Gas: heating and illuminating – Methane -containing product – or treatment or recovery process
Reexamination Certificate
1999-12-13
2003-07-01
Johnson, Jerry D. (Department: 1764)
Gas: heating and illuminating
Methane -containing product, or treatment or recovery process
C048S127500, C048S127700, C048S1970FM, C048S198200, C048S198300, C048S198700
Reexamination Certificate
active
06585784
ABSTRACT:
This invention relates to the combustion of natural gas having low methane concentrations and, without the invention, having a low heating value for the economic generation of power from gas turbines. More particularly, his invention relates to the combustion of a gas blend with a methane gas concentration of not more than about 40 volume percent, based upon the total volume of the gas. The gas blend includes hydrogen gas to increase the combustibility of the gas blend.
BACKGROUND OF THE INVENTION
Currently there are substantial methane gas reserves with relatively low methane gas concentrations. Many of these reserves have methane gas concentrations below 40 volume percent. Currently, impurities are removed from natural gas to make pipeline quality natural gas which normally have methane concentrations of from about 95+ to about 99+ volume percent. To fuel gas turbines to make electric power, converting natural gas having methane concentrations of not more than about 40 volume percent methane to pipeline quality natural gas becomes economically impractical because the conversion is capital intensive. Moreover, natural gas with methane concentrations of not more than 40 volume percent does not provide a reliable fuel source for gas turbines to generate power because natural gas with such low methane concentrations will not provide a stable flame for fuel combustion without special catalysts and without special balancing of oxygen with other combustibles.
SUMMARY OF THE INVENTION
The invention is directed to a method of fueling gas turbines from natural gas reserves with relatively low methane concentrations. The invention permits the use of such reserves to be used to fuel gas turbines to generate electric power. As described, these reserves currently can be used only after the removal of irmpurities to produce suitable gas turbine fuel. Also as previously described, the latter current technology is capital intensive, and at current natural gas prices, economically unattractive. The process of the invention can remove the impurities necessary for protection of the environment, leaves inert gasses, such as carbon dioxide, in the fuel to maxirnize mass flow through the gas turbine, and uses hydrogen gas or shifts just enough methane to hydrogen gas to produce a gas fuel blend of hydrogen and methane gas that not only is an acceptable fuel for gas turbines, but the blend is effective for providing flame stability (such as providing the gas with at least 110 BTUs per standard cubic foot of gas) and for producing more power than a standard natural gas having from about 95+ to about 99+ volume percent methane. The method of the invention includes providing a natural gas comprising not more than about 40 percent methane on a volume basis and mixing the methane of the natural gas with hydrogen gas to provide a hydrogen enhanced methane/hydrogen gas blend (which also may be called a hydrogen enhanced natural gas) which has sufficient hydrogen to provide flame stability during burning. Thereafter, if required, the hydrogen enhanced methane/hydrogen gas blend is dehydrated to remove a sufficient amount of water to provide a flame stable hydrogen enhanced dehydrated methane/hydrogen gas blend. In an important aspect, the hydrogen enhanced methane/hydrogen gas blend has at least about 6 volume percent hydrogen. The flame stable hydrogen enhanced dehydrated methane/hydrogen gas blend then is used to fuel an electric power producing gas turbine. The method of the invention is effective for increasing the power output of a gas turbine by at least about 10 percent as compared to gas turbine using a standard natural gas which comprises from about 95 to about 99+ volume percent methane. In most cases, output may be increased by at least about 20 and up to about 30 percent with these latter limits being imposed by the mechanical design limitations of the gas turbine.
In an important aspect, a portion of the methane from natural gas is catalytically converted or reformed into hydrogen gas which then forms the hydrogen enhanced methane/hydrogen gas blend. The reactions which to obtain this conversion include:
CH
4
+CO
2
→2CO+2H
2
CH
4
+2H
2
O→CO
2
+4H
2
In another important aspect, prior to the conversion reaction, hydrogen sulfide and other acid components such as COS, RSH and RSSR are removed from the natural gas using a physical solvent to provide a sweet natural gas. A physical solvent selectively removes hydrogen sulfide and other acid gases, but minimizes the removal of carbon dioxide and other inert gases such as helium, argon, and nitrogen. In this aspect, the physical solvent is selected from the group consisting of methanol, a blend of dimethyl ethers of polyethylene glycol (molecular weight about 280), propylene carbonate (b.p. of 240° C.), N-methyl-2-pyrrolidone (b.p. 202° C.), a blend of oligoethylene glycol methyl isopropyl ethers (b.p. about 320° C.), tri-n-butyl phosphonate (b.p. 180° C. at 30 mm Hg) and methyl cyano-acetate (b.p. 202° C.). The sweet natural gas is mixed with sufficient water to permit sufficient production of hydrogen from the methane to achieve flame stability or a BTU/Scf value of at least about 110. In this aspect, it is important that the hydrogen sulfide and other acid gases are removed prior to reforming a portion of the methane to hydrogen because the reformation is a catalyzed reaction where the catalyst may be poisoned by the hydrogen sulfide gas and other acid gases. Catalysts which are sensitive to the acid conditions and which may be used in this aspect of the invention include the C11 Series catalyst from United Catalyst Inc., R67 from Haldor Topsoe and G1-25 from BASF. High temperature “shift catalysts” for sweet natural gas generally are iron, chrome and copper. Low temperature “shift catalysts” for sweet natural gas generally are made from copper, zinc and aluminum.
In another important aspect, the reformation reaction is done under acid or sour conditions using catalysts such as a C25 Series catalyst from United Catalyst Inc., K8-11 catalyst from BASF and SSK catalyst from Haldor Topsoe. In general these catalysts are chrome molybdenum catalysts. In this aspect of the invention, the sour natural gas and water are mixed with the water being in amount which will result in a methane gas/water blend which will permit the formation or reformation of sufficient hydrogen gas to provide flame stability for the hydrogen rich methane/hydrogen gas blend which does not have in excess of 40 volume percent methane.
In another aspect, the natural gas reserves may have as low as 35, 25 or even less than 20 volume percent methane and still provide more power than pipeline quality methane. In practicing the invention, sufficient methane should be converted into hydrogen to produce a methane/hydrogen gas blend with at least 6 volume percent, and preferably from about 6 to about 10 volume percent hydrogen. This will produce a hydrogen enhanced methane/hydrogen gas blend with stable flammability that is very effective for fueling gas turbines for the generation of electric power.
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ExxonMobil Chemical Patents Inc.
Hooray James A.
Johnson Jerry D.
Ridley Basia
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