in the near future. 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 Reviews The present CO2 sources used in the US industries are quantified in Table 3. In this sense. usage of CO2. 6-7 Mt/y)14 represents one of the largest potential applications of CO2. includes the beverage industry (ca. three strategies are possible.15 Its favorable diffusion properties are the basis for application as blowing agent in polymer processing industries. methanol. energy saving.9.14-17 The benefits of using CO2 in EOR stems from the reduction of the viscosity due to mixing with CO2. e. and respiration of living matters also lead to dilute CO2 sources which nevertheless contribute significantly to the global CO2 emission. making use of its physical properties. and other carbonates (e. ref 9. in spray painting. Because CO2 is a safe gas. but due to the extra amount of oil produced. Japan.. It does not lead to a consumption of CO2 eventually.9. consumption of other materials might be decreased.g.1. Possible Strategies of Reducing CO2 Buildup in the Atmosphere In principle.75 Mt/y). 1. -929. In some cases.. CO2 usage can be divided into two groups: those using the physical properties and those using the chemical properties.9.14.14. In organic chemical industry. many power stations in the world are using coal as the energy source. It is also used as a pesticide to kill insects in fumigation.

especially seas and oceans. 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. It has even been suggested to add nutrients such as iron to ocean surface water for increasing the production of microorganisms. Aquifers. requiring 26-31% of the coal heating value. it remains to be seen if this storage can provide a longterm fixation of CO2.2. It can be achieved by increasing microalgae biomass or by fixing CO2 as CaCO3-like coral reefs. (ii) gas/solid adsorption systems.1. membrane technology might well be the basis for feasible CO2 separation processes. It is possible to store a large amount of CO2 into those underground reservoirs6 (total capacity estimated to be ca. Of course. 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. 1996 309 emission. they will be converted into SOx and NOx compounds. Therefore. in the case of flue gas from coal-fired plants. Depleted oil or gas fields are often porous. Storage or Disposal of CO2. due to the relatively low CO2 concentration. When a breakthrough occurs in the near future. CO2 Storage in Aquifers. Moreover.3-1. which in turn can be used as a CO2 adsorbent or calcium source. two-thirds of the world’s CO2 production due to human activities. for obvious reasons.12 For practical applications. by using monoethanolamine. as stated before.3.31 These quantities are very high. due to its low concentration.. 3. The costs are of course dependent on the source. However. 10. 2. CO2 may also form (bi)carbonates or it may dissolve in water or it may form clathrates.2.2. For USA. although the ecological impact of injecting large amount of CO2 into sea and ocean water is still uncertain.8 Gt of C/y. it was estimated that in the shallow sea banks near Japan. Introduction. and (iv) membrane separation technology.Reviews Energy & Fuels. however. the CO2 consumed to form carbonates may amount to 3% of the CO2 emitted by that country.g. In the above. lime can be obtained. (iii) cryogenic (fractionation) techniques. This generates additional costs. applications were summarized based on the physical properties of CO2. the separation will be expensive. CO2 is one of the cheapest and most abundant carbon-containing raw materials in the world. Moreover.11-13 (cf. there are various sulfur and nitrogen compounds in the coal.2. Separation by solvent absorption systems (e. or even to 3000 m.7 Gt of carbon.30 CO2 can be injected into 700-1000 m. this option might be of limited value. the usage of CO2 in these exhaust gases. If the best available technologies were used this would increase to about 60%. emission of CO2 would be halved. However. Thus. Figure 2). In the next chapter the potential application as a chemical feedstock is discussed systematically. Underground CO2 Storage. 2.5 The air separation/flue gas recycling process is reported to be the most energyefficient process analyzed. In many countries. Although combustion of fossil fuels is responsible for ca. 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).23 However. 2. CO2 can be utilized in a large number of processes. Chemical Reactions of CO2 3.28 It has been claimed that an increase of the end-use efficiency and the use of renewable energy sources in Sweden’s district heating and electricity sectors can result in 35% emission reductions and a net benefit of US $40/ton by the year 2010. CO2 has to be captured and separated or at least the exhaust gases have to be enriched.27 It can be estimated that replacement of oil by CH4 may result in 25% reduction of CO2 emission. 80-300 Gt of C in exhausted gas wells and 40-200 Gt of C in exhausted oil wells). from a practical point of view. No. these numbers are obviously prohibitively high. However. this would amount to 0. the correctness of these predictions remains to be proven.28 Of course. In recent years the potential application of CO2 as a chemical feedstock has received a lot of attention. it is a wise policy to diversify the use of energy sources. Usage of CO2. which considerably adds to the cost of the process. Vol. it has been estimated that carbon emission reduction of 10% is possible. which are usually catalyst poisons in downstream chemical processes. For instance. Examples are the following. and subarctic Pacific have a potential extra uptake of 2. In principle. Membrane technology is basically in the early stage of development. iron or calcium. the fraction of CO2 emission reduction achievable is much larger than most other routes. in practice. deep ocean water (as liquid CO2). constitute an important CO2 sink and buffer9. During coal combustion. from decomposition of CaCO3. It was also suggested to use large quantities of natural underground brine deposits to store CO2. As to the formation of coral reefs. proposals have been formulated to reduce CO2 emission and economic evaluations have been made. The other processes studied require over 50% of the coal heating value.3.. According to some authors. MEA) or by membrane technology appears to be the most viable technique. the amount of CO2 that can be stored additionally is in principle vast.1. Of course. and the resulting cost of electricity production increases by over 80%. This approach appears less practical due to the lack of a large calcium source.7. equatorial Pacific. 2.12 An exception might be those exhaust gases that are at a high temperature. Moreover. e. For any process aimed at reducing the emission to the atmosphere of CO2 produced.26 Currently electricity is produced at 30-40% efficiency. can be provided in a sensible way. it is not clear how the cations. 2. while the CO2 recovery is close to 100%. Several separation technologies are available:29 (i) gas/liquid scrubbing systems. 2. It is important to point out that this is a route that leads to direct and efficient reduction of CO2 emission. CO2 is rather inert and its .g. often is economically less feasible.11 storage in oceans is an important method to combat the CO2 problem. It was estimated that the Antarctic Ocean.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%). CO2 Separation.9. It is needless to say that such a process does not lead to a reduced emission of CO2. the cost of such a process was estimated to be in the range of $15-100/t of CO2.2.

