US20080040975A1 - Method for maximizing the value of carbonaceous material - Google Patents

Abstract

A method for pyrolyzing coal to produce a raw hydrogen-rich gas and a hot char composed of carbon that is divided into two streams, one gasified to make a second gas and one reacted with steam to produce hot activated carbon that is divided into a first sub-stream and a second sub-stream.

The hydrogen rich gas, after cleanup, is converted to methanol which, in turn, is synthesized into gasoline or synthetic natural gas. The second gas, after clean-up, fuels a turbine to generate electricity while exhausting a flue gas (N₂+CO₂) that is reacted with the first sub-stream of hot activated carbon and with hydrogen for synthesis into urea (CO(NH₂)₂).

The urea is mixed with the second sub-stream of activated carbon to produce a fertilizer which is introduced into soil to store plant nutrients.

This process produces fuel, electricity, and enhancement of plant growth.

Description

BACKGROUND OF THE INVENTION
• This invention relates to a clean and efficient poly-generation of various valuable products from carbonaceous materials such as bituminous coal, sub-bituminous coal, lignite, peat, coke, biomass, etc. This invention which is a continuation-in-part of the Applicant's pending patent application bearing Ser. No. 11/506,939 filed on Aug. 21, 2006, relates to the co-production of enhanced fuels and efficient electric power while mitigating the ill-effects caused to the environment by utilizing said carbonaceous materials as combustible fuels, particularly with respect to emitting carbon dioxide (CO₂) into the atmosphere. CO₂is commonly referred to as a “greenhouse gas” and is suspected of contributing to global warming. Specifically, this invention is an improvement of the Applicant's issued patent bearing No. 6,911,058 B2 issued on Jun. 28, 2005; this patent fails to address the ever-increasing ill effects to the environment caused by the emission of greenhouse gases, in particular by carbon dioxide (CO₂).
• Attempts are being made to capture CO₂where it is generated and to sequester it by introducing it under pressure into such places as deep wells and underground reservoirs for permanent storage—a costly, inefficient and questionable solution, except in cases wherein it is injected into oil or gas wells in order to recover residual oil or gas from such wells; however, the infrastructure related to the piping necessary to transport the CO₂to such wells is a major disadvantage; there is no assurance that CO₂will not leak out via fissures in such wells.
• The Applicant has discovered a method herein disclosed that reduces the formation of CO₂by being efficient while still using said carbonaceous fuels, and especially coal, and at the same time converting CO₂into a useful by-product such as urea, a valuable fertilizer that enhances the growth of biomass, a renewable energy resource in the agriculture sector.
• Before listing the objectives of the instant invention and proceeding with its description, coal will be used as the energy resource as an example, since more than four billion tons of coal are combusted yearly worldwide, but the instant invention is applicable to the use of carbonaceous materials in general.
OBJECTIVES OF THE INVENTION
• The main object of the instant invention is to maximize the value of said carbonaceous materials by making their efficient use possible and yet mitigating the ill-effects that they cause to the environment.
• Another object of the instant invention is to extract from the coal via pyrolysis a raw hydrogen rich gas which, after cleanup, is used as a resource to make valuable and sorely needed products such as gasoline or synthetic natural gas (SNG) while at the same time producing a hot char.
• Still another object of the present invention is to gasify a first stream of the hot char with air preferably, to produce a raw lean gas which, after cleanup, becomes an excellent fuel for combustion turbines which, when configured in a combined cycle mode, generate electric power most efficiently by virtue of mass and low NO_Xformation while emitting a flue gas composed mainly of nitrogen and carbon dioxide (N₂+CO₂).
• Yet another object of the instant invention is to pass steam through a second stream of said hot char in order to transform it to activated carbon.
• Therefore another object of the instant invention is to divide said activated carbon into two sub-streams wherein a “first” sub-stream is set aside for export to the agriculture sector for introduction into soils to stimulate more vigorous growth of crops by providing a cellular structure to store plant nutrients while at the same time sequestering carbon in Mother Earth whence it originated.
• Therefore another object of the instant invention is to elevate the temperature of the “second” sub-stream of said activated carbon to enable it to react with nitrogen (N₂) to thus activate the N₂.
• Further another object of the instant invention is to use off-peak power to electrolyze water to co-produce hydrogen (H₂) and oxygen (O₂).
• Further still another object of the instant invention is to react hot activated carbon (C) with flue gas (N₂+CO₂) and with hydrogen (H₂) to make urea (CO(NH₂)₂) while at the same time sequestering CO₂via the formation of urea, such as CO₂being produced in the generation of electric power.
• Further yet another object of the instant invention is to mix activated carbon with urea to make a super-fertilizer.
• Therefore yet another object of the instant invention is to utilize the O₂derived from electrolysis to serve as the oxidant in the pyrolysis of the coal.
• It is yet another object of the present invention to mix said hydrogen rich gas and said lean gas to create a fuel suitable to co-produce electric power and urea while sequestering carbon in the soil.
• It is still another object of the present invention to mix said hydrogen rich gas and said lean gas to create a fuel suitable to generate electric power while activated carbon is sequestered in soil.
