Process and Apparatus for Separation of a Gaseous Mixture

The invention relates generally to a system for the separation of gaseous mixtures containing essentially hydrogen (H.sub.2), methane (CH.sub.4) and carbon monoxide (CO) especially purified CO. Such a system generally comprises a physical low-temperature scrubbing step employing liquid methane as the scrubbing agent, as well as a downstream stripping and/or expansion step to separate H.sub.2 from the loaded methane, and thereafter a regeneration step to separate the loaded methane into enriched CO and CH.sub.4 fractions.

In a conventional process of this type ("Linde Reports on Science and Technology" No. 38, 1984, pages 37-47), carbon monoxide is scrubbed out at a low temperature in a scrubbing column by means of liquid methane from a crude gas, such as, for example, steam reformer gas, and H.sub.2 is withdrawn overhead from the scrubbing column. In order to obtain carbon monoxide as produce, CO is separated from methane in a regeneration column, for example by rectification, and the thus-purified CH.sub.4 is recycled into the scrubbing column. However, since a product CO of maximum purity is desired, the H.sub.2 content is reduced in a further process step, provided upstream of the regeneration, wherein the loaded methane from the scrubbing column is expanded and introduced into a stripping column. In this step, hydrogen, still contaminated with 20-60 mol-% of CO and 0.5-5 mol-% of CH.sub.4 is released. As contrasted with a mere expansion in an expansion tank, the stripping column is provided with heating means to evolve the contaminated hydrogen.

The proportion of CO remaining in the hydrogen represents, with regard to the yield of product CO, a loss of up to 10%, which has an adverse effect on the economy of the process. Typical yields of CO in the known process range from 94 to 97%.

Accordingly, in the conventional process, the yield of product CO is less than desired.

An object of this invention is to provide a process of the type discussed hereinabove and associated apparatus, wherein separation of the gaseous mixture leads to an increased yield of CO, while simultaneously minimizing the losses of CO in the H.sub.2 stripper and/or an expansion tank.

Upon further study of the specification and appended claims, further objects and advantages of this invention will become apparent to those skilled in the art.

These objects are attained according to this invention by bringing the gas obtained during expansion and/or stripping into contact with liquid methane.

The invention is based on the concept that the Co discharged with the H.sub.2 stream during expansion and/or, respectively, stripping represents substantially the sole source of losses in the process, since, on account of the low temperatures in the scrubbing column, all of the CO from the crude gas except for a few ppm is dissolved in the CH.sub.4. Furthermore, in the regeneration column, due to the designed bottoms temperature, CO remains dissolved in the regenerated methane only within the ppm range.

Advantageously, the gas obtained during expansion and/or stripping is brought into contact with a partial stream of regenerated methane whereby the additional expenditure for apparatus as compared with the conventional process is kept at a minimum. Also, during operation at less than design capacity, it is usually impossible, or uneconomical, to throttle the fluid flow in the cycle effecting the CO/CH.sub.4 separation (N.sub.2, CO, etc.). Therefore, in this way, with a partial-load operation of, for example, 90% full capacity, any excess regenerated methane from the bottom of the CO/CH.sub.4 column can be beneficially utilized.

It proved to be especially advantageous in regard to the yield of CO to bring the thus-obtained gas into contact with about 5-15%, preferably 7-10%, of the regenerated methane.

Losses of scrubbing medium by CH.sub.4 discharged together with the H.sub.2 and CO product streams are compensated for by the CH.sub.4 in the gaseous mixture proper which is to be separated. For example, when using a steam reformer gas, the latter contains between 2 and 10 mol-% of CH.sub.4, which is substantially more than the amount of losses. It is thus usually necessary to purge a portion of regeneration methane from the cycle to prevent a buildup of same.

In order to attain a maximally complete scrubbing out of the carbon monoxide from the gaseous mixture to be separated as well as from the gas released during expansion and/or stripping, it is preferred to utilize liquid methane having a temperature of about -182.degree. to -173.degree. C., especially -181.degree. to -178.degree. C.

Moreover, it proved to be extraordinarily advantageous to effect cooling during expansion and/or stripping, thus obtaining a maximally complete removal of the heat of solution.

Furthermore, the step of bringing the gas obtained during expansion and/or stripping into contact with regenerated methane is carried out in a preferred way in at least 3 and preferably 3 to 10 theoretical equilibrium stages.

The invention moreover concerns an apparatus for performing the process, comprising a scrubbing column and a regenerating column with an interposed stripping column and/or expansion tank. In a preferred embodiment of the apparatus according to this invention, the scrubbing and regenerating columns are joined by way of a conduit for regenerated methane leading from the bottom of the regenerating column to the head of the scrubbing column. Furthermore, according to the invention, the stripping column and/or the expansion tank are connected with the regenerating column by way of a branch conduit of the conduit for regenerated methane, leading to the head of the stripping column and/or of the expansion tank, and by way of a conduit for partially loaded methane connected to the bottom of the stripping column and/or expansion tank. In addition, the stripping column and/or the expansion tank contain, in the lower part, an inlet for loaded methane in communication with the bottom of the scrubbing column. In this way, a substantial reduction of the CO losses is attained by rescrubbing.

Another advantageous embodiment of the invention contains the feature that there are installed, in the expansion tank and/or in the stripping column, plates and/or, at the head, a cooling trap or cooling coil. Likewise, according to this invention, the individual plates can also in each case be designed as beds of packing elements. These additionally provided features bring about a reduction of the requirement for scrubbing medium and, respectively, CH.sub.4 at a given yield of CO to be achieved, and thus also result in lowering of the operating costs.

