This invention relates to a process for gasification of carbon containing fossil fuels, the conversion of carbon monoxide to carbon dioxide and sequestration of the carbon dioxide with a magnesium silicate mineral suspended in the molten salt. .
There is a growing demand for hydrogen for use as a clean fuel for many applications as well as for fuel in fuel cells. Coal and other fossil fuels are an abundant source of carbon that when reacted with oxygen and water produces hydrogen. Thus, gasification of coal is a logical source for the production of hydrogen. The purpose for doing so is to remove the carbon from the fuel so that it can be sequestered and not released to the atmosphere when burned. For example, there has been a recent breakthrough in producing natural gas from shale formations, adding substantially to reserves with a subsequent reduction in price. If it is continued to be used for fuel the carbon dioxide released will contribute to global warming. If the natural gas is converted to hydrogen by the method of this invention the carbon dioxide (CO2) can be sequestered. Reference herein to coal gasification is to be understood to also refer to any fossil fuel where the carbon is converted to CO2 and sequestered.
Gasifying coal is a 125 year old technology. If coal and steam are combined at about 1600° F. they react to form hydrogen and carbon monoxide (syngas). Depending on the coal type and the gasifier design, other products are present in the syngas, such as nitrogen, carbon dioxide, hydrogen sulfide, nitrogen oxides and mercury.
Carbon monoxide (CO) produced by gasification can be converted to carbon dioxide by the so called “water gas shift” reaction in which water and carbon monoxide are reacted to produce carbon dioxide and hydrogen. Many processes have been proposed for these purposes. However, a truly economical process is needed. The process must be simple in order to make it economical. If the syngas product is too expensive because the process and equipment are too elaborate then it will not be commercially viable.
The importance of reducing carbon dioxide emissions is illustrated by the U.S. Government sponsored $1.5 billion FutureGen project in Illinois that will demonstrate coal gasification with nearly complete carbon dioxide capture—with the carbon dioxide being injected into underground domes. The US Department of Energy has reported that the amount of CO2 produced from the combustion of fossil fuels in the United States will reach nearly 5.7 billion metric tons in 2009 with about 33% coming from the coal-fired electric power sector.
Among the many proposed schemes for CO2 capture is the use of abundant naturally occurring magnesium silicate minerals, particularity Olivine. Magnesium silicate reacts with CO2 to form MgCO3 a stable, nontoxic mineral that is may be easily disposed. The difficulty is that the reaction rate of magnesium silicate and CO2 is slow. O'Conner, et al have reported on the process of reacting Olivine with high pressure CO2 aqueous solution. O'Connor, W. K.; Dahlin, D. C.; Nilsen, D. N.; Rush, G. E.; Walters, R. P. & Turner, P. C. (2001b) Carbon dioxide sequestration by direct mineral carbonation: results from recent studies and current status. Zevenhoven and Kohlmann have proposed increasing the reaction rate by microwaving the Olivine; Ron Zevenhoven and Jens Kohlmann; CO2 SEQUESTRATION BY MAGNESIUM SILICATE MINERAL CARBONATION IN FINLAND; Second Nordic Mini-symposium on Carbon Dioxide Capture and Storage, Göteborg, Oct. 26, 2001, available at http://www.entek.chalmers.se/˜anly/symp/symp2001.html. According to R. D. Olaf Schuiling, Professor in Geochemistry, at the University of Utrecht, weathering (reacting with CO2) of Olivine and other magnesium silicate minerals is a possible solution for removing CO2 from the atmosphere—the abundant mineral would be finely ground and spread out over the surface of the earth and eventually atmospheric CO2 would react with it to produce magnesium carbonate.
None of these proposals appear commercially practical for in-situ CO2 capture from a gas stream, such as from flue gases, synthesis gas, natural gas or the like.
The present invention provides a solution by reacting CO2 in gas streams with magnesium silicate suspended in a molten salt. Coupled with gasification of fossil fuels in the same molten salt results in a superior integrated fossil fuel gasification process that eliminates CO2 emissions.
The process of this invention is, in one aspect, a low cost coal gasification/water gas shift process that optionally sequesters CO2 in a rock mineral. The process is conducted in one enclosed reactor vessel having a tubular pre-reactor disposed therein, from which the effluent reaction products and reactants may be further converted in a molten salt pool disposed in the bottom of the reactor vessel. In one embodiment the pre-reactor is a venturi pre-reactor in which all the reactants, including molten salt are combined. Molten salt catalyzes the reactions of the process and captures undesirable contaminants so that further gas cleaning is not required. Carbon dioxide is optionally removed by sequestration with a magnesium silicate rock mineral, such as Olivine or Serpentine. Molten salt is such an excellent catalyst and heat transfer medium that it is technically possible to achieve some degree of reaction without using a pre-reactor and simply pumping the reactants into the bath. However, the pre-reactor has proven much more effective, promoting more efficient reaction and especially in providing reaction heat to maintain the temperature to the salt pool.
In another aspect the process of the invention is a process for capture of carbon dioxide from a gas stream by reaction of the carbon dioxide with magnesium silicate mineral suspended in a molten salt. While the gasification reaction is preferable carried out at a temperature range of about 1500° F. and about 2000° F. the carbon dioxide capture reaction may be carried out at about at a temperature range of 350 to 2000° F.
