1. Field of the Invention
This invention relates to a system of processes for sequestering carbon in coal-burning power plant and producing hydrogen gas that take advantage of emission of CO and CO2 and heat from the plants. The use of this invention will lead to cheap hydrogen and hydride production and carbon sequestration and reduced global warming.
2. Background of the Invention
The United States leads the world in per capita CO2-emissions. In 2004, the total carbon release in North America was 1.82 billion tons. World-wide industrial nations were responsible for 3790 million metric tons of CO2 (Kyoto-Related Fossil-fuel totals). There is little doubt that the world is choking with greenhouse gases.
No one can deny that there is an urgent need to develop innovative solutions to reduce the emissions from our automobiles and from our coal or gas burning power plants. This invention may well provide an answer to the problem of greenhouse gas emissions and pave the way towards a clean energy future. The invention addresses carbon sequestration in coal or gas burning plants used for power generation or for manufacturing (cement, steel etc.). The chemical process that sequesters carbon gases (thus preventing them from escaping to the atmosphere) generates hydrogen as a byproduct.
Coal burning power plants currently produce electricity to satisfy the needs of a power hungry economy all over the world and in doing so also produce much of the greenhouse gases. While coal is used to generate electric power, it is also used for producing hydrogen by reaction with water. Therefore, its continued use would be of immense help to the world if only we can sequester the carbon. This invention helps to do exactly that and if we develop this technology, we could continue to use coal for many decades without any environmental degradation.
Currently steam methane reforming is the most common and the least expensive method to produce hydrogen [1]. Coal can also be reformed to produce hydrogen through gasification. Hydrogen production by methods that do not emit CO2 are either more expensive compared to those using fossil fuels or are in the very early stages of development [2-4]. Since the United States has more proven coal reserves than any other country, hydrogen production through a coal-based technology is a very attractive prospect. However, effective and low cost carbon sequestration technology has not yet been developed.
Hydrogen is widely regarded as the energy of the future, but to produce and use hydrogen—either by direct combustion or in a fuel cell—it is necessary to use other sources of energy. Thus using hydrogen or any other material to produce energy cannot be environmentally clean and economically viable unless the process by which it's produced sequesters carbon or is otherwise free of greenhouse gas emissions. The use of hydrogen is being promoted on a federal level with financial support, and we may eventually have hydrogen-using technology for our transportation and other energy needs. However, it is a sad fact that the production of the hydrogen to be used in that technology will most likely continue to be dependent on the use of fossil fuels for the foreseeable future, and it may not be viable either economically or environmentally. Solving this problem requires alternative methods of using coal to produce hydrogen and hydrides. Many hydrides are currently being considered for use in the on-board generation of hydrogen, and the cost of producing the hydride is an obviously critical factor in this evaluation. This project would use carbon to produce hydrogen with carbon sequestration.
Coal is used extensively in producing synthetic fuels [1]. Use of coal in gasifiers is well established and hydrogen may be produced by the reaction: C+2H2O=CO2+2H2. Gasifiers are operated between 500 to 1200° C., and use steam, oxygen and/or air and produce a mixture of CO22, CO, SO2, NOx, H2, CH4 and water. Treatment systems are available for SO2 and NOx but CO22 remains a problem. The CO produced can be further processed by the shift-gas reaction to produce H2 with production of CO2: CO+H2O=CO2+H2. The following is an extract from a report by National Academy of Engineering, Board on Energy and Environmental Systems [5] and shows the importance of the present study: “At the present time, global crude hydrogen production relies almost exclusively on processes that extract hydrogen from fossil fuel feedstock. It is not current practice to capture and store the by-product CO2 that results from the production of hydrogen from these feed stocks. Consequently, more than 100 Mt C/yr are vented to the atmosphere as part of the global production of roughly 38 Mt of hydrogen per year.”
