# Patent

## Title
Method and apparatus for reducing CO2 in a stream by conversion to a syngas for production of energy

## Abstract

A system and method for producing Syngas from the CO2 in a gaseous stream, such as an exhaust stream, from a power plant or industrial plant, like a cement kiln, is disclosed. A preferred embodiment includes providing the gaseous stream to pyrolysis reactor along with a carbon source such as coke. The CO2 and carbon are heated to about 1330° C. and at about one atmosphere with reactants such as steam such that a reaction takes place that produces Syngas, carbon dioxide (CO2) and hydrogen (H2). The Syngas is then cleaned and provided to a Fischer-Tropsch synthesis reactor to produce Ethanol or Bio-catalytic synthesis reactor.

## Background
This application is a continuation of patent application Ser. No. 13/085,175 filed Apr. 12, 2011 and issued as U.S. Pat. No. 8,507,567, which is a continuation of patent application Ser. No. 12/271,227 filed Nov. 14, 2008, issued as U.S. Pat. No. 7,932,298, which is a continuation-in-part of patent application Ser. No. 11/956,107, filed Dec. 13, 2007 and issued as U.S. Pat. No. 7,923,476, which applications are hereby incorporated herein by reference.


TECHNICAL FIELD
The present invention relates generally to the field of reducing the presence of carbon dioxide (CO2), and in specific embodiments, to reducing the carbon dioxide in a gaseous exhaust stream from power plants and other types of industrial plants, and forming a Syngas (CO+H2) that can, in turn, be used in the production of energy such as liquid fuels; for example, Ethanol.
BACKGROUND
Concern about global warming eventually leads to discussions about the need to reduce the amount of carbon dioxide that pours into the earth's atmosphere on a daily basis from power plants and other industrial factories. At the same time, concerns about dwindling supplies of fossil fuels have encouraged the development of liquid fuels such as Ethanol as future replacement fossil fuels. Unfortunately, most present methods of producing a liquid fuel such as Ethanol result in as much or more carbon dioxide being introduced into the atmosphere as does burning fossil fuels.
Therefore, a method for producing a Syngas, (easily convertible to Ethanol) from gaseous streams exhausted by industrial plants would offer many advantages in cost, as well as, an overall reduction in the carbon dioxide dumped into the atmosphere.
SUMMARY OF THE INVENTION
The present invention discloses methods and apparatus for reducing the carbon dioxide that is often present in gaseous streams exhausted or emitted from various power plants and types of industrial plants, such as a cement plant. For example, the typical gaseous exhaust stream of about 400,000 lbs/hr total from a cement plant will contain about 30%-40% (about 160,000 lbs/hr) of carbon dioxide (CO2). However, instead of being exhausted to the atmosphere, according to the invention, this gaseous stream is provided to a reaction chamber, such as, for example, a pyrolysis chamber. Reactions take place in the pyrolysis chamber such that the gaseous stream is converted to contain Syngas (CO+H2) and a reduced amount of carbon dioxide (i.e., about 75,195 lbs/hr). The reduction in carbon dioxide is about 53%, and the Syngas can then be cleaned and used as a feedstock for the production of Ethanol. For example, a bio-catalytic process such as a Fischer-Tropsch process could be used to produce the Ethanol.
More specifically, the process for reducing the carbon dioxide and forming the Syngas comprises maintaining a reaction chamber, such as a pyrolysis chamber, at a temperature of between about 400° C. and 5000° C. (typically between 400° C. and 2000° C.) and at a pressure of about one atmosphere or greater. Note, when using a Plasma Arc Gasification chamber, temperatures in the plasma arc zone can reach between 3000° C. and 7000° C. Heat is added as required since some desired reactions are endothermic. Although a pyrolysis chamber is used in a preferred embodiment, a conventional gasifier reactor, a gasification reactor or a plasma arc reactor is also believed to be suitable. A carbonaceous material such as coal, coke, solid waste, etc., is also provided to the reactor such that a Boudouard reaction (i.e. C+CO22CO) takes place.



