This application is related to Ser. No. 11/657,299, filed Jan. 25, 2007, Publication No. US-2008-0181845-A1; to Ser. No. 12/030,970, filed Feb. 14, 2008, Publication No. US-2009-0205254-A1; and to Ser. no. 12/040,883, filed Mar. 01, 2008, Publication No. US-2008-0210908-A1.
This invention relates generally to the production of hydrogen fuels, and particularly to a method and a system for producing a hydrogen enriched fuel suitable for use as an alternative fuel.
Gaseous alternative fuels, such as hydrogen and natural gas, are valued for their clean burning characteristics in motor vehicle engines. Various processes have been developed for producing hydrogen. These processes include electrolysis, exotic water splitting, and separation from industrial waste streams.
Hydrogen can also be produced by reforming natural gas. Typically, a multi-step process is used to convert a hydrocarbon fuel, such as methane, propane or natural gas, into a high purity hydrogen gas stream. The steps of the process typically include (1) synthesis gas generation, (2) water-gas shift reaction, and (3) gas purification (e.g., CO and CO2 removal). The hydrogen gas stream can then be used for a variety of purposes including mixture with other gases to produce an alternative fuel.
For example, a particularly clean burning gaseous alternative fuel known as HYTHANE comprises a mixture of hydrogen and natural gas. The prefix “Hy” in HYTHANE is taken from hydrogen. The suffix “thane” in HYTHANE is taken from methane, which is the primary constituent of natural gas. HYTHANE is a registered trademark of Brehon Energy PLC. HYTHANE typically contains about 5% to 7% hydrogen by energy, which corresponds to 15% to 20% hydrogen by volume.
For producing hydrogen, one type of reformer called a “steam reformer” uses a hydrocarbon fuel and steam (H2O). In the steam reformer, the hydrocarbon fuel is reacted in a heated reaction tube containing steam (H2O) and one or more catalysts. In general, the production of a high purity hydrogen gas by reforming requires high temperatures (800-900° C.). Steam reforming also produces impurities, particularly CO and CO2, which if not removed, are ultimately released to the atmosphere.
The production of a high purity hydrogen gas by reforming also requires large capital costs for the equipment, and large operating costs, particularly for power. In addition to these shortcomings, it is difficult to manufacture a compact embodiment of a steam reformer. It would be advantageous for a hydrogen production system to have a relatively compact size, such that alternative fuels could be produced at a facility the size of a gas station, rather than at a facility the size of a refinery.
Another process for producing hydrogen from natural gas involves the thermal decomposition of methane. For example, methane decomposes into hydrogen by the reaction:
CH4=C+2H2
For example, the thermal decomposition of natural gas has been used in the “Thermal Black Process” for producing carbon black and hydrogen. Using thermal decomposition, the energy requirements per mole of hydrogen produced (37.8 kJ/mol H2) is considerably less than the energy requirements of the steam reforming process (63.3 kJ/mol H2). However, the process still requires high temperatures (e.g., 1400° C.), high equipment costs, and high energy expenditures.
Recently, thermal decomposition of natural gas has been investigated in combination with various catalysts, which allow the reaction to proceed at lower temperatures. For example, U.S. Pat. No. 7,001,586 B2, to Wang et al. discloses a thermal decomposition process in which two catalysts having the formula NixMgyO and NixMgyCuzO, respectively, are used to decompose methane to carbon and hydrogen. The former needs a lower temperature from about 425° C. to 625° C., but the lifetime is shorter and the activity is lower. The latter's lifetime is longer and the activity is higher, but the required reaction temperature is much higher, from about 600° C. to 775° C. More importantly, however, these processes require high energy expenditures to heat the wall of the reactor, the gas and the catalysts.
It would be advantageous for a hydrogen production system to be capable of performance at lower temperatures and lower energy expenditures, with a variety of catalysts active for long periods, and with minimal carbon emissions (e.g., CO, CO2). In addition, it would be advantageous for a hydrogen production system to have a size and configuration adaptable to the production of alternative fuels containing hydrogen. The present disclosure is directed to a method and a system for producing a hydrogen enriched fuel that overcomes many of the shortcomings of prior art hydrogen production systems.
The foregoing examples of the related art and limitations related therewith are intended to be illustrative and not exclusive. Other limitations of the related art will become apparent to those of skill in the art upon a reading of the specification and a study of the drawings. Similarly, the following embodiments and aspects thereof are described and illustrated in conjunction with a system and method, which are meant to be exemplary and illustrative, not limiting in scope.
A method for producing a hydrogen enriched fuel includes the steps of providing a flow of methane gas, providing a catalyst, selectively heating the catalyst instead of the reactor walls and the methane gas using microwave irradiation at a selected microwave power, directing the flow of methane gas over the catalyst, and controlling the microwave power to produce a product gas having a selected composition.
