Patent Description:
The present invention generally relates to the treating or purifying of a gas stream, particularly removing nitrogen and carbon dioxide from a gas stream to produce hydrogen.

Hydrogen (H<NUM>) is one of the most important industrial gases, used widely in petroleum refineries and petrochemical plants. Hydrogen is also used in semi-conductor industry, steel production, food industry, power industry and the like. Lately, hydrogen has become a fuel of choice for fuel cell-operated systems like automobiles, forklifts, etc. Hydrogen is typically produced at large scale using high-temperature reforming or partial oxidation of methane and/or hydrocarbons or through gasification of carbonaceous feedstocks. Production of smaller volumes of hydrogen presents significant cost and reliability challenges and is not widely practiced in the industry, except through electrolysis of water.

With recent market penetration of fuel cell-based vehicles (including passenger cars, buses, trucks) and equipment (e.g., forklifts used in warehouses), on-site production of hydrogen in <NUM>-<NUM>/day quantities is a key enabling process technology for continued and accelerated growth of the overall fuel cell market and the fuel cell-based vehicular market in particular. There are no technically viable or cost-effective options for production of hydrogen on-site at this scale. Electrolysis of water using electricity in an electrochemical cell is expensive and suffers from reliability issues. Steam methane reformers or coal gasifiers cannot be scaled down in a cost-effective manner to produce these small quantities of hydrogen.

High-temperature reforming of methane and hydrocarbons produces an intermediate gas stream which is referred to as synthesis gas or "syngas". Syngas can also be produced from partial oxidation and gasification of organic feedstocks (coal, petroleum coke, biomass, oil, hydrocarbons).

When oxygen is used as the oxidizing agent in these processes, the syngas consists of primarily carbon monoxide (CO), H<NUM>, carbon dioxide (CO<NUM>), and steam. When air is used as the oxidizing agent, the large fraction of nitrogen (N<NUM>) in air becomes the major component in the syngas with CO, H<NUM>, CO<NUM> and steam representing minor components. For many processes, it is desirable to separate a high purity H<NUM> gas from the syngas. For syngas production based on the utilization of air rather than oxygen as an oxidizing agent, this increases the complexity of the H<NUM> separation process as the nitrogen, which is the majority component must also be removed. For example, polymer electrolyte membrane fuel cells for automotive applications require <NUM> percent or greater purity H<NUM> gas because contaminants within the H<NUM> gas can interfere with or poison electrocatalysts in the fuel cell. High purity H<NUM> may also be used in propellants, semiconductor manufacturing, analytical instrumentation, and as the starting material in the production of a variety of chemicals.

<CIT> discloses a method and system for producing a purified hydrogen stream. <CIT> discloses a method and system for the production of high purity H2. <CIT> discloses a method of extracting hydrogen from a gas mixture comprising hydrogen and carbon monoxide and optionally nitrogen, carbon dioxide, lower hydrocarbons and/or water.

Conventional processes to purify syngas generated using oxygen as the oxidizing agent to produce high-purity hydrogen require a series of gas processing and cleanup steps, including separate removal of CO<NUM> using solvent scrubbing, followed by pressure-swing adsorption to achieve the highest levels of H<NUM> purity. The tail gas produced by pressure swing adsorption is typically used as a fuel gas for heating value, resulting in significant loss of H<NUM>, rendering these processes to be inefficient and costly. For syngas generated using air as the oxidizing agent, the high nitrogen concentration in the syngas can only be separated by pressure-swing adsorption, but the resulting tail gas contains a large amount of nitrogen, which reduces its fuel value and increases H<NUM> losses. Because of these issues, syngas generated with air as the oxidant is not used for commercial hydrogen production as it is not cost competitive.

To address the foregoing problems, in whole or in part, and/or other problems that may have been observed by persons skilled in the art, the present disclosure provides methods, processes, systems, apparatus, instruments, and/or devices, as described by way of example in implementations set forth below.

While much of the disclosure focuses on N<NUM> and CO<NUM> removal processes. Another way to think of the disclosed process is that it separates a majority of the H<NUM> from the contaminants and then selectively removes any remaining impurities from the H<NUM>. The benefit of the unique combination of these individual separation steps is that H<NUM> loss can be minimized to near zero by recycle of the tail gas stream.

