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LITERATURE REVIEW:

Combustion exhaust gas is a gaseous mixture just as air is a gaseous mixture, though with a different composition
from that of air; Air is a mixture of nitrogen, oxygen, trace amounts of carbon dioxide and a few other distinct noble
gases, in different percentages: while, combustion exhaust gas from various sources mostly contain these pollutants;
nitrogen oxides, un-burnt hydrocarbons, carbon monoxide, carbon dioxide and sulfur dioxide, in varying percentages.
In the search and research for solutions to pollution, with the advent and application of catalytic converters to
combustion exhaust gas, carbon monoxide is converted to carbon dioxide, while nitrogen oxides are converted to
nitrogen and oxygen, and un-burnt hydrocarbons are converted to carbon dioxide and water.
However, global warming and acid rainfall still occur because of the carbon dioxide and sulfur dioxide still
contained in combustion exhaust gas treated with catalytic converters.
As avoiding such global environmental pollution presently proves to be better than possible, being actually already
proven as practical, economical and profitable; one would like ‘the biblical Mary’, definitely, have to ask, the –big
question- How can this thing be…? And here is the simple answer : By using gas compression, cryogenic fractional
distillation, and liquefaction to produce or separate and store carbon dioxide and sulfur dioxide from combustion
exhaust gas treated with catalytic converters: the carbon dioxide separated and stored (from combustion exhaust gas)
can be used for producing, fire extinguishers, carbonic acid etc; and the sulfur dioxide separated and stored (from
combustion exhaust gas) can be used for producing, fertilizers, food preservatives, bleach, sulfuric acid etc.
The realization or conclusion was reached upon the well known and long proven fact that: Gas compression,
cryogenic fractional distillation and liquefaction are well known practical methods for separating liquid as well as
gaseous mixtures into the individual liquids or gases that make up the mixtures.
Presently these methods are used in separating or producing and storing nitrogen, as well as oxygen, from air: and
they are also used in separating or producing and storing carbon dioxide, nitrogen and argon, from combustion exhaust
gas (containing 10% of oxygen by volume, preferably, for economical reasons).
It can further be concluded that immediate or later application(s) of the present realization or invention would
greatly benefit the environment and everyone [especially members of OPEC whose crude oil have high sulfur content,
because the present invention makes desulfurization of their crude oil unnecessary, as combustion of their (high sulfur
content) crude oil fractions would mean, more sulfur dioxide is separated and stored, from combustion exhaust gas,
using the present invention]: To be categorical, everyone who would benefit from the application of the present
invention are; crude oil fractions producers, marketers, and consumers, as well as industries that produce carbon
dioxide and sulfur dioxide, and industries that use carbon dioxide and sulfur dioxide as raw materials.
As carbon dioxide and sulfur dioxide are major useful industrial chemicals/raw materials, when both are produced
using the present invention, they may be sold by crude oil fractions consumers to crude oil fractions marketers, who in
turn sell off to industries that produce carbon dioxide and sulfur dioxide, and industries that use either of both
chemicals; these industries would of course spend less than they usually did to buy the chemicals produced this way: so
everyone profits.
These industries and crude oil fractions producers would also be principal and profiting partners in producing, and
marketing the present invention; they would also be responsible for integrating the present invention with presently
used -past, present day and future technology, so again everyone profits.

Note:
For the smooth integration of the present invention with various sources of combustion exhaust gas, the appropriate
apparatus recommended herein may be customized (size and shape wise), and set up (arrangement wise-by expert
fabricators and technicians) as it is convenient to manufacture, assemble, and use; being that, of course, the present
invention is by no means limited to the forms of embodiment described and illustrated, which have been given by way
of example: On the contrary, the present invention includes all technical equivalents to the means described, as well as
their combinations, if the latter are carried out according to the gist.
-The present invention is certainly practical and economical being a modified and simplified version of the already
known and proven practical and economical invention patent number 5100635. [As with Invention patent number
5100635, the present method provides an opportunity for reducing the cost for manufacturing liquid carbon dioxide,
same goes for sulfur dioxide, and it makes combustion exhaust gas a viable and attractive carbon dioxide (and sulfur
dioxide) source.] The present invention is also simpler and, cheaper to manufacture, and use, as its task is easier and, a
bit different from the task performed by invention patent number 5100635; being the task of the present invention is
easier and, different from that of invention patent number 5100635, the present invention therefore only employs some
parts of the process and apparatus employed in invention patent number 5100635, that is only the parts vital for
carrying out the task/agenda of the present invention-
-In other words, - the proof that the present invention is capable or viable, obviously derives from proof of previous
and numerous applications of the methods for separation of gaseous mixtures, mentioned above; the proof also derives
from numerous scientific reports prescribing that –trace or no emissions of carbon dioxide and sulfur dioxide in
combustion exhaust gas- would help much in solving the global warming and acid rainfall problems.
AIM:
Carbon dioxide and Sulfur dioxide separation or -production/extraction- from combustion exhaust gas, by gas
compression, cryogenic fractional distillation and the liquefaction, and storage of both gaseous compounds for later
use: Thereby making Crude Oil Fractions use Eco-Friendly, Economical and Profitable.