BRIEF DESCRIPTION OF THE DRAWINGS
For a more complete understanding of the present invention, and the advantages thereof, reference is now made to the following descriptions taken in conjunction with the accompanying drawing, in which:
FIG. 1 is a block diagram illustrating the processes of the present invention,
FIG. 2 is similar to FIG. 1, but includes an available process for converting municipal solid waste to Syngas that, in turn, uses the Syngas to provide the necessary power (e.g. electricity, steam and/or heat) to the pyrolysis reactor of the present invention,
FIG. 3 illustrates the process of FIG. 1 or 2 combined with another process for the production of Ethanol; and
FIG. 4, which includes FIGS. 4a and 4b, is a detailed example of FIG. 3 illustrating the use of a first and a second bio-catalytic reactor.



DETAILED DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS
The making and using of the presently preferred embodiments are discussed in detail below. It should be appreciated, however, that the present invention provides many applicable inventive concepts that can be embodied in a wide variety of specific contexts. The specific embodiments discussed are merely illustrative of specific ways to make and use the invention, and do not limit the scope of the invention.
Referring now to FIG. 1, there is illustrated a block diagram of the present inventive process. As shown, a reaction chamber 10 receives a gaseous stream or exhaust gases, as indicated by line 12, from a power plant or industrial plant 14 such as, for example only, a cement plant with a rotary kiln. The gaseous stream from a rotary kiln will typically comprise between about 55% to about 70% Nitrogen (N2) and about 45% to about 30% carbon dioxide (CO2) plus minute amounts of oxygen (O2) and other impurities. The reaction chamber 10 is preferably a pyrolysis reactor, but could also include a conventional gasifier or a plasma arc gasifier. Also provided to reactor 10 is a carbonaceous material as indicated by line 16 such as coke, coal, or another hydrocarbon source 18, such as biomass materials or municipal solid waste. In addition, as will be appreciated by those skilled in the art, since a pyrolysis reaction (i.e. the thermal decomposition of organic material by heating in the absence of oxygen and other reagents, except possibly steam) takes place at a relatively high temperature. A source of heat energy 22, including electricity and/or steam, is provided as indicated at line 20.
The reaction in the pyrolysis chamber typically will take place at about one atmosphere or one bar and at a temperature of between about 400° C. and 2000° C., and preferably at about 1330° C. The primary chemical reaction that takes place in the pyrolysis reactor is the reaction of the carbonaceous material such as carbon (C) with carbon dioxide (CO2) according to:

C+CO22CO,  Equation (1)

which is also sometimes referred to as the Boudouard reaction.

Other reactions that may occur in the reaction chamber are:

C+H2OCO+H2,  Equation (2)

often referred to as a gasification with steam;

CO+H2OH2+CO2,  Equation (3)

referred to as a water-gas shift reaction; and

CnHm+nH2OnCO+(n+1⁄2m)H2,  Equation (4)

for steam reforming.

