US 20090293348A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2009/0293348 A1 Olah et al. (43) Pub. Date: Dec. 3, 2009

(54) EFFICIENT AND SELECTIVE CHEMICAL Related U.S. Application Data RECYCLING OF CARBON DOXDE TO (63) Continuation of application No. 1 1/766,408, filed on METHANOL, DIMETHYL ETHER AND Jun. 21, 2007, which is a continuation-in-part of appli DERVED PRODUCTS cation No. 1 1/402,050, filed on Apr. 12, 2006, now Pat. No. 7,605,293. (75) Inventors: George A. Olah, Beverly Hills, CA (60) Provisional application No. 60/671,651, filed on Apr. (US); G.K. Surya Prakash, 15, 2005, provisional application No. 60/763,678, Hacienda Heights, CA (US) filed on Jan. 30, 2006. Publication Classification Correspondence Address: (51) Int. C. WINSTON & STRAWN LLP CIOL L/85 (2006.01) PATENT DEPARTMENT CIOL L/82 (2006.01) 1700 KSTREET, N.W. (52) U.S. Cl...... 44/448; 44/451 WASHINGTON, DC 20006 (US) (57) ABSTRACT An efficient and environmentally beneficial method of recy (73) Assignee: University of Southern California cling and producing methanol from varied sources of carbon dioxide including flue gases of fossil fuel burning power plants, industrial exhaust gases or the atmosphere itself. Con (21) Appl. No.: 121537,647 Verting carbon dioxide by chemical or electrochemical reduc tion seconardy treatment to produce essentially methanol, (22) Filed: Aug. 7, 2009 dimethyl ether and derived products. The Methanol Economy Process

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Methanol derived chemical products and materials Formaldehyde Urea resins Methyl tert-butyl ether Phenol resins (MTBE) Melamine resin Acetic acid Xylene resin thanol Poroformaldehyde Acetaldehyde Methane-di-isocyanate (MD( ) Acetic Anhydride ButOnediol Chloromethones Olyols Polyacetal Soprene HeXOmine OPthers Methyl methacrylate (MMA( ) Polymethyl methacrylate (PMMA( ) Methocrylotes Methonol C O O t 9 re si n S Methyl formate FormOmide HCN Formic acid Methyl amines Dimethyl formamide (DMF) Methylethonolomine Dimethylacetamide (DMAC) Tetromethyl ammonium hydroxide (TMAH( ) CorbOmotes H ig h e r O m n e S Dimethylity testatetereDhth Polyethyleneterephthalote (PET) Dimethyl ether (DME) Olefins ydrogen H2 Carbon monoxide CO Single cell proteins B e PRIOR ART iOchemicols Others FIG 1 Patent Application Publication Dec. 3, 2009 Sheet 2 of 2 US 2009/0293348 A1

The Methanol Economy Process

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EFFICIENT AND SELECTIVE CHEMICAL of the most efficient use of methanol is in fuel cells, particu RECYCLING OF CARBON DOXDE TO larly in direct methanol fuel cell (DMFC), in which methanol METHANOL, DIMETHYL ETHER AND is directly oxidized with air to carbon dioxide and water while DERVED PRODUCTS producing electricity. 0006 Contrary to gasoline, which is a complex mixture of CROSS-REFERENCE TO RELATED many different hydrocarbons and additives, methanol is a APPLICATIONS single chemical compound. It contains about half the energy density of gasoline, meaning that two liters of methanol pro 0001. This application is a continuation of application Ser. vides the same energy as a liter of gasoline. Even though No. 1 1/766,408 filed Jun. 21, 2007, which is a continuation methanol's energy content is lower, it has a higher octane in-part of application Ser. No. 1 1/402,050 filed Apr. 12, 2006, rating of 100 (average of the research octane number (RON) which claims the benefit of provisional applications 60/671, of 107 and motor octane number (MON) of 92), which means 651 filed Apr. 15, 2005 and 60/763,678 filed Jan. 30, 2006. that the fuel/air mixture can be compressed to a smaller vol The content of each application is expressly incorporated ume before being ignited. This allows the engine to run at a herein by reference thereto. higher compression ratio (10-11 to 1 against 8-9 to 1 of a gasoline engine), more efficiently than a gasoline-powered BACKGROUND engine. Efficiency is also increased by methanol's higher 0002 Hydrocarbons are essential in modern life. Hydro “flame speed,” which enables faster, more complete fuel com carbons are used as fuel and raw material in various fields, bustion in the engines. These factors explain the high effi including the chemical, petrochemical, plastics, and rubber ciency of methanol despite its lower energy density than industries. Fossil fuels, such as coal, oil and gas, are com gasoline. Further, to render methanol more ignitable even posed of hydrocarbons with varying ratios of carbon and under the most frigid conditions, methanol can be mixed with hydrogen, and is non-renewably used when combusted, form gasoline, with Volatile compounds (e.g., dimethyl ether), with ing carbon dioxide and water. Despite their wide application other components or with a device to vaporize or atomize and high demand, fossil fuels present a number of disadvan methanol. For example, an automotive fuel can be prepared tages, including the finite reserve, irreversible combustion by adding methanol to gasoline with the fuel having a mini and contribution to air pollution and global warming. Con mum gasoline content of at least 15% by volume (M85 fuel) sidering these disadvantages, and the increasing demand for so that it can readily start even in low temperature environ energy, alternative sources of energy are needed. ments M20 fuel (with 20% added methanol to gasoline) is 0003. One such alternative frequently mentioned is hydro presently introduced in China. Of course, any replacement of gen, and the so-called "hydrogen economy.” Hydrogen is gasoline in Such fuels will conserve oil resources, and the beneficial as a clean fuel, producing only water when com amount of methanol to add can be determined depending busted. Free hydrogen, however, is not a natural energy upon the specific engine design. Source, and its generation from hydrocarbons or water is a 0007 Methanol has a latent heat of vaporization of about highly energy-consuming process. Further, when hydrogenis 3.7 times higher than gasoline, and can absorb a significantly produced from hydrocarbons, any claimed benefit of hydro larger amount of heat when passing from liquid to gas state. gen as a clean fuel is outweighed by the fact that generation of This helps remove heat away from the engine and enables the hydrogen itself, mainly by reforming of natural gas, oil or use of an air-cooled radiator instead of a heavier water-cooled coal to synthesis gas (“syn-gas') a mixture of CO and H, is system. Thus, compared to a gasoline-powered car, a metha far from clean. It consumes fossil fuels, with a quarter of the nol-powered engine provides a smaller, lighter engine block, energy of the fuel being lost as heat. Hydrogen is also not a reduced cooling requirements, and better acceleration and convenient energy storage medium because it is difficult and mileage capabilities. Methanol is also more environment costly to handle, store, transport and distribute. As it is friendly than gasoline, and produces low overall emissions of extremely volatile and potentially explosive, hydrogen gas air pollutants such as hydrocarbons, NO, SO and particu requires high-pressure equipment, costly and non-existent lates. infrastructure, special materials to minimize diffusion and 0008 Methanol is also one of the safest fuels available. leakage, and extensive safety precautions to prevent explo Compared to gasoline, methanol's physical and chemical sions. properties significantly reduce the risk of fire. Methanol has 0004. It was suggested that a more practical alternative is lower volatility, and methanol vapor must be four times more methanol. Methanol, CHOH, is the simplest liquid oxygen concentrated than gasoline for ignition to occur. Even when ated hydrocarbon, differing from methane (CH4) by a single ignited, methanol burns about four times slower than gaso additional oxygen atom. Methanol, also called methyl alco line, releases heat only at one-eighth the rate of gasoline fire, hol or wood alcohol, is a colorless, water-soluble liquid with and is far less likely to spread to Surrounding ignitable mate a mild alcoholic odor, and is easy to store and transport. It rials because of the low radiant heat output. It has been esti freezes at -97.6°C., boils at 64.6°C., and has a density of mated by the EPA that switching from gasoline to methanol O.791 at 20° C. would reduce incidence of fuel-related fire by 90%. Methanol 0005 Methanol is not only a