In one aspect the process of the invention uses one reaction vessel, illustrated in
Fossil fuel (coal, coke and various grades of petroleum, biomass or natural gas) and olivine mineral are stored in a hopper 11 for feeding into the gasification reactor 10. These are mixed with water and recycle salt in mixer 12 and injected into pre-reactor 13 together with air (15) or oxygen. Reactor vessel 10 has an internal sump ring 22 for withdrawal of a salt/ash mixture from the reactor by way of a slip stream through conduit 25. This withdrawn mixture is washed in vessel 14 and the resulting washed salt is recycled to the reactor pre-reactor tube.
Startup heater 23 is provided to melt and preheat the salt at startup. Hydrogen product exits the reactor 10 by conduit 26. The reactor vessel is also provided with a means, 21, to draw off salt and contaminants at the bottom of the reactor vessel.
While the reactor may operate from atmospheric pressure to about 150 atmospheres, it is preferred that the operating pressure be maintained at about atmospheric up to about four atmospheres and more preferably at up to about one and a half to two atmospheres pressure. The process performs best at these lower pressures which eliminates the need for costly high pressure compression of the inlet gases. The construction and materials for the reactor vessel and other components of the system are selected to accommodate the operating temperatures and pressure.
It has been determined that an effective ratio of feed to salt is between 1 part feed per hour to 10-100 parts salt, and more preferably about 1-15. The preferred feed to water ratio is 1 part feed to 1-5 parts water, and more particularly 1-2. The preferred percentage of magnesium silicate in the reactor is between 5-20 percent of the salt content, and more preferably about 8 percent.
Referring to the reactor system in
There is provided a drain from the bottom of reaction vessel (21) to remove metals that are too heavy to come out with the ash.
If it is undesirable to have nitrogen in the product hydrogen gas, the gasification in the reaction vessel may be carried out without oxygen. In this embodiment of the invention, carbon (from) coal will react with steam (water) to form syngas. When oxygen is used, the required heat is generated by the reaction of oxygen and coal. When oxygen is not used heat must be supplied. While the reaction of CO2 with magnesium silicate produces some heat it is insufficient alone to maintain the temperature of the salt. This may be accomplished by indirect heating of the pre-reactor tube, as by providing an annular space around the tube and firing it with fuel and oxygen—the product hydrogen may be used as fuel, if desired.
As CO begins to form from the gasification reaction (C+H2O→CO+H2) the addition of extra water forms CO2 (C+2H2O→CO22H2) and additional H2, the water gas shift reaction (WGS). When the CO2 contacts magnesium silicate in the salt pool it is converted to MgCO3, effectively removing CO2 from the gas stream, enabling the WGS reaction to proceed faster. Gas leaving the top of the reactor is H2 (and N2 if air is used) and water vapor.
In another embodiment, illustrated in
Make-up salt is added, when needed to maintain the level of 250 by line 232. Product H2 and N2 are recovered through line 260.
As the coal and steam react to form C+H2O→H2+CO, excess water causes the reaction to proceed on to H2O+CO→H2+CO2. The CO2 immediately reacts with MgO→MgCO3. Removing the CO2 from the gas phase enhances the reaction of CO to CO2. Therefore the reaction of serpentine mineral acts as a catalyst for the shift reaction. The temperature will be from about 1500° F. to 2000° F., with 1700° F. to 1800° F. being preferred. The reaction products travel down the venturi pre-reactor tube and emerges above the surface of the molten salt bath (250) where any un-reacted carbon is converted. In a typical system the reactor vessel will be about six (6) feet in diameter and the venturi pre-reactor or about 12 to 24 inches in diameter, with the venturi throat about half the diameter of the pre-reactor.
In the reaction vessel in both described configurations, the molten salt level will be about 15 to 45 percent of the total height of the vessel with about ⅓ the height being especially preferred.
A number of different salts can be used but the most economical is sodium chloride. Its availability is virtually unlimited and disposal is benign. In one embodiment it is preferred to use lower melting salts for carbon dioxide capture, including eutectic mixtures with melting points of about 250 to 600° F. Other suitable salts include metal chlorides, carbonates, sulfates, sulfites, nitrates, nitrites, bromides, oxides, hydroxides, per chlorates and mixtures thereof. Pollutants entering the salt from the inlet gases and fossil fuel that accumulate in the salt must be purged from the system to keep the salt active and fluid. A constant bleed of the salt bath and a constant re-supply of salt must occur. A percentage of the purge stream will be sodium chloride (or other salt used in the molten salt bath). It can be recovered by water wash and recycling the water or it can be disposed of. The point is, due to the huge volume of salt involved it desirable that it be the most abundant and cheapest available, that is, sodium chloride.