DIAGRAM(S):
Schematic of the present invention [on last page of this document], tagged FIGURE 1.
FIGURE 1 -is a schematic process flow diagram, illustrating a method for the co-production of carbon dioxide and
sulfur dioxide according to the method of the present invention.

INVENTOR:
DeGarson Oghenekevwe, et al.

REFERENCE(S):
U.S. Patent number 5,100,635, issued to Krishnamurthy, et al. http://www.patentgenius.com.
U.S. Patent number 4,690,702, issued to Paradowski et al.
Other References:
Quoted within the document; Page 5.

ABSTRACT:
The present invention is directed to a method for extracting carbon dioxide and sulfur dioxide from combustion
exhaust gas pre-treated with catalytic converters to handle nitrogen oxides, un-burnt hydrocarbons and carbon
monoxide; the method comprises the steps of (a) treating the exhaust gas to remove particulate matter, (b) compressing
the exhaust gas to a pressure in the range from about 25 psia to about 200 psia, (c) purifying the exhaust gas to remove
trace contaminants, (d) separating the exhaust gas to produce a carbon dioxide rich fraction and a sulfur dioxide rich
fraction, (e) liquefying the carbon dioxide rich fraction and distilling off volatile contaminants to produce pure carbon
dioxide, (f) purifying the sulfur dioxide rich fraction to remove contaminants, and (g) cryogenically fractionally
distilling the sulfur dioxide rich fraction to produce pure sulfur dioxide.
As carbon dioxide and sulfur dioxide are major useful industrial chemicals/raw materials, the ones produced using
the present invention may be sold by crude oil fractions consumers to crude oil marketers, who in turn sell off to
industries where carbon dioxide and sulfur dioxide are useful; these industries would of course spend less than they
usually did to buy the chemicals produced this way: so everyone profits: These industries and crude oil fractions
producers would also be principal and profiting partners in producing, and selling the present invention; this includes
integrating the present invention with past, present day and future technology, so again everyone profits.
The present invention may apply to combustion exhaust from internal combustion engines, and gas flare points, and
for the smooth integration of the present invention with various sources of combustion exhaust gas, the appropriate
apparatus recommended herein may be customized and set up as is convenient.
- The present invention is certainly practical and economical being a modified and simplified version of the already
known and proven practical and economical invention patent number 5100635. The present invention is also simpler
and cheaper to manufacture and use as its task is easier and a bit different from the task performed by invention patent
number 5100635; as the task of the present invention is easier and different from that of invention patent number
5100635, the present invention therefore only employs some parts of the process and apparatus employed in invention
patent number 5100635, that is only the parts vital to the task/agenda of the present invention.
- In other words, - the proof that the present invention is capable or viable, obviously derives from proof of previous
and numerous applications of the methods for separation of gaseous mixtures, mentioned above; the proof also derives
from numerous scientific reports prescribing that –trace or no emissions of carbon dioxide and sulfur dioxide in
combustion exhaust gas- would greatly help solve the global warming and acid rainfall problems.
Claim:

We claim:

1. A method for extracting carbon dioxide and sulfur dioxide from combustion exhaust gas which comprises the steps
of:

(a) Treating the exhaust gas to remove particulate matter;

(b) Compressing the exhaust gas to a pressure in the range from about 25 psia to about 200 psia;

(c) Purifying the exhaust gas to remove trace contaminants;

(d) Separating the exhaust gas to produce a carbon dioxide rich fraction and a sulfur dioxide rich fraction;

(e) Liquefying the carbon dioxide rich fraction and distilling off components that are more volatile than carbon dioxide;

(f) Purifying the sulfur dioxide rich fraction to remove the ‘little’- ‘left over’ carbon dioxide that ‘escaped’ extraction;
and

(g) Cryogenically fractionally distilling the sulfur dioxide rich fraction to remove oxygen and argon there-from.

2. The method according to claim 1, wherein the exhaust gas in step (a) is treated with a water absorption shower to
remove particulate matter.

3. The method according to claim 1, wherein the exhaust gas in step (b) is compressed to a pressure in the range from
about 25 psia to about 120 psia.

4. The method according to claim 1, wherein the exhaust gas in step (c) is purified to remove ‘little’- ‘left over’
nitrogen oxide contaminants by treating the exhaust gas with ammonia in the presence of a selective catalyst to produce
nitrogen and water.