convenient and safe way to burns with a colorless flame, but additives can solve this store energy, but, together with its derived dimethyl ether problem. (DME), is an excellent fuel. Dimethyl ether is easily obtained 0009 Methanol also provides an attractive and more envi from methanol by dehydration and is an effective fuel par ronment-friendly alternative to diesel fuel. Methanol does not ticularly in diesel engines because of its high cetane number produce Smoke, Soot, or particulates when combusted, in and favorable properties. Methanol and dimethyl ether can be contrast to diesel fuel, which generally produces polluting blended with gasoline or diesel and used as fuels, for example particles during combustion. Methanol also produces very in internal combustion engines or electricity generators. One low emissions of NOx because it burns at a lower temperature US 2009/0293348 A1 Dec. 3, 2009 than diesel. Furthermore, methanol has a significantly higher DMFC is not dependent on generation of hydrogen by pro vapor pressure compared to diesel fuel, and the higher Vola cesses such as electrolysis of water or reformation of natural tility allows easy start even in cold weather, without produc gas or hydrocarbon. The DMFC is also more cost effective ing white Smoke typical of cold start with a conventional because methanol, as a liquid fuel, does not require cooling at diesel engine. If desired, additives orignition improvers, such ambient temperatures or costly high pressure infrastructure as octyl nitrate, tetrahydrofurfuryl nitrate, peroxides or higher and can be used with existing storage and dispensing units, alkyl ethers, can be added to bring methanol's cetane rating to unlike hydrogen fuel, whose storage and distribution requires the level closer to diesel. Methanol can also be used in the new infrastructure. Further, methanol has a relatively high manufacture of biodiesel fuels by esterification offatty acids. theoretical volumetric energy density compared to other sys 0010 Closely related and derived from methanol, and also tems such as conventional batteries and the H-PEM fuel cell. a desirable alternative fuel is dimethyl ether. Dimethyl ether This is of great importance for Small portable applications (DME, CHOCH), the simplest of all ethers, is a colorless, nontoxic, non-corrosive, non-carcinogenic and environmen (cellular phones, laptop computers, etc.), for which Small size tally friendly chemical that is mainly used today as anaerosol and weight of energy unit is desired. propellant in spray cans, in place of the banned CFC gases. 0015 The DMFC offers numerous benefits in various DME has a boiling point of -25° C., and is a gas under areas, including the transportation sector. By eliminating the ambient conditions. DME is, however, easily handled as liq need for a methanol steam reformer, the DMFC significantly uid and stored in pressurized tanks, much like liquefied petro reduces the cost, complexity and weight of the vehicle, and leum gas (LPG). The interest in dimethyl ether as alternative improves fuel economy. A DMFC system is also comparable fuel lies in its high cetane rating of 55 to 60, which is much in its simplicity to a direct hydrogen fuel cell, without the higher than that of methanol and is also higher than the cetane cumbersome problems of on-board hydrogen storage or rating of 40 to 55 of conventional diesel fuels. The cetane hydrogen producing reformers. Because only water and CO rating indicates that DME can be effectively used in diesel are emitted, emissions of other pollutants (e.g., NO PM, engines. Advantageously, DME, like methanol, is clean burn SO, etc.) are eliminated. Direct methanol fuel cell vehicles ing, and produces no soot particulates, black Smoke or SO, are expected to be virtually Zero emission vehicles (ZEV), and only very low amounts of NO, and other emissions even and use of methanol fuel cell vehicles offers to nearly elimi without after-treatment of its exhaust gas. Some of the physi nate air pollutants from vehicles in the long term. Further, cal and chemical properties DME, in comparison to diesel unlike ICE vehicles, the emission profile is expected to fuel, are shown in Table 1. remain nearly unchanged over time. New membranes based on hydrocarbon or hydrofluorocarbon materials with reduced TABLE 1. cost and crossover characteristics have been developed that Comparison of the physical properties of DME and diesel fuel allow room temperature efficiency of 34%. 0016 Methanol as indicated provides a number of impor DME Diesel fuel tant advantages as transportation fuel. Contrary to hydrogen, Boiling point C. -24.9 18O-360 methanol does not require any energy intensive procedures Vapor pressure at 20° C. (bar) S.1 Liquid density at 20° C. (kg/m) 668 840-890 for pressurization or liquefaction. Because it is a liquid at Heating value (kcal/kg) 6,880 10,150 room temperature, it can be easily handled, stored, distributed Cetane number SS-60 40-5S and carried in vehicles. It can act as an ideal hydrogen carrier Autoignition temperature (C.) 235 200-300 for fuel cell vehicles through on-board methanol reformers, Flammability limits in air (vol%) 34-17 O6-6.5 and can be used directly in DMFC vehicles. 0017 Methanol is also an attractive source of fuel for 0011 Currently, DME is exclusively produced by dehy static applications. For example, methanol can be used dration of methanol. A method for synthesizing DME directly directly as fuel in gas turbines to generate electric power. Gas from synthesis gas by combining the methanol synthesis and turbines typically use natural gas or light petroleum distillate dehydration steps in a single process has also been developed. fractions as fuel. Compared to such fuels, methanol can 0012 Another methanol derivative is dimethyl carbonate achieve higher power output and lower NO emissions (DMC), which can be obtained by converting methanol with because of its lower flame temperature. Since methanol does phosgene or by oxidative carbonylation of the methanol. not contain Sulfur, SO emissions are also eliminated. Opera DMC has a high cetane rating, and can be blended into diesel tion on methanol offers the same flexibility as natural gas and fuel in a concentration up to 10%, reducing fuel Viscosity and distillate fuels, and can be performed with existing turbines, improving emissions. originally designed for natural gas or other fossil fuels, after 0013 Methanol and its derivatives, e.g., DME, DMC, and relatively easy modification. Methanol is also an attractive biodiesel, have many existing and potential uses. They can be fuel since fuel-grade methanol, with lower production cost used, for example, as a substitute for gasoline and diesel fuel than higher purity chemical-grade methanol, can be used in in ICE-powered cars with only minor modifications to the turbines. Because the size and weight of a fuel cell is of less existing engines and fuel systems. Methanol can also be used importance in static applications than mobile applications, in fuel cells, for fuel cell vehicles (FCVs), which are consid various fuel cells other than PEM fuel cells and DMFC, such ered to be the best alternative to ICEs in the transportation as phosphoric acid, molten carbonate and Solid oxide fuel field. DME is also a potential substitute for LNG and LPG for cells (PAFC, MCFC, and SOFC, respectively), can also be heating homes and in industrial uses. used. 0014 U.S. Pat. No. 5.599,638 discloses a simple direct 0018 Methanol and dimethyl ether are also very conve methanol fuel cell (DMFC) and addresses the disadvantages nient materials for storage and transportation of energy with of hydrogen fuel cells. In contrast to a hydrogen fuel cell, the out the great disadvantage and potential danger of using US 2009/0293348 A1 Dec. 3, 2009 hydrogen. Hydrogen can readily converted with CO to methanol and/or DME thus providing a convenient safe form for storing and transporting energy produced from any -HO -HO 2 CHOH CHOCH -> SOUC. +HO 0019. In addition to these uses as fuels, methanol and Ethylene & Propylene methanol-derived chemicals have other significant applica HC=CH & H.C=CH-CH tions in the chemical industry. Today, methanol is one of the most important feedstock in the chemical industry. Most of 0022 Various catalysts, e.g., synthetic aluminosilicate the 32 million tons of annually produced methanol is used to Zeolite catalysts, such as ZSM-5 (a