Gas separation: processes – Selective diffusion of gases – Selective diffusion of gases through substantially solid...
Reexamination Certificate
1999-11-10
2001-10-09
Spitzer, Robert H. (Department: 1724)
Gas separation: processes
Selective diffusion of gases
Selective diffusion of gases through substantially solid...
C096S008000, C096S010000
Reexamination Certificate
active
06299669
ABSTRACT:
I. FIELD OF THE INVENTION
The present invention relates to a process of using a carbon membrane for separations, especially separations of CO
2
from natural gas.
II. BACKGROUND OF THE INVENTION
A. Introduction
The use of membranes for separation processes is well known. Certain carbon membranes are particularly useful for the separation of fluids, especially gases such as oxygen and nitrogen.
The membranes may be fabricated in various geometrical configurations, such as sheet formed membranes and hollow fibers. The membranes may, be symmetrical, asymmetrical, single-component or composite.
B. Problems With Existing Membranes
It is known that impurities including heavy, condensable hydrocarbons, i.e., C
6
and greater, substantially reduce separation performance of polymeric membranes. One study, for example, reported harsh performance declines in the range of 50% reduction in CO
2
/CH
4
selectivity for polyimide polymeric films due to saturated concentrations of toluene or n-hexane in mixed gas feeds of CO
2
/CH
4
. See J. Membrane Sci., 103, 73-82.
Carbon membranes have superior selectivities and productivities for many separations. However, like polymeric membranes, they also have the major problem of being vulnerable to fouling due to impurities in various hydrocarbon compounds. For example, certain hydrocarbon impurities cause selective fouling of the carbon membrane resulting in reduced selectivity.
Such impurities intolerance is reported in the scientific literature, e.g., one study showed that, for O
2
/N
2
separation, a carbon molecular sieve (“CMS”) membrane performance deteriorated rapidly with n-hexane saturated air feed, Carbon, 32 (1427), and another study showed that, with a mixed feed gas of 50/50 H
2
/CH
4
with toluene vapor at low pressures (150 psia), fluxes were reduced by 15 to 20%, and the H
2
/CH
4
selectivity was reduced by 14%. (J. Membrane Sci., 160,179-186).
Even small amounts of such hydrocarbons can significantly impair the performance of the membrane. Impurities may be removed from the fluid to be permeated by various filtration, separation or extraction techniques. These measures may involve the use of large, expensive equipment and are often not successful.
Another deficiency of known carbon membranes is an inability to perform well with high pressure feeds. The feed, e.g., for a natural gas-CO
2
separation process is typically directly from the well. It is desirable to avoid pressure loss through the purification process. Reducing the pressure to satisfy membrane pressure limits is economically disadvantageous. If pressure is reduced, expensive compressors may be required to increase the pressure of the stream for passage through an export pipeline.
C. Known Methods For Making Membranes
There are several patents describing processes for producing carbon membranes (both asymmetric hollow “filamentary” and flat sheets) and applications for various gas separations. These patents teach separations of O
2
/N
2
, H
2
/CH
4
, CO
2
/N
2
, or other separations. See, e.g., U.S. Pat. No. 4,685,940 for a Separation Device, U.S. Pat. No. 5,288,304 for Composite Carbon Fluid Separation Membranes, and EP Patent No. 459,623 for Asymmetric Hollow Filamentary Carbon Membrane And Process For Producing Same, each of which is incorporated herein by reference in their entireties. None of these patents teaches CO
2
/CH
4
separation, especially at high pressure or in the presence of impurities.
D. Deficiencies In Known Processes For Making Membranes
The prior art references do not teach a process for CO
2
—natural gas separation using a carbon membrane at high pressures and in the presence of impurities. Therefore, it would be advantageous to have a process of preparing a carbon membrane having high fouling resistance and having high selectivity and having good performance in high pressures. The process of the instant invention meets these needs.
III. SUMMARY OF THE INVENTION
The invention includes a process for separating CO
2
from natural gas including: contacting a mixture of CO
2
and natural gas with a first side of a carbon membrane in a manner to cause a portion of the mixture to pass through the carbon membrane to a permeate side. The resulting mixture on the permeate side becomes enriched in CO
2
over that of the mixture on the first side. The carbon membrane includes an asymmetric hollow filamentary carbon membrane, including a partial carbonization product of a symmetric hollow filament including an aromatic imide polymer material. The carbon membrane is at least 95 weight percent carbon, and has a dense layer located in the outside surface portion of the hollow filamentary membrane and a porous base layer continued from the dense layer and located in the inside portion of the hollow filamentary membrane. The contacting step occurs at a pressure of at least about 200 psia.
IV. BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1
depicts, in one embodiment of the invention, apparatus for the pyrolysis aspect of the invention.
FIG. 2
depicts, in one embodiment of the invention, apparatus for forming one or more pyrolyzed CMS's into a separation module.
FIG. 3
depicts, in one embodiment of the invention, a schematic diagram of the process of the invention.
REFERENCES:
patent: 4130403 (1978-12-01), Cooley et al.
patent: 4518399 (1985-05-01), Croskell et al.
patent: 4685940 (1987-08-01), Soffer et al.
patent: 5234471 (1993-08-01), Weinberg
patent: 5288304 (1994-02-01), Koros et al.
patent: 5334471 (1994-08-01), Sacripante et al.
patent: 5411721 (1995-05-01), Doshi et al.
patent: 5591250 (1997-01-01), Stern et al.
patent: 0459623B1 (1994-08-01), None
patent: 08-047626 (1996-06-01), None
Koros William John
Vu De Quang
Hadlock Timothy J.
Schulte Richard J.
Spitzer Robert H.
The University of Texas System
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