10.2 -115.0 +26. 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. It is interesting to compare CO2 with CO because often CO2 is present mixed with CO or it is (partially) converted into CO. these data might lead to a too optimistic view. thermodynamically not favored. 1996 Reviews Table 4.9 +172. Thermodynamics. when the Gibbs free energy ∆G° is considered it is clear that most of these reactions are associated with highly positive ∆G° values and.0 -134. Of course.8 -217. or reactions leading to products containing C-O bonds. It is no surprise that these reactions are associated with highly positive ∆G° values and are.3 +176.1 +46.8 +88.2 +58. Of course also CO2 reactions with a positive ∆H° do exist.6 -103. 2.2 -56. as a consequence. Tables 4 and 5 refer to exothermic reactions.4 +85.9 -31. So. The reason for the relatively favorable values of ∆G° for hydrogenation reactions is that water is produced. Vol.1. When producing a certain compound. In . reactions are energetically highly unfavorable.2 +170. as a consequence. in fact.4 +30. Table 6 gives some examples. 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) +152.1.3 +46.0 +208.8 -12.6 +235.9 -39.1 -166. none of these reactions is favorable for CO2 mitigation. 3.6 -44. in principle the first problem can be solved by developing a good catalyst. In the following it will be shown that this is in general true.1 +247. Table 5.9 ∆G° (kJ/mol) -29. the Gibbs free energy values are less favor- able: they are all more positive than the corresponding ∆H° values.9 +6.6 -10.7 -132.3 -14. However.6 -82.9 +15.8 -135.9 +209.6 a Aspen was used in calculating the data.5 +58. only a few reactions have both negative ∆G° and ∆H° values.6 ∆G° (kJ/mol) +34.6 -6. but when certain special conditions exist (high T or P. No.3 -264.8 -259.22 Although many exothermic reactions of CO2 (and CO) do exist. Upon closer examination of Table 4 it is apparent that all cases where ∆G° < 0.9 +7. it appears that for all the reactions in Tables 4 and 5. ∆H° and ∆G° values for some exothermic CO reactions are shown.1 +74.2 -63.5 -223.6 -49.9 -25. 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) -31.21-23 At first sight it might be surprising that so many exothermic conversions exist in view of the high stability of CO2. correspond to hydrogenations.8 -63.2 -96. The second point is of thermodynamic origin and not solvable by catalysis.8 +189. as a consequence. As hydrogen has to be produced at the cost of energy input.8 -26.6 -24.9 Aspen was used in calculating the data.7 +178.0 -13.310 Energy & Fuels.3 +119. In Table 5. Table 6. the penalty for breaking of these bonds does not exist.3 -38.7 -137. not favorable.4 -164.0 a Aspen was used in calculating the data.0 ∆G° (kJ/mol) +177.4 +51.1 -21. need for CO2 for chemical reasons) a practical process might be feasible. “free” energy available.6 -171. Table 4 shows the ∆H° and ∆G° values for several interesting exothermic CO2 reactions.6 -129.0 +25.5 +46. it is interesting to compare CO and CO2 as potential feedstocks. Inspection of the reaction equations reveals that no C-O bonds are broken and.6 -70.0 -11. In Table 5 also a few reactions with negative ∆G° are given which do not invlove hydrogenation.4 -221.6 -88.

9 -63.6 -217. whereas H2O is “free”. Vol. the endothermic reaction occurs while the heat of reaction is produced by the exothermic oxidation. many chemical reactions using CO2 are thermodynamically feasible. At all pressures ∆G is negative and as pressure increases it becomes more negative. reactions do exist in which no C-O bonds are broken. Heat might be available without cost so that chemical cooling is feasible. in the formic acid production in the former case H2O is consumed whereas in the latter case H2 is the reactant. It appears that as temperature increases the Gibbs free energies for the respective reactions change from positive to negative. in methanol production. There might be a surplus of hydrogen without an attractive outlet. and amines producing formamides. Figure 7.0 -134. thermodynamically.Reviews Energy & Fuels.6 ∆G° (kJ/mol) +34. In summary. At 900 K the reaction between CO2 and CH4 giving synthesis gas is associated with a ∆G° value of zero. For example. i. So.3.8 -115. In the latter case. endothermic and exothermic reactions are carried out simultaneously and. Gibbs free energy for CO2 hydrogenation to methanol as a function of reaction pressure.. Coming back to the comparison of CO and CO2.4 -31.2 +25.0 -24.6 -135. From a thermodynamic point of view. For the reaction between CO2 and C2H6 this applies at 800 K. Figure 6. 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 6 shows the ∆G° value for the reaction CO2(g) + 3H2(g) ) MeOH(l) + H2O(l) as a function of the total pressure. H2.8 -25. be it H2 or a hydrocarbon. the ratio can be tuned without the necessity to carry out a separate water gas shift. This class contains reactions with favorable ∆H and ∆G values.. at favorable conditions. as is done in partial oxidation. 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. It is obvious that the reaction enthalpies for the production of the same product from either CO or CO2 are comparable.6 Aspen was used in calculating the data. 10.3 +15. in many practical applications steam reforming of CH4 gives the wrong ratio (3:1). in many reactions a coreactant is present. However. too much H2. A similar situation has been found for the reaction between CO2. As this will lead to cooling of the mixture the term “chemical cooling” has been used. 2. The production of H2 requires energy. In practice favorable conditions (T. 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. it is appropriate to state that when the total production process is considered CO is much more favorable than CO2. Figure 7 shows the influence of temperature on the reaction of CH4 and C2H6 with CO2 to syngas. .2 -223. when CO2 is available at high temperature (>800 K) a reaction with CH4 or C2H6 is possible.8 -137. The former reaction is called “dry reforming”. although CO2 is the end product of energy-producing processes such as combustion. 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). CO2 can be present at very high temperature or pressure. i.8 +6. (2) 2CO2(g) + C2H6(g) ) 4CO(g) + 3H2(g).e.1 -10. It is obvious that the energy required is provided by the coreactant. pressure) can be chosen or. for instance hydrogen which reacts into water. When CO2 instead of H2O is used. The chemistry of a desired reaction might require CO2. reactions can be coupled. although in most cases CO is favored compared to CO2. Gibbs free energy as a function of reaction temperature for (1) CO2(g) + CH4(g) ) 2CO(g) + 2H2(g). thermodynamically.8 -131. it is clear that in general for a useful application of CO2 a special condition must exist. the reaction becomes more favorable.e. for example. Table 7 enthalpy and Gibbs free energy changes of some interesting and relatively favorable reactions starting from CO or CO2 are compared. Examples are the following.6 -82.7 -29.23 Also. No. Many process streams do exist where this principle might be used successfully. The stability of water is the reason that overall ∆G° becomes negative for many hydrogenation reactions.4 -129. 1996 311 Table 7.

it is used to prepare carbonates of La3+.21. Compared with air or oxygen. Various useful products. fine chemicals. and Na2CO3. pure carbon coordination (I). CO2 Reactivity. However. NaHCO3.g. CO2 can be viewed as an oxygen carrier. In some cases. Utilization as an Oxidizing Agent. in purification of water from swimming pools.g. In principle. Vol.2. the yield was reported to be >95%. Dy3+. Figure 10. It is a clean acid.35. Gd3+. Figure 9).. Utilization as an Acid. This weak acidity can be used in neutralization processes. 3. 10. it is less harmful or even harmless to the enzymes used in processes involving microorganisms or enzymes.312 Energy & Fuels. Due to its weak acidity.15 Of course. H2SO4 or HCl. Other features of CO2 chemistry make use of its acidity and oxidizing abilities. e. Eu3+.10 Development of suitable catalysts represents a major challenge for the catalysis community. or vice versa. the CO2 molecule prefers to adopt either a mixed carbon-oxygen coordination (III) or a pure oxygen coordination (II) to the metal center.14 it is slightly acidic. it does not lead to environmental problems associated with strong acids.37 3. Figure 11. these applications. a better selectivity to intermediate oxidation products in chemical industry. The acid properties of CO2 can be improved by converting it in an organic acid.3. CO2 can be used as an oxidizing agent.14 Coordination to metal centers may lead to further chemical reactions. e. the formation of S-CO2. Figure 9.38 At a temperature of 300-320 K and a pressure of 70-250 bar. 1996 Reviews Figure 8. many of the reactions are stoichiometrical. either as bicarbonate or carbonate. e.24. in general. Numerous reactions exist in which.g. intermediates in pharmaceutical and food industries can be produced. if they may lead to industrial processes.15 e. and often the reactions involve difficult conditions. 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.10 As shown in this figure. when it is dissolved in water.39 Although it might be thought that this is due to a different reaction kinetics.37 Figure 11 shows some possibilities. in principle. it has been reported that flue gas from coal combustion can be used directly for neutralization purposes without purification or concentration. CO2 is used to prepare various carbonates.10. The use of CO2 in neutralization has its merits. it is mainly caused by the lowering of the temperature. Examples of the use of CO2 as oxidizing agent are given later on. Possible routes of interaction between CO2 and a substrate (S) on a transition metal (M). M2O3.15 In this type of applications low cost technology is a must. Recent results indicate that. Indeed.15 Moreover. No. Besides CaCO3.9. However. CO2 can replace oxygen or air in oxidation processes. and mixed oxygen-carbon coordination (III).1. and Ho3+ by reacting an aqueous solution of the corresponding oxide.10 3. followed by CO2 insertion.32-34 A large number of studies in literature describe the coordination chemistry of CO2. the pH value it can reach is limited (from pH of 12-13 to 6-9). 2. a high concentration of CO2 is not needed and an application of CO2containing exhaust gas might be feasible without prior separation step. Possible interactions between CO2 and a substrate (S) on a transition metal (M) are schematically shown in the Figure 8. Stoichiometric and catalytic reactions involving CO2 and alkanes or alkenes. There are three possible bonding modes for CO2 (cf. CO2 is a mild oxidizing agent.2. only consume very small amounts of CO2 (typically . formic acid. can proceed either via S insertion. CO2 as an oxidant. this use may have beneficial results. due to the coordination to the active center (M).. Various modes of CO2 coordination to a metal center.36 Figure 10 illustrates the wide variety of metal-mediated reactions in which CO2 can take part. They would never lead to substantial reduction of CO2 content in the atmosphere. Catalysis will play a crucial role in CO2 conversion reactions. requiring expensive organometallic complexes. product between CO2 and a substrate S.22. with supercritical CO2. the activation energy might be lowered for the reaction.10... below 10-100 kt/y). CO2 is an acidic oxide. Nd3+.15. Sm3+. for most applications coal gas is too dirty to apply as acid and purification is absolutely necessary. namely. pure oxygen coordination (II).g.