zeolite developed by manufacture a large variety of chemical products and mate Mobil), silicoaluminophosphate (SAPO) molecular sieves rials, including basic chemicals such as formaldehyde, acetic such as SAPO-34 and SAPO-17 (UOP), as well as bi-func acid, MTBE (although it is increasingly phased out for envi tional Supported acid-base catalysts such as tungsten oxide ronmental reasons), as well as various polymers, paints, adhe over alumina (WO/Al2O), have been found to be active in sives, construction materials, and others. Worldwide, almost converting methanol to ethylene and propylene at a tempera 70% of methanol is used to produce formaldehyde (38%), ture between 250 and 350° C. The type and amount of the end methyl-tert-butyl ether (MTBE, 20%) and acetic acid (11%). product depend on the type of the catalyst and the MTO Methanol is also a feedstock for chloromethanes, methy process used. Depending on the operating conditions, the lamines, methyl methacrylate, and dimethyl terephthalate, weight ratio of propylene to ethylene can be modified among others. These chemical intermediates are then pro between about 0.77 and 1.33, allowing considerable flexibil cessed to manufacture products such as paints, resins, sili ity. For example, when using SAPO-34 according to an MTO cones, adhesives, antifreeze, and plastics. Formaldehyde, process developed by UOP and Norsk Hydro, methanol is produced in large quantities from methanol, is mainly used to converted to ethylene and propylene at more than 80% selec prepare phenol-, urea- and melamine-formaldehyde and tivity, and also to butene (a valuable starting material for a polyacetal resins as well as butanediol and methylene bis(4- number of products) at about 10%. When using an MTO phenyl isocyanate) (MDI; MDI foam is used as insulation in process developed by Lurgi with ZSM-5 catalysts, mostly refrigerators, doors, and in car dashboards and bumpers). propylene is produced at yields above 70%. A process devel Formaldehyde resins are predominantly employed as an oped by ExxonMobil, with ZSM-5 catalyst, produces hydro adhesive in a wide variety of applications, e.g., manufacture carbons in the gasoline and/or distillate range at selectivity of particle boards, plywood and otherwood panels. Examples greater than 95%. 0023 There is also a methanol to gasoline (MTG) process, of methanol-derived chemical products and materials are in which medium-pore Zeolites with considerable acidity, shown in FIG. 1. e.g., ZSM-5, are used as catalysts. In this process, methanol is 0020. In producing basic chemicals, raw material feed first dehydrated to an equilibrium mixture of dimethyl ether, stock constitutes typically up to 60-70% of the manufacturing methanol and water over a catalyst, and this mixture is then costs. The cost offeedstock therefore plays a significant eco converted to light olefins, primarily ethylene and propylene. nomic role. Because of its lower cost, methanol is considered The light olefins can undergo further transformations to a potential feedstock for processes currently utilizing more higher olefins, C-C alkanes, and Co-Co aromatics such as expensive feedstocks such as ethylene and propylene, to pro toluene, Xylenes, and trimethylbenzene. duce chemicals including acetic acid, acetaldehyde, ethanol, (0024. Olah has developed independently MTO and MTG ethylene glycol, styrene, and ethylbenzene, and various syn process using Supported bifunctional acid-base non Zeolitic thetic hydrocarbon products. For example, direct conversion catalysts. With decreasing oil and gas reserves, it is inevitable of methanol to ethanol can be achieved using a rhodium that synthetic hydrocarbons would play a major role. Thus, based catalyst, which has been found to promote the reductive methanol-based synthetic hydrocarbons and chemicals avail carbonylation of methanol to acetaldehyde with selectivity able through MTG and MTO processes will assume increas close to 90%, and a ruthenium catalyst, which further reduces ing importance in replacing oil and gas-based materials. The acetaldehyde to ethanol. The possibility of producing ethyl listed uses of methanol is only illustrative and not limiting. ene glycol via methanol oxidative coupling instead of the 0025 Methanol besides mentioned and other related uses usual process using ethyleneas feedstock is also pursued, and can also be used as a source of single cell proteins. A single significant advances for synthesizing ethylene glycol from cell protein (SCP) refers to a protein produced by a microor ganism which degrades hydrocarbon Substrates while gaining dimethyl ether, obtained by methanol dehydration, have also energy. The protein content depends on the type of microor been made. ganism, e.g., bacteria, yeast, mold, etc. The SCP has many 0021 Conversion of methanol to olefins such as ethylene uses, including uses as food and animal feed. and propylene, also known as methanol to olefin (MTO) 0026 Considering the numerous uses of methanol, it is technology, is particularly promising considering the high clearly desirable to have improved and efficient methods of demand for olefin materials, especially in polyolefin produc producing methanol. Currently, methanol is almost exclu tion. The MTO technology is presently a two-step process, in sively made from synthesis gas obtained from incomplete which natural gas is converted to methanol via Syn-gas and combustion (or catalytic reforming) of fossil fuel, mainly methanol is then transformed to olefin. It is considered that natural gas (methane) and coal. methanol is first dehydrated to dimethyl ether (DME), which 0027 Methanol can also be made from renewable biom then reacts to form ethylene and/or propylene. Small amounts ass, but such methanol production also involves Syn-gas and of butenes, higher olefins, alkanes, and aromatics are also may not be energetically favorable and limited in terms of formed. scale. As used herein, the term “biomass” includes any type of US 2009/0293348 A1 Dec. 3, 2009 plant or animal material, i.e., materials produced by a life 0031. The existing processes invariably employ extremely form, including wood and wood wastes, agricultural crops active and selective copper-based catalysts, differing only in and their waste byproducts, municipal Solid waste, animal the reactor design and catalyst arrangement. Because only waste, aquatic plants, and algae. The method of transforming part of syn-gas is converted to methanol after passing over the biomass to methanol is similar to the method of producing catalyst, the remaining Syn-gas is recycled after separation of methanol from coal, and requires gasification of biomass to methanol and water. There is also a more recently developed Syn-gas, followed by methanol synthesis by the same pro liquid phase process for methanol production, during which cesses used with fossil fuel. Use of biomass also presents Syn-gas is bubbled into liquid. Although the existing pro other disadvantages, such as low energy density and high cost cesses have methanol selectivity greater than 99% and energy of collecting and transporting bulky biomass. Although efficiency above 70%, crude methanol leaving the reactor still contains water and other impurities, such as dissolved gas recent improvements involving the use of “biocrude.” black (e.g., methane, CO, and CO), dimethyl ether, methyl for liquid obtained from fast pyrolysis of biomass, is somewhat mate, acetone, higher alcohols (ethanol, propanol, butanol), promising, more development is needed for commercial and long-chain hydrocarbons. Commercially, methanol is application of biocrude. available in three grades of purity: fuel grade, 'A' grade, 0028. The presently existing method of producing metha generally used as a solvent, and 'AA' or chemical grade. nol involves Syn-gas. Syn-gas is a mixture of hydrogen, car Chemical grade has the highest purity with a methanol con bon monoxide and carbon dioxide, and produces methanol tent exceeding 99.85% and is the standard generally observed over a heterogeneous catalyst according to the following in the industry for methanol production. The Syn-gas genera equations: tion and purification steps are critical in the existing pro cesses, and the end result would largely depend on the nature CO+2H2gsCH3OH AH28-21.7 kcal/mol and purity of the feedstock. To achieve the desired level of purity, methanol produced by the existing processes is