5. The method according to claim 1, wherein the exhaust gas in step (c) is purified to remove ‘little’- ‘left over’ carbon
monoxide contaminants by treating the exhaust gas with an oxidation catalyst.

6. The method according to claim 1, wherein the exhaust gas in step (c) is purified to remove trace- contaminants by
treating the exhaust gas with a potassium permanganate scrubber.

7. The method according to claim 1, wherein the exhaust gas in step (c) is purified to remove water vapor by treating
the exhaust gas with a desiccant.
8. The method according to claim 1, wherein the exhaust gas in step (d) is separated by pressure swing adsorption to
produce a carbon dioxide rich fraction and a sulfur dioxide rich fraction.

9. The method according to claim 1, wherein the sulfur dioxide rich fraction in step (f) is purified to remove
contaminants by passing the sulfur dioxide fraction through a bed of zeolite molecular sieves.

Note: Molecular weight, Critical Temperature and Critical Pressure of CO2/carbon dioxide, 56g/mol, 31 degree
Centigrade and 73 Atm respectively. Molecular weight, Critical Temperature and Critical Pressure of SO2/sulfur
dioxide, 64.06g/mol, 157.6 degree Centigrade and 78.84 bar respectively. [1 Atm = 1.01325 bar]
O2 = 32, C = 24, S = 32.
Description: BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention is directed to a method for producing carbon dioxide, and (perhaps optionally) sulfur dioxide,
from a combustion exhaust gas. - More particularly, the present invention is directed to a method for separating carbon
dioxide and sulfur dioxide from combustion exhaust gas treated with catalysts or catalytic converters to handle nitrogen
oxides, un-burnt hydrocarbons and carbon monoxide

2. Description of the Prior Art

The commercial preparation of carbon dioxide and sulfur dioxide is well known in the art. Carbon dioxide is normally
produced as a by-product from chemical processes for producing ammonia, hydrogen, ethanol, ethylene oxide, and
gasoline, as well as in fermentation reactions and carbonate decompositions.

The preparation of carbon dioxide generally involves the steps of crude gas generation, purification and separation,
compression and liquefaction, drying, and rectification distillation.

Generation of crude carbon dioxide involves the combustion of liquid fuels such as fuel oil, or solid fuels such as
anthracites, coke, charcoal, and the like, with excess air to promote complete oxidation of the fuel and to provide a
carbon dioxide rich combustion exhaust gas.

Purification of the combustion exhaust gas generally involves several separate treatments to provide a gas having high
purity. These purification treatments include -washing, -absorption, -adsorption, -desorption, and the -removal of
reducing substances. Washing generally involves a water absorption shower (water wash) to remove solids (soot,
carried off ashes, etc.) and at the same time to cool the combustion gases. Various scrubbing solutions are generally
employed to remove contaminants and to reduce the components in the combustion gas mixture to carbon dioxide,
nitrogen, and oxygen. The combustion exhaust gas may also be passed through a tower containing a re-circulating
oxidizing solution such as potassium permanganate to remove traces of organic impurities carried with the gas.

The washed and scrubbed combustion gas is then separated to obtain a carbon dioxide rich fraction. In one separation
method, the combustion gas mixture is circulated through a counter-current shower of an absorbing solution such as
potassium carbonate, mono-ethanol-amine, and the like. Carbon dioxide can be desorbed by heating the carbon dioxide
saturated solution to a temperature above 100.degree. C. In another separation method, the combustion mixture is
separated by selectively adsorbing the carbon dioxide on a zeolite bed in a pressure swing adsorption system.

The purified and separated carbon dioxide is then compressed to a pressure in the range from about 230 psia to about
400 psia, dried by contacting the gas with a desiccant that can be regenerated, and then the gas is liquefied by lowering
the temperature of the gas. Finally, a rectification distillation step eliminates the small amount of nitrogen, oxygen, and
argon to provide carbon dioxide having a purity of about 99.9% by volume.

The commercial preparation of sulfur dioxide is well known in the art. Sulfur dioxide is used to make sulfuric acid,
being converted to sulfur trioxide, and then to oleum, which is made into sulfuric acid. Sulfur dioxide for this purpose
is made when sulfur combines with oxygen.

Sulfur dioxide can be prepared by burning sulfur: S8 + 8 O2 → 8 SO2

The combustion of hydrogen sulfide and organosulfur compounds proceeds similarly.

2 H2S(g) + 3 O2(g) → 2 H2O(g) + 2 SO2(g)

Roasting sulfide ores such as iron pyrites, sphalerite (zinc blende) and cinnabar (mercury sulfide) also releases SO2:
4 FeS2(s) + 11 O2(g) → 2 Fe2O3(s) + 8 SO2(g)
2 ZnS(s) + 3 O2(g) → 2 ZnO(s) + 2 SO2(g)
HgS(s) + O2(g) → Hg(g) + SO2(g)

Sulfur dioxide is a by-product in the manufacture of calcium silicate cement: CaSO4 is heated with coke and sand in
this process: 2 CaSO4(s) + 2SiO2(s) + C(s) → 2 CaSiO3(s) + 2 SO2(g) + CO2(g)

Action of hot sulfuric acid on copper turnings produces sulfur dioxide.