Other devices, apparatus, systems, methods, features and advantages of the invention will be or will become apparent to one with skill in the art upon examination of the following figures and detailed description. It is intended that all such additional systems, methods, features and advantages be included within this description, be within the scope of the invention, and be protected by the accompanying claims.

The invention can be better understood by referring to the following figures. In the figures, like reference numerals designate corresponding parts throughout the different views.

As used herein, the term "syngas" refers to synthesis gas. In the context of the present disclosure, syngas is a mixture of at least carbon monoxide (CO) and diatomic hydrogen gas (H<NUM>). Depending on the embodiment, syngas may additionally include other components such as, for example, water, air, diatomic nitrogen gas (N<NUM>), diatomic oxygen gas (O<NUM>), carbon dioxide (CO<NUM>), sulfur compounds (e.g., hydrogen sulfide (H<NUM>S), carbonyl sulfide (COS), sulfur oxides (SOx), etc.), nitrogen compounds (e.g., nitrogen oxides (NOx), etc.), metal carbonyls, hydrocarbons (e.g., methane (CH<NUM>)), ammonia (NH<NUM>), chlorides (e.g., hydrogen chloride (HCl)), hydrogen cyanide (HCN), trace metals and metalloids (e.g., mercury (Hg), arsenic (As), selenium (Se), cadmium (Cd), etc.) and compounds thereof, particulate matter (PM), etc..

As used herein, the term "natural gas" refers to a mixture of hydrocarbon (HC) gases consisting primarily of methane and lesser amounts of higher alkanes. Depending on the embodiment, natural gas may additionally include non-HC species such as one or more of those noted above, as well as carbon disulfide (CS<NUM>) and/or other disulfides, and mercaptans (thiols) such as methanethiol (CH<NUM>SH) and ethanethiol (C<NUM>H<NUM>SH), thiophene, and other organosulfur compounds.

As used herein, the term "fluid" generally encompasses the term "liquid" as well as term "gas" unless indicated otherwise or the context dictates otherwise. The term "fluid" encompasses a fluid in which particles are suspended or carried. The term "gas" encompasses a gas that includes or entrains a vapor or liquid droplets. The term "fluid," "liquid" or "gas" encompasses a "fluid," "liquid" or "gas" that includes a single component (species) or a mixture of two or more different components. Examples of multicomponent mixtures include, but are not limited to, syngas and natural gas as described above.

As used herein, the term "process gas" generally refers to any gas initially containing H<NUM> and one or more contaminants. A process gas at an initial stage of a gas processing method as disclosed herein, i.e., when introduced into a gas processing system as disclosed herein, may also be referred to as a "raw gas" or a "feed gas. " A process gas after undergoing contaminant removal according to a gas processing method as disclosed herein may also be referred to as an "enhanced gas," a "purified gas," or a "permeate stream. " The term "process gas" generally is not limiting as to the composition of the gas at any particular stage of the gas processing method. For example, the term "process gas" does not by itself provide any indication of the concentrations of H<NUM> or any contaminants in the gas at any particular time. Examples of process gases include, but are not limited to, syngas and natural gas as described above. Further examples of process gases are gases that include one or more of: CO, CO<NUM>, H<NUM>, N<NUM>, and hydrocarbon(s) (HCs).

As used herein "selectivity" of a gas separation membrane in separating a two-component gas mixture is defined as the ratio of the gas permeances of the two components in a gas mixture. Selectivity may be obtained directly by contacting a gas separation membrane with a known mixture of gases and analyzing the permeate. Alternatively, a first approximation of the selectivity is obtained by measuring permeance of the gases separately on the same gas separation membrane.

The present disclosure provides methods for purifying a syngas in which N<NUM> is the majority component (i.e., has the highest mole fraction of any component in the syngas) to produce a purified H<NUM> gas stream. In various embodiments as illustrated in <FIG>, an exemplary gas processing system <NUM> may comprise a syngas reaction unit <NUM>. In a non-limiting embodiment, the syngas reaction unit <NUM> may have a raw gas feed (indicated by stream <NUM> in <FIG>) that serves as a fuel, and an oxidizer feed (stream <NUM>) such as air, enriched air, and oxygen, in certain embodiments, the oxidant may also contain steam and/or CO<NUM>. The raw gas feed (stream <NUM>) may be, for example, a low-quality hydrocarbon stream from an industrial process or from a natural gas or crude oil production process. The fuel may also comprise natural gas containing primarily methane (CH<NUM>). In certain embodiments, the fuel to the syngas reaction unit <NUM> may be coal, petroleum coke, biomass, or any other carbonaceous feedstock.

