Patent Grant
8978413
In recent years the demand for rare gases, in particular Krypton and Xenon, is becoming very important. New applications and advances in electronics, medical, glass insulation etc. are greatly contributing to this high demand.
Krypton and Xenon are produced as the by-products of a cryogenic air separation plant. The basic recovery scheme is well known in the art. Since Kr and Xe are heavier than oxygen and will accumulate in liquid oxygen, the recovery technique usually calls for the refining of a liquid oxygen purge stream of the low pressure column of a double column cycle. The rare gases contained in the purge stream are further concentrated in a first concentrating column along with other heavy components in liquid oxygen such as hydrocarbons, CO2, nitrogen oxide etc. For safety considerations, the limit of this first concentrating operation corresponds to about 10% of the limit of flammability of hydrocarbons in oxygen. The first concentrated stream is then either treated in an on-site purification plant or transported to a central purification center where it is vaporized, heated and treated in a catalytic reactor at high temperature of about 500° C. to remove the hydrocarbons. This oxidation reaction forms CO2 and moisture. The mixture is then dried, its CO2 content is removed in an adsorber. The dried and CO2-free mixture is then cooled and distilled to yield the product which is usually a mixture of Kr and Xe. The product is then further refined to remove oxygen, argon and some other impurities such as CFC compounds, green house gases, remaining traces of hydrocarbons etc. and to yield pure Krypton and pure Xenon as final products.
Kr and Xe are present in very small concentration in atmospheric air (1.14 ppm Kr and 0.086 ppm Xe by volume). Therefore it is currently only economically viable to produce Kr—Xe in large oxygen plants, preferably above 1000 T/D and even larger.
If the purification portion of the process can be a standardized process to refine different types of first concentrated streams, either from an oxygen plant, nitrogen plant, low purity or high purity oxygen plant etc. then the same remark cannot be applied for the process involved to extract a stream containing Krypton and Xenon from the air separation columns. Indeed, because of the above-mentioned variety of air separation plants/processes, it is not possible to have one type of extraction process applicable for all types of air separation plants. For example, a plant producing gaseous oxygen product from the low pressure column would require a different type of rare gases extraction from a plant producing liquid oxygen product for pumping from the low pressure column.
Heavy industrial demand for oxygen for gasification, IGCC, GTL, oxyfuels have increased significantly the size of trains of oxygen plants. Because of the limitation of the size of distillation columns by transport regulations the technological trend in cryogenic process is shifting toward elevated air pressure plants wherein the feed air and the columns' pressure are at higher pressure than traditional oxygen plants. The triple column process is designed to address this type of application and there is a need to provide a technique for extracting rare gases from this type of process.
This triple column process is described in details in several patent such as U.S. Pat. No. 5,231,837, and U.S. Pat. No. 5,341,646.
The technique of recovering Krypton and Xenon from an oxygen plant have been covered extensively in several patents:
U.S. Pat. No. 6,776,004: this prior art taught the technique of recovering rare gases of a mixing column plant for oxygen production. The liquid purge of the low pressure column is treated in an enrichment column reboiled by the top gas of the mixing column to recover the rare gases.
PCT WO 2004/023054: air feeds to the high pressure column is separated into a nitrogen rich stream and 2 oxygen rich liquid streams: rare gases rich liquid and rare gases lean liquid. The rare gases-rich stream is treated in a column located above the crude argon column to yield a Krypton Xenon concentrate at the bottom.
U.S. Pat. No. 6,662,593: the rare gases in the feed air are confined in a rare gases rich liquid stream of the high pressure column and then its oxygen content is stripped in a side column to yield the rare gases concentrate stream. By extracting the rare gases prior to the final distillation in the low pressure column the oxygen product can be quite lean in rare gases and can then be pumped and vaporized to high pressure as final product without incurring losses of rare gases.
U.S. Pat. No. 6,612,129: Krypton and Xenon containing liquid from the high pressure column is partially evaporated in the top condenser of the side-arm argon column of the double column plant. The liquid purge and the vaporized streams of the condenser are then treated in an enrichment column to yield the Krypton Xenon concentrate at the bottom.
U.S. Pat. No. 6,220,054: a column is used to treat the bottom liquid of the crude argon column to yield final oxygen product which is depleted of Krypton and Xenon since the feed to the crude argon column is also depleted in Krypton and Xenon. A stream concentrated in Krypton and Xenon is extracted at the bottom of the low pressure column.
As can be seen, most of the prior art addressed the rare gases recovery for oxygen plant equipped with argon production for high purity oxygen and in some cases, mixing column. Those processes operate at relatively low pressure at about 1.5 to 2 bar in the low pressure column which would yield an air pressure of about 6 to 7.5 bar. Higher pressure than these values would deteriorate the distillation performance especially for the argon recovery. Elevated pressure plant in contrary produces low purity oxygen and operates at about 10 to 16 bar air pressure with the low pressure column operates at about 4 to 6 bar. In order to maintain a good oxygen recovery rate an intermediate column is used to generate more liquid nitrogen reflux from the top of the intermediate column.