Cu(s) + 2H2SO4(aq) → CuSO4(aq) + SO2(g) + 2H2O(l)


REFERENCES:

U.S. Pat. No. 3,493,339, issued to Weir et al., discloses a method for producing carbon dioxide and separating argon
which comprises combusting a carbonaceous material in a mixture of argon and oxygen and separating the combustion
products to obtain carbon dioxide and argon.

U.S. Pat. No. 4,414,191, issued to Fuderer, discloses a pressure swing adsorption method for purifying hydrogen for
ammonia synthesis. Nitrogen at elevated pressure is used as the purge gas in the pressure swing adsorption separation
and the nitrogen in the purified gas is employed in the ammonia synthesis stream.

U.S. Pat. No. 4,797,141, issued to Mercader et al., discloses a method for obtaining carbon dioxide and nitrogen from
the oxygen rich exhaust gas of an internal combustion engine or turbine. The method comprises the steps of cooling the
exhaust gas, separating carbon dioxide from the cooled gas by absorbing the carbon dioxide in an alkaline solution,
recovering the carbon dioxide by liberating the gas from the carbonated solution, compressing and liquefying the
carbon dioxide, recovering the nitrogen by purifying the gas to remove contaminants, and compressing and liquefying
the nitrogen.

U.S. Pat No. 4,690,702, issued to Paradowski et al. , discloses a method and an apparatus for cryogenic fractional
distillation of a gaseous feed comprising a contact purifying –refrigeration column into the bottom of which is injected
a partially condensed gaseous feed, the said column producing in its head portion a residue gas and in its bottom
portion a liquid which is injected into a fractionating column producing in its head portion a distillate which is at least
partially condensed and injected into the head portion of the column to recover in the bottom liquid of this column the
heavy compounds contained in the vaporized fraction of the gaseous feed.

U.S. Pat. No. 5,100, 635, issued to Krishnamurthy, et al., discloses a method for carbon dioxide production from
combustion exhaust gases with nitrogen and argon by-product recovery; basically, preferably working with combustion
exhaust gas containing less than about 10% oxygen by weight which comprises the steps of (a) treating the exhaust gas
to remove particulate matter, (b) compressing the exhaust gas to a pressure in the range from about 25 psia to about 200
psia, (c) purifying the exhaust gas to remove trace contaminants, (d) separating the exhaust gas to produce a carbon
dioxide rich fraction and a nitrogen rich fraction, (e) liquefying the carbon dioxide rich fraction and distilling off
volatile contaminants to produce pure carbon dioxide, (f) purifying the nitrogen rich fraction to remove contaminants,
and (g) cryogenically fractionally distilling the nitrogen rich fraction to produce pure nitrogen.

While the above methods provide improvements in the production of carbon dioxide, none but one of these methods
are entirely satisfactory.

Conventional sources for producing carbon dioxide are carbon dioxide rich gases such as waste gases from ammonia,
hydrogen, ethanol, and ethylene oxide plants. These carbon dioxide sources are not always available or are not always
reliable especially at locations of high carbon dioxide demand. Other common problems with the production of carbon
dioxide are low product yield and energy inefficient separation methods. Conventional gas generation methods do not
teach the preparation of food grade carbon dioxide as well as pure nitrogen and argon from combustion exhaust gases.
Hence there was a need for an improved method for producing carbon dioxide.

U.S. Pat. No. 5,100, 635, issued to Krishnamurthy, et al., is the needed improved method for producing food grade
carbon dioxide from combustion exhaust gas, as well as pure nitrogen and argon as by-products.

However the present invention [being the modified and, simplified version of the invention U.S. Pat. No. 5,100, 635,
issued to Krishnamurthy, et al.], would well perform the task of carbon dioxide and sulfur dioxide extraction from
combustion exhaust gas and the liquefaction and storage of both gaseous compounds for later use.

With the present invention therefore:


1. The ecological system is better protected from global warming caused significantly by the release of green
house gas-carbon dioxide in combustion exhaust gas; and
2. The ecological system is better protected from acid rains caused by reactions between atmospheric water and
the carbon dioxide and sulfur dioxide in combustion exhaust gas.

This is so also, because the present invention is aimed at economical, eco-friendly and profitable energy crude
fraction(s) use; and the modified -methods or -technologies disclosed here show this to be practical and viable for the
energy industry and its end users.

