This invention pertains to conversion of natural gas to hydrocarbon liquids. More particularly, natural gas is converted to reactive hydrocarbons and the reactive hydrocarbons are reacted with additional natural gas to form hydrocarbon liquids.
Natural gas often contains about 60–100 mole per cent methane, the balance being primarily heavier alkanes. Alkanes of increasing carbon number are normally present in decreasing amounts. Carbon dioxide, nitrogen, and other gases may be present.
Conversion of natural gas into hydrocarbon liquids has been a technological goal for many years. The goal has become even more important in recent years as more natural gas has been found in remote locations, where gas pipelines may not be economically justified. A significant portion of the world reserves of natural gas occurs in such remote regions. While liquefied natural gas (LNG) and methanol projects have long attracted attention by making possible conversion of natural gas to a liquid, in recent years the advent of large scale projects based upon Fisher-Tropsch (F-T) technology have attracted more attention. A review of proposed and existing F-T projects along with a discussion of economics of the projects has recently been published (Oil and Gas J., Sep. 21 and Sep. 28, 1998). In this technology, natural gas is first converted to “syngas,” which is a mixture of carbon monoxide and hydrogen, and the syngas is converted to liquid paraffinic and olefinic hydrocarbons of varying chain lengths. The F-T technology was developed for using coal as a feed stock, and only two plants now operate using natural gas as feedstock—in South Africa and in Malaysia. A study showed that for a plant producing 45,000 bbls/day (BPD) of liquids in a U.S. location in 1993, investment costs would have been about $38,000 per BPD production (Oil and Gas J., Sep. 28, 1998, p. 99). Improved designs are said to lower investment cost to the range of $30,000 per BPD for a 20,000 BPD facility. Such a plant would use about 180 MMSCFD of natural gas, 10 million GPD of raw water and 150 BPD of normal butane, and would produce excess steam, which could be used to produce 10 megawatts of electricity.
The conversion of natural gas to unsaturated hydrocarbons and hydrogen by subjecting the hydrocarbons in natural gas to high temperatures produced by electromagnetic radiation or electrical discharges has been extensively studied. U.S. Pat. No. 5,277,773 discloses a conversion process that subjects methane plus hydrocarbons to microwave radiation so as to produce an electric discharge in an electromagnetic field. U.S. Pat. No. 5,131,993 discloses a method for cracking a hydrocarbon material in the presence of a microwave discharge plasma and a carrier gas, such as oxygen, hydrogen and nitrogen, and, generally, a catalyst. U.S. Pat. No. 3,389,189 is an example of patents relating to production of acetylene by an electric arc.
Methane pyrolysis to acetylene and hydrogen by rapid heating in a reaction zone and subsequent rapid quenching has also been extensively investigated. Subatmospheric pressures and specific ranges of velocities of hydrocarbon gases through the reaction zone are disclosed in U.S. Pat. No. 3,156,733. Heat is supplied by burning of hydrocarbons.
Although the prior art has disclosed a range of methods for forming acetylene or ethylene from natural gas, an energy-efficient process for converting natural gas to a liquid that can be transported efficiently from remote areas to market areas has not been available. What is needed is a process that does not require large capital and operating expenditures such as required by the prior art processes. Also, the process should be energy efficient.
A process for conversion of natural gas to a hydrocarbon liquid for transport from remote locations is provided. In one embodiment, the natural gas is heated to a temperature at which a fraction of the natural gas is converted to hydrogen and a reactive hydrocarbon such as acetylene or ethylene. The stream is then quenched to stop any further reactions and then reacted in the presence of a catalyst to form the liquid to be transported, predominantly naphtha or gasoline. Hydrogen may be separated after quenching and before the catalytic reactor. Heat for raising the temperature of the natural gas stream is provided by burning of a portion of the natural gas feed stream. Hydrogen produced in the reaction is available for further refining or in generation of electricity by oxidation in a fuel cell or turbine. In another embodiment, heat produced from the fuel cell is used to generate additional electricity. In another embodiment, the acetylene portion of the reactive hydrocarbon is reacted with hydrogen to form ethylene prior to reacting to form the liquid to be transported. In another embodiment, hydrogen produced in the reaction is burned to raise the temperature of the natural gas stream and the acetylene portion of the reactive hydrocarbon is reacted with hydrogen to form ethylene prior to reacting to form the liquid to be transported. In still another embodiment, hydrogen produced in the process is used to generate electrical power, the electrical power used to heat the natural gas stream, and the acetylene portion of the reactive hydrocarbon stream is reacted with hydrogen to form ethylene prior to reacting to form the liquid to be transported.
U.S. Pat. No. 6,130,260 and application Ser. No. 09/574,510 filed May 19, 2000, are incorporated by reference herein.
2CH4→C2H6+H2→C2H4+H2→C2H2+H2→2C+H2.
The desired products from this series of reactions are ethylene and acetylene. Suppression of the last reaction or last two reactions may be required to achieve the desired products. This may be accomplished by such methods as adjusting the reaction temperature and pressure, and/or quenching after a desired residence time. The desired hydrocarbon products of the reactions are designated herein as “reactive products.” It is preferred to maintain the pressure of the natural gas within the reaction chamber of combustion furnace 10 to between 1 and 20 bars to achieve the reactive products. The reactive products resulting from the reaction in combustion furnace 10 leave combustion furnace 10 through furnace outlet stream 18.