It would then appear that when coal is used in gasifiers or in direct burning in power- and other manufacturing-plants, CO2 and CO are prominent among other gases released to atmosphere. Their emission is not only harming the environment but as considered here is also a waste of resources. For industry this has been an economic issue.
This invention provides a clear economic incentive to sequester carbon (CO2 and CO) without significantly affecting our current modes of operations i.e. the coal-burning power plants. It will also show that hydrogen will be produced at much lower costs and with zero emission of greenhouse gases.
Many new coal-burning power plants are now in the offing. This is the right time to act.
Related patents include the following.
U.S. Pat. No. 7,132,090, D. Dziedzic, K. B. Gross, R. A. Gorski, J. T. Johnson, Sequestration of carbon dioxide.
US patent application 20030017088, W. Downs and H. Sarv Method for simultaneous removal and sequestration of CO2 in a highly efficient manner.
US patent application 20010022952, G. H. Rau and K. G. Caldeira Method and apparatus for extracting and sequestration carbon dioxide
U.S. Pat. No. 5,261,490, T. Ebinuma Method for dumping and disposing of carbon dioxide gas and apparatus therefore.
U.S. Pat. No. 6,667,171, D. J. Bayless, M. L. Vis-Morgan and G. G. Kremer Enhanced practical photosynthetic CO2 mitigation.
U.S. Pat. No. 6,598,407, O. R. West, C. Tsouris and L. Liang Method and apparatus for efficient injection of CO2 in ocean.
U.S. Pat. No. 5,562,891, D. F. Spencer and W. J. North Method for the production of carbon dioxide hydrates.
U.S. Pat. No. 5,293,751, A. Koetsu Method and system for throwing carbon dioxide into the deep sea.
U.S. Pat. No. 6,270,731, S. Kato, H. Oshima and M. Oota Carbon dioxide fixation system.
U.S. Pat. No. 5,767,165, M. Steinberg and Y. Dong Method for converting natural gas and carbon monoxide to methanol and reducing CO2 emission.
U.S. Pat. No. 6,987,134, R. Gagnon How to convert carbon dioxide into synthetic hydrocarbon through a process of catalytic hydrogenation called CO2 hydrocarbonation.
U.S. Pat. No. 7,282,189 B2 Zauderer Production of hydrogen and removal and sequestration of carbon dioxide from coal-fired furnaces and boilers.
U.S. Pat. No. 2006/0048517 A1 Fradette et al. Process and a plant for recycling carbob dioxide emissions from power plants into useful carbonated species.
U.S. Pat. No. 2004/0126293 Geerlings et al. Process for removal of carbon dioxide from flue gases.
U.S. Pat. No. 6,669,917 B2 Lyon Process for converting coal into fuel cell quality hudyrogen and sequestration-ready carbon dioxide.
U.S. Pat. No. 7,083,658 B2 Andrus Jr. et al. Hot solids gasifier with CO22 removal and hydrogen production.
U.S. Pat. No. 2006/0185985 A1 Jones Removing, carbon dioxide from waste streams through co-generation of carbonate and/or bicarbonate minerals.
The present invention provides a system of reactions to sequester carbon and produce hydrogen from sodium hydroxide and CO or CO2 and carbon or natural gas. The carbon gases are produced in industrial plants burning coal and thus available at no cost. These gases also can be obtained at relatively high temperature; the reaction of CO or CO2 and carbon with sodium hydroxide is exothermic and hence no additional heating may be required. The CO or carbon or natural gas and CO2 would react to form sodium carbonate and thus carbon will be sequestered. The main points are: We continue to use coal burning power plants for electric generation and other uses; The emitted gases mostly CO and CO2 (the green-house gases causing global warming) at modest temperatures and hydroxide are fed into chemical reactors built adjacent to the power plant; Chemical reactions between gases and hydroxide and carbon or natural gas produce solid carbonate and hydrogen; The reactant NaOH is produced preferably with a non-fossil energy source (nuclear, hydro-, solar- or wind-) and the products carbonate and hydrogen are sold reducing the cost of the power plant and generating electricity; Electric or thermal power is produced from coal-burning plants with zero emission of greenhouse gases, and Hydrogen is produced economically with zero emission because of the low materials cost and low energy cost due to use of hot gases; use of hydrogen in transport will further reduce CO2-emission.