The techniques used in the Invention here disclosed- are simple and age old as well as common place to those in the
energy industry.
SUMMARY OF THE INVENTION

The present invention is directed to a method for extracting carbon dioxide and sulfur dioxide from combustion exhaust
gas pre-treated with catalytic converters to handle nitrogen oxides, un-burnt hydrocarbons and carbon monoxide; the
method comprises the steps of (a) treating the exhaust gas to remove particulate matter, (b) compressing the exhaust gas
to a pressure in the range from about 25 psia to about 200 psia, (c) purifying the exhaust gas to remove trace
contaminants, (d) separating the exhaust gas to produce a carbon dioxide rich fraction and a sulfur dioxide rich fraction,
(e) liquefying the carbon dioxide rich fraction and distilling off volatile contaminants to produce pure carbon dioxide,
(f) purifying the sulfur dioxide rich fraction to remove contaminants, and (g) cryogenically fractionally distilling the
sulfur dioxide rich fraction to produce pure sulfur dioxide.
As carbon dioxide and sulfur dioxide are major useful industrial chemicals/raw materials, the ones produced using
the present invention may be sold by crude oil fractions consumers to crude oil marketers, who in turn sell off to
industries where carbon dioxide and sulfur dioxide are useful; these industries would of course spend less than they
usually did to buy the chemicals produced this way: so everyone profits: These industries and crude oil fractions
producers would also be principal and profiting partners in producing, and selling the present invention; this includes
integrating the present invention with past, present day and future technology, so again everyone profits.
The present invention may apply to combustion exhaust from internal combustion engines, and gas flare points, and
for the smooth integration of the present invention with various sources of combustion exhaust gas, the appropriate
apparatus recommended herein may be customized and set up as is convenient.
The present invention is clearly practical and economical being a modification of the already known practical and
economical invention patent number 5100635. The present invention is also simpler and cheaper to manufacture and
use as its task is easier and a bit different from the task performed by invention patent number 5100635; as the task of
the present invention is easier and different from that of invention patent number 5100635, the present invention
therefore only employs some parts of the process and apparatus employed in invention patent number 5100635, that is
only the parts vital to the task/agenda of the present invention.
DETAILED DESCRIPTION OF THE INVENTION

Applicants will find that the production and application of the present invention is, economical, eco-friendly, efficient
and profitable –for manufacturers of the present invention, crude oil fractions producers, marketers, and consumers, as
well as industries where carbon dioxide and sulfur dioxide are useful raw materials.

The Conversion of contaminants in the combustion exhaust gas to an easily disposable form and separation and
recovery of the useful components (CO2 and SO2) also provides an efficient and attractive option to meet clean air
regulations and environmental control.

The present invention is directed to a method for extracting carbon dioxide and sulfur dioxide from combustion exhaust
gas pre-treated with catalytic converters to handle nitrogen oxides, un-burnt hydrocarbons and carbon monoxide; the
method comprises the steps of (a) treating the exhaust gas to remove particulate matter, (b) compressing the exhaust gas
to a pressure in the range from about 25 psia to about 200 psia, (c) purifying the exhaust gas to remove trace
contaminants, (d) separating the exhaust gas to produce a carbon dioxide rich fraction and a sulfur dioxide rich fraction,
(e) liquefying the carbon dioxide rich fraction and distilling off volatile contaminants to produce pure carbon dioxide,
(f) purifying the sulfur dioxide rich fraction to remove contaminants, and (g) cryogenically fractionally distilling the
sulfur dioxide rich fraction to produce pure sulfur dioxide.
As carbon dioxide and sulfur dioxide are major useful industrial chemicals/raw materials, the ones produced using
the present invention may be sold by crude oil fractions consumers to crude oil marketers, who in turn sell off to
industries where carbon dioxide and sulfur dioxide are useful; these industries would of course spend less than they
usually did to buy the chemicals produced this way: so everyone profits: These industries and crude oil fractions
producers would also be principal and profiting partners in producing, and selling the present invention; this includes
integrating the present invention with past, present day and future technology, so again everyone profits.
The present invention may apply to combustion exhaust from internal combustion engines, and gas flare points, and
for the smooth integration of the present invention with various sources of combustion exhaust gas, the appropriate
apparatus recommended herein may be customized and set up as is convenient.
The present invention is clearly practical and economical being a modification of the already known practical and
economical invention patent number 5100635. The present invention is also simpler and cheaper to manufacture and
use as its task is easier and a bit different from the task performed by invention patent number 5100635; as the task of
the present invention is easier and different from that of invention patent number 5100635, the present invention
therefore only employs some parts of the process and apparatus employed in invention patent number 5100635, that is
only the parts vital to the task/agenda of the present invention.