In an alternative embodiment, shown in
In another alternative embodiment, shown in
The materials of construction of combustion furnace 10, high temperature reactor 110, and hydrogen combustion furnace 210 are not standard. Specialty materials such as tungsten, tantalum or ceramics may be used. The temperature rise should occur in a short period of time. The furnaces may be of the double-radiant-section box-type as pictured in FIG. 19.5, p. 681, of D. Q. Kern, Process Heat Transfer, McGraw-Hill Book Co., New York (1950). The furnace may use tantalum (Ta) or silicon/carbide tubing. Steam pressures will be low, about 6 psig. Kinetic calculations indicate a suitable time for heating the natural gas to the reaction temperature is in the range from about 1 millisecond to about 100 milliseconds. To stop the reactions and prevent the reverse reactions or further reactions to form carbon and other hydrocarbon compounds, rapid cooling or “quenching” is essential, typically in 10 to 100 milliseconds. As shown in
Furnace outlet stream 18 is typically essentially one part alkene/alkyne mixture to three parts methane. In particular, “lean” natural gas, i.e., gas with 95% or greater methane reacts to mostly acetylene as a reactive product. Where the natural gas is lean, it is desirable to operate the furnace in the upper end of the desired range to achieve a higher content of alkynes, in particular acetylene. In contrast, in a richer stream, it may be desirable to operate at a temperature lower in the desirable range to achieve a higher content of alkenes, primarily ethylene.
As shown in
As shown in
As further shown in
for acetylene,
nCH4+C2H2=naphtha/gasoline+H2,
and for ethylene,
mCH4+C2H4=naphtha/gasoline+H2.
This reaction must be catalyzed to suppress the reaction of acetylene to benzene and to enhance the conversion to hydrocarbon liquids such as naphtha or gasoline, which is preferred for the method of this invention.
Liquefaction reactor 30 shown in
The reaction to produce naphtha or gasoline is thermodynamically favorable. The equilibrium thermodynamics for the reactions of acetylene and ethylene with methane are more favorable at low to moderate temperatures (300–1000 K). It is well known in the chemical industry that alkanes of ethane and higher can be converted to higher molecular weight hydrocarbons using acid catalysts, such as the zeolites H-ZSM-5 or Ultrastable Y (USY). Applicants have discovered that the amount of Bröenstead Acid sites on the catalyst should be maximized in comparison to the Lewis acid sites. This may be accomplished by increasing the silica to alumina ratio in the catalyst (Y Zeolites typically have Si/Al ratios of 2–8 whereas ZSM-5 typically has an Si/Al ratio of 15–30,000). Other alkylation catalysts are known in the chemical industry. In the present invention, the reaction of acetylene and ethylene to benzene is suppressed and the reaction of these reactive hydrocarbons with methane is enhanced. Steam may be introduced into the reactor to achieve the desired conversion results. The preferred reactor conditions are temperatures in the range from about 300 to about 1000 K and pressure in the range from about 2 to about 30 bar. The products of the liquefaction reaction leave liquefaction reactor 30 through catalytic reactor outlet stream 32.
As shown in
Note that processing steps may be added after liquefaction and before product separator 40 or, alternatively, after product separator 40, to convert the hydrocarbon liquids such as naphtha or gasoline or to heavier compounds such as diesel.
In still another embodiment, as shown in
C2H2+H2→C2H4
Traditional catalysts for conversion of alkynes to alkenes are used to convert acetylene to ethylene. These include nickel-boride, metallic palladium, and bimetallic catalysts such as palladium with a group 1b metal (copper, silver or gold). Some natural gas feed streams contained trace amounts of sulfur compounds that may act as a poison for the hydrogenation catalyst. In addition, incoming sulfur compounds may react in the hydrogen combustion furnace to form catalyst poisons, such as COS and H2S. It is preferable to remove or reduce the concentration of these catalyst poisons by means well known by those in the art, such as activated carbon or amine.
The products of the reaction that occurs in hydrogenation reactor 310 are conveyed to hydrogen separator 20 through hydrogenation outlet stream 312. Because the conversion from acetylene to ethylene is not complete, hydrogenation outlet stream 312 contains both acetylene and ethylene, as well as hydrogen and some higher-molecular-weight alkynes and alkenes. In alternative embodiments, after leaving high temperature reactor 110 in
In another alternate embodiment also shown in
Although the present invention has been described with reference to specific details, it is not intended that such details should be regarded as limitations upon the scope of the invention, except as and to the extent that they are included in the accompanying claims.
This application is a continuation patent application of, and claims priority to, commonly owned patent application U.S. Ser. No. 09/803,122, filed Mar. 9, 2001, issued now as U.S. Pat. No. 6,602,920, entitled, “Method for Converting Natural Gas to Liquid Hydrocarbons,” by Hall et al., which itself is a continuation-in-part of commonly owned application Ser. No. 09/574,510, filed May 19, 2000, now U.S. Pat. No. 6,323,247, B1, which issued on Nov. 27, 2000 and is entitled, “Method for Converting Natural Gas to Liquid Hydrocarbons,” by Hall, et al., which itself is a continuation of commonly owned application Ser. No. 09/199,502, filed Nov. 25, 1998, now U.S. Pat. No. 6,130,260, which issued on Oct. 10, 2000 and is entitled, “Method for Converting Natural Gas to Liquid Hydrocarbons,” by Hall, et al., all of which are assigned to the assignee of the present patent application, and all of which are incorporated by reference herein for all purposes.
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Number | Date | Country | |
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Parent | 09803122 | Mar 2001 | US |
Child | 10611564 | US | |
Parent | 09199502 | Nov 1998 | US |
Child | 09574510 | US |
Number | Date | Country | |
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Parent | 09574510 | May 2000 | US |
Child | 09803122 | US |