An embodiment of the present invention provides for a complete sequestration of carbon and hydrogen production using CO from coal-burning power plant. In such a case, sodium hydroxide reacts with CO producing hydrogen and carbonate and no carbon is released in the environment.
Another embodiment of the present invention provides the production of carbonate and hydrogen using CO2 from coal-burning power plant and reacted with carbon and sodium hydroxide. In such a case, sodium hydroxide reacts with carbon and CO2 producing hydrogen and carbonate and no carbon is released in the environment.
Another embodiment of the present invention provides the production of carbonate and hydrogen using CO2 or CO or any mixture thereof from coal-burning power plant and reacted with natural gas, water and sodium hydroxide. In such a case, sodium hydroxide reacts with water, natural gas and CO/CO2 producing hydrogen and carbonate and no carbon is released in the environment.
Another embodiment of the present invention provides the production of hydrogen if the industrial CO or CO2 is not available. In such a case, sodium hydroxide reacts with water and carbon or natural gas producing hydrogen and no carbon is released in the environment.
Another embodiment of the present invention provides for further sequestration of CO2 by reaction of the unsold Na2CO3 with water and CO2.
Another embodiment of the present invention provides for the existing coal-burning power plants to be retrofitted with the reactor design presented in
Finally, hydrogen produced in the reactor is used to produce hydrides, specifically magnesium hydride at a low cost,
The use of hydroxide in sequestering carbon from processes using fossil-fuel has been suggested in many publications and in some patents (Table 1). A technique to use the carbonation reaction for use with coal-burning power plants has been described by Jones (US 2006/0185985 A1) who uses the reaction:
NaOH+CO2=Na2CO3 (or bicarbonate)
The strategy adopted in this work differs in using several reactions that produce hydrogen as well as form the carbonate. Production of hydrogen with zero emission and using the carbonate gainfully are important aspects of the present invention. Unlike the reactions used in this invention, the Skyonic method relies on a single direct carbonation reaction. Others have used solids such as CaS (U.S. Pat. No. 7,083,658 B2 Andrus Jr. et al.) and CaO (U.S. Pat. No. 6,669,917 B2 Lyon) with different effects. Others use hydroxide reaction with CO2 involving CaO (Lin et al., 11, Xu et al.9), magnesium and calcium silicates (Zevenhoven et al, 10) and alkali hydroxide (Ishida et al. 8). Finally the ZECA (Zero Emission Coal Alliance) process uses Ca(OH)2.
The purpose of this invention and the tremendous advantages it entails for reduction in global warming gases needs to be fully understood from the study of the description along with the drawings herein.
The present invention provides a novel method of sequestering carbon producing hydrogen with carbon sequestration; the novelty lies in the fact that gases produced in a coal-burning plant are used both for the energy and for the substance to react with sodium hydroxide reducing the cost simultaneously with eliminating the emission. The invention relies on processes described below.