Several magnesium silicate minerals are suitable for use in reacting with the CO2, including serpentine [Mg3(Si2O5)(OH)4], enstatite (MgSiO3), and olivine, which actually represents a mineral group encompassing the solid-solution series between magnesium-rich (forsterite, Mg2SiO4) and iron-rich (fayalite, Fe2SiO4). Wollastonite 9CaSiO2) is also suitable. Mineral as used herein means a naturally occurring solid formed through geological processes that have a characteristic chemical composition, a highly ordered atomic structure, and specific physical properties. In some aspects fly-ash can also be used but is generally less effective.
The process is capable of gasification of all grades of coal, petroleum coke, petroleum, biomass and natural gas, with capture and disposal of inherent pollutants, including CO2.
Only hydrogen and nitrogen (if air is the oxygen source) are produced in one embodiment of the invention.
The sequestration of CO2, produces a residue of reacted magnesium silicate product and other solids. This residue and ash can be used as landfill, and possibly for road and building material.
Waste water is recycled through the system and/or used for boiler water makeup, etc.
While the gasification process with in situ carbon dioxide capture is an important aspect of the present invention, the ability to capture carbon dioxide from any gas stream is an equally important aspect. While there has been, and continue to be, many attempts to accelerate the reaction rate of the CO2/magnesium silicate reaction no one has yet found a suitable solution—the reaction rate is simply too slow in all the studies to date. Suspending the magnesium silicate in molten salt provides a solution.
The process for capture of CO2 from a gas stream is described by reference to
One embodiment is shown by referring to reactor vessel 102 in
It might be expected that magnesium carbonate would decompose at the process conditions. References to the temperature for decomposition vary widely. Many MSDS sheets list the decomposition temperature ate about 250° C. (482° F.). The online encyclopedia, Wikipedia under the heading magnesium carbonate lists the decomposition temperature at 540° C. (1004° F.) but also states that the decomposition temperature is in the range of 800-1000° C. (1472-1832° F.). It is therefore surprising that the suspended magnesium silicate does not decompose but instead forms stable magnesium carbonate at the temperatures of the invention, i.e. at 1500-2000° F.
Mineral magnesium silicate is fed from bin 101 (
As the gas flows through and out of the salt it forms froth on the surface. The gas, from which CO2 has been removed, passes out of the reactor vessel 102 by conduit 121. Inside the reaction vessel is a sump ring 108 for removal of salt and minerals. The froth, 109, spills over into the sump ring together with salt and minerals and pass through conduit 110 into a water wash unit 103. The salt mixture is also removed from the reactor vessel by conduit 128 into the water wash vessel 123. In vessel 123 the salt mixture is mixed with water to remove the salt from the solids. The salt, soluble in water, is recycled as an aqueous solution to reactor vessel 102 through conduit 122.
Water insolubles from wash unit 103 that are removed through conduit a 124 will be predominately a mixture un-reacted magnesium silicate mineral and magnesium carbonate. This mixture is removed from vessel 103, through conduit 124, and optionally dried for disposed. Disposal presents no environmental problems since both magnesium silicate minerals and magnesium carbonate are common natural materials. These harmless compounds they may be disposed of in any expedient way as by use as landfill, used as component of concrete or even dumped at sea.
Alternatively the minerals may be separated and the recovered magnesium silicate mineral and/or product of the separation be reused in the CO2 capture process.
Drain 125 is utilized to remove any metals or other heavy components of the salt from the reactor vessel.
The following test illustrates the efficacy of the gasifier reactor to achieve a high degree of gasification of powdered high sulfur coal.
A prototype reaction vessel consisting of a 11″×29″ inconel vessel fitted with a 6.5″×36″ stainless steel pre-gasifier tube that is notched on the bottom and extends to 2″ off the bottom of the vessel was used for these tests. The vessel was filled with 40 pounds of NaCl salt and 2 pounds of olivine. It was heated by external electric heaters to 1750° F. and created a depth of 10 inches molten bath. A coal slurry ground to an average of 50 microns was mixed with two parts water to make a pumpable slurry. The slurry was pumped into the reactor at a flow rate of 3 ounces per minute. After ten minutes a sample of the outlet gas was collected and sent to a commercial lab for analysis. They reported:
H2−—99.8%
CO—0%,
CO2—0%
Sulfur—0%.
Several repetitive tests were run with duplicate results.
Another test was run with no olivine in the salt bath and the results were:
H2—77%
CO2—17%.
This shows that CO2 would be available for enhanced oil recovery or other purposes if desired.
In the foregoing specification, the invention has been described with reference to specific embodiments thereof. It will, however, be evident that various modifications and changes can be made thereto without departing from the broader spirit and scope of the invention as set forth in the appended claims. The specification and drawings are, accordingly, to be regarded in an illustrative rather than a restrictive sense. Therefore, the scope of the invention should be limited only by the appended claims.
This application is a Continuation-In-Part of a U.S. application Ser. No. 12/623,399 filed Nov. 21, 2009, which is a Continuation-In-Part of a U.S. application Ser. No. 12/283,862 filed Sep. 16, 2008 and claims the benefit of U.S. Provisional Application, No. 60/994,182, filed Sep 18, 2007.
Number | Date | Country | |
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Parent | 12623399 | Nov 2009 | US |
Child | 13422005 | US | |
Parent | 12283862 | Sep 2008 | US |
Child | 12623399 | US |