In certain embodiments, the syngas reaction unit <NUM> may comprise an internal combustion engine operated under fuel-rich conditions to partially oxidize the fuel (as opposed to operating the engine to completely combust the fuel) to produce syngas (stream <NUM>) comprising N<NUM>, H<NUM>, CO, and various contaminants. The syngas (stream <NUM>) may flow to a water-gas shift (WGS) unit <NUM> along with a water feed (stream <NUM>) to produce an enhanced gas (stream <NUM>) having a higher H<NUM> to CO ratio than the syngas (stream <NUM>). The enhanced gas (stream <NUM>) flows to a purification unit <NUM> which comprises one or more separation processes as discussed below to remove a portion of the contaminants from the enhanced gas (stream <NUM>). The purification unit <NUM> produces a high purity H<NUM> gas (stream <NUM>) and a tail gas (stream <NUM>) comprising N<NUM>, CO<NUM>, and other contaminants, as well as residual H<NUM>.

In certain embodiments, the syngas reaction unit <NUM> may comprise a gasification unit operated to partially oxidize carbonaceous feedstocks to produce syngas (stream <NUM>). In case of high-sulfur carbonaceous fuels used in syngas reaction unit <NUM>, a desulfurization system operating at temperatures between <NUM> to <NUM>°F (<NUM> to <NUM>) as disclosed in the <CIT> is used prior to sending the syngas to the WGS unit to reduce the total sulfur concentration to less than <NUM> ppmv, preferably below <NUM> ppmv, and more preferably below <NUM> ppmv. Syngas from the desulfurization unit may flow to the water-gas shift (WGS) unit <NUM> along with a water feed (stream <NUM>) to produce an enhanced gas (stream <NUM>) having a higher H<NUM> to CO ratio than the syngas (stream <NUM>). The enhanced gas (stream <NUM>) flows to a purification unit <NUM> which comprises one or more separation processes as discussed below to remove a portion of the contaminants from the enhanced gas (stream <NUM>). The purification unit <NUM> produces a high purity H<NUM> gas (stream <NUM>) and a tail gas (stream <NUM>) comprising N<NUM>, CO<NUM>, and other contaminants, as well as residual H<NUM>.

In certain embodiments, the syngas reaction unit <NUM> may comprise a partial oxidation system for which air is an oxidant operated to partially oxidize hydrocarbon feedstocks to produce syngas (stream <NUM>). Syngas from the syngas reaction unit may flow to the water-gas-shift (WGS) unit <NUM> along with a water feed (stream <NUM>) to produce an enhanced gas (stream <NUM>) having a higher H<NUM> to CO ratio than the syngas (stream <NUM>). The enhanced gas (stream <NUM>) flows to a purification unit <NUM> which comprises one or more separation processes as discussed below to remove a portion of the contaminants from the enhanced gas (stream <NUM>). The purification unit <NUM> produces a high purity H<NUM> gas (stream <NUM>) and a tail gas (stream <NUM>) comprising N<NUM>, CO<NUM>, and other contaminants, as well as residual H<NUM>.

In various embodiments, the syngas (stream <NUM>) may have an initial H<NUM> to CO ratio of about <NUM> to about <NUM>. In certain embodiments, the initial H<NUM> to CO ratio may range from about <NUM> to about <NUM>. In certain embodiments, the second H<NUM> to CO ratio (i.e., the ratio in the enhanced gas (stream <NUM>)) may range from about <NUM> to about <NUM>. In certain embodiments, the second H<NUM> to CO ratio may range from about <NUM> to about <NUM>. In certain embodiments, the second H<NUM> to CO ratio may range from about <NUM> to about <NUM>.