For existing power stations, where CO2 is produced, we may choose this alternative and use CO2 to react with water and Sodium hydroxide according to the reaction:
4NaOH(c)+C(c)+CO2(g)=2Na2CO3(c)+2H2(g)ΔH=−6.62 E4(600 K) (1)
One may compare this reaction with the combination of the gasifier reaction C+2H2O=CO2+2H2 and the CO2 absorbing reaction 2NaOH+CO2=Na2CO3+H2O to accomplish similar result. It is shown in
C+CO2=2CO
and reaction (1). Reaction (2) may also be considered as a combination of
2NaOH+CO2=Na2CO3+H2O and
2NaOH+C+H2O=Na2CO3+2H2
CO is not produced in coal burning because high ratio of air to coal is used. However if the heating requirement for the plant is fully met with a lower ratio such that CO is actually produced in some quantity, we could use the CO for producing hydrogen according to the following reaction
2NaOH(c)+CO(g)=Na2CO3(c)+H2(g)ΔH=−119E5 J (600 K) (2)
An equilibrium calculation in
C+Air(N24,O2 1 mole)=CO2, ΔH=−2.746E5 J
C+Air(N2 2, O2 0.5 mole)=0.763CO+0.118 CO2+0.12C, ΔH=−6.628E4 J
Process III. Hydrogen Production with Zero Emission
We may consider reaction (3), if CO or CO22 are not available from an industrial plant:
2NaOH(c)+C(c)+H2O(l)=Na2CO3(c)+2H2(g)ΔH=6.458 E4 (600 K)
Reaction (3) was proposed by Saxena [6]. While this is an endothermic reaction, less amount of solids are required to produce the same amount of hydrogen. This may be helpful if the cost structure of the sodium compound alters in time. In this process 20 kg of NaOH will yield 26.5 kg of Na2CO3 for each 1 kg of hydrogen.
It is possible to consider a combination of the reactions. For example, reactions (1) and (3) or (1) and (2) may be combined respectively as follows:
6NaOH+CO2+2C+H2O=3Na2CO3+3H2, (3a) and
6NaOH+(1−x)CO2+xCO+C=3Na2CO3+3H2. (3b)
Combination of the reactions may be optimized by taking into consideration the costs of the energy, products and reactants.
We may also consider the use of cheaply available natural gas as follows:
2NaOH+CH4+H2O=Na2CO3+4H2 (4)
for hydrogen production. For sequestration of carbon with hydrogen production, we use
4NaOH+CH4+CO2=2Na2CO3+4H2 (5)
4NaOH+CH4+CO+H2O=2Na2CO3+5H2 (6)
Several mixed reactions between (5) and (6) are feasible and may be optimized as before.
The excess carbonate can be further used to sequester additional CO2 according to the reaction:
Na2CO3+CO2+H2O=2NaHCO3 (7)
This reaction takes place at 25° C. and does not require heating.
Hydrogen formed in the above procedure may be directly used for synthesizing hydrides. A hydride which may be synthesized at the site is Mg+H2=MgH2. This reaction is exothermic (DH=−76 KJ/mol) and with a well ground metal would proceed rapidly to completion.
Experiments were conducted to verify the theoretical predictions for reactions (2) and (3) using an in-house method involving measurement of evolving hydrogen by break-down laser spectroscopy (
The reaction between NaOH and CO was studied using the same experimental setup. Both reactions were first explored with temperature increasing at a fixed rate, reaction (3) between 110 to 700° C. (
Design of an Integrated Plant for Power and Hydrogen Generation with Zero Emission
The only raw material required is coal (or natural gas), sodium chloride and water. To minimize the costs it is essential that an integrated design of the plant is used. It should consist of:
We can consider the following type of situations. Although we deal with separate reactions below, in actual practice the composition of the feeder stock in the reactor will be determined by optimizing the desired yield of products using the several reactions. Such composition would be variable depending on the supply and demand of the products.
In such a case, we use the reaction (2) and reaction (6) as described under Process II and Process IV
In such a case, we have to consider the reaction in a closed system for the reactions (2) and (5). The reaction (2)
4NaOH(c)+C(c)+CO2(g)=2Na2CO3(c)+2H2(g)ΔH=−6.62 E4 (600 K)
may be considered as a combination of
2NaOH+CO2=Na2CO3+H2O and
2NaOH+C+H2O=Na2CO3+2H2
Catalysis of the reactions was not employed in our experiments but if needed can be used as has been discussed in detail in literature [1]. A high production rate would result if the hydrogen is formed by continuous flow processes. As envisaged here, the equilibrium calculations are for a closed system with a complete conversion of fixed ratio of reactants and production of the carbonate and hydrogen. Catalysis and partial conversion of the reactants will affect the costs.