The method can be performed in a reactor having a reaction chamber with microwave transparent walls. In addition, the catalyst can comprise a metal, such as a Ni-based compound prepared by coprecipitation. On the surface of the catalyst reactions occur in which methane (CH4) dissociates into hydrogen (H2) and solid carbon (C) in the form of fibrous carbon. In addition, some of the methane gas fails to react (methane slip) such that the product gas comprises methane and hydrogen. The catalyst is selected and formulated to remain stable under operating conditions (e.g., gas flow rate, microwave power, catalyst amount), such that costs are minimized. In addition, the catalyst maintains active characteristics through many hours of reactions.
The flow of methane gas and the microwave power can be controlled such that the composition of the product gas approximates the chemical composition of HYTHANE. For example, the product gas can comprise from about 20% to 30% hydrogen by volume, and from about 70% to 80% methane by volume. Advantageously, the product gas contains almost no carbon impurities (e.g., CO, CO2), as carbon is converted to solid fibrous carbon which drops out of the product gas as a useful by-product. In addition, the product gas contains only negligible amounts of higher order hydrocarbons (e.g., C2H4, C2H2, C3H6, C3H8, C3H4).
A system for producing a hydrogen enriched fuel includes a methane gas source configured to provide a methane gas flow. The system also includes a reactor having a reaction chamber in flow communication with the methane gas source configured to contain a catalyst, and to circulate the methane gas in contact with the catalyst. The system also includes a microwave power source configured to heat the catalyst in the reaction chamber to form a product gas having a selected volumetric percentage of hydrogen and methane.
In an alternate embodiment of the method, the product gas is further processed to recover hydrogen in substantially pure form. To recover substantially pure hydrogen, the product gas can be flowed under a vacuum through a Pd/Ag membrane coated on a porous metal or ceramic plate.
Exemplary embodiments are illustrated in the referenced figures of the drawings. It is intended that the embodiments and the figures disclosed herein are to be considered illustrative rather than limiting.
The following definitions are used in the present disclosure. HYTHANE means a hydrogen enriched alternative fuel comprised of hydrogen and methane and impurities included in hydrogen and natural gas.
Methane slip means unreacted methane which passes through a system without reacting.
Microwave irradiation means electromagnetic irradiation in the range of 0.3 to 300 GHz.
Method
Referring to
As also shown in
A preferred metal for the catalyst comprises Ni, or an alloy containing Ni. For example, the metal can comprise NiAl, or Ni doped with Cu, Pd, Fe, Co, or an oxide such as MgO, ZnO, Mo2O3 or SiO2. Specific catalysts include Ni81Al, Ni93Al, Ni77Cu16Al, Ni54Cu27Al and Ni83Mg6Al. In addition, nickel based catalyst precursors can be prepared by coprecipitation from a mixed aqueous solution of nitrates with sodium carbonate.
The following Table I provides information on catalyst preparation of nickel-based precursors for the above catalysts. These catalysts were prepared by coprecipitation from a mixed aqueous solution of nitrates with sodium carbonate.
However, rather than Ni or an alloy thereof, the catalyst can comprise another metal, such as a metal selected from group VIII of the periodic table including Fe, Co, Ru, Pd and Pt. In any case the catalyst is selected and formulated to remain stable under reaction conditions for long periods of time. In the examples to follow there was no indication that the catalyst was going to be deactivated, even after over 16 hours of reaction time.
As also shown in
Heating the catalyst by microwave irradiation provides the following advantages:
a.) volumetric heating, fast,
b.) selectively heating the catalyst instead of the reactor wall and the methane gas, high efficiency,
c.) low temperature gradient,
d.) hot spot to prevent serial reaction of product,
e.) may also influence catalytic reaction by changing the electronic properties of the catalyst in the microwave electromagnetic field.
In the examples to follow, the microwave generator was operated at a power of about 250 watts, and the catalyst was heated to a temperature of from about 600 to 700° C. However, it is to be understood that the method can be practiced at a microwave power that is selected to achieve a desired product gas composition. For example, a representative range for the microwave power can be from 150 watts to 300 watts. Also in the examples to follow, the microwave generator was operated at a frequency of 2.45 GHz. For performing microwave irradiation, the reactor and the holder for the catalyst must be made of a microwave transparent material able to withstand high temperatures. One suitable material for the reactor and the holder comprises quartz.
As also shown in
As also shown in
System
Referring to
The reactor 12 (
The supply conduit 24 (
The supply conduit 24 (
The supply conduit 24 (
In addition to the reaction chamber 22 (
The reactor 12 (
The microwave generator 14 (
The system 10 (
Using the previously described method (
In
Example 2 was performed using the same conditions as outlined above for Example 1 but with the catalyst comprising Ni81Al rather than Ni54Cu27Al.
In
From these two examples it was determined that a product gas containing 30% by volume of H2 can be produced continuously and stably by microwave heating a Ni54Cu27Al catalyst. A product gas containing 20% by volume of H2 can be produced continuously and stably by microwave heating a Ni81Al catalyst.