The present invention is a process for recovering rare gases from a multiple column oxygen plant, wherein the multiple column oxygen plant comprises a higher pressure column, a lower pressure column, a middle pressure intermediate column, and a low pressure intermediate column, said middle pressure intermediate column comprising a first bottom reboiler and said low pressure intermediate column comprising a second bottom reboiler. The process includes providing a first oxygen rich liquid stream containing rare gases from the higher pressure column, wherein said first oxygen rich liquid stream is introduced to the first bottom reboiler. The process also includes removing a second oxygen rich liquid stream rich in rare gases from the bottom of the middle pressure intermediate column, wherein said second oxygen rich liquid stream is introduced to the low pressure intermediate column. The process also includes removing a first liquid purge stream concentrated in rare gases is removed from the low pressure intermediate column, wherein said first liquid purge stream is further concentrated downstream. And the process includes removing a third oxygen rich liquid stream lean in rare gases at a location that is at least one tray above the first bottom reboiler, wherein said third oxygen rich liquid stream is introduced to the lower pressure column.
For a further understanding of the nature and objects for the present invention, reference should be made to the following detailed description, taken in conjunction with the accompanying drawings, in which like elements are given the same or analogous reference numbers and wherein:
Illustrative embodiments of the invention are described below. While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof have been shown by way of example in the drawings and are herein described in detail. It should be understood, however, that the description herein of specific embodiments is not intended to limit the invention to the particular forms disclosed, but on the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention as defined by the appended claims.
It will of course be appreciated that in the development of any such actual embodiment, numerous implementation-specific decisions must be made to achieve the developer's specific goals, such as compliance with system-related and business-related constraints, which will vary from one implementation to another. Moreover, it will be appreciated that such a development effort might be complex and time-consuming, but would nevertheless be a routine undertaking for those of ordinary skill in the art having the benefit of this disclosure.
As illustrated in
In some plants low pressure air expander 12 expanding air feed into the low pressure column 200 is used. This expanded stream 15 also contained rare gases which would be lost if sent to the low pressure column 200. In this case it is possible to send the expanded air 15 to the bottom of column 400 in order to wash out the contained rare gases and maintaining high recovery of Kr and Xe.
In the process without rare gases production, the bottom stream of the intermediate column 300 is normally divided into 2 portions: the first one is vaporized in the overhead condenser of the intermediate column, the second one is fed as liquid feed to the low pressure column 200. If the same process is applied for rare gases production, the Kr—Xe contained in the second portion of bottom liquid feeding the low pressure column 200 would have been lost in the liquid oxygen product 30. In order to remedy this situation a liquid stream 32 free of Kr—Xe is extracted at a tray located above the bottom reboiler to substitute this second portion of bottom liquid. By doing so the process efficiency is essentially unchanged, and the bottom stream 31 containing the rare gases can be isolated and treated, either in a column or a vaporizer, to recover the rare gases prior to sending it to the low pressure column 200 to produce oxygen. A fraction 33 of stream 32 is used to reflux the KrXe column 400 to further improve the recovery of rare gases.
In reference to the process described in
In this process simulation, stream 32 is extracted at 2 trays above the bottom reboiler. In another embodiment, stream 32 may be extracted at least one tray above the bottom reboiler. Range of composition of stream 31:
Stream 32 has very low content of Kr and Xe, preferably a maximum at about 1.5 ppm of Kr and 0.01 ppm Xe. The rich liquid 10 is fed to the bottom of the intermediate column.
In another embodiment described in
It is also possible to just vaporize the bottom liquid 31 in the condenser 72 without the use of the column 400 or 401 as illustrated in
A Krypton recovery higher than 96% and a Xenon recovery higher than 99% in the liquid purge bottom are expected for this type of process as illustrated in
| Number | Name | Date | Kind |
|---|---|---|---|
| 4433989 | Erickson | Feb 1984 | A |
| 5231837 | Ha | Aug 1993 | A |
| 5341646 | Agrawal et al. | Aug 1994 | A |
| 5730004 | Voit | Mar 1998 | A |
| 5852940 | Higginbotham et al. | Dec 1998 | A |
| 5966967 | Agrawal et al. | Oct 1999 | A |
| 5970743 | Herron et al. | Oct 1999 | A |
| 6220054 | Rathbone | Apr 2001 | B1 |
| 6318120 | Ha | Nov 2001 | B1 |
| 6351970 | Hahn et al. | Mar 2002 | B1 |
| 6564581 | Pompl | May 2003 | B2 |
| 6612129 | Schwenk | Sep 2003 | B2 |
| 6662593 | Higginbothan et al. | Dec 2003 | B1 |
| 6776004 | Rottmann et al. | Aug 2004 | B2 |
| 20030110795 | Schwenk | Jun 2003 | A1 |
| 20060021380 | Jaouani et al. | Feb 2006 | A1 |
| Number | Date | Country |
|---|---|---|
| 2004023054 | Mar 2004 | WO |
| Entry |
|---|
| Cook, Gerhard A., “Argon, Helium, and the Rare Gases”, p. 428. |
| Mcketta, John J. Rare Gas Separation and Purification, Encyclopedia of Chemical Processing and Design, vol. 26, p. 184. |
| Number | Date | Country | |
|---|---|---|---|
| 20110302956 A1 | Dec 2011 | US |