We use the steel reactor vessel whose dimension will depend on the size of the coal-burning plant (
3. The Reaction to Produce Hydrogen with Zero-Emission
We may use the hot steam from the coal-burning plants and could use the same set up as shown in
We may also use natural gas in sequestering carbon and producing hydrogen according to Process IV reactions using the same plant design as shown in
CO2 is bubbled through several tanks with water and carbonate until all of it is absorbed. The size and number will depend on the size of the power plant.
6. Hydride Production
The evolving hydrogen may be fed into additional reactors with some pressure (2 atmospheres) with well stirred magnesium metal to form hydrogen. Since the reaction is exothermic no additional heating may be necessary.
Cost Analysis
The cost of NaOH in the market may fluctuate wildly depending on the supply and demand. The following calculations are based on an assumed cost of producing NaOH which may vary from $50 to $200 per ton and a selling price for Na2CO3. We note that if nuclear, hydro or geothermal energies are used, the price would be much less. Although examples of calculations are given here using separate reactions, in actual practice the composition of the feeder stock in the reactor will be determined by optimizing the desired yield of products using the several reactions. The production of NaOH (chloralkali process) may involve in simplified form a reaction such as
2Na+2H2O+2e−=2NaOH+H2
In industrial production which employs NaCl, there is formation of chlorine in addition to hydrogen. The energy consumption to produce 1 ton of Cl2 by electrolysis with diaphragm is around 2720 kWh. This gives us 2413 kWh per 1 ton of NaOH. To produce 1 ton of NaOH one needs 1.463 ton of NaCl. Chlorine (888 kg) and H2 (25 kg) are byproducts of the electrolysis. Thus the cost of 1 ton NaOH production is:
1.463×price of NaCl $/ton+(2413×Price of electricity $/kWh)−(0.888×price Cl2$/ton)−(25×price H2$/kg)
Cl2 price varies from $220 to $240 (http://www.the-innovation-group.com/ChemProfiles/Chlorine.htm). Rock Salt price is ca.$60(http://www.ct.gov/dot/lib/dot/documents/dsalt/winterops.pdf). Construction cost, labor, water etc., which are not included in this estimation, of course, will increase the price of NaOH as well as the supply and demand for chlorine. With price for Cl2 and NaCl $220 and $60, respectively and electricity cost of $0.09/kWh, the cost of 1 ton NaOH is quite small. However, it must be emphasized that this energy must not be obtained from burning coal, otherwise the CO22 production would continue to exceed all amounts that we can lock in Na2CO3. It may be possible for several reactors to operate using off-peak power.
For the reaction:
2NaOH+C+H2O=Na2CO3+2H2
The requirements are 80 kg of NaOH producing 106 kg of Na2CO3 and 4 kg of hydrogen; to the latter we can add the already produced 2 kg of H produced while manufacturing NaOH (sale of chlorine should also be considered). Table 2 shows the material costs. To this we must add the energy costs as well as also consider that this is a zero emission product.
Reaction (3), however, is not useful (in terms of reducing greenhouse gases) for coal-burning power plants even though it is a zero-emission process. For coal-burning power plants, we use the reaction:
4NaOH+CO2(or mixture of CO2 and CO)+C=2Na2CO3+2 H2 (2)
The requirements are 160 kg of NaOH producing 212 kg of Na2CO3 and 4 kg of hydrogen; to the latter we can add the already produced 4 kg of H produced while manufacturing NaOH as discussed above. The costs are shown in Table 1 for variously assumed cost of producing the reactant at the plant. To this we must add the energy costs, which will be much less than that for reaction (2) because we will be using hot gases from the power plant. Furthermore, the power plant will be used for generating thermal or electric power.