Importantly, as seen from Equation (1), the carbon (C) provided by the source 18 combines with one of the oxygen (O) atoms of the carbon dioxide (CO2) molecules to form two molecules of carbon monoxide (2CO) which, of course, reduces the amount of carbon dioxide (CO2) in the reaction chamber. In addition, as indicated by Equation (2), if water (i.e. steam) is available in the pyrolysis reactor, the carbon (C) will also react with the water (H2O) to produce carbon monoxide and free hydrogen (H2). It will also be appreciated that all of the carbon dioxide (CO2) will not be converted to 2CO (i.e. carbon monoxide). Further, the steam (H2O) may also react with some of the carbon monoxide (CO) to reform some carbon dioxide (CO2) and some hydrogen (H2) as indicated by Equation (3). Consequently, the pyrolysis reactor discharges Syngas as indicated on line 24 comprised of carbon monoxide (CO), hydrogen (H2) and a reduced amount of carbon dioxide (CO2), as indicated by block 26. Also, as shown, there will typically be a vitrified slag or ash product 28 produced by the process depending upon the temperature of the pyrolysis reactor. The chemical content of the vitrified slag or ash will, of course, vary depending upon the carbonaceous source and temperature of the pyrolysis reactor.
The Syngas may then be provided to an emission control system 30 to remove impurities and clean up the Syngas. The Syngas control and cleanup system will remove impurities in the Syngas from the pyrolysis reactor. Depending upon the feed to the pyrolysis reactor, the impurities in the Syngas could be about 0.5 wt. % chlorine and 0.8 wt. % sulfur based upon an elemental analysis of the feed, as an example. Most of the sulfur is converted to hydrogen sulfide (H2S) but some is converted to carbonyl sulfide (COS). Chlorine is converted to hydrogen chloride (HCl). Trace elements of mercury and arsenic can be found in the Syngas prior to cleaning Some particulate carryover occurs with the Syngas from the pyrolysis reactor. Selection of the technology for gas cleanup depends upon depends upon the purity requirements of downstream processes using the Syngas.
Particulate control is typically a Metal Candle filter or Water scrubber in combination with a cyclone. Sulfur recovery is typically a Claus plant. The acid gases such as hydrogen chloride are recovered by solvent-based processes such as Selexol or Rectisol.
Also as shown, the carbon dioxide (CO2) in the Syngas is removed and may be returned to the pyrolysis reactor, as indicated by dotted line 12a. Thus, Syngas comprised of carbon monoxide (CO) and hydrogen (H2) is available for further processing, as indicated at block 32.
An example of the process of reducing the carbon dioxide in a gaseous stream from a power plant or rotary cement kiln is as follows:
In the embodiment shown in FIG. 4A, the total output gaseous stream from a rotary kiln of 398,600 lbs/hr is provided to a reactor 10, such as for example, a pyrolysis reactor. The total gaseous stream output includes about 160,000 lbs/hr (≈40%) of carbon dioxide (CO2). Also in the embodiment of FIG. 4A, a carbonaceous source of about 43,663 lbs/hr of coke or coal (C) and a similar amount of steam (H2O) is provided. The temperature of the reactor is maintained at about 1330° C. and at about one atmosphere (one bar) of pressure. The output of the pyrolysis reactor will be a raw or uncleaned Syngas comprised of about 156,147 lbs/hr of carbon monoxide (CO); 2,545 lbs/hr of hydrogen (H2) and about 75,195 lbs/hr of carbon dioxide (CO2). Also, as is clearly shown in the embodiment of FIG. 4A, none of the 43,660 lbs/hr of carbonaceous material 18 (carbon/coke) provided to the reactor 10 remains in the reactor 10 as carbonaceous material (C). However, as is also shown, about 21,190 lbs/hr of the 43,660 lbs/hr of the water/steam (H2O) remains unused in the reactor 10 of FIG. 4A (i.e., does not react). Likewise, the 230,843 lbs/hr of nitrogen (N2) that was in the gaseous stream 14 also remains unused. Thus, it is seen that at this stage of the process the carbon dioxide (CO2) has been reduced by about 53%. As is well known, the input mass to the reactor must, of course, equal the mass output from the reactor. The inputs and outputs of reactor 10 shown in FIG. 4A. are clearly equal. Specifically, the mass input equals 485,920 lbs/hr and comprises 230,843 lbs/hr of N2+160,000 lbs/hr of CO2+7,757 lbs/hr of O2+43,660 lbs/hr of Carbon/Coke+43,660 lbs/hr of Water/Steam. Likewise, the mass output also equals 485,920 lbs/hr and comprises 230,843 lbs/hr N2+156,147 lbs/hr of CO+2,545 lbs/hr H2+75,195 lbs/hr of CO2+21,190 lbs/hr of H2O. Also note, the Oxygen (O2) has been depleted to zero by the reactions in the reactor as noted in FIG. 4A. In addition, the carbon monoxide (CO) in the Syngas provides a significant economic advantage, since as will be discussed later; some bio-catalytic processes effectively use carbon monoxide (CO) as feed stock for organisms in bioreactors that produce Ethanol.
As will be appreciated by those skilled in the art, other known ecologically friendly processes can be combined with the inventive process described above. As an example and referring to FIG. 2, there is shown the process of, FIG. 1 wherein the source 22 of electricity, steam or heat energy is the product of a plasma arc gasification process that uses various waste products such as municipal solid waste (MSW) as a fuel source. As shown, the MSW 34 is provided to the plasma arc gasifier 36 along with an oxygen source 38 and a carbon material 40 such as coke provide a dirty or raw Syngas as indicated by line 42a. Other byproducts 44 include metals and vitrified slag. The dirty Syngas is then provided to an emission control system 45 to remove various other byproducts 46 from the Syngas such as sulfur and hydrochloric acid, etc. This leaves a clean Syngas provided on line 42b that is then used to provide the required steam and heat energy used by the pyrolysis reactor 10.
Referring now to FIG. 3, there is again shown the process of FIG. 1. However, as shown, the produced Syngas is now further processed to provide Ethanol. As shown, the Syngas 32 is provided by line 50 to a water-gas shift reactor 52 and then to a bio-catalytic reactor 54 such as a Fischer-Tropsch synthesis reactor. As known by those skilled in the art, the Fischer-Tropsch reactor may be used to convert the Syngas to Ethanol 56. More specifically, assuming that a flow of Syngas comprised of about 156,147 lbs/hr of carbon monoxide (CO), 2,545 lbs/hr of hydrogen (H2), 75,105 lbs/hr of carbon dioxide CO2) is provided to the water-gas shift reactor 52, about 8,051 lbs/hr of water (steam) will be required to adjust the carbon monoxide (CO) and hydrogen (H2) molar ratio to 3.00 moles of carbon monoxide (CO) for 1.00 each mole of hydrogen (H2). This adjustment is according to the reaction represented by:

CO+H2O→CO2+H2.  Equation (5)

Thus, it will be appreciated that the water-gas shift reactor 52 can be adjusted to produce Syngas having a wide range of molar ratios to meet the needs of various downstream processes that convert or use Syngas. Various downstream processes presently in use may successfully operate with carbon monoxide CO to hydrogen H2 ratios that range between 0.2 to 5.0 moles of carbon monoxide to 5.0 to 0.2 moles of hydrogen.

More specifically, a mass flow rate of 156,147 lbs/hr of carbon monoxide (CO) represents 5,574.7 lbmole/hr, and 2.545 lbs/hr of hydrogen (H2) represents 1,262.4 lbmole/hr of hydrogen (H2). Therefore, as an example, the water-gas shift reactor may be set to shift or rearrange the amount of carbon monoxide (CO) and hydrogen (H2) such that the final mixture ratio comprises 5,127.8 lbmole/hr of carbon monoxide (CO) and 1,709.3 lbmole/hr of hydrogen (H2). This shift is selected to facilitate the reaction that produces Ethanol (C2H5OH). The reaction is shown below in Equation (6).

CO+H2+H2O→C2H5OH.  Equation (6)

Therefore, similar to the above discussion, this reaction takes place with a carbon monoxide (CO) to hydrogen (H2) molar ratio of between 3.0 and 0.2 of carbon monoxide to 1.0 of hydrogen. With this adjustment, the production of Ethanol at 100% of its actual experimental yield from a bio-catalytic reactor is 60,136 lbs/hr of Ethanol, is about 80,120,000 gallons/yr after distillation.