∆G° ) +130. Oxidative Dehydrogenation of Hydrocarbons. CO and cracking products. It is. a valuable product is produced.44.g. If high-temperature CO2 is used in the oxidation of alkanes. and water. where a large gas flow containing 15% CO2 and H2O has to be cooled from ca. which is a mild oxidant.44 PhCH3(l) + CO2(g) f C6H6(l) + H2(g) + 2CO(g) ∆H° ) +210. in general. which gets sticky above 1100 K. It was interesting to find that the presence of CO2 suppresses cracking products and deactivation of the catalyst by coking.g.1 kJ/mol.1. Indeed. all carbonaceous materials can be gasified into CO which is a useful product. Y. ∆G° ) -151. Carbon Gasification. Total combustion occurs. we think that in the near future membrane separation by inorganic membranes will probably provide the possible route to use high-temperature CO2.42 3.2.. at present. 1996 313 3. ∆G°1098 K ) 70. ∆G° ) -306.Reviews Energy & Fuels. one of the undesired byproducts is CO2. the heat of reaction needed is provided by the formation of H2O. As the former are highly endothermic and the latter highly exothermic. not even at 1098 K.0 kJ/mol CH4 (32) The thermodynamic data show that the equilibrium is not favorable.0 kJ/mol (37) Essentially. also ethylene. 2CH4(g) + O2(g) f C2H4(g) + 2H2O(l) ∆H° ) -424..5 kJ/mol (35) This reaction might be a good example for a process based on a membrane reactor. no technology is available to separate CO2 from the flue gas at high temperature. When the CO2 source is at high temperature. the reaction proceeds at 673 K over a Pd-La2O3-Al2O3 catalyst to give benzene with 90% selectivity. it is no surprise that selectivities in combination with high yields are disappointing up to the present.0 kJ/mol. Oxidation of Alkyl Groups in Aromatic Compounds. CO2 production is suppressed. 1900 K to 1100 K. the reactions are much more favorable.2 kJ/mol. 10.47 Usually air is used. though rather highly endothermic.or Zn-doped H-ZSM-5 catalysts.3. One may also think of using CO2.45 although its activity is still too low for practical use.3 kJ/mol (39) It is clear that all these CO2 based oxidative dehydrogenation reactions are thermodynamically unfavorable. to a significant extent. This reaction.45 The desired reaction usually is C2H6(g) + CO2(g) f C2H4(g) + CO(g) + H2O(l) ∆H° ) +842. ∆G° ) 105. 673-873 K. Vol. No. A modern example is gasification of waste material. It is a crucial reaction in coal gasification. If carbon is reacted with CO2. the selectivity for ethane and ethylene in oxidative coupling of methane can be enhanced. “chemical cooling” (use of its chemical potential) is possible.47 that CO2 can be used in the dehydrogenation or aromatization of lower alkanes (e. An alternative is the use of CO2 rather than O2: C3H8(g) + CO2(g) f CO(g) + H2O(l) + C3H6(g) ∆H° ) 118. or alkenes are the products. CO. difficult to reach high selectivities in oxidative dehydrogenation. 2. It is sometimes defended that for coal utilization underground gasification is the technology of the future.41.45 Moreover. has potential merits.3. Alkylaromatic compounds can react with CO2 in the presence of catalysts containing Pd and oxides of La. of propane) over Ga. and H2 are produced. a mixture of O2 and CO2 might lead to a feasible process.5 kJ/mol (38) In the reaction using K-Cr-Mn on silica catalysts. Because of the large scale. lower alkanes. e. in general.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. and the intermediates are much more reactive than the reactant. The alternative is to add heat from an external source or to start with a high-temperature reactant.7 kJ/mol CH4.7 kJ/mol. the heat required is produced by partial oxidation of the coal. Ethane was reported to be active in the dehydrogenation by CO2 over the same catalysts. It was reported46.46. Carbon gasification is also carried out in the manufacture of active carbon to obtain the desirable porosity. Sm. Alkanes can be dehydrogenated (aromatized) into aromatics. Although.3. Another example is the oxidative dehydrogenation of propane into propylene:46. It is not illogical to expect that use of CO2. PbO/ MgO catalyst was considered to be the best system studied so far. it was reported that by using CO2/O2 mixtures instead of oxygen. Underground coal gasification is studied on a scale near to demonstration scale.2 kJ/mol. may lead to higher selectivities in this type of reactions. because it is to be used in the reduction of iron ore. When CO2 is used instead of air or oxygen. CO. and Ce to give dealkylated derivatives and synthesis gas.6 kJ/mol CO2 (29) This highly endothermic reaction is widely carried out. CO is obtained in the reverse Boudouard reaction: CO2 + C ) 2CO ∆H° ) +172.e. i. In fact. Another example is already shown in Figure 7. This reaction is not limited to coal. ceramic membranes have been developed which can be used for gas separations at much higher temperatures. As complex radical chain reactions are involved. An example of using CO2 in chemical cooling is an advanced iron ore reduction process. CH4. 3. which is normally carried out autothermally. than the polymer membranes.43 For toluene and CO2 (1:1). An example is the oxidative coupling of CH4 which has drawn a lot of attention. the potential amounts of CO2 involved are enormous. Hydrocarbons can be dehydrogenated in several ways.3.3 kJ/mol (36) . ∆G° ) +120.47 C3H8(g) + 1/2O2(g) f C3H6(g) + H2O(l) ∆H° ) -165. in contrast to O2-based analogous processes.44-47 An often applied method is oxidative dehydrogenation. CO2(g) + 2CH4(g) f C2H6(g) + CO(g) + H2O(g) ∆H°1098 K ) 196.