For those embodiments utilizing an internal combustion engine as the syngas reaction unit <NUM>, mechanical energy produced by the engine may be used to directly power or to operate a generator to produce electricity for a variety of equipment in the purification unit <NUM> such as pumps, compressors, controllers, etc. Alternatively, the power or electricity may be used for any other desired purpose. Additionally, in certain embodiments the WGS unit <NUM> may generate heat energy which may be utilized by other steps of the process <NUM>. Although <FIG> may use an internal combustion engine with a fuel and oxidizer feed, such an arrangement is optional and various embodiments may use any source of syngas containing H<NUM> and CO. Likewise, any generation of power or heat within the process <NUM> and its subsequent use is optional.

The WGS reaction is utilized to shift a gas comprising the reactants of water and CO to the products of CO<NUM> and H<NUM> by reacting the CO with steam over a catalyst bed. WGS is an industrially important process utilized to increase the H<NUM> to CO ratio to meet the downstream process requirements of a particular application. For example, WGS finds applications in pre-combustion CO<NUM> capture where a fuel is partially oxidized, as discussed above for <FIG>, to produce syngas predominantly consisting of CO and H<NUM>. This syngas is shifted to maximize the H<NUM> and CO<NUM> concentrations, and CO<NUM> may be subsequently removed to produce high purity H<NUM>. WGS also finds widespread applications in chemicals production where the H<NUM> to CO ratio needs to be adjusted as per the process requirements, such as methanol and Fischer-Tropsch applications.

WGS is a moderately exothermic reversible reaction and is expressed by: <MAT> where <MAT> is the enthalpy of reaction at <NUM> Kelvin (K).

The equilibrium constant of the reaction decreases with increasing temperature. The reaction is thermodynamically favored at low temperatures and kinetically favored at high temperatures. As there is no change in the volume from reactants to products, the reaction is not affected by pressure.

The equilibrium of this reaction shows significant temperature dependence and the equilibrium constant decreases with an increase in temperature, that is, higher carbon monoxide conversion is observed at lower temperatures. In order to take advantage of both the thermodynamics and kinetics of the reaction, the industrial scale WGS is conducted in multiple adiabatic stages with interstage cooling in-between the reactors.

The water gas shift process uses steam to shift CO to CO<NUM> and produces H<NUM> in the process. In addition to being a reactant, the steam also serves to move the equilibrium of the water gas shift forward to higher H<NUM>, controlling the temperature rise from the exothermic water gas shift reaction, which if left unchecked could deactivate the catalyst. The steam is also required to prevent coking on the catalyst surface, which also deactivates the catalyst.

Traditionally, WGS is carried out using two reactors in series to carry out a high temperature shift (HTS) followed by a low temperature shift (LTS). Water is added to the syngas fed to the first reactor (WGS <NUM>). The water may be in the form of steam. Alternatively, this water may be in the form of liquid water for which the thermal energy needed to generate steam is extracted from the sensible heat in the feed gas via direct mixing of the feed gas and liquid water via a spray nozzle or atomizer. The use of liquid water enables additional cooling of the feed gas to the desired temperature for the shift reaction in the first reactor and the consumption of water generated during cooling of the enhanced gas downstream of the water gas shift reactors. The syngas from the outlet of the first reactor (WGS <NUM>) is cooled to the desired shift inlet temperature by using the excess heat to generate and/or raise the temperature of steam and the cooled syngas is fed to the second reactor (WGS <NUM>).

No specific limitations are placed on the configuration of the shift reactors. Generally, each shift reactor may have any configuration suitable for carrying out the WGS reaction. For this purpose, each shift reactor generally may include a vessel having an inlet and an outlet, and a shift catalyst in the vessel. Depending on the type of shift catalyst utilized, each shift reactor may include a structural support for the shift catalyst.

In some embodiments, the first shift reactor (WGS <NUM>) is configured or operated to carry out a high temperature shift (HTS) reaction, while the second shift reactor (WGS <NUM>) is configured or operated to carry out a LTS reaction. In some embodiments, in an HTS reaction the inlet temperature of the gas fed to a shift reactor ranges, for example, from <NUM> to <NUM> °F (<NUM> to <NUM>). In some embodiments, in a LTS reaction the inlet temperature of the gas fed to a shift reactor ranges, for example, from <NUM> to <NUM> °F (<NUM> to <NUM>). Depending on the type of shift reaction performed in the respective shift reactors, the HTS and LTS reactors may contain different type of catalysts.