• These and other objects of the present invention will become more apparent to those skilled in the art to which this invention pertains from the following description and appended claims. Reference is now being made to the accompanying drawings forming a part of this specification. It is to be noted that the embodiments shown herein are for the purpose of description and not limitation.
BRIEF DESCRIPTION OF THE DRAWINGS
• FIG. 1 is a process-flow diagram in block form of the invention with the components and process streams being numerically identified.
• FIG. 2 is a process-flow diagram in block form of the invention with the components and process streams being identified with words.
• Before proceeding with the detailed description of the invention by making use of the drawings, it is to be noted that for the sake of clarity reference will be made to the numerals and to the words to represent the various components and process streams.
DETAILED DESCRIPTION OF THE DRAWINGS
• Referring toFIG. 1,numeral10 denotes a pyrolysis chamber and numeral11 a char gasifier;numeral12 denotes a gas clean-up system for the hydrogen rich gas from pyrolysis, and numeral18 denotes a gas clean-up system for lean gas made ingasifier11; numeral13 represents a methanol plant andnumeral14 represents a gasoline conversion plant;numerals15,16, and17 represent a combined-cycle power generation assembly withnumeral15 denoting a gas turbine,numeral16 denoting a heat-recovery steam generator andnumeral17 denoting a steam turbine;numeral21 represents a rectifier to change the power from alternating current to direct current andnumeral19 represents an electrolysis chamber to split water into H₂and O₂. Numeral20 denotes a urea plant for synthesizing hot activated carbon, flue gas (N₂+CO₂) and hydrogen into carbon monoxide and urea—namely CO+CO(NH₂)₂.Numeral63 is a char activator to make activated carbon andnumeral64 represents a reheater to reheat the activated carbon.
• Before describing the operation of the instant invention, it is to be noted that the various streams incorporated in the method would include pressure boosting and pressure let-down equipment, such as compressors, expanders, and miscellaneous valves as required, depending upon the prevailing conditions to enable the navigation of the flow of each stream. Since the use of such equipment is common practice in the field of chemical engineering and is known in the art to which this invention pertains, the Applicant has obviated the inclusion of such equipment in the drawings, even though such equipment will be used in the application of the instant invention.
Operation
• Assuming that the process is already at steady state and referring to bothFIGS. 1 and 2 in combination, coal denoted by stream60 is fed intopyrolysis chamber10 wherein O₂—stream22 is injected into it to such an extent as to combust a small portion of the coal to generate the thermal energy required to devolatilize the coal to yield a rich raw gas having a high H₂content—stream23, which is directed to richgas cleanup system12. By controlling the O₂input intochamber10, the conditions withinpyrolysis chamber10 are maintained highly reducing while converting the coal into a hot char which is divided into two parts,stream27 andstream31.Stream27 is fed intogasifier11 where it is reacted preferably with air,stream51 which is derived from the compressor (not shown) ofgas turbine15, thus converting the carbon in the hot char into a hot raw lean gas—stream67 and slag—stream26. Hot char, being mostly carbon and highly reactive by virtue of its cellular and porous structure, is efficiently gasified with air.
• Hot char stream31, the second part of the char fromstream24, is directed to the activator denoted bynumeral63 for converting the hot char into activated carbon by means of steam-stream33;stream66 denotes the off-gas fromactivator63;stream55 represents the activated carbon discharged fromactivator63. During the activation of the hot char with steam, it loses temperature by virtue of the water-gas reaction that takes place.
• Activatedcarbon stream55 is, in turn, further divided intosub-stream58 andsub-steam61, withsub-stream58 being fed intoreheater64 where the temperature of the activated carbon is raised by making use of the elevated temperature of the hot, raw lean gas-stream67, by directly contacting the activated carbon contained inreheater64. The partially cooled raw leangas leaves reheater64 asstream25 and is directed to lean gas cleanup18. In bothcleanup systems12 and cleanup18, the sulfur in the gases is removed, and it leavescleanup12 viastream28 and cleanup18 viastream29; these two sulfur streams join to form stream44.
• The cleaned rich gas which essentially is CO+2H₂leaves cleanup12 viastream46 and is directed to methanol plant13 where the rich gas is converted to methanol which, in turn, is directed asstream47, togasoline plant14 where the methanol is converted to gasoline via Exxon Mobil's process known as “MTG” for short. The clean lean gas which essentially is N₂+CO leaves cleanup18 viastream30 to which CO—stream48, is added toform stream32 whichfuels gas turbine15; air tocombust stream32 is furnished bystream52 which is compressed prior to entering the combustion chamber (not shown) ofgas turbine15. The flue gas exhausting from the gas turbine is passed through heatrecovery steam generator16 to raise steam which is directed tosteam turbine17 viastream50. Bothgas turbine15 andsteam turbine17 are each followed by a generator (not shown) to generate electric power most efficiently via the combined cycle mode which power leaves asstreams37 and38, respectively, to formstream39. The flue gas leaving heat-recovery steam generator16, which is made up of nitrogen and carbon dioxide (N₂+CO₂) is denoted bystream34. A portion of the steam generated in heat-recovery steam generator16 is withdrawn as a side stream which is denoted bynumeral36; this side stream of steam together with H₂stream49 form stream53 which is directed to high-temperature electrolysis system19 in order to increase the efficiency of H₂generation. It is to be noted thatside stream36 may also be withdrawn fromsteam turbine17.