usually CO+3He sOHOH+H2O AHosk-9.8 kcal/mol purified by Sufficient distillation. Another major disadvantage of the existing process for producing methanol through syn gas is the energy requirement of the first highly endothermic 0029. The first two reactions are exothermic with heat of steam reforming step. The process is also inefficient because reaction equal to -21.7 kcalmol' and -9.8 kcalmol', it involves transformation of methane in an oxidative reaction respectively, and resultina decrease in Volume. Conversion to to carbon monoxide (and some CO), which in turn must be methanol is favored by increasing the pressure and decreasing reduced to methanol. the temperature according to Le Chatelier's principle. The 0032. It is highly desirable and advantageous to produce third equation describes the endothermic reverse water gas methanol without first producing Syn-gas. It would be further shift reaction (RWGSR). Carbon monoxide produced in the advantageous to use an abundant, practically unlimited third reaction can further react with hydrogen to produce resource Such as carbon dioxide via its chemical recycling as methanol. the carbon source to produce methanol. For example, U.S. 0030 Synthesis gas for methanol production can be Pat. No. 5,599.638, the entire content of which is incorpo obtained by reforming or partial oxidation of any carbon rated herein by reference thereto, discloses production of aceous material, such as coal, coke, natural gas, petroleum, methanol, and related oxygenates and hydrocarbons, based heavy oil, and asphalt. The composition of syn-gas is gener on a carbon dioxide-based regenerative fuel cell concept. ally characterized by the stoichiometric number S. corre 0033. When hydrocarbons are burned they produce car sponding to the equation shown below. bon dioxide and water. It is of great significance, if this process can be reversed and an efficient and economic process can be found to produce methanol from carbon dioxide and S = (moles H2 - moles CO2) water to be Subsequently used for energy storage, fuels and T (moles CO+ moles CO2) production of synthetic hydrocarbons. In plant photosynthe sis, carbon dioxide is captured from the air and converted with Ideally, S should be equal to or slightly above 2. A value above water and Solar energy into new plant life. Conversion of plant 2 indicates excess hydrogen, while a value below 2 indicates life into fossil fuel, however, is a very long process. Thus, it it relative hydrogen deficiency. Reforming offeedstock having is highly desirable to develop a process for chemical recy a higher H/C ratio, such as propane, butane or naphthas, leads cling carbon dioxide to produce hydrocarbon in a short, com to S values in the vicinity of 2, ideal for conversion to metha mercially feasible time scale. nol. When coal or methane is used, however, additional treat 0034 Carbon dioxide is known to be photochemically or ment is required to obtain an optimal S value. Synthesis gas electrochemically readily reduced to formic acid with form from coal requires treatment to avoid formation of undesired aldhyde and methanol being formed in only smaller amounts. byproducts. Steam reforming of methaneyields Syn-gas with Direct electrochemical reduction of CO into methanol under a stoichiometric number of 2.8 to 3.0, and requires lowering pressure also provides methyl formate. Catalytic hydrogena the S value closer to 2 by adding CO or using excess hydro tion of carbon dioxide with hydrogen gas using heteroge gen in some other process such as ammonia synthesis. How neous catalysts provides methanol together with water as well ever, natural gas is still the preferred feedstock for methanol as formic acid and formaldehyde. As the generation of needed production because it offers high hydrogen content and, addi hydrogen from water or still existing hydrocarbon Sources, tionally, the lowest energy consumption, capital investment primarily methane is highly energy consuming, the produc and operating costs. Natural gas also contains fewer impuri tion of methanol with equimolar amount of water as well as ties Such as Sulfur, halogenated compounds, and metals which other side products from carbon dioxide is not practical. No may poison the catalysts used in the process. efficient ways for the selective high yield, high selectivity US 2009/0293348 A1 Dec. 3, 2009

economical chemical conversion of carbon dioxide to metha ongoing depletion from the environment results in a number nol alone is presently known. High selectivity laboratory of significant problems and challenges. Upon human use, reduction of carbon dioxide to methanol was achieved only fuels and fuel products are not environmentally renewed on a with complex metal hydrides, such as lithium aluminum human time scale duration, as the combustion products car hydride which is extremely costly and therefore not suited for bon dioxide and water do not recycle back to form new fuels. the bulk production of methanol. Furthermore, carbon dioxide is a greenhouse gas, which 0035. Attempts have been made to chemically convert when produced in large Volumes contributes to global warm CO to methanol and Subsequently to a hydrocarbon by cata ing and environmental calamities. lytic or electrochemical hydrogenation. Catalysts based on 0039) Photosynthesis—nature's way of recycling carbon metals and their oxides, in particular copper and Zinc, have dioxide, allows plants to grow by taking in and converting been developed for this process. These catalysts are unexpect carbon dioxide and water into carbohydrates in the presence edly similar to the ones currently used for the conventional of sunlight. Photosynthesic conversion of carbon dioxide methanol production via Syn-gas. It is now realized that from plant life to fossil fuels, however, requires the presence methanol is most probably formed almost exclusively by of vast territories of forestoragricultural land and energy, and hydrogenation of CO contained in Syn-gas on the Surface of the process is extremely slow (in the magnitude of millions of the catalyst. To be converted to methanol, CO present in the years). Syn-gas first undergoes a water gas shift reaction to form CO 0040 Presently, the only known way to mitigate the car and H2, and the CO, then reacts with hydrogen to produce bon dioxide emission in fuel gases of fossil fuel burning methanol. One of the limiting factors for large scale use of power plants and other emission is by way of separating, such methanol conversion process is the availability of the collecting, and Subsequently sequestering carbon dioxide in needed CO, and H. While CO, can be obtained relatively old oil field Subterranean geological formations or at the easily in large amounts from various industrial exhausts, bottom of the seas. Sequestration is, however, a costly pro hydrogenis presently mainly produced from fossil fuel-based cess, as well as one that has only temporary mitigating effects Syn-gas and therefore has limited availability. Further, gen due to the potential danger that dynamic geological events eration of hydrogen from fossil fuels has a high energy could lead to catastrophic release of large amounts of seques requirement. Eventually, however, hydrogen is to be pro tered carbon dioxide, and to a renewed environmental hazard, duced by electrolyzing splitting water, however, also in e.g. from the Suffocating effects of this dangerous gas. It is a highly energetic processes. goal of the present invention to find a practical and economi 0036). Other methods for hydrogen production from fossil cal Solution to overcome these problems. fuels have been investigated, including the “Carnol process, in which thermal decomposition of methane produces hydro SUMMARY OF THE INVENTION gen and Solid carbon. The generated hydrogen is then reacted 0041 Our invention relates to various embodiments of an with CO to produce methanol. This process is advantageous environmentally carbon neutral use of utilizing and recycling over methane steam reforming for requiring relatively less carbon dioxide from industrial or natural Sources, as well as energy, about 9 kcal for producing one mole of hydrogen, and from the air itself into methanol dimethyl ether and derived for producing a solid byproduct (carbon) that can be more products. This method comprises separating the carbon diox easily handled, stored and used, compared to CO emissions ide from any