Method for the production of hydrogen-containing gaseous mixtures

Abstract

A method for the production of a hydrogen-containing gas composition, such as a synthesis gas including hydrogen and carbon monoxide. The molar ratio of hydrogen to carbon monoxide (H2:CO) in the synthesis gas can be well-controlled to yield a ratio that is adequate for the synthesis of useful products such as methane or methanol, without the need to remove carbon oxides from the gas stream to adjust the ratio.

Description

Statement Regarding Federally Funded Research None BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is directed to a method for the production of valuable hydrocarbon products by reacting a carbonaceous material and steam in a molten metal to form a synthesis gas that can be used to produce high-value hydrocarbon products. More particularly, the present invention is directed to a method for the production of a synthesis gas that includes a controlled ratio of hydrogen to carbon monoxide by contacting a carbonaceous material and a reactive metal with steam, wherein a portion of the steam reacts with the carbonaceous material and a portion of the steam reacts with the reactive metal. The synthesis gas can be used to form high-value hydrocarbon products, such as methane or methanol. 2. Description of Related Art Recently, the United States and other countries have experienced a shortage of natural gas and as a result, natural gas prices for consumers hav...

AI Technical Summary

Benefits of technology

It is a particular advantage of the present invention that the synthesis gas extracted from the reactor has a controlled molar ratio of hydrogen to carbon monoxide (H2:CO) without requiring additional steps for the removal of carbon oxides to adjust the ratio prior to the synthesis of useful products such as methanol or methane. Accordingly, it is preferred that the molar ratio of H2:CO in the gas stream extracted from the reactor is at least 1:1 and more preferably is at least about 1.5:1. In particular, the synthesis gas can be extracted from the reactor and provided to a methanol production step with a H2:CO molar ratio of at least about 2:1 (theoretical stoichiometric requirement), more particularly about 2.1:1 (the preferred requirement established by practice). The synthesis gas provided to a methane production step can be controlled to have a H2:CO molar ratio of at least about 3:1, the theoretical stoichiometric requirement. Thus, according to one embodiment, the gas stream extracted from the reactor has a H2:CO molar ratio of from about 2:1 to 3:1.

that the synthesis gas extracted from the reactor has a controlled molar ratio of hydrogen to carbon monoxide (H2:CO) without requiring additional steps for the removal of carbon oxides to adjust the ratio prior to the synthesis of useful products such as methanol or methane. Accordingly, it is preferred that the molar ratio of H2:CO in the gas stream extracted from the reactor is at least 1:1 and more preferably is at least about 1.5:1. In particular, the synthesis gas can be extracted from the reactor and provided to a methanol production step with a H2:CO molar ratio of at least about 2:1 (theoretical stoichiometric requirement), more particularly about 2.1:1 (the preferred requirement established by practice). The synthesis gas provided to a methane production step can be controlled to have a H2:CO molar ratio of at least about 3:1, the theoretical stoichiometric requirement. Thus, according to one embodiment, the gas stream extracted from the reactor has a H2:CO molar ratio of from about 2:1 to 3:1.

After production of the synthesis gas, it can be converted to a hydrocarbon compound having either a gaseous, liquid or solid form. According to one preferred embodiment of the present invention, the synthesis gas is converted to methane. Methods for converting synthesis gas to methane are known to those skilled in the art. Typically, the synthesis gas is contacted with a catalyst at an elevated temperature. The catalysts can be, for example, nickel or molybdenum based catalysts supported on a carrier such as alumina. Examples of methanation catalysts and reaction conditions are illustrated in U.S. Pat. No. 4,540,714 by Pedersen et al., U.S. Pat. No. 4,525,482 by Ohaski et al. and U.S. Pat. No. 4,130,575 by J¥m. Each of the foregoing U.S. patents is incorporated herein by reference in its entirety.

The methane formed from the synthesis gas can be burned directly in a combined cycle generator to produce electricity. Although the synthesis gas can be burned directly, it is generally more economical to convert the synthesis gas to methane.

Methods of converting synthesis gas to methanol are known in the art and involve the contact of the synthesis gas, under pressure, with catalysts such as copper / zinc / chromium oxide. Examples of processes for converting synthesis gas to methanol and other alcohols are disclosed in U.S. Pat. No. 4,348,487 by Goldstein et al., U.S. Pat. No. 4,843,101 by Klier et al, U.S. Pat. No. 5,703,133 by Vanderspurt et al., and U.S. Pat. No. 6,248,796 by Jackson et al., which are incorporated herein by reference in their entirety. Synthesis gas can also be converted to synthetic crude using known Fischer-Tropsch processes.

To conserve heat it may be desirable to keep the synthesis gas stream exiting baghouse at its elevated temperature (400° C. to 500° C.) prior to its being converted into methanol or methane. To do so, anhydrous ammonia may be injected into the gas stream to react with the acid gas components producing ammonium sulfide ((NH4)2S), ammonium chloride (NH4Cl) and ammonium fluoride (NH4F). The ammonium salts that are produced may be removed from the gas stream, for example by pulsed ceramic filters. Thereafter, the purified gas stream can proceed directly to a conversion step without significant reheating.

Problems solved by technology

Recently, the United States and other countries have experienced a shortage of natural gas and as a result, natural gas prices for consumers have increased substantially.

Coal however, because of its high carbon content, generates large quantities of carbon dioxide (CO2), and the use of coal for electricity generation is a major contributor to the 5.5 billion tons of CO2 emitted by the United States per annum.

Furthermore, only 30 percent of the heat generated by burning coal is converted into electricity and 70 percent is wasted to the atmosphere.

Typically, methanol is produced using syngas derived from natural gas, which exerts further pressure on the price and availability of natural gas.

The Lurgi gasifying process has the highest H2 to CO ratio, however, it can only utilize coal in the size range of 2 mm to 50 mm.

The resulting requirement for disposal of material smaller than 2 mm imposes an onerous economic burden on the Lurgi process.

Any change in coal rate or steam rate, for the intended purpose of affecting the H2:CO ratio, would destroy the heat balance.

A significant limitation of the foregoing methods for producing syngas is that the synthesis gas must be treated to remove carbon oxides before the gas product can be used to produce high-value products such as methane or methanol.

Process steps to eliminate carbon oxides from the gas stream are relatively costly.

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