• An alternating electric current stream denoted bynumeral40 is directed to rectifier21 where it is converted to direct electric current to form streams42 and43 which are introduced intoelectrolysis system19 in order to electrolyze the steam contained in stream53 to yield a larger output of H₂-stream56 and also producing O₂asstream22; this larger output of H₂is directed tosynthesis system20, while the O₂, after being compressed (not shown), is directed topyrolysis chamber10 asstream22.
• Referring now to the flue gas, stream34 (N₂+CO₂) is split to create a bleed of flue gas to maintain system balance denoted bynumeral35, to result instream57 which joins H₂stream45 (the net H₂produced in electrolysis system19) to formstream65. The activated carbon (C)—stream68 and the flue gas (N₂+CO₂) together with the H₂—stream65 are respectively introduced intourea plant20 to produce urea (CONH₂)₂)+CO as stream69. The CO, asstream48, is separated from stream69 to result in the formation of urea asstream59 whence this stream joinsactivated carbon sub-stream61 to form a super-fertilizer for export denoted bystream62.
• It is to be noted that the hot activated carbon may be reacted with the flue gas by itself in a reactor to form CO and cyanogen (C₂N₂), and the H₂may then be added in a subsequent reaction to form the urea. Further, the formation of urea may also occur via the ammonia (NH₃) route by reacting N₂with 3H₂to make 2NH₃and subsequently reacting the 2NH₃with CO₂to form CO(NH₂)₂+H₂O, the conventional method of making urea.
• The step of making urea may be obviated by making use of the method to make activated carbon from a portion of the char, activating such portion, and sequestering it in the soil to enhance it by introducing cellular structure to store plant nutrients and to provide time release of such nutrients to result in causing the vigorous growth of plant life.
• In summation, it is submitted that the method described herein for maximizing the benefits derived from a carbonaceous material such as coal which contains sulfur in an environmentally acceptable manner while co-producing liquid fuel, electric power and urea is comprised of pyrolyzing the coal with oxygen to produce a raw hydrogen (H₂) rich gas and a hot char which is cellular in structure and substantially composed of carbon (C). The hot char so produced is divided into two streams, with the first stream being directed to a gasifier that is air blown to make a raw lean gas which is made up of nitrogen and carbon monoxide (N₂+CO) and a second stream being activated with steam to produce activated carbon that is further divided into a “first” sub-stream of activated carbon and a “second” sub-stream of activated carbon whose use will be described hereinafter.
• Subsequent to the cleaning of the H₂rich gas and the lean gas, including the removal of mercury from these gases, the cleaned H₂rich gas (syngas) may be converted to one or more chemicals, but preferably to methanol which, in turn, is converted to a transportation fuel such as gasoline, a most valuable liquid fuel. The cleaned lean gas fuels a gas turbine that is part of a combined-cycle system to generate electric power most efficiently by virtue of its large N₂content which contributes a large mass flow of gases through the gas turbine while exhausting an off-gas (flue gas) made up of N₂+CO₂. This flue gas which is reacted with activated carbon and H₂, is synthesized with 2H₂to produce urea which is characterized chemically as NH₂.NH₂.CO or CO(NH₂)₂plus CO. Alternatively, the formation of the urea may be the conventional route of making urea by first forming ammonia (NH₃) and, in turn, reacting two molecules of NH₃with CO₂to form CO(NH₂)₂, and H₂O as by-product; in this case, the N₂in the flue gas is separated from the CO₂prior to reacting with the NH₃.
• Preferably during off-peak periods, the excess of the electric power that can be generated for which there is no demand, such power is utilized to electrolyze steam in a high-temperature electrolysis system to generate H₂and O₂, with the H₂produced being the source for the H₂needed in synthesizing the N₂+CO₂(with the aid of hot activated carbon) into urea. Preferably, some of the H₂produced via electrolysis is recycled with the steam fed to the electrolysis system to enhance the production of H₂. The O₂which is co-produced via electrolysis is used in the pyrolysis of the coal mentioned above.
• The “first” sub-stream of activated carbon serves to activate N₂in the flue gas (N₂+CO₂) to make possible the formation of urea according to the following chemical reaction: (N₂+CO₂)+C+2H₂→CO+CO(NH₂)₂, wherein the CO is separated from the urea and is added to the lean gas to become part of the fuel for the gas turbine mentioned above.
• The urea so formed is mixed with the “second” sub-stream of activated carbon, mentioned above, to produce a super-fertilizer which is put into the soil, not only for the sequestration of carbon (C) directly and carbon dioxide (CO₂) indirectly via the urea, but also to provide storage for plant nutrients in the abundant cellular structure of the activated carbon, thus:
• • Contributing to the efficient use of plant nutrients via their storage in the cells of activated carbon:
  • Increasing plant yield via the conservation of the nutrients; and,
  • Reducing CO₂emissions by converting the CO₂in the flue gas into a component of the super-fertilizer while at the same time sequestering a portion of the carbon from the coal back into the soil.
    From an economic standpoint, the formation of a super-fertilizer made from low-cost carbon (char from coal pyrolysis), low-cost hydrogen (electrolyzing steam with off-peak power), and flue gas (a waste off-gas) can be sold to the farming community at a very attractive price when compared to urea made from natural gas, thus helping produce abundant plant life to retain water in the soil that will increase forest land and abundant food for mankind.

