Thursday, June 25, 2009

Catalytic CO2 Recycling

This seems to be the day for talking about CO2. A correspondent brought this paper to my attention and it is intriguing because it represents significant investment and serious engineering effort.

My problem stems from the reality that CO2 is already at the bottom of the energy well in any universe unable to produce perpetual motion. Yet here we have a serious effort to convert CO2 back into exothermic products. Going through the work I see nothing to think otherwise so far except to assume that the external inputs described will drive the system. After all that is what happens with Mother Nature thanks to the sun.

Otherwise, pushing water uphill is a lousy business bet.

I left the diagrams out and I do not have the link for the article itself, but there is enough here.

It ultimately needs an efficient way to split water, and we have had recent progress on that front. That at least might result in an efficient system that may in some manner be useful. The nano tube reactor needs explanation as does the proprietary catalyst at least as to performance. I would have expected to see more on this already.


Catalytic CO2 Recycle (CCRTM) Technology

Mega Symposium, August 25, 2008
Manuscript Control #8

AUTHORS:

*John Ralston, Director, Recycle CO2 (RCO2) Inc., P.O. Box 3442, Kingsport, TN, 37664 USA

Erik Fareid, CEO, RCO2TM AS, Berghagen 8, 1403 Langhus, Norway

ABSTRACT

A process has been developed and patents have been applied for in most of the countries of the world for the recycling of CO2 from the flue gas produced in hydrocarbon combustion. The CO2 is catalytically converted to two useful products, methane and water, both of which have market value. Oxygen is also generated in this process. The methane produced can be used to generate electricity. This is an energy efficient process for the recycling of CO2. This process consists of three chemical reactions; the combustion of methane, the splitting of water, and the hydrogenation of CO2. All these reactions are described below.

INTRODUCTION

RCO2 AS is a small research company located in Norway. Investors from Europe, Eastern Europe, and the USA have invested money in RCO2 AS to develop a technology that will recycle CO2 into useful products. Nalco/Mobotec have invested in this development. Most of the technologies in use and being developed today to capture or sequester CO2 require the isolation, compression, and transport of the CO2 to a burial site. The CCR technology will eliminate these requirements.

The KEY word concerning the CCR technology is the word “RECYCLE”. This is a new concept relating to CO2 that many people cannot understand and/or accept. Today many waste products are recycled. The most prominent are aluminum, plastics, and paper. Why do we recycle these waste products? The answer is to conserve energy. When energy is conserved, CO2 is reduced. By recycling aluminum 95% of the energy needed to produce aluminum is saved. By recycling plastics 70% of the energy is saved and by recycling paper 40% of the energy is saved. CO2 is also a waste product. By recycling CO2 up to 76% of the energy can be saved.

EXPERIMENTAL

Chemical Reactions

There are three basic chemical reactions involved in the CCR technology. These are:

combustion of methane

CH4 + 2O2 = CO2 + 2 H2O ΔH300K= -803 kJ/mol

splitting of water

4 H2O = 4 H2 + 2 O2 ΔH300K= +242 kJ/mol

hydrogenation of carbon dioxide (methanation)

CO2 + 4 H2 = CH4 + 2 H2O ΔH300K= -165 kJ/mol


Brief descriptions of these reactions are as follows:

1. Combustion of Methane

The combustion of methane will take place in a gas turbine and consists of the burning of the amount of methane produced in the methanation reaction mixed with the amount of natural gas that will need to be added to keep the turbine at capacity. The oxygen produced in the splitting of water reaction will be mixed with the combustion air to reduce the amount of nitrogen resulting in mainly CO2 and water in the flue gas. The gas turbine will produce electricity using about 35 % of the energy generated in the gas turbine. The remaining 65% of the energy generated will be combined with the excess energy generated by the hydrogenation of CO2 reaction and will be used to drive the water splitting reaction. The result will be that at least 90% of the energy generated will be used efficiently in an optimized system.

2. Splitting of Water

The splitting of water to produce “green” hydrogen is the key reaction of this process. It is absolutely essential that the energy used to split the water is not energy that will generate additional CO2. There are several ways to generate “green” hydrogen. These are:

1. Electrolysis of water using a combination of solar and wind energy.
2. Photo chemical reaction using energy directly from the sun
3. Thermal chemical reaction using membrane separation
4. Production of hydrogen from biomass gasification

From this list we will be operating pilot plants using the first three possible ways to produce “green” hydrogen. The first and the last ways are commercial processes already. In an actual commercial installation it may be necessary to use a combination of two or more of these ways to generate hydrogen depending on the unit generating the CO2.and the location of this unit In this paper we would like to briefly describe the other two ways to split water that are under consideration. One of the most interesting is the photo chemical reaction using free energy from the sun. It is expected that this process will be a commercially available during the first quarter of 2009. The diagram below shows how this process will operate.

