Gas separation: processes – Solid sorption – Including reduction of pressure
Reexamination Certificate
2002-03-12
2003-08-26
Spitzer, Robert H. (Department: 1724)
Gas separation: processes
Solid sorption
Including reduction of pressure
C095S105000, C095S130000, C095S139000, C095S143000
Reexamination Certificate
active
06610124
ABSTRACT:
FIELD OF THE INVENTION
This invention relates to the purification of natural gas, and, more particularly, to the removal of nitrogen and/or carbon dioxide and recovery of C
3+
hydrocarbon from natural gas by use of a novel pressure swing adsorption (PSA) process.
BACKGROUND OF THE INVENTION
The removal of nitrogen and acid gases such as carbon dioxide from natural gas is of considerable importance inasmuch as nitrogen and carbon dioxide can be present to a significant extent. Nitrogen and carbon dioxide contamination lower the heating value of the natural gas and increase the transportation cost based on unit heating value.
Applications aimed at removing nitrogen, carbon dioxide, and other impurities from natural gas steams streams provide significant benefits to the U.S. economy. In 1993, the Gas Research Institute (GRI) estimated that about one third of the natural gas reserves in the U.S. are defined as sub-quality due to contamination with nitrogen, carbon dioxide, and sulfur. Many of these reserves, however, have discounted market potential, if they are marketable at all, due to the inability to cost effectively remove the nitrogen and carbon dioxide. Nitrogen and carbon dioxide are inert gases with no BTU value and must be removed to low levels (4% total inerts typically and 2% carbon dioxide) before the gas can be sold.
Concurrently, the U.S. has proven reserves of natural gas totaling 167 trillion cubic feet. Over the past five years, annual consumption has exceeded the amount of new reserves that were found. This trend could result in higher cost natural gas and possible supply shortages in the future. As the U.S. reserves are produced and depleted, finding new, clean gas reserves involves more costly exploration efforts. This usually involves off shore exploration and/or deeper drilling onshore, both of which are expensive. Moreover, unlike crude oil, it is expensive to bring imports of natural gas into North America, therefore pricing of natural gas could be expected to rise forcing end users to seek alternative fuels, such as oil and coal, that are not as clean burning as gas. While base consumption for natural gas in the U.S. is projected to grow at 2-3% annually for the next ten years, one segment may grow much more rapidly. Natural gas usage in electric power generation is expected to grow rapidly because natural gas is efficient and cleaner burning allowing utilities to reduce emissions. Accordingly, there is a need to develop a cost-effective method of upgrading currently unmarketable sub-quality reserves in the U.S. thereby increasing the proven reserve inventory.
Methods heretofore known for purification of natural gas, in particular, nitrogen removal, may be divided roughly into three classifications:
(a) Methods involving fractional distillation at low temperature and (usually) high pressure, i.e. cryogenics. Since nitrogen has a lower boiling point than methane and the other hydrocarbons present in natural gas, it may be removed as a gas on liquefying the remaining constituents which are then revaporized.
(b) By selective adsorption of the methane and higher hydrocarbons on an adsorbent such as activated carbon. The adsorbed gases are then desorbed to give a gas free of nitrogen.
(c) Miscellaneous processes involving selective diffusion through a series of organic membranes, formation of lithium nitride by treatment with lithium amalgam, absorption of the nitrogen in liquid ammonia or in liquid sulfur dioxide.
The principal disadvantage of the fractional distillation and adsorption processes is that they remove the major component, methane, from the minor component, nitrogen, instead of the reverse. In cryogenic processing, almost the entire volume of natural gas must be refrigerated, usually compressed, and then heated again. Accordingly, cryogenic processing is expensive to install and operate, limiting its application to a small segment of reserves. Cryogenic technology is believed only capable of cost effectively purifying reserves, which exceed 50,000,000 standard cubic feet of gas per day. Gas reserves that do not fit these criteria are not currently being purified. The potential value of this gas.is totally lost as the wells are usually capped. The processes suggested under paragraph (c) above are handicapped by an unsatisfactory degree of separation or by the use of very expensive materials.
In smaller-scale natural gas operations as well as in other areas such as synthesis gas and coke oven gas processing, adsorption processes can be especially well suited. The adsorption capacities of adsorption units can, in many cases, be readily adapted to process gas mixtures of varying nitrogen content without equipment modifications, i.e. by adjusting adsorption cycle times. Moreover, adsorption units can be conveniently skid-mounted, thus providing easy mobility between gas processing locations. Further, adsorption processes are often desirable because more than one component can be removed from the gas. As noted above, nitrogen-containing gases often contain other gases that contain molecules having smaller molecular dimensions than nitrogen, e.g., for natural gas, carbon dioxide, oxygen and water.
U.S. Pat. No. 2,843,219 discloses a process for removing nitrogen from natural gas utilizing zeolites broadly and contains specific examples for the use of zeolite 4A. The process disclosed in the patent suggests use of a first nitrogen selective adsorbent zeolite in combination with a second methane selective adsorbent. The molecular sieve adsorbent for removing nitrogen is primarily regenerated during desorption by thermal swing. A moving bed adsorption/desorption process is necessary for providing sufficient heat for the thermal swing desorption. The moving bed process specifically disclosed in this patent is not practical and it does not provide a cost efficient method for the separation of nitrogen from natural gas in view of high equipment and maintenance costs and degradation of the adsorbent by attrition due to contact with the moving adsorbent particles.
Despite the advantageous aspects of adsorption processes, the adsorptive separation of nitrogen from methane has been found to be particularly difficult. The primary problem is in finding an adsorbent that has sufficient selectivity for nitrogen over methane in order to provide a commercially viable process. In general, selectivity is related to polarizability, and methane is more polarizable than nitrogen. Therefore, the equilibrium adsorption selectivity of essentially all known adsorbents such as large pore zeolites, carbon, silica gel, alumina, etc. all favor methane over nitrogen. However, since nitrogen is a smaller molecule than methane, it is possible to have a small pore zeolite which adsorbs nitrogen faster than methane. Clinoptilolite is one of the zeolites which has been disclosed in literature as a rate selective adsorbent for the separation of nitrogen and methane.
U.S. Pat. No. 4,964,889 discloses the use of natural zeolites such as clinoptilolites having a magnesium cation content of at least 5 equivalent percent of the ion-exchangeable cations in the clinoptilolite molecular sieve for the removal of nitrogen from natural gas. The patent discloses that the separation can be performed by any known adsorption cycle such as pressure swing, thermal swing, displacement purge or nonadsorbable purge, although pressure swing adsorption is preferred. However, this patent is silent as to specifics of the process, such as steps for treating the waste gas, nor is there disclosure of a high overall system recovery.
It is well-known to remove acid gases such as hydrogen sulfide and carbon dioxide from natural gas streams using an amine system wherein the acid gases are scrubbed from the feed with an aqueous amine solvent with the solvent subsequently stripped of the carbon dioxide or other acid gases with steam. These systems are widely used in industry with over 600 large units positioned in natural gas service in the U.S. The amine solvent suppliers compete vigorously and the amines used ra
Dolan William Bachop
Mitariten Michael J.
Engelhard Corporation
Lindenfeldar Russell G.
Spitzer Robert H.
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