Claims (31)

1. A method for maximizing the value of carbonaceous material in an environmentally acceptable manner comprising the following steps:

pyrolyzing the carbonaceous material in an atmosphere which is deficient of oxygen to produce a first gas and a hot char which possesses a cellular structure that is essentially made up of carbon;

dividing said char into two streams comprising a first stream of char and a second stream of char;

gasifying said first stream of char to produce a second gas;

utilizing said first stream of gas and said second stream of gas as fuels for the formation of one or more than one subsequent form of energy while emitting a flue gas containing carbon dioxide (CO₂) into the atmosphere, said CO₂being a greenhouse gas and being suspected of causing global warming; and

sequestering said second stream of char in soil in order to compensate for at least a portion of the CO₂emitted into the atmosphere while increasing the capability of the soil to retain nutrients in the cellular structure of the sequestered char to result in an increase in the yield of plant growth from said soil, said increase of plant growth being a greater consumer of CO₂than if said second stream of char were not sequestered in the soil.

2. The method as set forth inclaim 1 wherein said first gas and said second gas are cleaned prior to the step of utilizing said gases as fuels for the formation of one or more subsequent form of energy.

3. The method as set forth inclaim 1 wherein said second stream of char is activated to convert it to activated carbon by enhancing the capability of its cellular structure to absorb nutrients.