Generally, the shift catalyst may be provided and supported in any form suitable for carrying out the WGS reaction. For example, the shift catalyst may be provided as a fixed bed that is positioned in the shift reactor such that gases are able to flow through the catalyst bed. The composition of the shift catalyst may depend on the operating temperature of the shift reactor and the composition of the gas to be processed by the shift reactor.

For those embodiments utilizing an internal combustion engine as the syngas reaction unit <NUM>, the syngas will contain a trace levels of unreacted oxygen. Typically, the presence of strong oxidizing agents like oxygen in the feed stream to a WGS unit will cause deactivation of the active metal oxidation state in the WGS catalyst. With the first WGS reactor (WGS <NUM>) containing a HTS catalyst, the operating conditions and oxygen concentration are suitable for the catalytic conversion of any trace concentrations of oxygen present in the syngas feed from the engine operated to produce syngas into water with minimal adverse effect on catalyst activity. Therefore, in this embodiment, no separate oxygen removal system is needed.

Similarly, the standard iron-based HTS catalyst can tolerate up to <NUM> ppmv of sulfur compounds without any significant deactivation due to sulfur poisoning. Because of this, the trace quantifies of sulfur present in the feed natural gas for safety reasons (leak detection) will not impact the performance of the WGS process. Similarly, for the gasification embodiment using high sulfur carbonaceous feed and a desulfurization unit to reduce the sulfur concentration to less than <NUM> ppmv will enable use of a conventional HTS catalyst without any issue. These sulfur compounds will remain in the enhanced gas for ultimate removal in a more appropriate downstream separation process and no separate polishing sulfur removal is envisioned in this embodiment.

No specific limitations are placed on the type or configuration of the heat exchangers used in this the WGS process or purification processes. This means that any heat reduction system enabling control of the effluent syngas temperature to meet the temperature specification for the downstream process is satisfactory. Examples of potentially suitable heat exchangers are water cooled, air cooled, and/or other liquid coolants used with refrigeration cycles. Alternatively, the use of sensible heat of the feed gas to vaporize water and its cooling effect are particularly well suited for the WGS process enabling recycle of condensed water collected during cooling downstream of the WGS process while also providing steam for the WGS reaction.

The output of the WGS system <NUM> (stream <NUM>) may be the input to the purification unit <NUM>. <FIG> illustrates an exemplary purification unit <NUM> according to various embodiments. The enhanced gas flows to first separation unit <NUM>. According to the presently claimed invention, the first separation unit <NUM> comprises a membrane unit. The membrane unit may comprise a dense membrane with a H<NUM> selective composition, allowing H<NUM> to preferentially flow through the membrane unit in the permeate stream <NUM>, while certain contaminants, namely N<NUM> and CO<NUM>, are removed in the retentate stream <NUM>. The membrane may comprise a semi-permeable polymer (various membrane materials are known in the art, for example, but without limitation, such as a polyimide, polyamide, polyvinyl acetate, polysulfone, polytetrafluoroethylene (PFTE), cellulose acetate, other cellulose derivatives, polyether ether ketone, polybenzimidazole, polyolefins, etc.), a ceramic, a carbon compound, activated carbon, or a metallic compound. The H<NUM> selectivity, which is generally defined as the permeability of H<NUM> versus that of other gases in the mixture, of the membrane may range from <NUM> to <NUM>, and the area of contact of the membrane may be determined from characteristics of the output stream <NUM> of the WGS system <NUM> and operating characteristics (e.g., temperature and pressure) of the membrane unit. In various embodiments, the membrane unit may operate at a temperature ranging from -<NUM>°F to <NUM>°F (-<NUM> to <NUM>) and a pressure ranging from <NUM> atm to <NUM> atm (<NUM> kPa to <NUM>,<NUM> kPa). The membrane used for this purpose are preferably in the form of hollow fibers or flat sheets, and are modularized into spiral-wound design, plate and frame design, or hollow fiber design. For example, one such spiral-wound membrane is the commercially available cellulose acetate membrane modules supplied by UOP (Des Plaines, IL) for CO<NUM> separation from methane and one such hollow fiber membrane module is commercially supplied by Air Liquide (Houston, TX) for on-board nitrogen generation systems for N<NUM> separation from air.

