Method for reducing CO2, CO, NOX, and SOx emissions

Hazardous or toxic waste destruction or containment – Containment – Geologic – marine – or extraterrestrial storage and containment

Reexamination Certificate

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C588S252000, C405S129100, C071S061000, C071S063000, C423S354000, C423S359000, C423S220000, C423S420000

Reexamination Certificate

active

06447437

ABSTRACT:

CROSS-REFERENCE TO RELATED APPLICATIONS
(Not Applicable)
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates generally to chemical, geological, and photosynthetic sequestration of CO
2
, pollution control systems, and particularly to a method for removal of CO
2
, CO, NO
x
, and SO
x
emissions, for reduction of NO
3

contamination of surface water and groundwater, and for sequestration of inorganic carbon into soil and subsoil earth layers.
2. Description of the Relevant Art
The rise in anthropogenic greenhouse gas emissions, particularly CO
2
, is attributed largely to the increased use of fossil fuels. Fossil fuels, particularly coal, oil, and natural gas, are the primary fuels of industrialized society. These fuels supply abundant energy at low cost. Currently 22 gigatons (Gt) of CO
2
per year (equivalent to 6 Gt C/yr) is emitted as a result of the use of fossil fuels. Coal is the fuel most widely used for the generation of electricity worldwide because it is readily available, easily transportable, and relatively inexpensive. Approximately 70% of all the electricity used in the United States is generated from coal and natural gas. Oil-derived products dominate transportation fuels. Worldwide, coal-fired power plants result in about 1.8 of the 6 Gt C/yr of CO
2
emissions. The remainder is from the use of fossil fuels in transportation, industry, and residences.
The increasing effects of CO
2
emissions and global warming have challenged the industrialized world to find new and better ways to meet the increasing need for energy while reducing greenhouse gases. A treaty recently negotiated in Kyoto, Japan, would require developed nations to reduce their emissions of greenhouse gases below 1990 levels by the year 2010. New strategies for economically controlling the emissions of greenhouse gases are therefore required.
The process of photosynthesis removes more CO
2
from the atmosphere than any other reaction. Each year, land-based green plants remove about 403 Gt CO
2
(equivalent to 110 Gt C) from the atmosphere and the oceans draw approximately 385 Gt CO
2
as well. An enhancement as small as 6% for terrestrial or ocean photosynthesis is sufficient to remove 22 Gt CO
2
(6 Gt C), or the entire amount of CO
2
emitted into the atmosphere annually from the use of fossil fuels. The requirements of the recent Kyoto Treaty could be satisfied by an increase of only 0.62% in annual global photosynthetic biomass production, if the increased biomass is in a stable form such as woody products.
In many parts of the world, land-based photosynthesis in the form of crop production is limited by the lack of fertilizers. Nitrogen in the form of ammonium, NH
4
+
, is the most-needed fertilizer since it is an essential substrate for the synthesis of all amino acids—and thus proteins, chlorophyll, and many lipid molecules of membranes. All are important components of photosynthetic membranes. An increase in the use of fertilization can dramatically enhance photosynthetic activity by stimulating more green plants to grow. This would result in the capture of more sunlight energy and the fixation of more CO
2
. A more abundant supply of environmentally friendly fertilizers and appropriate fertilization of trees can be a positive contribution to global CO
2
sequestration.
SUMMARY OF THE INVENTION
According to the invention, industrial combustion facilities can be integrated with greenhouse gas-solidifying fertilizer production reactions so that CO
2
, CO, NO
x
, and SO
x
emissions are converted into carbonate-containing fertilizers, primarily NH
4
HCO
3
and (NH
2
)
2
CO, that can enhance the sequestration of CO
2
into soil and the earth subsurface, reduce the problem of NO
3

runoff, and stimulate photosynthetic fixation of CO
2
from the atmosphere. Therefore, CO
2
emission sources, such as from a fossil fuel-fired power plant, are directed to a reactor before they can be emitted through smokestacks. In the reactor, CO
2
is converted to at least one selected from the group consisting of NH
4
HCO
3
and (NH
2
)
2
CO. The NH
4
HCO
3
and/or (NH
2
)
2
CO is then applied into soil to enhance carbonization of soil and subsoil earth layers and to stimulate photosynthetic fixation of CO
2
from the atmosphere.
The production of NH
4
HCO
3
and (NH
2
)
2
CO is summarized by the reactions:
2CO
2
+N
2
+3H
2
+2H
2
O →2NH
4
HCO
3

CO
2
+N
2
+3H
2
→(NH
2
)
2
CO↓+H
2
O
Methane (CH
4
) and/or carbon monoxide (CO) can be utilized instead of hydrogen gas according to the following reactions:
5CO
2
+4N
2
+14H
2
O+3CH
4
→8NH
4
HCO
3

CO
2
+4N
2
+2H
2
O+3CH
4
→4(NH
2
)
2
CO↓
3CO+N
2
+5H
2
O→2NH
4
HCO
3
↓+CO
2
The invention is also useful for removing NO
x
and SO
x
emissions by the following reaction pathway:
wherein R is at least one selected from the group consisting of CO, H
2
and CH
4
.
Catalysts are used to catalyze the reactions of the invention. Preferred catalysts include, but are not limited to, nanometer-structured and/or hybridized metallocatalysts of Ru, Os, W, Fe, Pt, Pd, and Ni.
Important features and advantages of the invention include the following:
1. Integration of combustion facilities with greenhouse gas—solidifying fertilizer production reactions—conversion of CO
2
, CO, SO
x
, and NO
x
. emissions into carbonate-containing fertilizers (primarily, ammonium bicarbonate and urea);
2. Sequestration of CO
2
by enhanced carbonation of soil and subsoil terrains through the application of the carbonate-containing fertilizers;
3. Enhancement of photosynthetic fixation of CO
2
from the atmosphere by the technology-driven production of carbonate-containing fertilizers.
This invention utilizes waste heat from combustion facilities and converts various industrial waste gases, including CO
2
, CO, H
2
, CH
4
, N
2
, NH
3
, NO
x
, and SO
x
, into commercial products, primarily fertilizers. It has the capability to solidify as much as 90% of the CO
2
from flue gas and place the carbonate-containing fertilizers into soil and subsoil earth layers, which at the same time can reduce NO
3

contamination of surface water and groundwater. Based on the current annual world consumption of nitrogen fertilizers, as much as 315 million tons of CO
2
per year from smokestacks could potentially be placed as bicarbonate into soil by worldwide use of this invention. In addition, this invention has the potential to remove CO, SO
x
, and NO
x
emissions and to enhance photosynthetic fixation of CO
2
from the atmosphere. Therefore, the invention also has significant value in improving energy efficiency, enhancing economic competitiveness, and reducing environmental impacts of both the fossil energy system and the fertilizer industry.


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patent: 4197281 (1980-04-01), Muenger et al.
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patent: 5834722 (1998-11-01), Tokunaga et al.
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patent: 6162409 (2000-12-01), Skelley et al.
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Lee, J.W., et al., “Molecular ionic probes: a new class of Hill reagents and their potential for nanofabrication and biometallocatalysis,” J. Phys., Chem., 102:2095-2100(1998).
Blanco, J., et al., “Two-bed catalytic system for Nox/SOx removal,” Catal. Today 42:85-92 (1998).
Lee, J.W., et al., “Bioelectronics and biometallocatalysis for production of fuels and chemicals by photosynthetic water splitting,” Appl. Biochem. Biotechnol., 51/52:295-305 (1995).
Lee, J.W., “Photosynthetic water splitting: in situ photorecipitation of metallocatalysts for photoprevolution of hydrogen a

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