4. The method as set forth inclaim 1 wherein said first gas is a hydrogen (H₂) rich gas which is suitable for making an upgraded chemical.

5. The method as set forth inclaim 1 wherein the step of utilizing said first gas and second gas as fuels for the formation of one or more than one subsequent form of energy is further characterized by the step of utilizing both gases as fuels for electric power generation.

6. The method as set forth inclaim 4 wherein said upgraded chemical takes the form of methanol.

7. The method as set forth inclaim 4 wherein said upgraded chemical takes the form of synthetic natural gas.

8. The method as set forth inclaim 6 wherein said methanol is converted into a transport fuel.

9. The method as set forth inclaim 8 wherein said transport fuel comprises gasoline.

10. The method as set forth inclaim 1 wherein the step of gasifying said first stream of char to produce a second gas is further characterized by the step of injecting an oxidant to implement the step of gasifying said char to produce a hot second gas at an elevated temperature.

11. The method as set forth inclaim 10 wherein steam is injected in addition to said oxidant.

12. The method as set forth inclaim 10 wherein said step of injecting an oxidant comprises the injecting of air to give said second gas additional mass and low NO_Xformation properties when it is combusted.

13. The method as set forth inclaim 12 further comprising the use of said second gas with its additional mass to fuel a combustion turbine to efficiently generate electric power.

14. The method as set forth inclaim 13 being further characterized by said combustion turbine being part of a combined cycle configuration for the generation of electric power while emitting an off-gas as a waste flue gas consisting mainly of N₂+CO₂.

15. The method as set forth inclaim 14 wherein said combined cycle configuration is operated at a full load continuously to generate the maximum amount of electric power despite off-peak period.

16. The method as set forth inclaim 15 wherein the excess electric power generated during off-peak period is used to electrolyze water to produce economical H₂and O₂.

17. The method as set forth inclaim 16 wherein said water takes the form of steam that is electrolyzed in a high-temperature electrolysis system.

18. The method as set forth inclaim 17 wherein said high-temperature electrolysis comprises the recycling of H₂with said steam to provide a more efficient electrolysis system in the production of H₂.

19. The method as set forth inclaim 14 wherein said flue gas consisting of N₂+CO₂is combined with H₂generated via electrolysis to form a mixture of flue gas (N₂+CO₂) plus hydrogen (H₂).

20. The method as set forth inclaim 3 wherein the step of activating said second stream of char to convert it to activated carbon is further characterized by the step of sub-dividing said second stream of char into a “first” sub-stream and a “second” sub-stream.

21. The method as set forth inclaim 20 wherein said “first” sub-stream is heated in order to create a hot “first” sub-stream of hot activated carbon (C).

22. The method as set forth inclaim 10 wherein said step of injecting an oxidant to implement the step of gasifying said char to produce a hot second gas at an elevated temperature is further characterized by the step of directing said hot second gas to heat said “first” sub-stream of activated carbon referred to inclaim 21 to increase its reactivity.

23. The method as set forth onclaim 19 wherein said mixture of flue gas (N₂+CO₂) plus hydrogen (H₂) is further combined with said “first” sub-stream of hot activated carbon (C) referred to inclaim 21 to form urea.

24. The method as set forth inclaim 23 wherein said urea is further mixed with said “second” sub-stream of activated carbon (C) referred to inclaim 20 to form an enhanced urea for the vigorous growth of plant life.

25. The method as set forth inclaim 1 wherein said carbonaceous material is coal.

26. The method as set forth inclaim 14 wherein the step of emitting an off-gas as a waste flue gas consisting mainly of N₂+CO₂is further characterized by the step of separating the N₂from the CO₂.

27. The method as set forth inclaim 26 comprises the reacting of the CO₂with ammonia 2(NH₃) to form urea (NH₂.NH₂.CO) plus water (H₂O).

28. The method as set forth inclaim 1 wherein said carbonaceous material contains sulfur.

29. The method as set forth inclaim 1 wherein said first gas and said second gas are combined, cleaned and utilized to generate electric power while emitting a flue gas which is suspected to create a harmful effect to the environment.

30. The method as set forth inclaim 2 wherein said first gas and said second gas are cleaned comprises the removal of mercury from both gases.

31. The method as set forth inclaim 1 wherein said first gas and said second gas are utilized for the poly-generation of various products.

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