Hydrogen permeation in dense membranes may occur through a solution-diffusion mechanism, wherein the gas molecules initially adsorb or dissolve onto the surface of the membrane material. Once adsorbed onto the membrane surface, the gas molecules may diffuse through the membrane material. In various embodiments, because the hydrogen selectivity of the membrane is much greater than the selectivity for each individual contaminant, very little of the contaminants (e.g., N<NUM>, CO, CO<NUM>, sulfur compounds) in the gas permeate through the membrane surface and such contaminants leave the membrane unit <NUM> in the retentate stream <NUM>.

The permeate stream <NUM> may flow to a first heat exchanger <NUM> to remove water prior to increasing the pressure of the permeate stream <NUM> by compressor <NUM>. Excess heat generated by the compression step may be removed by a second heat exchanger <NUM>. The resulting pressurized stream <NUM> may flow to a second separation unit <NUM>. The pressurized stream <NUM> may have a pressure ranging from <NUM> bar to <NUM> bar (<NUM> kPa to <NUM>,<NUM> kPa) and a temperature ranging from <NUM>°F to <NUM>°F (<NUM> to <NUM>). According to the presently claimed invention, the second separation unit <NUM> comprises a pressure swing adsorption (PSA) unit. PSA is based on one or more adsorbent beds <NUM> that capture contaminants in the pressurized stream <NUM> thereby allowing the H<NUM> to pass through the PSA unit, and then later releasing the adsorbed contaminants at a lower pressure (generally, lower than the pressure of the pressurized stream <NUM>) when the adsorbent bed <NUM> is regenerated. This regenerate stream is the tail gas stream <NUM> in <FIG>. Multiple adsorbent beds <NUM> may be utilized simultaneously so that a continuous stream of H<NUM> at purities greater than <NUM> percent may be produced. In a two-bed PSA process, the feed mixture contacts the first adsorbent bed containing adsorbents which preferentially adsorb certain components of the mixture. The less adsorbed component will break through the bed faster and produce a stream with high content of this component. The feed flow is switched to a second adsorbent bed before the other component(s) break through and the first bed is regenerated by desorbing the adsorbed compounds through the reduction of the total pressure of the system. The same process is repeated at the second adsorbent bed and for the complete PSA process. Other variations of PSA process with multiple beds operates under the same principle.

The adsorbent in PSA systems may be chosen for their ability to discriminate between different gases in a mixture. In certain embodiments, the adsorbent may be chosen to preferentially remove CO<NUM> from the pressurized stream <NUM>. When multiple adsorbent beds <NUM> are used, the adsorbent in each adsorbent bed may be selected to preferentially remove one or more target contaminants. For example, one (or more) adsorbent beds <NUM> may target CO<NUM>, while another adsorbent bed <NUM> targets H<NUM>S, and yet another adsorbent bed <NUM> may target CO. The adsorbent works on the principle that gases under elevated pressures are attracted to a surface of a solid based on their affinity and may be captured or adsorbed onto that surface. Generally, the higher the pressure, the more gas that will be adsorbed. Once the pressure is reduced, the gas tends to desorb. Thus, an adsorbent bed <NUM> operating under pressure removes one or more contaminants from the pressurized stream <NUM>, and the purified H<NUM> stream <NUM> flows out of the PSA unit <NUM>. Once the adsorbent reaches its adsorption capacity, flow of the pressurized stream <NUM> to the adsorbent bed <NUM> is shut off and the pressure allowed to fall. As the pressure falls, the contaminants desorb from the surface of the adsorbent and flow out of the PSA unit <NUM> in the tail gas stream <NUM>. The adsorbent may be any type known in the art, such as zeolites, activated carbon (including molecular sieves), alumina, silica gel, and resins.