We may also consider the use of cheaply available natural gas as follows:
2NaOH+CH4+H2O=Na2CO3+4H2
The requirements are 80 kg of NaOH and 16 kg of CH4 which produces 106 kg of Na2CO3 and 8 kg of hydrogen; to the latter we can add the already produced 2 kg of H produced while manufacturing NaOH as discussed above. The cost of NaOH is (80×0.15=$12.0), the cost of CH4 based on ($0.04/kg) is ($0.16) selling price of Na2CO3 is $10.6 resulting in $1.86 for 10 kg of hydrogen produced for less than $0.16 per kg. To this we must add the energy costs. A hybrid process (a combination of reactions), which uses hot gases from the power plant, may be possible and energy efficient. Any one reaction or combination of reactions may be employed, adapted to local conditions as appropriate. The cost calculations for the reactions with natural gas are shown in Table 2 and are certainly quite exciting.
The invention addresses principally the sequestration of carbon and production of hydrogen. The question of clean air involves minor and trace components of natural fossil-fuels e.g. sulfur, mercury, nitrous oxides etc. The removal of these has been researched very well and can be handled appropriately as needed by adding the necessary reagents to sodium hydroxide.
Tables 2 and 3 show various other models of price variation and the effect on the price of carbon sequestration.
It is to be emphasized that the production of NaOH should be preferably done using electricity from a nuclear or other alternate source (byproducts chlorine and hydrogen in this manufacturing process are sold reducing the production cost of NaOH). If off-peak power is used to advantage, the processes would yield results no matter the source of power. It is possible to use the energy from the same plant but all CO2 emitted will not be sequestered; the advantage of hydrogen produced and used for applications that would otherwise emit CO2 should be considerd.
Reactions (1) to (7) used in this invention or the reaction described by Jones (US 2006/0185985 A1) and other carbonation reactions cannot sequester CO2 effectively if electric energy from coal-burning power plants is to be used for the production of NaOH. It can be easily demonstrated that several tons of CO2 has to be emitted in forming one ton of NaOH if fossil fuel is used. The current market price of NaOH and Na2CO3 would permit several coal/natural gas burning power plants to operate with profit but as the products (Na2CO3, and Cl2) saturate the market, additional power plants could be retrofitted if NaOH price can be brought down substantially by using alternate energy sources and off-peak power. It is all possible because the raw materials (NaCl and coal) are almost inexhaustible.
An alternative would be to consider only a 10% reduction in CO2 in a power plant 500 megawatt size. In such a situation we will produce about 1 to 1.5 million tons of solid material per year and it will be possible to manage the flow of material through the reactor.
The chlor-alkali process requires significant energy which must come from some source. If available, the energy can be used from the same power plant, which may amount to 30% of the total plant energy resulting in more CO2 emission than the process can sequester. However, since the energy if not used this way would have resulted in even more CO2 emission. By using this method, we reduce the CO2 by some percent (depending on the target, see [00108]) and produce hydrogen which will replace the energy from coal in a variety of applications. When hydrogen replaces gasoline in transportation, the overall effect of green-house-gas emission will be substantial.
The references recited here are incorporated herein in their entirety, particularly as they relate to teaching the level of ordinary skill in this art and for any disclosure necessary for the commoner understanding of the subject matter of the claimed invention. It will be clear to a person of ordinary skill in the art that the above embodiments may be altered or that insubstantial changes may be made without departing from the scope of the invention. Accordingly, the scope of the invention is determined by the scope of the following claims and their equitable equivalents.
This application claims benefit of priority under 119(e) to the provisional application entitled “Carbon sequestration and production of hydrogen and hydride” U.S. Ser. No. 60/982,473, filed Oct. 25, 2007, and this application is a continuation-in-part of international application PCT/US08/55586, claiming priority under 35 USC 120 to filing date 2 Mar. 2008. Not applicable. Not applicable.
No federal government funds were used in researching or developing this invention.
Number | Date | Country | |
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60982473 | Oct 2007 | US |
Number | Date | Country | |
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Parent | PCT/US08/55586 | Mar 2008 | US |
Child | 12552898 | US |