An alternate embodiment of the method includes the additional step of further processing the product gas to recover hydrogen in substantially pure form. One method for recovering pure hydrogen is to flow the product gas under a vacuum through a Pd/Ag membrane coated on a porous metal or ceramic substrate. U.S. Pat. No. 6,165,438, to Willms et al., which is incorporated herein by reference, discloses an apparatus and method for the recovery of hydrogen from a gas containing hydrocarbons.
Thus the disclosure describes an improved method and system for producing a hydrogen enriched fuel. While the description has been with reference to certain preferred embodiments, as will be apparent to those skilled in the art, certain changes and modifications can be made without departing from the scope of the following claims.
Number | Name | Date | Kind |
---|---|---|---|
4435376 | Porter et al. | Mar 1984 | A |
4574038 | Wan | Mar 1986 | A |
5015349 | Suib | May 1991 | A |
5131993 | Suib | Jul 1992 | A |
5139002 | Lynch et al. | Aug 1992 | A |
5205912 | Murphy | Apr 1993 | A |
5205915 | Ravella et al. | Apr 1993 | A |
5266175 | Murphy | Nov 1993 | A |
5277771 | Murphy | Jan 1994 | A |
5277773 | Murphy | Jan 1994 | A |
5366712 | Violante et al. | Nov 1994 | A |
5372617 | Kerrebrock et al. | Dec 1994 | A |
5516967 | Pandey et al. | May 1996 | A |
5525322 | Willms | Jun 1996 | A |
5972175 | Tanner et al. | Oct 1999 | A |
6165438 | Willms et al. | Dec 2000 | A |
6509000 | Choudhary et al. | Jan 2003 | B1 |
6592723 | Cha | Jul 2003 | B2 |
6759025 | Hong et al. | Jul 2004 | B2 |
6783632 | Cha | Aug 2004 | B2 |
6875417 | Shah et al. | Apr 2005 | B1 |
6994907 | Resasco et al. | Feb 2006 | B2 |
6998103 | Phillips et al. | Feb 2006 | B1 |
7001586 | Wang et al. | Feb 2006 | B2 |
7011768 | Jensen et al. | Mar 2006 | B2 |
7094386 | Resasco et al. | Aug 2006 | B2 |
7094679 | Li et al. | Aug 2006 | B1 |
7119240 | Hall et al. | Oct 2006 | B2 |
7625544 | Liu et al. | Dec 2009 | B2 |
20020103405 | Hatanaka | Aug 2002 | A1 |
20020146366 | Cha | Oct 2002 | A1 |
20030129122 | Chen | Jul 2003 | A1 |
20030206855 | Cha | Nov 2003 | A1 |
20040265223 | Etievant et al. | Dec 2004 | A1 |
20050063900 | Wang et al. | Mar 2005 | A1 |
20050065391 | Gattis et al. | Mar 2005 | A1 |
20050288541 | Sherwood | Dec 2005 | A1 |
20060021510 | Henley et al. | Feb 2006 | A1 |
20060037432 | Deevi et al. | Feb 2006 | A1 |
20060163054 | Spitzl et al. | Jul 2006 | A1 |
20060269669 | Jiang et al. | Nov 2006 | A1 |
20070031299 | Jiang et al. | Feb 2007 | A1 |
20070266825 | Ripley et al. | Nov 2007 | A1 |
20080156630 | Lee et al. | Jul 2008 | A1 |
20080159944 | Park | Jul 2008 | A1 |
20080181845 | Zhu | Jul 2008 | A1 |
20080210908 | Zhu | Sep 2008 | A1 |
20090205254 | Zhu et al. | Aug 2009 | A1 |
Number | Date | Country |
---|---|---|
5187699 | Feb 2000 | AU |
2031959 | Jun 1991 | CA |
2084196 | Jan 1992 | CA |
2103211 | May 1994 | CA |
2103330 | May 1994 | CA |
2338494 | Feb 2000 | CA |
2453841 | Jan 2003 | CA |
1423331 | Feb 1976 | EP |
0435591 | Jul 1991 | EP |
0600738 | Jun 1994 | EP |
0601797 | Jun 1994 | EP |
1881944 | Jan 2008 | EP |
2827591 | Jan 2003 | FR |
6219970 | Sep 1994 | JP |
2004-324004 | Nov 2004 | JP |
2004324004 | Nov 2004 | JP |
2007000774 | Jan 2007 | JP |
2006011876 | Nov 2006 | KR |
9307285 | Jul 1994 | MX |
9307330 | Jul 1994 | MX |
9202448 | Feb 1992 | WO |
0005167 | Feb 2000 | WO |
03008328 | Jan 2003 | WO |
WO 2006107144 | Oct 2006 | WO |
2006123883 | Nov 2006 | WO |
WO2008090466 | Jul 2008 | WO |
WO2008090467 | Jul 2008 | WO |
WO 2009145936 | Mar 2009 | WO |
WO 2009103017 | Aug 2009 | WO |
Number | Date | Country | |
---|---|---|---|
20080173532 A1 | Jul 2008 | US |