In various embodiments, all or a portion of the tail gas stream <NUM> is recycled to a point upstream of the first separation unit <NUM> by combining the tail gas stream <NUM> with the enhanced gas stream <NUM> prior to flowing into the first separation unit <NUM>. Although the adsorbent is selected to remove contaminants from the H<NUM> stream, some H<NUM> may be adsorbed and then discharged in the tail gas stream <NUM>. Without recycling this stream, the H<NUM> in the tail gas <NUM> would be lost and overall recovery of H<NUM> by the process <NUM> may not be as good as with recycling of the tail gas <NUM>. By recycling all of the tail gas <NUM>, the process <NUM> may achieve a H<NUM> recovery rate of greater than <NUM> percent of the H<NUM> contained in the feed gas. Recycling less than <NUM> percent of the tail gas will reduce the H<NUM> recovery rate accordingly. For example, H<NUM> recovery of <NUM> percent or greater, <NUM> percent or greater, or <NUM> percent or greater may be achieved by varying the amount of tail gas recycled. In some embodiments, the amount of the tail gas recycled may range from about <NUM> percent to about <NUM> percent of the tail gas. If none of the tail gas <NUM> is recycled, then the H<NUM> recovery rate may be as low as <NUM> percent. In order to properly condition the tail gas <NUM> for recycling, the tail gas <NUM> may flow to a compressor <NUM> to increase pressure generally to that of the enhanced gas stream <NUM>, and may then flow to a heat exchanger <NUM> to remove excess heat caused by compression. The conditioned tail gas <NUM> may then be mixed into the enhanced gas stream <NUM>. In certain embodiments, the pressure of the recycled tail gas <NUM> may range from about <NUM> atm to about <NUM> atm (about <NUM> kPa to about <NUM>,<NUM> kPa) and matches that of stream <NUM>.

In various embodiments, the recycled tail gas stream <NUM> may range from about <NUM> percent to about <NUM> percent by volume of the purified H<NUM> stream <NUM>, and may range from about <NUM> percent to about <NUM> percent by volume of the enhanced gas stream <NUM>. Thus, extremely high H<NUM> recovery rates (i.e., greater than <NUM> percent) may be achieved by a relatively small recycle stream. Table <NUM> presents the results of a material balance for the process illustrated in <FIG>, demonstrating production of a high purity H<NUM> stream containing <NUM> percent H<NUM>.

<FIG> illustrates a general flow diagram of various embodiments of a method <NUM> for producing a purified hydrogen gas stream. At step <NUM>, a feed gas containing N<NUM> as the majority component, H<NUM>, and CO flows into a processing unit <NUM> to produce an enhanced gas <NUM>. The feed gas has an initial H<NUM> to CO ratio, and the enhanced gas <NUM> contains CO<NUM> and has a second H<NUM> to CO ratio greater than the initial H<NUM> to CO ratio. The enhanced gas <NUM> flows into a purification unit <NUM> at step <NUM>. The purification unit <NUM> is designed to produce high purity H<NUM> and comprises a unit <NUM> to produce a stream <NUM> largely depleted of N<NUM>, CO<NUM> and other non-H<NUM> gases and a unit <NUM> to produce a purified H<NUM> stream. The purification unit <NUM> produces a purified H<NUM> gas stream <NUM> and a tail gas <NUM>. At step <NUM>, at least a portion of the tail gas <NUM> is recycled to a point upstream of the N<NUM> removal unit <NUM>. According to the presently claimed invention, the purification unit comprises a N<NUM> removal unit to remove N<NUM> and a CO<NUM> removal unit to remove CO<NUM>, wherein the N<NUM> removal unit comprises a membrane separation unit configured to receive the enhanced gas, and wherein the CO<NUM> removal unit comprises a pressure swing adsorption (PSA) unit.

<FIG> illustrates another general flow diagram a method <NUM> for producing a purified hydrogen gas stream according to various embodiments. At step <NUM>, a feed gas containing N<NUM> as the majority component, H<NUM>, and CO flows into a processing unit <NUM> to produce an enhanced gas <NUM>. The feed gas has an initial H<NUM> to CO ratio, and has a second H<NUM> to CO ratio greater than the initial H<NUM> to CO ratio. The enhanced gas <NUM> flows into contact with a membrane in a membrane unit <NUM> to produce a permeate stream <NUM> and a retentate stream <NUM> at step <NUM>. The membrane may have a H<NUM> selective composition. A concentration of H<NUM> in the permeate stream <NUM> is greater than a concentration of H<NUM> in the enhanced gas <NUM>, and the retentate stream <NUM> may comprise N<NUM> and other contaminants that are removed from the enhanced gas <NUM>. At step <NUM>, the permeate stream <NUM> flows into contact with an adsorbent material in one or more adsorption columns <NUM> to produce a purified H<NUM> gas stream <NUM>. The adsorbent material may comprise a sorbent compound effective for removing N<NUM> or H<NUM>O or CO or CO<NUM> from the permeate stream <NUM>. At step <NUM>, the adsorbent material in one or more of the adsorption columns <NUM> may be regenerated to produce a tail gas <NUM>. At least a portion of the tail gas <NUM> is recycled to the enhanced gas stream <NUM> at a point upstream of the membrane unit <NUM>.