With this process the energy from the sun is collected and magnified and sent to the nanotube reactor. The collector/magnifier has the capability to generate energy up to the equivalent of 50 suns. The collector/magnifier is programmed to follow the sun as it moves across the sky. The reactor consists of many nanotubes and a proprietary catalysis that will split water at ambient temperature. The water for this process is the water that has been generated and separated from the combustion of natural gas and methanation reactions. This water has been heated using the waste heat from the combustion of natural gas and the heat generated from the methanation reaction. The hydrogen generated is sent to the methanation reactor to be mixed with the flue gas coming from the combustion of natural gas. The oxygen generated is sent to the combustion reaction to be mixed with the combustion air. It will be necessary to store both the hydrogen and oxygen to maintain a supply of both during periods of time when the energy of the sun is not available. The storage of both hydrogen and oxygen will be necessary no matter which type process is used to generate “green” hydrogen. The hydrogen can be stored at 200 psi without any compression necessary.

This reaction will take place in a specifically designed reactor in the presence of an efficient membrane and a proprietary catalyst. The energy required to drive this reaction will come from the excess energy developed by the combustion of natural gas and the methanation reaction. No additional energy will be added to complete this reaction. The amount of hydrogen produced will depend on the amount of excess energy from the combustion of natural gas and energy developed during the methanation reaction that is available. For 100% conversion of CO2 to methane additional energy will be needed to produce more hydrogen. The oxygen generated will be mixed with the combustion air to the turbine to reduce the formation of NOx and make the turbine more efficient. It is estimated that enough hydrogen will be generated by the combination of two or more ways to generate “green” hydrogen will convert between 55 to 70% of the CO2 generated to methane.

3. Methanation

Methanation is a well known chemical reaction used in the production of urea. It is also know as the Sabatier reaction. Shown below is one way this reaction will be used in the CCR technology.

ENERGY EFFICIENCY

The CCR Technology will improve the energy efficiency of a gas turbine. It will also result in a more efficient use of energy compared to a gas turbine with combined cycle. In the diagram below it can be noted that a gas turbine with combined cycle will be 59% energy efficient.

However, a gas turbine with CCR will increase the efficiency of the turbine to more than 90% because 61.5% of the energy is returned in the form of methane recycled from the CO2. The amount of CO2 recycled to methane can be increased by adding more renewable energy such as sun energy to the water splitting reaction. The gas turbine with CCR will reduce CO2 emissions compared to combined cycle. The CO2 emissions will be reduced by 61.5%


STATUS OF DEVELOPMENT

Currently three pilot plants are in operation to develop the necessary information to continue onto the commercialization step. These pilot plants are located as follows:

NTNU, Norway
CNRS, France
Desert Research Institute, USA

Each pilot plant will be using a different way to split water to produce hydrogen which will be reacted with the CO2. At an actual installation one or more ways to split water may be used depending on type of installation and its location. Once the way or ways that will be used has been determined, material and energy balances can be developed. It is estimated that the development work at these three pilot plants locations will be completed by the end of 2009. An additional pilot plant will be built in Smithfield, VA using at least two different ways to split hydrogen.

COMPARISON WITH OTHER CO2 CAPTURE TECHNOLOGIES

With the CCR technology being developed by RCO2 there is no isolation, no compression, no transportation, and no sequestration of the CO2. This immediately can be equated to a considerable savings. It will also produce revenue since by using the CCR technology the amount of natural gas needed for combustion in a gas turbine can be reduced by at least 55% and still produce the same amount of electricity. As a result, the CCR technology has the potential to produce revenue. It will be commercially advantageous to use the CCR technology even if CO2 reduction regulations are not put into effect.

SUMMARY

The sole objective of the CCR technology being developed by RCO2 is to reduce the current cost of removing CO2 from flue gas. The laboratory phase has been completed. Pilot plants will be operated in France, Norway, and the USA as the next step to commercialize the CCR technology. When fully developed the CCR technology will not only recycle CO2, but also will result in a more energy efficient way to generate electricity using natural gas.

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