Fuel such as natural gas, methane, coke, coal, fuel oil, or similar carbon-containing compounds may be combusted with
air. The fuel supply may also be waste or exhaust gases from other sources. For example, in a combined cycle power
plant, a gas engine or turbine may be initially used and the exhaust gas from the engine is further combusted in a fired
heater with supplementary fuel to generate steam. The combustion exhaust gas may be obtained from a number of
sources such as a power plant, cement and lime plants, and chemical plants such as ammonia plants and hydrogen
plants. Chemical plant waste gases from refinery fluid catalytic cracking unit regeneration gases and combustion
exhaust gas from incinerators may also be used. Combustion exhaust gas from automobiles and crude fraction fuelled
power generators may also be used.

Now for the task intended to be performed by Invention-patent no 5100635, it is practical but not economical to
produce CO2, N2, and argon from combustion exhaust gases from internal combustion engines or turbines: because as
such combustion exhaust gases contain high amounts of oxygen, the gas separation is uneconomical. This is so because
typically an internal combustion engine uses 70% to 300% excess air to ensure complete combustion of the fuel and to
prevent the engine or turbine from overheating during the combustion process. This level of excess air means that the
oxygen concentration in the exhaust gas will be very high, typically about 17%. Because there is no substantial
reduction in the oxygen concentration in the exhaust gas of an engine compared to the oxygen concentration in air
(about 20%), there is no appreciable energy or capital cost savings advantage for producing nitrogen from the carbon
dioxide depleted exhaust gas from an engine compared to the conventional production of nitrogen from air.

However with the slightly different aim/agenda of the present invention [being producing carbon dioxide and sulfur
dioxide from combustion exhaust gases from internal combustion engines], regardless of the amount of oxygen present
in the combustion exhaust gas, the task of the present invention is both practical and economical. This is because the
present invention is just invention patent number 5100635 -modified, and simplified.

The method for extracting carbon dioxide and sulfur dioxide from a combustion exhaust gas can be better understood
by reference to FIGURE 1 [contained on the last page of the document] in which like numerals refer to like parts of the
invention drawn as FIGURE 1 (FIG. 1).
Although the present invention is described and illustrated in connection with preferred embodiments, applicants intend
that modifications and variations may be used without departing from the spirit of the present invention.

Referring to FIG. 1, combustion exhaust gas (stack gas, combustion gas, exhaust gas, feed gas, waste gas) is fed
through gas feed conduit 1 to pre-purification unit 2 to remove particulate matter from the combustion exhaust gas.

This is combustion exhaust gas pretreated with catalysts or catalytic converters to handle nitrogen oxides, un-burnt
hydrocarbons and carbon monoxide.

Pre-purification unit 2 may be a washing column wherein combustion gas is admitted from the bottom of the unit and a
water absorption shower is administered to the gas from the top of the unit to remove solids (soot, carried off ashes,
etc.).

The washing column may at the same time cool the gas.

The pre-purified combustion exhaust gas is then fed through gas feed conduit 3 to compressor 4. Compressor 4
compresses the combustion gas to the separation pressure. In general, the combustion exhaust gas is compressed to a
separation pressure in the range from about 25 psia to about 200 psia, preferably from about 25 psia to about 120 psia,
and more preferably from about 40 psia to about 100 psia.

The compressed combustion exhaust gas is then fed through gas feed conduit 5 to the purification unit -6 where trace
contaminants such as nitrogen oxides, and water are removed. For example, nitrogen oxides (NO.sub.x, NO, NO.sub.2)
maybe removed by treating the feed gas with ammonia and a selective catalyst (commercially available, for example,
from Norton Company, Ohio) to convert the nitrogen oxides to nitrogen and water. Other methods to remove nitrogen
oxides include moving bed adsorption on activated carbon (Bergbau-Forschung process) and potassium permanganate
scrubbing may also be included in the purification to reduce trace contaminants such as NO.sub.x to the desired level.
The presence of nitrogen oxides and sulfur oxides in the combustion exhaust gas should be reduced to less than about 1
ppm to meet food grade specifications for liquid carbon dioxide products. Levels of carbon monoxide in the exhaust
gas at concentrations higher than ambient can be removed by catalytic oxidative conversion to carbon dioxide. Water
vapor can be removed, for example, by passing the feed gas through a tower containing a desiccant that can be
regenerated, such as silica gel, alumina, or zeolite. Silica gel may be periodically regenerated by passing dry nitrogen
heated to a temperature above 100.degree- Centigrade, through the tower.

The purified combustion exhaust gas is then passed through gas feed conduit 7 to separation unit 8 to separate the gas
to produce a carbon dioxide rich fraction and a sulfur dioxide rich fraction. The separation of the feed gas can be
carried out by any conventional method.