This reaction does not produce carbon dioxide (CO2). Therefore, from the start of the industrial gaseous stream 14 containing 160,000 lbs/hr of carbon dioxide (CO2) to the discharge of the pyrolysis reactor 10, the reduction in emitted carbon dioxide (CO2) is 75,105 lbs/hr, or a reduction of about 53%. The water-gas shift adds about 19,667 lbs/hr of carbon dioxide (CO2) for a total of 94,862 lbs/hr of carbon dioxide (CO2) rather than the original 160,000 lbs/hr for about a total 40% reduction. Of course, in addition to the reduction in exhausted CO2, there is a bonus of 60,136 lbs/hr (or 80,120,000 gallons/yr) of Ethanol.
Referring to FIG. 4, there is shown a more detailed block flow diagram for producing Ethanol that uses two bio-catalytic reactors in series and which illustrates the flow rate of gases, steam, and carbonaceous materials, etc. The reference numbers of common elements or systems are the same as in FIG. 3. However, as shown, rather than a single bio-catalytic converter 54, there is a first bio-catalytic converter 54a that results in the 80,114,836 gallons/yr of Ethanol (block 56) after being distilled as indicated at 58. As is also shown, however, the tail gas from the bio-catalytic converter 54a comprises 94,862 lbs/hr of carbon dioxide (CO2), as well as 21,714 lbs/hr of carbon monoxide (CO) and 1,897 lbs/hr of hydrogen (H2) as indicated in block 60. Therefore, according to this embodiment, the tail gas of block 60 is provided to a second bio-catalytic converter 54b, that is assumed to operate at a 50% yield rather than 100%. Another water-gas shift, as discussed above, is also indicated. The output of the second bio-catalytic converter 54b is another 6,055,899 gallons/yr of Ethanol, as indicated at block 64, after passing the gas through a second distillation process 62 for a total of 86,170,735 gallons/yr. Since the process does not add carbon dioxide (CO2), the tail gas indicated at block 66 from the second bioreactor 54b still contains the 94,802 lbs/hr. of carbon dioxide (CO2) but reduced carbon monoxide (CO). However, if we assume the discharge of the tail gas from the second reactor to the atmosphere is accomplished with a flare burn-off, an additional 19,638 lbs/hr of carbon dioxide (CO2) may be added to the 94,862 lbs/hr. to give a total of 114,500 lbs/hr of carbon dioxide (CO2). This still represents a 28.4% reduction of carbon dioxide (CO2) plus the bonus of 86,170,735 gallons/yr of Ethanol.
Although the present invention and its advantages have been described in detail, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Moreover, the scope of the present application is not intended to be limited to the particular embodiments of the process, machine, manufacture, composition of matter, means, methods and steps described in the specification. As one of ordinary skill in the art will readily appreciate from the disclosure of the present invention, processes, machines, manufacture, compositions of matter, means, methods, or steps, presently existing or later to be developed, that perform substantially the same function or achieve substantially the same result as the corresponding embodiments described herein may be utilized according to the present invention. Accordingly, the appended claims are intended to include within their scope such processes, machines, manufacture, compositions of matter, means, methods, or steps.

## Claims

1. A process for producing syngas that reduces the amount of carbon dioxide in a gaseous stream, the process comprising:
providing a reaction chamber, said reaction chamber selected to be one of a pyrolysis reactor, a conventional gasifier or a plasma arc gasifier;
providing a carbonaceous material in said reaction chamber;
providing H2O to said reaction chamber;
introducing a gaseous stream containing carbon dioxide (CO2) into said reaction chamber;
maintaining said reaction chamber at a temperature of between 400° C. and 5000° C. and at a pressure of about one bar or greater to react materials in said reaction chamber, the reacting materials consisting essentially of said carbonaceous material, said H2O and said carbon dioxide (CO2) in said gaseous stream to form syngas comprising carbon monoxide (CO) and hydrogen (H2), wherein an amount of CO2 in said syngas is at least 53% less than an amount of CO2 that was provided in said gaseous stream; and
discharging said formed syngas.

2. The process of claim 1, wherein said H2O provided as a reactant into said reaction chamber is steam.

3. The process of claim 1, wherein the reaction chamber is maintained at a temperature of between 400° C. and 2000° C.

4. The process of claim 1, wherein said reaction chamber is maintained at a temperature of about 1330° C.

5. The process of claim 1, wherein the reaction of said materials that react in said reaction chamber comprises a Boudouard reaction.

6. The process of claim 1, wherein said carbon monoxide and hydrogen in said discharged formed syngas are provided to a bio-catalytic reactor to produce Ethanol.

7. The process of claim 6, wherein said bio-catalytic reactor is a Fischer-Tropsch synthesis reactor.

8. The process of claim 6, wherein an output of said bio-catalytic reactor is provided to another bio-catalytic reactor to provide additional Ethanol.

9. The process of claim 1 further comprising providing said formed syngas to a water-gas shift reactor to adjust the carbon monoxide (CO) and hydrogen (H2) molar ratio to between 0.2 to 5.0 molecules of carbon monoxide (CO) and 5.0 to 0.2 molecules of (H2).