where the catalyst is based on copper. is used to generate energy under special conditions. these reactions are very fast and highly exothermic.3. (2) direct hydrogenation into useful products. e. adipic.4. These processes are promising since they use renewable energy. formic acid.7 kJ/mol.7 kJ/mol. WGS reaction: CO(g) + H2O(l) f CO2(g) + H2(g) ∆H° ) +6. steam gasification of coal C(s) + H2O(l) ) CO(g) + H2(g) ∆H° ) +178.56 Some can be used as a building block in C1 chemistry.56 in most cases.58 (“dry reforming”) CO2(g) + CH4(g) ) 2CO(g) + 2H2(g) ∆H° ) +223.50 3. succinic.33.49-51 The economic feasibility of many processes depends strongly on fuel prices. e.g.9..22. The selectivities reported are not high.314 Energy & Fuels. in special cases. dicarboxylic acid. Oxidation or Combustion of Metals. So. The use of CO2. HOOC-(CH2)n-COOH.g. 1996 Reviews 3.54 and synthesis gas without CO2 and H2O deactivates the catalyst by reducing copper essentially to Cu0... methanation.5 kJ/mol (41) Actually. ∆G° ) +100.2 kJ/mol CO. Vol. followed by reactions of the class of C1 chemistry.4. hydrogen is the most commonly used reducing agent. and (3) reactions to other products via MeOH. in space ships. 2. which is the most commonly used. With respect to catalytic reduction of CO2 or CO. we conclude that only when cheap electricity is available. It is also successfully used in applications where the reducing capacity of a gas flow has to be decreased. Moreover. with n ) 0. are well studied and technically viable and. a syngas mixture with a H2/CO ratio of 3 is produced. which belong to the class of so-called C1 chemistry. CO2 reforming of CH4. reactions directly aimed toward CO2 reduction are treated separately. An example is MeOH synthesis. 2 which is usually achieved via the water-gas shift (WGS) reaction (45) or partial oxidation. Several routes can be proposed to use CO2 in hydrogen reduction: (1) conversion to products via synthesis gas. CO2 is added to the reactant mixture in order to prevent the complete reduction of Cu oxide to metallic copper.55. the major products obtained are hydrogen. etc.1. 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. steam reforming of methane H2O(l) + CH4(g) ) CO(g) + 3H2(g) ∆H° ) +229. e.4. Regardless of the route.8 kJ/mol (31) partial oxidation of methane CH4(g) + 1/2O2(g) ) CO(g) + 2H2(g) ∆H° ) -59. as a consequence. Combustion of metals. ∆G° ) -257. Mg or Li. The latter is not desired because in that case expensive hydrogen is converted into water. In some cases. electrochemical processes can be attractive. formaldehyde. in catalyst calcination. the synthesis of . methanol.14. 4. a mild oxygen carrier. more complex molecules..48 CO2 is used. Fischer-Tropsch reaction. the productivity of catalytic chemical reductions is much higher than that of the corresponding electroreduction. to prevent the active phase from oxidation to too high an oxidation state or in special treatment. favorable conditions are present for a runaway. in the partial oxidation of methane. The byproduct formed in oxidation reactions is either CO2 or water. CO2 can be converted first to synthesis gas. Electrochemical Reduction. 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). CO. while the other two reactions produce syngas with a H2/ CO ratio of 1. 3. methane reforming with CO2 is clearly a largely applied reaction in industry.7 kJ/mol (44) It should be mentioned that in steam reforming of methane (eq 40). respectively. ∆G° ) -19. the ratio should be ca. in the manufacture of uranium fuel particles. Synthesis gas can be produced via several reactions.35. Conversion to Products via Syngas Route.55.49-54 The optimal oxidation state has been suggested to involve slightly oxidized Cu or Cu+. 3.4. It is interesting to analyze the reactions occurring in terms of the products obtained.5 kJ/mol CH4.2.g. oxygen. e.2.4.48 When using oxygen.3 kJ/mol CO (43) So. In all these examples. Electrochemical reduction can be carried out catalytically or noncatalytically.g. Reduction of CO2. is in this respect preferable over that of air. Electrocatalytic reduction deserves further study since it increases the efficiency of the process. CO/ H2. ∆G° ) +161. It should be pointed out that most products from electrochemical reduction can also be made by catalyzed chemical reduction routes.5 kJ/mol (40) CO2 reforming of methane57. and. The WGS reaction is a crucial reaction in ammonia and MeOH synthesis. economically feasible.9. 2. Although the previous paragraphs.7 kJ/mol. an overpotential is needed for the reaction to proceed. deal with reactions in which CO2 is reduced. 3. forming large amounts of CO2. MeOH synthesis. partial oxidation of CH4 and partial oxidation of coal.2 kJ/mol (45) The WGS reaction often plays a role in reactions involving CO and H2. The most important are steam reforming of CH4. In many cases. For MeOH synthesis.7 kJ/mol CH4 (42) ∆H° ) 2CO(g) + O2(g) f 2CO2(g) 283. No. 10. and 6. i. can be obtained. use is made of the mildly oxidizing capacity compared to oxygen and air. and methane.5 kJ/mol. Reduction of CO2 can proceed electrochemically or chemically. in some cases.2 kJ/mol. Catalytic Reduction with H2.1. Also in other syngas reactions.32 The reactions. and suberic acids. ∆G° ) +170.e.52. There are reports of electroreduction processes which use solar energy as an energy source.. Therefore. ∆G° ) -562. such as oxalic. ∆G° ) -86. which discuss CO2 as an oxidant.

68.67 Another interesting application of methanol decomposition is the following.15H2 f CH4 (46) (47) (48) fossil fuels. are as follows:62 CH4 efficiency CO2 emission (mol MeOH/ (mol CO2/ mol MeOH) mol CH4) 0. Methane can be produced in a hydropyrolyzer in which a carbonaceous feedstock (e. thermodynamics are in general not favorable and process schemes leading to a net CO2 consumption are only possible in special cases. its CH4 efficiency is lower than the other processes.62. ∆G° ) -10. measures to prevent Hydrogen can be produced by catalytic decomposition of methane at 1273-1373 K:62. HYDROCARB process. respectively. prevented from entering the atmosphere.9 By the reverse reaction of MeOH synthesis.95 1.32. can be used as fuel for engines.63 The CARNOL process is similar to the HYDROCARB process in that they both contain processes of methane pyrolysis and methanol synthesis. methanol decomposition.33CH3OH steam + CO2 reforming (eq 52) 1. The separation of the carbon produced is less difficult as compared to other processes.05 0.66 syngas can be obtained in situ. CO2 can be directly hydrogenated into several products.66 The energy needed for MeOH decomposition can be provided by heat exchanging with the hot exhaust gas from the engines.49. as a consequence.g. or a combination of steam/CO2 reforming.94H2 ) CH4 + 0. CO2 gasification is applied.845 1.5CO2 f 2CH3OH CARNOL process (eq 53) 0.Reviews Energy & Fuels. Direct CO2 Hydrogenation.63 From the viewpoint of CO2 emission.63 CH4 f C + 2H2 (49) After separation.68. MeOH.62. Table 8.039 1.962 0. 5%) is mixed with syngas in the synthesis of methanol.44O0.64.63 In the former process biomass and fossil fuels are converted simultaneously producing methanol and carbon black.g.5C + CH3OH CH1.08H2O CH1.. 1996 315 Figure 13. In such a way large amounts of CO2 are consumed while at the same time the WGS reaction is avoided. No. When the carbon is stored.68H2 f CH4 + 0.63 Table 8 shows the methane efficiency and CO2 emission per mol MeOH produced for the four processes. e. in practice CO2 (ca. coal (bituminous) and oil. and instead of hydrogasification. Syngas of the right composition can be produced from methane directly by combining CO2 and H2O reforming. It is not surprising that several processes based on renewable energy carriers have been suggested. Methanol is more corrosive than gasoline and as a consequence. either pure or mixed with other fuels. which reduces process cost. fuel methanol.7 kJ/mol (3) Actually. CO2(g) + 3H2(g) f CH3OH(l) + H2O(l) ∆H° ) -137. In CO2 conversion processes.59-63 The reactions for hydrogenolysis of biomass.66H2O CH0. an energy penalty exists. CARNOL process.5CO2 + CH4 f 0.5CH4 + H2O + 0. biomass) can be converted to methane.66-71 It was reported that using MeOH as a fuel less environmentally harmful gases.66 + 1. Comparison of Various MeOH Production Processes from Methane63 Figure 12. If syngas from MeOH decomposition is injected into a diesel or gasoline engine.2. viz. an essentially zero emission of CO2 is realized by removing carbon from the cycle. hydrocarbons.67.8O0. Due to its lower heat capacity (compared with gasoline) a larger tank is needed. as mentioned above.99 0.62 Figure 12 illustrates the HYDROCARB process. of course.62.8 kJ/mol. e. syngas with a H2/CO ratio of less than 2 is preferred and the WGS reaction can be applied to tune the syngas composition. 50% of the carbon produced is stored and.63 Of course. SOx. which is stored. Carbon can be sold as a natural commodity. 2. For small-scale applications of syngas this often is a convenient route..684 steam reforming (eq 50) H2O + CH4 f CH3OH + H2 CO2 reforming (eq 51) CO2 + CH4 + 0.2. 10. Methanol as fuel has also disadvantages.71 Engines designed specially for using methanol will show even better performance.g. the CARNOL process is superior to steam reforming.59 Promising processes are the HYDROCARB and CARNOL processes... Vol. CO2 reforming.08 + 1. the hydrogen can be used in the hydrogenation processes.4.71 Note that most of the engines used in testing the environmental effect of fuels were designed for using fuels other than methanol. In this process.49 It is not necessary to apply the WGS reaction in order to arrive at the desired ratio.33H2 f 1.01 0. The feedstock in CARNOL process is methane instead of biomass and .7 + 1. the combustion efficiency can be greatly enhanced. whereas the carbon can be used as a fuel or stored permanently or for future use.63 Figure 13 shows the CARNOL process. 3. since carbon is produced and stored.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.65 An interesting example is methanol synthesis. although formaldehyde emission is increased. and NOx are produced. process higher alcohols.