available source containing same and producing generated by methane steam reforming or partial oxidation. methanol by reducing the carbon dioxide thus obtained under However, the thermal decomposition of methane requires conditions sufficient to produce methanol; utilizing the heating it to temperatures of above 800° C. and gives only methanol thus produced under conditions Sufficient to gener relatively low yield of hydrogen. The process, in any case, ate upon its combustion energy and to chemically absorbing requires Substantial development for commercial application. and recycling formed carbon dioxide in a carbon neutral 0037. If methanol is to be produced on a large scale from cycle. recycling carbon dioxide, such a process will be based on the 0042. The carbon dioxide obtained from such sources is abundant Supply of carbon dioxide in the atmosphere and in typically converted to methanol by catalytic, photochemical industrial exhausts of fossil fuel power burning power plants or electrochemical hydrogenation. The conversion to metha and cement plants. It would at the same time also mitigate the nol, however, forms a reaction mixture also containing formic greenhouse effect of CO that is causing in a significant way acid and formaldehyde. These can be without separation of the man caused global climate change (i.e., global warming). the reaction mixture, in a Subsequent treatment step con The present invention now provides such a process to obtain ducted under conditions sufficient to produce formaldehyde these benefits. Furthermore, while it is of critical importance and formic acid themselves converted to methanol using to curtail excessive man caused carbon dioxide emissions into modifications of the so-called Canizzaro-Tischenko reac the atmosphere, this alone will not be sufficient to reverse the tions. Converting the formaldehyde with co-formed formic damage that has already occurred. Thus, in addition to use acid as a hydrogen source is also feasible, without separation every method for reducing the emission of excess carbon of the reaction mixture, into methanol, and by reacting some dioxide due to human activities into the atmosphere, it would of the formic acid with methanol to form methyl formate, be of great benefit to also be able to remove and recycle excess followed by hydrogenating the methyl formate under condi carbon dioxide from the atmosphere to mitigate and reverse tions sufficient to form methanol. The hydrogen needed for the harmful problem of carbon dioxide buildup in the atmo the hydrogenation of methyl formate can be obtained from sphere. electrolysis of water, by decomposing at least some of the 0038. Furthermore, natural fossil fuel resources (petro formic acid from the reaction mixture or by the reaction of leum oil, natural gas, coal, etc.) and their products are con methane with carbon dioxide (dry reforming). tinuingly being depleted. Humankind is greatly dependent on 0043. The available source of carbon dioxide is preferably these carbon based fossil fuels and fuel products, and their an exhaust stream from a fossil fuel burning power or other US 2009/0293348 A1 Dec. 3, 2009 industrial plants, or a natural source accompanying natural products will also lead to a significant reduction of carbon gas. These available sources would otherwise be released into dioxide, a major greenhouse gas, in the atmosphere thus the atmosphere. The utilization of the exhaust stream as a mitigating global Warming. Source for chemical recycling avoids emitting the carbon 0050 Carbon dioxide conversion to methanol from the dioxide into the atmosphere. The available source of carbon mentioned generally sources also provides also formic acid dioxide may also the air of our atmosphere with the carbon and formaldehyde by either chemical, photochemical or elec dioxide obtained by absorbing atmospheric carbon dioxide trochemical reduction. Formic acid and formaldehyde thus onto a suitable adsorbent followed by treating the adsorbent produced, in a Subsequent process step, can be Subsequently to release the adsorbed carbon dioxide therefrom. By remov further substantially converted to methanol. The conversion ing and recycling carbon dioxide from the atmosphere pro of formaldehyde itself can be conducted in the presence of a vides a source that is inexhaustible. Suitably, the adsorbent is Solid Supported basic catalyst oran organometallic catalyst to treated by sufficient heating or is subjected to sufficient give methanol and formic acid, or methyl formate. Alterna reduced pressure to release the adsorbed carbon dioxide. tively, dimerization of formaldehyde gives methyl formate, 0044) The methanol that is produced can also be dehy which upon catalytic hydrogenation yields methanol as the drated under conditions sufficient to produce dimethyl ether. only product. The dimethyl ether can be used as a suitable fuel; to be used 0051 Carbon dioxide is captured and obtained from men as a substitute for Diesel fuel or household gas. Combustion tioned high concentration sources of its generation instead of of such fuel will of course generate carbon dioxide, but as its release into the atmosphere. Carbon dioxide can, however, carbon dioxide can be recovered and recycled for use in the also be obtained by separating it from the atmosphere itself production of methanol and or dimethyl ether this creates with a Suitable adsorbent (see co-pending application Ser. No. again an environmentally carbon neutral cycle. The methanol 11/780,244 filed Jul.19, 2007) followed by desorption treat or dimethyl ether as indicated can be also utilized as conve ment to release the adsorbed carbon dioxide therefrom. This nient energy storage and transportation materials in the afore can be achieved by heating to release the adsorbed carbon mentioned cycles. dioxide, by treating it under reduced pressure or by a suitable combination of both. BRIEF DESCRIPTION OF THE DRAWINGS 0052. In another embodiment of the invention to utilize needed hydrogen only in producing methanol without water 0045. The features and benefits of the invention will as by-product, carbon dioxide is first reduced chemically, become more evident from review of the following detailed such as in its thermal reaction with carbon or electrochemi description of illustrative embodiments and the accompany cally to carbon monoxide, which is Subsequently catalytically ing drawings, wherein: converted with hydrogen to methanol. 0046 FIG. 1 shows known examples of methanol-derived 0053 A further route to methanol is based on the use of chemical products and materials; and methane or natural gas as the hydrogen source in the reductive 0047 FIG. 2 schematically illustrates the present inven conversion of carbon dioxide (dry reforming) or using a Suit tive process, termed the METHANOL ECONOMY and its able combination with Steam reforming (wet reforming) carbon neutral chemical recycling. called bi-reforming (see co-pending application Ser. No. 1 1/850,501 filed Sep. 5, 2007) to provide a 1:2 molar mixture DETAILED DESCRIPTION OF THE PREFERRED of carbon monoxide and hydrogen, which Subsequently can EMBODIMENTS react to produce exclusively methanol. As the reforming of carbon dioxide with methane generates hydrogen, this hydro 0048. The present invention relates to the efficient and gen can also be used for the hydrogenation of methyl formate economical conversion of carbon dioxide from flue gases of to methanol in the previously discussed embodiments. fossil fuel burning power plants, industrial exhaust gases, 0054 Methanol produced according to the discussed new CO accompanying natural gas or from the atmosphere itself processes can be used for any of the practical mentioned to methanol or dimethyl ether, with their Subsequent applica purposes such as for energy storage and transportation, as a tion for energy storage and transportation, fuels for internal fuel in internal combustion engines or fuel cells, to produce combustion engines and fuel cells, conversion to synthetic derived fuels (such as dimethyl ether), dimethyl carbonate hydrocarbons and their products, synthetic proteins and other (and the like), to produce ethylene, propylene, and related for products. The carbon dioxide to methanol conversion is a synthetic hydrocarbons and all their derived products includ permanent, safe and economical alternative to sequestration, ing and not limiting single cell