Hydrogenation of CO2 is another option of methanol synthesis.

It is mainly used for the purpose of mitigating greenhouse effects of power plants and cement factories. Hence, production facility should be build near these plants to lower transport cost of CO2. For this reaction, H2 is obtained from water electrolysis which is a costly process. Also, CO2 can be captured from air in which 0.037% concentration. Reactions are : CO2 + 3H2 CH3OH + H2O CO2 + 2H2O + electrons CO + 2H2 (+ 3/2 O2) CH3OH First reaction is catalytic hydrogenation and second is electrical reduction of CO2 via hydrogen. As told before, hydrogen for first reaction comes from water electrolysis and in second reaction, electrons can be provided via power. Electric cost must also be considered for first reaction like electrolysis cost of first reaction. When looking these both methods, only advantage of methanol production is reduction of CO2 emission of fossil fuel burning power plants. However, process cost of production is very high considering new technology methods. First reaction mechanism is applied by Mitsui Chemical Inc. of Japan in Osaka. From March of 2010, they have yield 33,000 gallons (U.S. equivalent) of methanol. H2 is obtained by photoelectrocatalyst hydrogen production technology. This newly developed process uses highly efficient thin film, anatase titania photocatalyst that has a quantum efficiency of 60%. After capturing H2, it is mixed with CO2. Carbondioxide source of company is their own process waste system. After mixing, gas is pumped to high-activity catalyst unit. Zinc oxide and copper are used as catalysts. Efficiency of unit for methanol is 82%. Hence, unused amount (18%) of CO2 is feed back loop for same unit.

Set-up cost for plant is around 14 million dollars and photoelectrocatalysis unit (plus solar array) is not discussed. For 33,000 gallons of methanol / year (around 90 tonnes per year) is not feasible but can be considered side plant of CO2 emitting plants. Hence, in our project, this method is not in consideration. Alternatively, there is another process method of producing methanol by hydrogenation of carbondioxide. In Korea Institute of Science and Technology, new method, carbon dioxide hydrogenation to form methanol via a reverse-water-gas-shift reaction ( the CAMERE process), is examined. The trick is firstly converting CO2 to CO and water by reverse-water-gas-shift reaction to remove water before methanol synthesis. By removal of water, catalyst is used more efficiently. In result, the overall methanol yield increased up to 89% to 69%. In conventional way of production, pure CO2/H2 mixture was used in copper element catalysis and one step reaction was leading to methanol and water. But water was covering catalyst surface and inhibiting the adsorbtion of CO2 for next reaction. Hence, elimination of water became an obligation for higher efficiency in catalytic reaction. There are two reactions of CO2 hydrogenation: CO2 + 3H2 CH3OH + H2O (H = -49.43 kJ/gmol (exothermic)) CO2 + H2 CO + H2O (H = +41.12 kJ/gmol (endothermic)) As it is seen, two reactions compete with each other in terms of hydrogenation. First reaction favors lower temperatures than second reaction. In process, two reactors are used. First reactor is conversion of CO2 to CO in 773 K, 10 atm. Then, removal of water comes. After separator, syn gas is directly compressed to methanol reactor with catalysis. Because of lack of water, reaction occurs more effectively. In

second reactor (methanol reactor), first reaction occurs at 523K and 30 atm. Also, feed should be given at 0.1 concentration of CO2 in second reactor for higher efficiency (13.4%). Catalyst efficiencies are given below:

As it is seen, even in progress catalyst, efficiency is not high.

Methanol synthesis reaction is aligned after RWReactior. At RWReactor, the CO2 conversion to CO was 61% per pass and CO2 composition in the outlet is 39% in carbon base. After removal of water, gas mixture is sent to methanol production reactor. The difference of methanol synthesis reactor is reduction of recycle gas volume. The rest of unreacted gas should be recycled. In conclusion, methanol production is increased from 37.01 tones/h to 47.87 tones/h with respect to conventional hydrogenation of CO2. Comparison between two is given below:

Material balances are :

Operation and equipment cost comparison:

When evaluating feasibility table of production process, it becomes clear to understand the irrationality of starting this kind of process. Even these values are taken from by production maximization, efficiency of catalysts are too low. It was given in the table. Also, experiment does not include cost of H2 production and does

not consider alternative H2 sources. In our first example of Mitsui factory in Osaka (the plant is established), set up cost is around 14 million dollars. If H2 production is included, the cost goes beyond even 40 million dollars. This kind of facility can not overcome a production like 50 000 tones/year but it is suitable to reduce CO2 emission and evaluate excess amount of CO2.