<FIG> illustrates another general flow diagram a method <NUM> for producing a purified hydrogen gas stream according to various embodiments. At step <NUM>, a feed gas containing N<NUM> as the majority component, H<NUM>, and CO and reduced sulfur species including H<NUM>S and COS may flow into a processing unit to remove this sulfur and to produce a product gas with low sulfur (<<NUM> ppmv). At step <NUM>, this product gas may flow into a processing unit <NUM> to produce an enhanced gas <NUM>. The product gas flowing into processing unit <NUM> has an initial H<NUM> to CO ratio, and has a second H<NUM> to CO ratio greater than the initial H<NUM> to CO ratio. The enhanced gas <NUM> flows into contact with a membrane in a membrane unit <NUM> to produce a permeate stream <NUM> and a retentate stream <NUM> at step <NUM>. The membrane may have a H<NUM> selective composition. A concentration of H<NUM> in the permeate stream <NUM> is greater than a concentration of H<NUM> in the enhanced gas <NUM>, and the retentate stream <NUM> may comprise N<NUM> and other contaminants that are removed from the enhanced gas <NUM>. At step <NUM>, the permeate stream <NUM> flows into contact with an adsorbent material in one or more adsorption columns <NUM> to produce a purified H<NUM> gas stream <NUM>. The adsorbent material may comprise a sorbent compound effective for removing N<NUM> or H<NUM>O or CO or CO<NUM> from the permeate stream <NUM>. At step <NUM>, the adsorbent material in one or more of the adsorption columns <NUM> may be regenerated to produce a tail gas <NUM>. At least a portion of the tail gas <NUM> is recycled to the enhanced gas stream <NUM> at a point upstream of the membrane unit <NUM>.

Aspen HYSYS® (Aspen Technology, Inc. , Bedford, MA) process models were developed for the H<NUM> purification process illustrated in <FIG>. The syngas (feed) was assumed to be that produced by partial oxidation of methane and air. Table <NUM> presents the results of a material balance on the purification process as calculated by the HYSYS model.

The above Example is for illustrative purposes only and does not restrict the invention to the processes used in the example.

In general, terms such as "communicate" and "in. communication with" (for example, a first component "communicates with" or "is in communication with" a second component) are used herein to indicate a structural, functional, mechanical, electrical, signal, optical, magnetic, electromagnetic, ionic or fluidic relationship between two or more components or elements. As such, the fact that one component is said to communicate with a second component is not intended to exclude the possibility that additional components may be present between, and/or operatively associated or engaged with, the first and second components.

Claim 1:
A method for producing a purified hydrogen gas stream, the method comprising:
flowing a feed gas containing nitrogen gas (N<NUM>) as the majority component, hydrogen gas (H<NUM>), and carbon monoxide (CO) and having an initial H<NUM> to CO ratio into a processing unit to produce an enhanced gas containing carbon dioxide (CO<NUM>) and having a second H<NUM> to CO ratio greater than the initial H<NUM> to CO ratio;
flowing the enhanced gas into a purification unit comprising a N<NUM> removal unit to remove N<NUM> and a CO<NUM> removal unit to remove CO<NUM>, wherein the purification unit produces a purified hydrogen gas stream and a tail gas; and
recycling at least a portion of the tail gas to a point upstream of the N<NUM> removal unit,
wherein flowing the enhanced gas into the purification unit comprises flowing the enhanced gas into the N<NUM> removal unit to produce a permeate stream and a retentate stream, and flowing the permeate stream into the CO<NUM> removal unit to produce the purified hydrogen gas stream and the tail gas,
wherein the N<NUM> removal unit comprises a membrane separation unit configured to receive the enhanced gas,
and wherein the CO<NUM> removal unit comprises a pressure swing adsorption (PSA) unit.