proteins. (underground or under the sea storage) wherein carbon diox 0055. The present invention relates to efficient new and ide through methanol is converted to useful and essential economical ways of converting varied carbon dioxide Sources products making it a renewable general carbon Source for (both containing high and low combustions) into methanol. fuels, synthetic hydrocarbons and their products. High concentration carbon dioxide sources are those fre 0049. The present invention discloses an environmentally quently accompanying natural gas in amounts typically form neutral and efficient process of recycling carbon containing 2 to 35%, those from flue gases of fossil fuel (coal, natural fuels and converting carbon dioxide formed upon their com gas, oil, etc.) burning power plants, exhaust of cement plants, bustion or by any source to methanol. Suitable carbon dioxide fermentation plants and other industrial sources. In one Sources can be industrial exhaust streams from hydrocarbon embodiment of the invention carbon dioxide formed together (fossil fuel) burning powerplants, cement and other industrial with methanol formaldehyde and formic acid which by plants, natural gas fields, under carbon dioxide accompanies chemical conversion or photochemical or electrochemical the hydrocarbon gases, and the like, as well as carbon dioxide reduction can further produce methanol. The invention of the atmosphere itself. The use of this process of converting teaches that, without separation of the product mixture in a carbon dioxide to methanol and/or dimethyl ether and their Subsequent treatment step, the mixture can be converted US 2009/0293348 A1 Dec. 3, 2009 exclusively to methanol making the overall process both sphere is low (only 0.037%), the atmosphere offers an abun selective and high yielding. In another embodiment, reduc dant and unlimited Supply when CO is recycled. For using tion of carbon dioxide can give methyl formate, which is atmospheric carbon dioxide efficiently, CO absorption Subsequently hydrogenatively converted exclusively into facilities are needed. This can be addressed by using efficient methanol. Inafurther embodiment, the chemical reduction of CO absorbents such as polyethyleneimines, polyvinylpy carbon dioxide with carbon or its electrochemical reduction ridines, polyvinylpyrroles, etc., on Suitable nano-structured produces carbon monoxide, which then is converted to Solid carriers (e.g., active carbon, polymers, silica or alu methanol with utilization of needed hydrogen to form only mina), which allow absorption of even the low concentration the desired product. In this embodiment the initial reduction of atmospheric CO (see co-pending patent application Ser. of carbon dioxide significantly (by a third) decreases the No. 1 1/780,244 filed Jul.19, 2007). CO can also be captured overall amount of hydrogen needed for producing methanol. using basic absorbents such as calcium hydroxide (Ca(OH)) 0056. The present invention discloses the efficient and and potassium hydroxide (KOH), which react with CO to economical conversion of carbon dioxide, either from flue form calcium carbonate (CaCO) and potassium carbonate gases or fossil fuel burning power plants, from natural gas (K2CO), respectively. CO absorption is an exothermic reac wells, varied industrial exhaust gases or from the atmosphere tion, which liberates heat, and is readily achieved by contact itself, to methanol. Both catalytic, photochemical or electro ing CO with an adequate base. After capture, CO is recov chemical reduction of carbon dioxide can be utilized with any ered from the absorbent by desorption, through heating, energy source available (conventional, alternative, atomic, vacuum (or reduced pressure) or electrochemical treatment. etc). The environmental and economic benefits of reductive Calcium carbonate, for example, is thermally calcinated to chemical conversion of carbon dioxide emission instead of release carbon dioxide. As desorption is an endothermic, sequestration are a significant part of the present invention. At energy-demanding step, the appropriate treatment can be the same time, carbon dioxide provides a renewable source of chosen to optimize absorption and desorption with the lowest methanol (together with dimethyl ether) that can be used for possible energy input. Thus, CO can be recycled by opera safe energy storage and transportation, production of fuels for tion of absorbing-desorbing columns in convenient cycles intent combustion engine and fuel cells, feedstock for pro with modest heating and/or under reduced pressure to cause ducing synthetic hydrocarbons and their products and related desorption of CO to take place. materials. 0062. When methanol, methanol-derived fuels or syn 0057 The use of carbon dioxide based methanol is highly thetic hydrocarbons are combusted (oxidatively used), they desirable as it can decrease and eventually replace the world's release CO and water, thus providing the basis for a revers reliance on fossil fuels. In addition, the reduction in carbon ible methanol cycle, the artificial version of the natural pho dioxide emissions as well as the removal of excess carbon tosynthetic recycling of CO. In contrast to the nonrenewable dioxide from the atmosphere will assist in reducing global fossil fuel Sources such as oil, gas, and coal recycling carbon warming and eventual restoring atmospheric conditions to a dioxide from industrial and natural sources to produce metha suitable levels, thus preserving the planet's climate for future nol not only addresses the problem of diminishing fossil fuel generations. resources by providing an unexhaustible carbon source, but 0058. The present invention overcomes many of the diffi also helps alleviate global warming due to greenhouse effect, culties in economically converting carbon dioxide to metha which is significantly caused by mankind's activity that is nol. Regardless, how energy is generated, any source of increasing the carbon dioxide content in the atmosphere. energy must be stored and transported. Hydrogen claimed as 0063. The effective hydrogenative recycling of carbon the future clean energy is exceedingly difficult and intrinsi dioxide disclosed herein provides new methods of producing cally dangerous to store, handle and transport. Its conversion methanol in an improved, efficient, and environmentally ben with CO to methanol, a convenient liquid and derived prod eficial way, while mitigating CO caused climate change (glo ucts offers a convenient, safe way of energy storage as well as bal warming). The use of methanol and derived dimethyl a renewable, eventually carbon natural source for synthetic ether as energy storage and transportation materials elimi hydrocarbons and their varied products. nates many difficulties excessive cost and danger of using 0059. The energy needed to generate hydrogen for cata hydrogen for Such purposes. They are also excellent transpor lytic or electrochemical conversion of carbon dioxide to tation fuels and convenient raw materials for producing Syn methanol can be obtained from any available source of thetic hydrocarbons and their related products. The economy, energy, Such as still existing fossil fuels atomic, Solar, wind, safety and versatility of methanol makes the disclosed recy geothermal, etc. Photolytic, thermal, enzymatic, and other cling of carbon dioxide further desirable. means of cleaving of water to hydrogen are also feasible. 0064. As known in the art, methanol can be easily treated 0060 CO emissions from fossil fuel burning power to produce varied derived compounds including dimethyl plants and varied industries can be captured on-site. Separa ether, produced by dehydration of methanol, and dimethyl tion of CO from such industrial exhausts is well-developed. carbonate, produced by reaction of the methanol by oxidative The major advantage in the newly disclosed chemical recy carbonylation. Methanol and methanol-derived compounds, cling of these sources to methanol and derived products is that e.g., DME and DMC as oxygenated fuels, can be easily carbon dioxide is not released into the atmosphere and serves blended with gasoline and used in internal combustion or as renewable carbon source for fuels and varied essential Diesel engines with only minor modifications. For example, products. methanol can be added to gasoline up to 85% by volume to 0061 The separation and use of atmospheric CO, allows obtain commercially viable M20 or M85 fuels. Methanol can chemical recycling of CO as a renewable and unlimited also be used to generate electricity in fuel cells, by either first source of carbon. CO absorption facilities can be placed catalytically reforming methanol to H and CO or by reacting proximate to a hydrogen production site to enable Subsequent methanol directly with air in our co-invented direct methanol methanol synthesis. Although the CO content in the atmo fuel cell (DMFC) (see U.S. Pat. No. 5,928,806). DMFC US 2009/0293348 A1 Dec. 3, 2009 greatly simplifies the fuel cell technology and makes it readily chemical recycling of carbon dioxide results in mitigating the available to a wide range of applications, including portable global warming to ensure the well being of future genera mobile electronic devices and electricity generators. tions. 