In one embodiment, the combustion exhaust gas may be circulated through carbon dioxide absorption columns
(alkaline solutions such as mono-ethanolamine, potash, etc.) wherein carbon dioxide is absorbed to form a carbonated
solution and sulfur dioxide and the remaining gases pass though the column. The carbonate solution can be regenerated
by passing steam or fluid at a temperature of about 125.degree- Centigrade, -through the carbonated solution; this will
at the same time release the absorbed carbon dioxide where there is little or no other gas to mix with, meaning high
purity carbon dioxide is all that is left for compression/liquefaction.

In another embodiment the combustion exhaust gas is separated into a carbon dioxide rich fraction and a sulfur dioxide
rich fraction using the Invention U.S. Pat No. 4,690,702, issued to Paradowski et al. as unit 8: In this case unit 8 is an
apparatus set up according to the process disclosed in sheet 1 of 3 of the schematic process flow diagrams of the
Invention U.S. patent 4,690,702, issued to Paradowski et al.

In another preferred embodiment, the combustion exhaust gas is separated through carbon dioxide absorption columns
having lime water/calcium hydroxide [Ca (OH) 2]. On absorption of CO2 (carbon dioxide), when saturated with CO2,
Ca (OH) 2 becomes Ca (HCO3) which is then heated/decomposed to produce steam/water (H2O), Calcium oxide
(CaO) residue, and CO2 which is then collected over water then later dried with a desiccant that can be regenerated.
Lime water is recovered for reuse when the CaO residue is made to react with water (H2O), preferably recovered from
water formed when Ca (HCO3) was heated/decomposed.
In a preferred embodiment, the combustion exhaust gas is separated in a pressure swing apparatus into a carbon dioxide
rich stream and a sulfur dioxide rich stream. The carbon dioxide rich fraction from separation unit 8 is then fed through
gas feed conduit 9 to liquefaction unit 10 wherein the carbon dioxide is liquefied and the volatile contaminants are
removed by distillation to produce pure carbon dioxide. Liquid carbon dioxide is produced by conventional processing
steps that include compressing the gas to a pressure between about 230 psia and about 400 psia and cooling the gas to a
temperature between about -8.degree- Fahrenheit, and about -50.degree- Fahrenheit. The more volatile impurities are
removed from the liquid carbon dioxide by distillation. Pure carbon dioxide is then vented from liquefaction unit 10
through feed conduit 11 to carbon dioxide product reservoir 12.

The sulfur dioxide rich fraction from separation unit 8 is then fed through gas feed conduit 13 to purification unit 14
where the sulfur dioxide (and nitrogen) rich fraction is purified to remove trace contaminants. Preferably, the sulfur
dioxide (and nitrogen) rich fraction is purified by passing the gas through a bed of zeolite molecular sieves to remove
trace contaminants such as carbon dioxide.

Pure sulfur dioxide gas is then generated by cryogenic fractional distillation. The sulfur dioxide (and nitrogen) rich
fraction from nitrogen purification unit 14 is fed through gas feed conduit 15 to heat exchanger 16 where the feed gas is
cooled to close to the liquefaction point of sulfur dioxide (with cooling energy derived from the outgoing product gas
stream). Cooled sulfur dioxide gas from heat exchanger 16 is fed through gas feed conduit 17 to feed expander 18
where the sulfur dioxide gas is further cooled and partially liquefied. Cooled sulfur dioxide gas from feed expander 18
is fed through gas feed conduit 19 to sulfur dioxide generator 20 where pure sulfur dioxide is cryogenically fractionally
distilled from oxygen, nitrogen and argon. Pure sulfur dioxide product gas passes from sulfur dioxide generator 20
through gas feed conduit 21 to sulfur dioxide product reservoir 22.

The carbon dioxide and sulfur dioxide depleted combustion exhaust gas is then released to the environment through gas
feed conduit 23.
………………………………………………………………………………………………………………………………

As set out above, carbon dioxide and sulfur dioxide can preferably be separated by pressure swing adsorption. In a
pressure swing adsorption system (PSA), a gaseous mixture is passed at an elevated pressure through a bed of an
adsorbent material which selectively adsorbs one or more of the components of the gaseous mixture. Product gas,
enriched in the un-adsorbed gaseous component(s), is then withdrawn from the bed. The adsorption bed may be
regenerated by reducing the pressure of the bed.

The term "gaseous mixture", as used herein, refers to a gaseous mixture, such as air, primarily comprised of two or
more components having different molecular size. The term "enriched gas" refers to a gas comprised of the
component(s) of the gaseous mixture relatively un-adsorbed after passage of the gaseous mixture through the adsorbent
bed.

The enriched gas generally must meet a predetermined purity level, for example, from about 90% to about 99%, in the
un-adsorbed component(s). The term "lean gas" refers to a gas exiting from the adsorption bed that fails to meet the
predetermined purity level set for the enriched gas. When the strongly adsorbed component is a desired product, a co-
current depressurization step (co-current with respect to direction of the feed gas) and a co-current purge step of the
strongly adsorbed component are added.