In total, the invention provides the advantage that yields of CO higher than about 99% can be attained thereby.

The invention is usable in all processes for separating gaseous mixtures consisting essentially of H.sub.2, CH.sub.4 and CO, such as, in particular, steam reformer gas. Of course, the invention can also treat other gaseous mixtures containing still further, inert gas components, such as, for example, nitrogen, argon or helium. These components then will occur in the individual gaseous streams in correspondence with their solution or condensation characteristics, without altering the course of the process according to this invention.

In the process according to the invention, the stripping column is generally operated at a pressure of about 2 to 20 bar, preferably 3 to 10 bar, and at a head temperature of generally about -185.degree. to -160.degree. C. and a bottom temperature of about -170.degree. to -140.degree. C. The gaseous and liquid streams generally have the following concentration of components

This range of composition is also valid for an expansion tank coupled with a contact column.

The entire text of all applications, patents and publications, if any, cited above and below, and of corresponding German application P 37 39 724.9 (the priority document), are hereby incorporated by reference.

Various other objects, features and attendant advantages of the present invention will be more fully appreciated as the same becomes better understood when considered in conjunction with the accompanying drawing wherein:

FIG. 1 is a schematic illustration of both the process and apparatus aspects of the embodiment in which the loaded methane is subjected to both expansion and stripping.

In accordance with FIG. 1, crude gas is fed under high pressure (20 bar) and at -181.degree. C. via conduit 1 into the lower section of a scrubbing column 2. The crude gas consists of 70 mol% hydrogen, 22 mol% carbon monoxide, and 5 mol% methane, as well as a residual proportion of 3 mol% inert gases.

The rising crude gas is scrubbed herein with purified, low-temperature CH.sub.4 conducted counter-currently and introduced via conduit 3 at the head of the scrubbing column 2. During this step, the CO is dissolved in the CH.sub.4, and the hydrogen is withdrawn via conduit 4 as a first product from the head of the scrubbing column 2 and passed on to further usages (not illustrated). This hydrogen still contains about 1.5 mol% CH.sub.4 as well as CO and inert gases in the ppm range.

In order to remove CO most efficiently by scrubbing, liquid methane is utilized at -180.degree. C., and the resultant heat of solution is removed by means of a cooling trap 5, which is in most cases are indirect heat exchanges fed with N.sub.2 or CO in liquid form.

The lowest temperature of the methane employed is limited by the methane solidification point. (The melting point of pure methane is -182.5.degree. C.)

From the bottom of the scrubbing column 2, by means of conduit 6 and valve 7 wherein expansion is performed to an intermediate pressure of 5 bar, CO-loaded scrubbing medium and, respectively, methane still containing additionally about 4 mol% H.sub.2, are removed and introduced into an H.sub.2 stripper 8 containing, for example, 12 theoretical plates, at between the 5th and 6th theoretical plates. A heating coil 9 to produce the stripping vapor is provided in the bottom of H.sub.2 stripper 8.

Via conduit 10, purified methane at a temperature of -180.degree. C. is introduced at the head of the H.sub.2 stripper 8. This methane, thus recycled, scrubs out CO that has remained in the H.sub.2 released during the stripping step. In order to enhance the efficacy of the scrubbing step and/or for reducing the amount of scrubbing medium required, a cooling trap 11 is arranged below the CH.sub.4 feed point.

An H.sub.2 fraction with 93.8 mol% H.sub.2, 3.0 mol% CH.sub.4 and 3.0 mol% CO, as well as residual inert gases is withdrawn via conduit 12 from the head of the H.sub.2 stripper 8.

The methane (39.6 mol% CO, 59.8 mol% CH.sub.4), presently loaded practically only with CO, is conducted from the bottom of the stripper 8 via conduit 13 at a temperature of -165.degree. C. and a pressure of 2 bar to a regenerating or rectifying column 14 equipped with a indirect heating means 15, e.g., a heating coil, in the bottom. By means of heating means 15, a temperature of -153.degree. C. is set in the bottom.

At the end of rectification, the CO product is withdrawn via conduit 16. In this case, the yield of CO is 99.7%.

The regenerated methane is brought, from the bottom of the rectifying column 14 via conduit 17 by means of a pump 18 to crude gas pressure and cooled in a heat exchanger 19 to crude gas temperature. Thereafter, the regenerated methane is recycled into the scrubbing and stripping operations via conduits 3 and 10, respectively.

In order to preclude enrichment of the methane or any inert gases in the scrubbing medium cycle, a partial stream of the purified methane is continuously removed by way of conduit 20.

If the concentration of H.sub.2 in the CO product may be up to 0.1-0.5 vol% the stripping section of column 8 (section underneath the feed point) may be omitted. This results in a lower bottom temperature of -180.degree. to -150.degree. C. and a higher H.sub.2 concentration of 0.05 to 0.3 vol%. The absorber section (above feed point) remains unchanged.

The preceding examples can be repeated with similar success by substituting the generically or specifically described reactants and/or operating conditions of this invention for those used in the preceding examples.

From the foregoing description, one skilled in the art can easily ascertain the essential characteristics of this invention, and without departing from the spirit and scope thereof, can make various changes and modifications of the invention to adapt it to various usages and conditions.