0065. In addition to being a convenient safe energy storage 0070. As methanol is readily dehydrated to dimethyl ether, and transportation material and fuel, methanol and methanol the disclosed conversion of carbon dioxide to methanol is also derived DME are useful starting materials for various chemi adaptable to produce dimethyl ether for fuel and chemical cals such as formaldehyde, acetic acid, and varied other prod applications as previously noted. ucts including polymers, paints, adhesives, construction 0071. The disclosed new efficient production and recy materials, synthetic chemicals, pharmaceuticals, single cell cling of methanol from industrial or natural carbon dioxide sources, or even from the air itself, provides the needed raw proteins and the like. material for replacing the diminishing fossil fuel through the 0066 Methanol and/or dimethyl ether can also be conve METHANOL ECONOMY process. The conversion of car niently converted in a single catalytic step to ethylene and/or bon dioxide to methanol requires significant energy, which propylene (e.g., in the methanol to olefin or MTO process), can be provided by any energy source including offpeak the building blocks for producing synthetic hydrocarbons and electric power of fossil fuel (e.g., coal) burning power plants, their products. atomic energy or any alternative energy sources (Solar, wind, geothermal, hydro, etc.). As indicated, energy generated must be conveniently stored and transported. The conversion of CO to methanol allows storage and transportation of energy as a liquid product in an economic and safe way much more 0067. This means that the hydrocarbon fuels and products Suitable than highly volatile hydrogen gas. Methanol and/or currently derived from oil and natural gas can be obtained dimethyl ether are efficient fuels for internal combustion from methanol, which itself can be obtained from the chemi engines or direct oxidation methanol fuel cells (DMFC as cal recycling of natural or industrial CO2 sources. A further well as raw materials for olefins, synthetic hydrocarbons and utilization of methanol can be ready conversion to ethanol via other products). The present invention significantly extends hydration of derived ethylene. The overall conversion is the scope of the utilization of carbon dioxide for the produc tion of methanol and/or dimethyl ether from natural or indus trial sources, even to the air itself. 0068. Many further applications are known and can be 0072. Using the previously described principles of the applied to carbon dioxide derived methanol. It should be invention, a new and inventive way is now disclosed to render emphasized that there is no preference for any particular fossil fuels and their products renewable on the human time energy source needed for producing methanol. All sources, scale and environmentally carbon neutral on combustion, including still existing fossil fuels alternative sources and allowing the mitigation of excess carbon dioxide and the atomic energy can be used. Energy once produced must be, prevention of its build up in the atmosphere to counteract the however, stored and transported, for which methanol is pre resultant global warming effects, through the use of new ferred in contrast to difficult to handle and essentially hazard useful fuels and products and the recycling of the emissions ous hydrogen. from the combustion of such fuels and products. 0069. The improved and efficient selective conversion of 0073. The present invention describes a process for effec carbon dioxide, which can be from atmospheric or industrial tive environmental recycling of carbon dioxide and methanol. exhaust sources, to methanol according to the present inven Without being limiting, this process ensures extraction of tion also provides the needed raw material for what is now carbon dioxide, its conversion to methanol and/or dimethyl termed as the METHANOL ECONOMY process. This ether, energy production obtained from the use of methanol allows convenient storage and transport of energy as a con and/or dimethyl ether, further extraction of the carbon dioxide Venient, safe liquid product that can be used as a fuel in bi-product obtained in the energy-generating methanol and/ internal combustion engines or in fuel cells and as a starting or dimethyl ether reaction, and repeating a desired number of material for synthetic hydrocarbons and their varied products. times in cycles the above sequence of steps. Even if initial, The METHANOL ECONOMY process encompasses both temporary carbon dioxide storage would be affected by the efficient direct conversion of still available natural gas sequestration to develop, such stored CO can subsequently resources to methanol or dimethyl ether (as disclosed in U.S. conveniently used to produce methanol. patent application Ser. No. 1 1/402,051 filed Apr. 12, 2006, the 0074. In these embodiments, the carbon dioxide can be entire content of which is incorporated herein by reference obtained from any available source disclosed herein, such as, thereto) with first producing Syn-gas as well as the presently without being limiting. These include high CO containing disclosed reductive chemical conversion of carbon dioxide. emissions of power plants burning fossil fuels, fermentation The concept of the METHANOL ECONOMY process pre processes, calcination of limestone, other industrial or natural sents significant advantages and great economic possibilities. sources, as well as even the low CO content of the atmo In the METHANOL ECONOMY process, methanol is used sphere. In any embodiment, the methanol in the present as (1) convenient energy storage medium, which allows con invention can be obtained from any available source. Such as, Venient and safe storage and handling; (2) readily transported without being limiting, the processes described in the present and dispensed fuel, including for internal combustion engines application, alternative agricultural and live sources, or any and methanol fuel cells; and (3) feedstock for synthetic other industrial or naturally occurring process. hydrocarbons and their products currently obtained from oil 0075. In a preferred embodiment of the invention, the and gas resources, including polymers and even single cell carbon dioxide source is an exhaust stream from fossil fuel proteins, which can be used for animal feed or human con burning power or industrial plant, or a source accompanying sumption. The environmental benefits obtained by disclosed natural gas. A non-limiting utility of the present invention is US 2009/0293348 A1 Dec. 3, 2009