10. The process of claim 9, wherein said formed syngas comprising adjusted carbon monoxide (CO) and hydrogen (H2) is provided to a Fischer-Tropsch synthesis reactor.

11. The process of claim 1, wherein a portion of the H2O remains in the reaction chamber after said materials react in said reaction chamber.

12. A process for producing syngas that reduces the amount of carbon dioxide in a gaseous stream, the process comprising:
providing a reaction chamber;
providing a carbonaceous material into said reaction chamber;
providing H2O to said reaction chamber;
introducing a gaseous stream containing carbon dioxide (CO2) to said reaction chamber;
maintaining said reaction chamber at a temperature of between 400° C. and 5000° C. and at a pressure of about one bar or greater to react materials in said reaction chamber, wherein the reacting materials consisting essentially of said carbonaceous material, said H2O and said carbon dioxide (CO2) in said gaseous stream to reduce said CO2 and to form syngas comprising carbon monoxide (CO) and hydrogen (H2), wherein a mole ratio of H2O consumed to carbonaceous material consumed provided to the reactor chamber is about 34.33% and having an amount of CO2 that is less than the amount of CO2 that was provided in said gaseous stream; and
discharging said formed syngas.

13. The process of claim 12, wherein said formed syngas comprising carbon monoxide and hydrogen is provided to a bio-catalytic reactor to produce Ethanol.

14. The process of claim 13, wherein an output of said bio-catalytic reactor is provided to another bio-catalytic reactor to produce additional Ethanol.

15. The process of claim 12, further comprising the step of providing said carbon monoxide (CO) and hydrogen (H2) in said discharged formed syngas to an emission control system to remove impurities prior to providing said formed syngas to a water-gas shift reactor.

16. A process for producing syngas that reduces the amount of carbon dioxide in a gaseous stream, the process comprising:
providing a reaction chamber;
providing a carbonaceous material in said reaction chamber;
providing H2O to said reaction chamber;
introducing a gaseous stream containing carbon dioxide (CO2) to said reaction chamber;
maintaining said reaction chamber at a temperature of between 400° C. and 5000° C. and at a pressure of about one bar or greater to react materials in said reaction chamber, wherein said reacting materials consisting essentially of said carbonaceous material, said H2O and said carbon dioxide (CO2) from said gaseous stream to reduce said CO2 and to form a syngas output, said syngas output consisting essentially of carbon dioxide (CO2), nitrogen (N2), carbon monoxide (CO) and hydrogen (H2);
discharging said formed syngas output; and
providing said formed syngas comprising carbon monoxide (CO) and hydrogen (H2) to a water-gas shift reactor to adjust the carbon monoxide (CO) and hydrogen (H2) molar ratio to between 0.2 to 5.0 molecules of carbon monoxide (CO) and 5.0 to 0.2 molecules of hydrogen (H2).

17. The process of claim 16, wherein said reaction chamber is selected to be one of a pyrolysis reactor, a conventional gasifier or a plasma arc gasifier.

18. The process of claim 16, wherein said H2O provided as a reactant into said reaction chamber is steam.

19. The process of claim 16, wherein the reaction chamber is maintained at a temperature of between 400° C. and 2000° C.

20. The process of claim 16, wherein said reaction chamber is maintained at a temperature of about 1330° C.

21. The process of claim 16, wherein the reaction of said materials that react in said reaction chamber comprises a Boudouard reaction.

22. The process of claim 16, further comprising the step of providing said carbon monoxide (CO) and hydrogen (H2) in said discharged formed syngas to an emission control system to remove impurities prior to providing said formed syngas to said water-gas shift reactor.

23. The process of claim 16, wherein said molar adjusted carbon monoxide and hydrogen are provided to a bio-catalytic reactor to produce Ethanol.

24. The process of claim 23, wherein said bio-catalytic reactor is a Fischer-Tropsch synthesis reactor.

25. The process of claim 23, wherein an output of said bio-catalytic reactor is provided to another bio-catalytic reactor to provide additional Ethanol.