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.3.72. This is a route which can produce gasoline from nonoil sources.49 MeOH is a bulk product which is widely used in chemical industry.66-68. 3. Fischer-Tropsch reactions are also possible:49. citric .. Photoreduction of CO2. and esters. MeOH can be converted to gasoline.49 Using the Mobil MTG (methanol-to-gasoline) process.74 3.26.10. The problem. 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 Many useful products can be produced from methanol.9.5. Osaka et al.10. NR2). Kisch et al.66. Figure 14. Vol. 2. however.73 Via dehydrogenation. mainly because of changes in the composition of the gasoline pool.75-78 is solar energy or another form of light. No. the limited efficiency. In many cases.49.72 nCO2 + (3n + 1)H2 f CnH2n+2 + 2nH2O nCO2 + 3nH2 f CnH2n + 2nH2O (54) (55) Besides these products.2.49.72 With the phase-out of the tetraalkyllead-type antiknocking agents in petrol.80 is used for the CO2 conversion. it provides a means to use the hydrocarbons in remote oil production sites or refineries.0 kJ/mol. such as aldehydes. e. they certainly lead to CO2 mitigation. The carbonylation of methanol is currently the most important synthetic route to acetic acid.5 kJ/mol. leading to CO2 emission.33.72 In the production of oxygenates compared to hydrocarbons. derivatives of formic acid: 9. ∆G° ) +46. ∆G° ) -132. ethers. 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.67-71 In some countries. this reaction is not attractive: hydrogen is more expensive than methane. can be synthesized. CO2 can be converted to HCOX.4.68 MeOH can be produced from hydrocarbons for which there is no outlet.316 Energy & Fuels. other products. This is illustrated for formic acid and formaldehyde: Higher alcohols can be manufactured by reaction with syngas. 3. natural gas is a byproduct of oil winning and for convenience the natural gas is flared.5 kJ/mol (57) This reaction is interesting due to its mild reaction conditions and wide applications. Compounds with activated hydrogen in the molecule can react with CO2 by insertion of CO2 into the C-H bond. It is too early to assess the potential of photoreduction. Reactions with Compounds Having Activated Hydrogen Atoms.22 For example. the octane pool needs to be modified by the addition of either alcohols or esters. ∆G° ) +34. MTBE. acids. 1996 Reviews corrosion should be taken. in Germany. Matsuoka et al. less hydrogen is consumed and the thermodynamics is more favorable. For example.g.3 kJ/mol (1) CO2(g) + 2H2(g) f HCHO(g) + H2O(l) ∆H° ) -11. Reactions to Other Products via MeOH. OR.67 An elegant solution is to convert the useless hydrocarbons via synthesis gas into methane which can be easily and safely stored and shipped.g.75 reported the heterogeneous photocatalysis of CO2 to formate by irradiation of light with λ g 290 nm. Since renewable energy79. ∆G° ) -8.3. 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. 3-5% MeOH is added to the gasoline to enhance the octane number... is the selectivity of the reactions and in particular. Synthesis gas to MeOH is the only alcohol synthesis reaction with both a high selectivity (>99%) and a high productivity (>1 g MeOH/g catalyst‚h).33 H2 + CO2 + HX f HCOX + H2O (56) Some of these products are quite useful. esters or amides of formic acid.77 reported the photoreduction of CO2 to formic acid at irradiation of light with λ g 290 nm.4.4 kJ/mol (4) Of course.76 described photocatalytic fixation of CO2 in oxoglutaric acid to isocitric acid.67 The simplest example of direct hydrogenation of CO2 is the production of methane. CO2(g) + 4H2(g) f CH4(g) + 2H2O(l) ∆H° ) -259.34.7 kJ/mol.49 This reaction can be viewed as a combination with Fischer-Tropsch reactions. 10.73 MeOH is the first choice in the recent Japanese national program for CO2 conversion.50. formaldehyde can be produced:73 CH3OH f HCHO + H2 (58) CO2(g) + H2(g) f HCOOH(l) ∆H° ) -31. Scope of production of chemicals via MeOH-based routes. The energy needed for photoreduction of CO29.9 kJ/mol.72 All the other alcohol products suffer from a lack of productivity and/or selectivity. Only a few publications have appeared.71 The methanol consumption is increasing tremendously. economically.g. e.73 Figure 14 summarizes the major possible reactions into useful products from MeOH. e. For example. OM.6 kJ/mol (2) In the presence of H2 and HX (X ) OH.