The selectivity of the adsorbent material in the bed for a gaseous component is generally governed by the volume of the
pore size and the distribution of that pore size in the adsorbent. Gaseous molecules with a kinetic diameter less than, or
equal to, the pore size of the adsorbent are adsorbed and retained in the adsorbent while gaseous molecules with a
diameter larger than the pore size of the adsorbent pass through the adsorbent. The adsorbent thus sieves the gaseous
molecules according to their molecular size, The adsorbent may also separate molecules according to their different
rates of diffusion in the pores of the adsorbent.

Zeolite molecular adsorbents adsorb gaseous molecules with some dependence upon crystalline size. In general,
adsorption into zeolite is fast and equilibrium is reached typically in a few seconds. The sieving action of zeolite is
generally dependent upon the difference in the equilibrium adsorption of the different components of the gaseous
mixture.

When air is separated by a zeolite adsorbent, nitrogen is preferentially adsorbed over oxygen and the pressure swing
adsorption method may be employed to produce an oxygen enriched product. When carbon dioxide, nitrogen, and
argon are separated by a zeolite adsorbent, carbon dioxide is the adsorbed component and nitrogen and argon are the
un-adsorbed components.
The sieving action of carbon molecular sieves is generally not dependent upon differences in equilibrium adsorption
but rather by differences in the rate of adsorption of the different components of the gaseous mixture. When air is
separated by carbon molecular sieves, oxygen is preferentially adsorbed over nitrogen and the pressure swing
adsorption method may be employed to produce a nitrogen enriched product. When argon and oxygen are separated by
carbon molecular sieves, argon is the un-adsorbed component and oxygen is the adsorbed component.

As a gaseous mixture travels through a bed of adsorbent, the adsorb-able gaseous components of the mixture enter and
fill the pores of the adsorbent. After a period of time, the composition of the gas exiting the bed of adsorbent is
essentially the same as the composition entering the bed.

This period of time is known as the break-through point. At some time prior to this breakthrough point, the adsorbent
bed must be regenerated. Regeneration involves stopping the flow of gaseous mixture through the bed and purging the
bed of the adsorbed components generally by venting the bed to atmospheric or sub-atmospheric pressure.

A pressure swing adsorption system generally employs two adsorbent beds operated on cycles which are sequenced to
be out of phase with one another by 180.degree. so that when one bed is in the adsorption step, the other bed is in the
regeneration step. The two adsorption beds may be connected in series or in parallel. In a serial arrangement, the gas
exiting the outlet end of the first bed enters the inlet end of the second bed. In a parallel arrangement, the gaseous
mixture enters the inlet end of all beds comprising the system. Generally, a serial arrangement of beds is preferred for
obtaining a high purity gas product and a parallel arrangement of beds is preferred for purifying a large quantity of a
gaseous mixture in a short time cycle.

As used herein, the term "adsorption bed" refers either to a single bed or a serial arrangement of two beds. The inlet end
of a single bed system is the inlet end of the single bed while the inlet end of the two bed system (arranged in series)is
the inlet end of the first bed in the system. The outlet end of a single bed system is the outlet end of the single bed and
the outlet end of the two bed system (arranged in series) is the outlet end of the second bed in the system. By using two
adsorption beds in parallel in a system and by cycling (alternating) between the adsorption beds, product gas can be
obtained continuously.

Between the adsorption step and the regeneration step, the pressure in the two adsorption beds is generally equalized by
connecting the inlet ends of the two beds together and the outlet ends of the two beds together. During pressure
equalization, the gas within the pores of the adsorption bed which has just completed its adsorption step (under high
pressure) flows into the adsorption bed which has just completed its regeneration step (under low pressure) because of
the pressure differential which exists between the two beds. This pressure equalization step improves the yield of the
product gas because the gas within the pores of the bed which has just completed its adsorption step has already been
enriched. It is also common to employ more than one pressure equalization step. When a number of pressure
equalizations steps are employed, it is common to have more than two beds in the adsorption system.

Gas separation by the pressure swing adsorption method is more fully described in "Gas Separation by Adsorption
Processes", Ralph T. Yang, Ed., Chapter 7, "Pressure Swing Adsorption: Principles and Processes" Buttersworth 1987,
which reference is incorporate herein by reference.

Throughout this application, various publications have been referenced. The disclosures in these publications are
incorporated herein by reference in order to more fully describe the state of the art.

It will be understood that the embodiments described herein are merely exemplary and that a person skilled in the art
may make many variations and modifications without departing from the spirit and scope of the invention, so for the
smooth integration of the present invention with various sources of combustion exhaust gas, the appropriate apparatus
recommended herein may be customized and set up as is convenient.

All such modifications and variations are intended to be included within the scope of the invention as defined in the
appended claims.