in connection with coal and other fossil fuel burning power formate conversion is about 85 to 90%. A similar reductive plants and industries producing large amounts of carbon conversion can also be achieved electrochemically. dioxide. After obtaining and separating from the source, and withdrawing from sequestration storage facilities, the carbon Example 5 dioxide is then Subjected to hydrogenative chemical conver I0083 Methyl formate is catalytically reduced with formic sion to form methanol, and/or, in Subsequent reaction or reac acid over Pt/C, Rh/C, Ru?C, copper chromite and the like tions, to further form dimethyl ether or other carbon based catalyts in the gas phase at atmospheric pressure in the tem fuels and products. The energy required for the process can come from any Suitable energy source, including, but not perature range of 100-200° C. Selectivity to methanol is over limited to, excess energy from fossil burning power plants in 70-90% and methyl formate conversion is 50% in a single off peak use periods, alternative energy sources, atomic pass. energy sources, etc. Various energy sources are well known in Example 6 the art. On combustion of the carbon based fuels and prod ucts, the released carbon dioxide bi-product is then converted I0084 Methane is reformed with carbon dioxide and (dry again to methanol, as described above, and the cycle is reforming) steam (wet reforming) in proportions to give a 1:2 repeated a desired number of times. mixture of carbon monoxide and hydrogen under conditions 0076. In an alternative embodiment of the invention, the of our co-pending “bi-reforming Patent applications. This carbon dioxide source is the air of our atmosphere. The car mixture is Subsequently used to produce methanol according bon dioxide is separated and absorbed by using means either to the equation CO+2H->CHOH. The carbon monoxide disclosed in the art and/or described in the present applica formed can also reacted as in examples 1-3 with methanol to tion, and it is then recycled, as described in the foregoing give methyl formate, which according to Examples 4 and 5 sections. can be hydrogenatively converted doubling the amount of methanol under moderate temperatures and pressures. EXAMPLES I0085. These examples illustrate the general utility of the present process of carbon dioxide to methanol conversion but 0077. The following examples illustrate but not limit the skilled practitioners can utilize the disclosure and teachings utility of the present process. They are based on the use of provided herein to generate a suitable variation thereof. The known suitable or modified chemical reactions that are process allows production of derived fuels, products thereof applied to the processes of the invention. and other applications reducing or replacing reliance on fossil fuels. At the same time it also safeguards the environment by Example 1 significantly reducing carbon dioxide emissions and the pres ence of harmful lighter carbon dioxide content in the atmo 0078 Carbon dioxide in water is known to be electro sphere. The present invention provides a convenient way to chemically reduced to formic acid and formaldehyde with recycle carbon dioxide to either prevent its emission into the methanol formed in Smaller amounts while avoiding methane atmosphere or to remove part of it from the atmosphere to formation in aqueous media over Sn, Pb, In, Zn, Au, Cu, Pd and related electrodes at room temperature in the range of generate a renewable fuel such as methanol or dimethyl ether. 40-90% current efficiency. Example 7 007.9 The above mentioned product mixture containing formic acid and formaldehyde when passed over a Supported I0086 CO is electrochemically reduced in aqueous solu basic catalyst in a tube reactor at temperatures between 100 tions over gold and related catalysts at the cathode to CO and and 300° C. forming methanol and methyl formate in overall also H. (by concomitant electrolysis). The CO and H mix yield of 40 to 50%. ture (syngas) is catalytically converted to methanol (see co pending bireforming application). Example 2 What is claimed is: 1. An environmentally beneficial method of preparing a 0080 Carbon dioxide is reacted with a suitable carbon renewable fuel, which method comprises: source (such as charcoal and the like) attemperatures of 550 obtaining carbon dioxide from a natural or chemical source to 900° C. to produce carbon monoxide in what is called the that would otherwise be present in or discharged into the Boudouard reaction. CO then is reacted with methanol to give atmosphere; and methyl formate and catalytically hydrogenative converted to producing an energy storage and transportation material or produce a doubled amount of methanol. a fuel Sufficient to generate energy by hydrogenatively converting the carbon dioxide thus obtained under con Example 3 ditions Sufficient to produce methanol as the material or 0081 Carbon dioxide is electrochemically reduced to car fuel. bon monoxide and Subsequently is reacted further as in 2. The method of claim 1, wherein the methanol is pro Example 7. duced by reducing the carbon dioxide under conditions Suf ficient to produce a reaction mixture containing formic acid Example 4 with concomittant formation of formaldehyde and small amounts of methanol and methane, followed, without sepa 0082. The methyl formate obtained by the processes of ration of the reaction mixture, by a treatment step conducted Examples 1-3 is catalytically reduced with molecular hydro under conditions sufficient to convert the formaldehyde to gen in the gas phase over copper chromite or noble metal formic acid and methanol. catalysts at atmospheric pressure in the temperature range of 3. The method of claim 2, wherein the methanol is pro 100-230° C. Selectivity to methanol is >90% and methyl duced by generating carbon monoxide from the carbon diox US 2009/0293348 A1 Dec. 3, 2009

ide through a high temperature reaction with carbon, reacting Source, without separation of the reaction mixture, into the carbon monoxide with the previously produced methanol methanol, including reacting of the formic acid with metha under conditions sufficient to form methyl formate, followed nol to form methyl formate, followed by hydrogenating the by catalytically hydrogenating the methyl formate under con methyl formate under conditions sufficient to form double the ditions sufficient to form additional methanol. starting amount of methanol. 4. The method of claim 1, wherein the methanol is pro 9. The method of claim8, wherein the hydrogen needed for duced by reducing the carbon dioxide under conditions Suf the hydrogenation of methyl formate is obtained at least some ficient to produce a reaction mixture containing formic acid part from cleavage of the formic acid from the reaction mix with concomittant formation of formaldehyde and small ture. amounts of methanol and methane, augmenting the reaction 10. The method of claim 1, wherein the hydrogen needed mixture by reacting, without separation of the reaction mix for the hydrogenative conversion of carbon dioxide is ture, the formaldehyde into methanol with some of the formic obtained by the reforming of methane or natural gas or by acid used as a hydrogen source, and reacting some of the electrolysis of water using an available energy source. formic acid with methanol to form methyl formate, followed by catalytically hydrogenating the methyl formate under con 11. The method of claim 1, which further comprises com ditions sufficient to form methanol. busting the fuel to form an exhaust stream that contains car 5. The method of claim 1, which further comprises trans bon dioxide and in a manner that allows collection of the porting the thus produced methanol fuel to a facility where the exhaust stream, and recovering the carbon dioxide of the fuel is to be combusted to generate energy. exhaust stream for use as the chemically recyclable source of 6. The method of claim 5, which further comprises com carbon dioxide for preparing additional fuel. busting the methanol fuel in a power plant to form an exhaust 12. The method of claim 10, wherein the exhaust stream is stream that contains carbon dioxide, and recovering the car obtained by combusting the fuelina fossil fuel burning power bon dioxide of the exhaust stream for use as the chemically or industrial plant. recyclable source of carbon dioxide for preparing additional 13. The method of claim 1, which further comprises dehy fuel. drating the methanol under conditions sufficient to produce 7. The method of claim 1 wherein the methanol is produced dimethyl ether; using the dimethyl ether as the fuel or as a by hydrogentatively converting the carbon dioxide to form a component of the fuel. reaction mixture that contains methanol, formic acid and 14. The method of claim 13, which further comprises uti formaldehyde, followed, without separation of the reaction lizing. as the convenient energy storage and transportation mixture, by a treatment step conducted under conditions Suf materials, the methanol or dimethyl ether in order to mini ficient to convert the formaldehyde and formic acid to metha mize or eliminate the disadvantages or dangers inherent in the nol. use and transportation of hydrogen, LNG or LPG. 8. The method of claim 7, which comprises reacting the formaldehyde with the co-formed formic acid as a hydrogen c c c c c