However. Saturated Hydrocarbons. CO2 reforming is not restricted to methane. in principle. Unsaturated Hydrocarbons. ∆G° ) +58..1. alkynes. CO2 can react with monoalkenes.13. the production of salicylic acid amounted to 25 kt/y.22 3. In principle. respectively. No. ethylene carbonate has also an excellent potential.9 Due to the large reactor volume and. unsaturated hydrocarbons are more reactive than saturated ones. Radicals are formed and in this reactive environment CO2 might show reactivity and interesting products could be formed.6. paraffins which do not contain activated hydrogen can be carboxylated only under drastic conditions. ∆G° ) +170. Vol. Carboxylation of hydrocarbons with activated hydrogen has received a lot of attention.83 reactions with monoalkenes.57. For example.22 The process takes place at elevated temperatures. dienes. ethylene and propylene. thermodynamics is not favorable. 2. the most popular drug of all.5 kJ/mol. various lower carboxylic acids.8 kJ/mol (31) It has been commercialized under the name SPARG process. To the same category belongs microbiologically enhanced oil recovery.g. e. the costs for product extraction and purification may not be favorable.10 . 1996 317 3. In contrast to activatedhydrogen-containing hydrocarbons.10. and other substituted hydrocarbons.22 COONa CO2 + [H+] COOH OH (61) ONa OH The product is mainly used in the production of aspirin.1 kJ/mol (11) In view of the low reactivity of both CO2 and CH4. cycloalkenes.58 CO2(g) + CH4(g) f 2CO(g) + 2H2(g) ∆H° ) +247.22 CO2(g) + C2H4(g) f CH2dCHCOOH(l) CH3CHdCH2 + CO2 f CH2(COOH)CHdCH2 (15) (64) Both products are very useful. leading to.6. the long residence time. Under such conditions temperatures of say 333 K and pressures up to 130 bar exist. CO2 methane reforming is probably the most interesting reaction with saturated hydrocarbons. Figure 15 shows that a wide variety of products can be made.9.6. Moreover. Some compounds with active hydrogen and their carboxylation products. In 1980 in USA. for providing the energy for heating the CO2 and for the enthalpy of the endothermic reforming reaction. e. other products may be produced: CO2(g) + CH4(g) f CH3COOH(l) ∆H° ) -13. An original suggestion is to use underground reservoirs as reactor. n) (63) NaOOCCH2CCH2COONa HCN (60) CH2–COOH [H+] OH NaOOCCH2CCH2COONa CN HO–C–COOH CH2–COOH The reaction of sodium phenolate with CO2. as a consequence. 3.22.22 Figure 15.10. it is possible to use supercritical liquid CO2 to extract the oxygenates formed and to bring them to the surface for further concentration.Reviews Energy & Fuels.. allowing the synthesis of oxygenates.9. 10.22 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 . Reactions with Hydrocarbons without Activated Hydrogen Atoms. the socalled Kolbe-Schmitt process. typically at 800-900 K.2. Levy et al.1. propylene carbonate is a tonnage petrochemical solvent.2.g. Monoalkenes.3 kJ/mol. ethylene carbonate and propylene carbonates:9. It has been suggested to carry out cracking of hydrocarbons in the presence of CO2. at 743-753 K catalyzed by triethylamine and calcium chloride.82 3. as stated before. The reactions of CO2 with unsaturated hydrocarbons can be subdivided into9. the conversion might be acceptable.10. has been used in the industrial synthesis of salicylic acid since 1874:9.6.81 described a 20 kW reforming/ methanation installation based on a solar furnace. Of course. higher hydrocarbons may also be converted: nCO2 + CnH2n+2 f 2nCO + (n + 1)H2 (62) Moreover. a high temperature is called for and an acceptable selectivity can probably not be reached.

2.6. Reactions with dienes are illustrated by that of isoprene: [Ru] Figure 16. 3. e.6. No. for instance.10 [A] CO2 [B] O O (69) O O [A] CO2 [B] O O (70) O CO2 [B. and 1-pentene can react similarly.9.10 The large variety of new lactones presented in this section may become of interest as fine chemicals which may be useful.. The byproducts are products Copolymer of styrene and a conjugated diene. for example. The reactions with ethylene or propylene epoxide are shown below. is used to introduce a carboxylic groups.C] + O O (71) O [A] = Pd(dba)2/PPh3 [B] = Pd(dppe)2 [C] = Pd(PPh3)4 O (dba = dibenzylidineacetone) (dppe = 1.86 Two esters and a pyrone are formed from allene in the presence of a Pd catalyst as shown below. leading to γ-lactones by using Pd catalysts.3-dienes proved to be more reactive than monoenes. 1. beer.84 reported a Ru-catalyzed reaction of ethylene and CO2.10 Many attempts of reacting dienes. and in animal products. 1996 Reviews Other organic carbonates also may have applications as solvents or additives. CH2dCH2 + CO2 9 CH3CH2CO2CH2CH3 + 8 CH3CH2OH + CH3CH2COOH (65) Ethylene. though the yields were low (around 5%). In a great number of stoichiometric reactions. Dienes. CO2 insertion into the dimer occurs. 6%). A challenging goal in CO2 chemistry is the development of catalysts for these conversions. and butter fat. or coconuts. pork. However.85 However. Linkage modes of isoprene and piperylene with butadiene and CO2. After alcoholic fermentation. though only in low yield (ca.10 O CH2 C CH2 + CO2 [cat] O O O OH + CO2 [cat] O O OH (68) + O O O O (67) O O OH O O Ni and Ru compounds catalyze the formation of δ-lactones. predominantly on the diene units (carboxylated polymers). and wine.3. Butadiene can also react with CO2 and an epoxide catalytically. of the reactions between butadiene and CO2 (lactones). Lapidus et al. 2-butene. the aromatic components of black tea.318 Energy & Fuels.g. Cyclic methylenecyclopropanes are more reactive than linear alkenes. propionic acid. Cycloalkenes. 10.2-bis(diphenylphosphino)ethane) . 2. rum.2.2. The application of lactones as herbicides or pharmaceuticals is also under investigation. These products. propylene. 1-butene.10 H2CdCHsCMedCH2 + CO2 f Me2CdC(CO2H)CH2CHdCMeCHdCH2 + Me2CdC(CO2H)CH2CHdCHCMedCH2 (66) Apparently. and its ethyl ester were formed in yields of up to 38% at 450 K and 700 atm. and the octadienyl esters. Vol. other than butadiene. in beef. but only stoichiometrically. substituted δ-valerolactone (lactones of substituted 5-hydroxypentanoic acid) might be interesting chemicals in pharmaceutical industry. 3. ethanol. many of these reactions cannot be carried out catalytically. comparable lactones are found. strawberries.10 Both in plants. with CO2 failed. hydrogenated in the presence of CO2. in the production of fragrances. numerous lactones act as flavorings in whiskey. copolymerization of butadiene and CO2 with isoprene or piperylene yielded novel lactones. A great number of natural compounds are known which have a similar lactone structure.10 as shown in Figure 16.

We. Polycarbonates are appealing in the sense that they constitute a type of chemical change of CO2 molecules. such as 3-hexyne or 4-octyne.83 Low permeability of oxygen is one of the characteristics of this material. esters.g.9.Reviews Energy & Fuels. A higher density of CO2 is not conceivable.22 Many catalyst systems can catalyze this reaction. polycarbonates with the structure shown below are the products: 22 nXCH2 CH2X + nKO–R–OK OCOCH2 CO2 crown ethers CH2OCOOR CH2–. Thus.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. The reactions are given below. C( O) O n 3. in principle. substituted pyrones are obtained. possibly for steric reasons.22 The synthesis of macromolecules with controlled molecular weight is of importance for molecular design of polymeric materials.22 For example.83 Of great interest is the polymerization of propylene carbonate to yield high molecular weight polymers. lactones.10 n-Bu CO2+ 2n-BuC CH [Ni] n-Bu O O (73) With other substituted alkynes.(74) 3.8. Derien et al. Alkynes. CO2 can react with alkynes (e. expect that this polymer will not be stable enough under ambient conditions. catalyzed by NiII(dppe)Cl2 (dppe ) 1.β-unsaturated acids. which will be described in the following section. propyne).10. It is also possible to synthesize polycarbonates by CO2 reaction with epoxides. No. The product is a high molecular weight aliphatic polycarbonate. 2.6. CO2 can form copolymers with epoxides9. Reactions with Other Substituted Hydrocarbons. producing unsaturated organic carbonates. Vol. those having an 18-membered ring were found to give the best results. a method for long-term CO2 fixation as organic polymers. Br (1) . 1-hexyne reacts with CO2 producing 4. however. Figure 17 shows some of them.10 + CO2 diols by the promotion of crown ethers.2. (1) [Pd] n + 2nKX (75) R= X = Cl. Because of the high oxygen content they . 1-butyne. 3. reactions with polymers giving carboxy-terminated polymers (functionalization of polymers) were reviewed by Quirk et al. while phenyl and diphenyl acetylene did not react..2-bis(diphenylphosphino)ethane). etc.83 under mild conditions catalyzed by organometallic catalyst systems. can react similarly. It was reported that using aluminum porphyrin catalyst or diethylzinc-water catalyst.89 reported the electrochemical reaction between CO2 and bromobenzene. 3.22.6dibutyl-2-pyrone.6. the copolymer has a very narrow molecular weight.7.3.9. –CH2 C(CH3)2 O O codimer [Pd] O O O O [1] (1) O O O O copentamers (72) cotrimers O cotetramers O A number of crown ethers can be used. Production of Polycarbonates. Amatore et al. Alkynes with internal triple bonds.88 The products of CO2 with hydrocarbons may lead to polymers with special properties. This reaction has been claimed to be the first example of the synthesis of an alternative copolymer with a narrow molecular weight distribution. [cat] O + CO2 O O O (76) n O + nCO2 [cat] O–C–O O n (77) CH2–CHR + CO2 O (CH2–CHR–O–C–O)n O (78) CO2 + C6H5Br + 2e f C6H5COO.22 Synthesis of polycarbonates represents.4. The best compound in this respect would be the polycarbonate. . Reaction with Epoxides. CO2 is able to react with many other substituted hydrocarbons. CO2 can react with R.+ Br. carboxylic acids. which after hydrolysis leads to benzoic acid nearly quantitatively. 10. 1996 319 The reaction of unsubstituted methylenecyclopropane with CO2 leads to 3-methyl-2-buten-4-olide in yields up to 80%.83 These polymers can also be strengthened by inorganic carbonates.87 reported that the incorporation of CO2 into nonactivated alkynes gives R.ω-dibromo compounds and the potassium salt of Many epoxides are copolymerizable. These should be long lasting and finally biodegradable and should have very large markets.

possess a low heat of combustion and decompose at a relatively low temperature. H2. Reaction with Alcohols and Ethers. 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. for example. and PVC.10 At room temperature ethylene carbonate is a solid which melts at 310 K and boils at 520 K. while Et3N is a representative amine cocatalyst. which are otherwise difficult to prepare.33 Epoxides can be considered as a type of cyclic ethers. at 453 K is exclusively propylene carbonate. CH ) 3 (79) Chemische Werke Huls adopted this reaction for an ¨ industrial process. The aliphatic polycopolymer was confirmed to be biodegradable.9.22 CH2 CH + CO2 OCH3 CH CH2 x C O CH2 CH O CH CH2 (85) y HO HCO O CH2 OCH3 OCH3 OCH3 .9 Many useful products.10 Cl O O O + Cl2 –HCl The major applications of cyclic carbonates are illustrated in Figure 18. 1996 Reviews Figure 17.2-propanediol formates from CO2. and plants using the Huls process ¨ were built in Germany and Romania.9.10 It is possible to produce vinylene carbonate via chlorinating and subsequently dehydrochlorinating.83 The product of the thermal decomposition of CO2-propylene oxide copolymer.10 These two cyclic carbonates are used as high-boiling solvents for natural and synthetic polymers such as lignin.22 Figure 18.320 Energy & Fuels. and propylene oxide. can be made from cyclic carbonates.9 Those long-lasting biodegradable polymers should have large markets.33 ROH + CO2 + H2 f HCOOR + H2O R) Me. Vinyl methyl ether gives a copolymer with CO2 when heated at 350 K without any added catalyst. nylon. Other ethers can also react with CO2. whose reactions with CO2 have already been described.3-epoxypropane). the general reaction equation is22 O ROH + CO2 R′OM ROCOH (83) Alkyl formates can be produced. The diepoxide of butadiene leads to erythritol (HOCH2[CH(OH)]2CH2OH) dicarbonate. Chemistry based on carbonates. catalyzed by several transition metal complexes and tertiary amines under 25 atm of CO2 and H2 at 413 K:22. CO2 can also react with epoxides to form cyclic organic carbonates:10 R CH2–CH–R + CO2 O [cat] Other examples of epoxides that can form cyclic carbonates with CO2 are styrene epoxide and epichlorohydrin (1-chloro-2. Propylene carbonate has also an exceptionally high boiling point (516 K).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)4.9 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. Alcohols can react with CO2 in the presence of a metal alkoxide. Cyclic ethers for copolymerization with CO2 by an organozinc catalyst system. Et. 10. Pr (84) O O O –HCl O O O (80) The reaction for linear carbonates is illustrated by the synthesis of 1. 3. 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. 2. 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. which makes it applicable in controlled release drug systems. Vol. cellulose ester. No.

10. Thus when heated at 393-433 K in the presence of triethylenediamine. Reaction with Nitrogen Compounds. Aliphatic amines can be carboxylated by CO2. time ) 4 h.10. giving polyurea:9 NH2(CH2)nNH2 + CO2 (PhO)2POH Ternary copolymerization is also possible such as that of Reaction with NH3. N(C2H4)3N. Vol.Reviews Table 9.10. cyclic phosphonite and acrylic compounds (e. CO2 + RNH2 + HOP(OC6H5)2 O RNHCNHR + C6H5OH + (OH)2POC6H5 (88) Pyr 313 K Many symmetrical ureas can be similarly synthesized (cf. Table 11.22 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. .22 Some diamines may form copolymers with CO2 and acrylonitrile (CH2dCHsCN). acrylonitrile).1. with carbamate and amino alcohol (the decarboxylation product of the former) as the products. Symmetrical Ureas from CO2 and Amines22 aminea aniline o-toluidine isopropylamine cyclohexylamine N-methylaniline diphenylamine diethylamine a Energy & Fuels. CO2..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.g. compounds with an -O-C(O)-N. b Based on the amine used.2.22 Reactions may take place between CO2.10 Urea or (alkyl-) substituted ureas can be further reacted to produce derivatives. can be obtained from the CO2 reaction with amines. R-amino acids are obtained. ammonia and amines. 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 O NH2 100 NH2 O 2 HOP(OC6H5)2 ) amine ) 50 mmol in 40 mL of pyridine.22 Table 12 shows some examples.22 O NH(CH2)nNHCO m (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. 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 1–x (90) It was reported that various carbamates. 2. an epoxide. 3. yielding a 1:1:1 copolymer with molecular weight of ca.22 RCH2NH2 + CO2 H2O2 (30%) 283–323 K. 3. and an amine. CO2 can react with various nitrogen-containing compounds. e. No. Examples of the Synthesis of Carbamates22 a 2NH3 + CO2 f H2O + NH2CONH2 (86) In fact. Table 9). 10. C (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.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. this process belongs to bulk chemical production (1985: 42 Mt/y). 20000. T ) 313 K. 1996 321 Table 10. Reactions with Amines and Imines. Table 11 gives some examples of the cyclic carbamates.g.10. Diamine can react further with CO2 with various N-phosphonium salts of pyridine.9.22 3. HCl D.

can be used in chemical synthesis. The ring-opening reaction is facilitated only by acidic reagents. Another example is the use of CO2 in fumigation to replace chemical pesticides traditionally used. not only is the use of poisonous phosgene prevented but also the production cost is reduced. Substitution for Other Chemicals.. amine and epoxide. diphenyl carbonates. part of the H2S is combusted in air giving SO2.90 Sodium hydroxide is often used to inhibit the reaction by neutralizing carbon dioxide in the air. Here. This substitution can be either direct or indirect. Reactions with Sulfur Compounds. which can substitute other chemicals. 50 bar.25 O H2NCNH2 + 2ROH O ROCOR + 2NH3 (99) CH2CH2NCO RO m (94) Ethylen. can in many cases directly replace phosgene (COCl2. useful intermediates in the chemical industry. Direct substitution opportunities for CO2 (after Lipinsky). Epoxide.11. 3. Many processes exist for the conversion of H2S in waste streams in a useful product. 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. CO2 can be used to substitute air:91 The old process using phosgene may result in Clcontaining byproducts. 10. for example. and waste water treatment. Nevertheless. dimethyl carbonates. e.93 CH2CHOCNH2 OH CS2 + CO2 f 2COS (98) In the reaction with diamines. e.22 R2NH + CO2 + H2C CHOCH2CH3 R2NC(O)OCH CH3 308–373 K 70 h OCH2CH3 (92) The extremely high positive values of ∆H° and ∆G° do not need further comment.25 Urea. from primary amine carbonates obtained from CO2 (dialkylcarbonates) deserves specific attention.90 Aziridines are useful chemicals in paper making industry.31 The synthesis of isocyanates. 2. 353 K.25 There is a market for dialkyl carbonates as solvents and as chemical intermediates for the production of plastics. 2 Oligomer of ethylene oxide was formed.8 kJ/mol (95) By using urea. organic cyclic carbonates. can react further with urea to form polyurethanes. di(hydroxyethyl) carbamates are formed which. textile industry.22 This type of reactions is undesired.25 Carbamate esters can be prepared from CO2.2 mol each.and propylenimines also react with CO2 to form soluble polymers. a product from CO2. Figure 19. The idea of direct substitution is illustrated in Figure 19. CO2 can also react with aziridines to form products which possess urethane (H2NCO2C2H5) linkages.15 CO2 is registered at the US Environmental Protection Agency .g. even at low temperatures. ∆G° ) 494. Examples of Products Formed by the Reaction of CO2. 22 h. that for dimethyl carbonate is estimated to be about 105 tons per year. with an annual market of 8 Mt) in the production of organic carbonates. 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 O O b a CO . vinyl ether and amines (dimethyl or diethyl). they react with ammonia and several amines.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.9 kJ/mol.25 O COCl2 + 2ROH ROCOR + 2HCl (100) 2H2S(g) + 4CO2(g) f 2SO2(g) + 4CO(g) + 2H2(g) ∆H° ) 578.322 Energy & Fuels. The reaction is often very exothermic which may lead to explosion. diethyl carbonates. No. The most prominent process is the Claus process. 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. 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..12. that are harmful to the environment. leading to deterioration of the aziridines. 0. Many chemicals can be made from CO2.94 3. Vol.g.9. in contrast to that of epoxides which is facilitated by both acidic and basic reagents. 1996 Reviews Table 12.

of course. 0. amino alcohols. the whole process of CaCO3 production cannot contribute to the reduction of CO2. MeOH and other gasoline or diesel substitutes are potential candidates. and biomasses. lactones. lactones acids.. or electricity. esters. geothermal energy. paper. and this decomposition itself produces CO2. CO2-containing gases at severe conditions (high temperature or high pressure) can lead to an attractive process. (co)polymers (urethane) as a nonrestricted pesticide.5 Mt/y) of the TiO2.13. urea derivatives. (co)polymers ureas. and ink industries. 10.25 This is an example of indirect substitution. Moreover. (co)polymers (polyureas) carbamates. (co)polymers acids.Reviews Energy & Fuels. The most ideal energy source is of course a renewable energy. In fact. esters. tidal. Therefore. for example hydrogen. Taking the capacity of photosynthesis as 3000 kg carbon/ha annually. Even an atmosphere of 60% CO2 is sufficient to kill 100% of all insects via desiccation caused by hyperventilation. there is an energy penalty with CO2 reactions: energy input is needed for the reaction or for the production of a reactant. an option is to use a higher fraction of natural gas (methane) which produces the lowest amount of CO2. In bulk chemistry not so many favorable reactions exist. 200 Gt/y of glucose are produced by this process. esters. cheaper. An example is using CO2 in methane reforming. the capacity of CO2 mitigation via bioconversion is very limited. Bioconversion CO2 can be converted biochemically or biologically.97 Walker98 reported the synthesis of tar. in which products from CO2 may substitute one or another chemicals. No. (amino-) acids. directly or indirectly. The equilibria change when the reaction conditions are changed.15 not only are the CFCs replaced by the harmless CO2. In fine chemistry several reactions with a negative Gibbs free energy exist. This application of CO2 is environmentally beneficial. Concluding Remarks CO2 emission is mainly caused by the combustion of fossil fuels. Until now. has been replaced by CaCO3. 4. Considering the potential amounts of CO2 to be utilized chemically. which can be easily made from lime and CO2. esters. In general. Of course. lactones.10 One should realize that this reaction uses atmospheric CO2 with a very low concentration (ca. An example of indirect substitution is the replacement of CFCs. but here the volumes involved are much higher. Some of these products are of great technical interest. This example shows that due to the large area of land needed.3-dienes.g. the most important reaction is photosynthesis: 10 a Allenes and 1. c Dihalogen substituted. used in the past in industry. such as solar. Only in special situations CO2 conversion is favorable in CO2 mitigation. lactonesb acids. This replacement leads to cost savings. Saving energy is a direct method of reducing CO2 emission. The major reactions and their products are listed in Table 13. lactones. It is not surprising that thermodynamically the conversion of CO2 is unfavorable. MeOH as engine fuel leads to environmental advantages over gasoline at equivalent . 1996 323 Table 13. Unfortunately. After splitting into carbon and oxygen or after reduction. However. each year 475 000 hectares of agricultural land will become free. and the energy sector is the major contribu- tor to CO2 emission. lactones acids. organic carbonates. In a certain sense. but also the harmful effect of CFCs on the depletion of ozone layer is reduced. 2. Another example is the replacement of relatively expensive TiO2 ($2000/ton) by cheap CaCO3 ($200-500/ ton) in paint.25 CaCO3 is one of the most stable carbon compounds. coupled with solar energy input.100 Carbon dioxide can react in different ways with a large variety of compounds. lactones acids. e. unsaturated organic carbonates carbonates. hydro. the volumes involved are too modest. The limited number of publications in this research area show that this new territory is still to be exploited. lactones acids. Vol. rubber. The products that may be obtained are. the latter refers to the use of reaction products of CO2 as described above. The increase of the energy efficiency in the energy sector is extremely important in reducing CO2 emissions. carbamates. the CO2 problem is an energy problem. The CO2 production from various fossil fuels is per unit of energy quite different. esters. (co)polymers (polycarbonates) symmetrical ureas. wind. Currently. 3. almost half (ca. esters. CO2 may be utilized directly or indirectly. CO2 as a Carbon Source.and ash-free carbon from CO via the Boudouard reaction (reverse reaction of eq 29). which make the processes safer. 3% CO2 emitted can be used in photosynthesis. esters. aminoacids. 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. ca. one may think of numerous cases.15 Moreover. because of the low volumes involved. It was estimated13 that in The Netherlands. none of the man-made catalysts could compete with this catalyst made by mother nature. b With longer C-C chain than the original monomer. An example is “chemical cooling” of hot gases in the chemical process industry.99 5.96. When solid CO2 is used to replace CFCs in the in-transit refrigeration. since energy is needed for the decomposition of CaCO3. acids. esters. and various polymers or copolymers. 0. efficient agricultural technology might result in the sequestration of larger amounts of CO2. the production of bulk products is relevant whereas fine chemicals are not very interesting. 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). or environmentally better. 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. polycarbonates lactones. carbamates. insects cannot develop a resistance to it.4%) and solar energy to produce organic fuel substituent with a high selectivity and a high rate at ambient temperature.

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