MXPA98003330A - Method of production of hydrogen using membrane of electrolyte sol - Google Patents

Abstract

A process for producing synthesis gas and hydrogen by passing a mixture of compressed and heated oxygen-containing gas into a reactor having at least one solid electrolyte oxygen ion transport membrane for separating transported oxygen. The organic fuel reacts with oxygen to form the synthesis gas. The resulting synthesis gas is separated in the hydrogen gas through at least one solid electrolyte hydrogen transport membrane to separate the hydrogen transported therein or differently separated

Description

METHOD OF HYDROGEN PRODUCTION USING SOLID ELECTROLYTE MEMBRANE FIELD OF THE INVENTION This invention relates to the production of hydrogen gas using a solid electrolyte membrane and, more particularly to the production of hydrogen gas, initially producing gas synthesis using a solid electrolyte ion transport membrane and separating the hydrogen gas using another solid electrolyte membrane.

CROSS REFERENCE The United States Patent Application Serial No. (Attorney Case No. D-20215) entitled "Method for Producing Oxidized Product and Generating Power Using a Solid Electrolyte Membrane Integrated with a Turbine", presented concurrently with this, is incorporated in this by reference.

BACKGROUND OF THE INVENTION The solid electrolyte ion and mixed conductive ion transport membranes have been used to extract oxygen from the gases at temperatures within the range of about 500 ° C to about 1200 ° C. The optimum operating temperature for gas transport depends on the membrane itself, particularly the material from which it is constructed. The ionic conductivity is also a function of the operating temperature and increases as the operating temperature increases. At operating temperatures less than about 500 ° C; in addition to the low ionic conductivity of the ion transport membranes, the kinetic limitations of the surface on the membrane can also restrict the oxygen flow, that is, the amount of oxygen per unit area, that is, the amount of oxygen per unit of area per unit of time. Operating temperatures for ion transport membranes greater than about 1200 ° C are undesirable also due to material or construction constraints (such as sealing, multiplication and thermal stress) are exacerbated at higher temperatures. One of the most attractive features of the oxygen ion transport membrane system is the infinite selectivity of the membrane for oxygen transport and the fact that oxygen is driven by the ratio of oxygen activities on opposite sides of the membrane. the membrane. Therefore, high oxygen flows are possible with a reaction occurring on the anode side. Likewise, it is possible to transport oxygen from a stream containing oxygen at low pressure to a reactive environment at high pressure. At elevated temperatures, oxygen-carrying materials contain mobile voids of oxygen ion that provide conduction sites for the selective transport of oxygen ions through the material. The transport is driven by the difference in partial pressure across the membrane, as the oxygen ions flow from the side with the higher partial pressure of oxygen than that with the lowest partial pressure of oxygen. The ionization of oxygen molecules towards the oxygen ions takes place on the "cathode side" of the membrane and the oxygen ions are then transported through the ion transport membrane. The oxygen ions deionize on the "anode side" through the membrane to reform the oxygen molecules. For materials that exhibit only ionic conductivity, the external electrodes can be placed on the surfaces of the electrolyte and the electric current is transported in an external circuit. In the materials of "mixed conduction", the electrons are transported towards the cathode internally, completing in this way the circuit and avoiding the necessity of external electrodes. Double phase conductors, in which an oxygen ion conductor is mixed with an electronic conductor, are a mixed conductor type. Partial oxidation reactions ("POx") and / or steam reforming reactions involving carbonaceous supplies are common methods for producing synthesis gas. The synthesis gas and its main components, carbon monoxide and hydrogen, are valuable industrial gases and important precursors for the production of chemical products that include ammonia, alcohols (including methanol and higher carbon alcohols), synthesis fuels, acetic acid, aldehydes, ethers and others. Supplies that include natural gas, coal, naphtha and fuel oils are commonly used to produce synthesis gas by partial oxidation or steam reforming reactions. These reactions can be represented as follows: CmHn + m / 2 02 = m CO + n / 2"H2 POx, exothermic CmHn + m H20 = CO + (m + n / 2) H2 SR, endothermic where CmHn is a hydrocarbon supply To improve the reaction rates and the selectivity of certain products, an external catalyst can be used in the form of a fixed or fluidized bed, or a plurality of catalyst tubes The components of individual synthesis gas, mainly hydrogen and carbon monoxide , can be obtained using a number of conventional gas separation methods known in the art such as those based on pressure swing adsorption, temperature swing adsorption, polymer membranes, and cryogenic distillation.The water-gas shift reaction can be carried to increase the yield of hydrogen by converting the CO in the synthesis gas to H2 and C02 through the reaction with steam (CO + H20 = C02 + H 2) The conventional partial oxidation processes often use oxygen molecules produced by traditional gas separation processes that typically operate at temperatures below 100 ° C. Since the partial oxidation reaction itself typically requires a high operating temperature of more than 800 ° C, the integration between the partial oxidation reaction and the traditional oxygen separation has not been done previously. As a result, the conventional partial oxidation reaction has often been characterized by low feed conversion, low hydrogen to carbon monoxide ratio and low selectivity of hydrogen and carbon monoxide. Additionally, the external oxygen supply typically required in a partial oxidation reaction is significantly added to the capital and operating costs, which can add up to 40% of the total production cost of synthesis gas. In addition, inefficiencies are introduced in accordance the largest amount of carbon monoxide gas produced in the partial oxidation reaction product requires a two-stage shift conversion when only hydrogen is required as the final product. The shift conversion is also added to the cost of the process. Steam reforming reactions are also used for synthesis gas production. Since the steam reforming process produces more hydrogen per mole of organic fuel than the partial oxidation reaction, this process is more advantageous for the production of hydrogen and mixtures with a high H2 / CO ratio. (That is, a ratio greater than 2). However, steam reforming is an endothermic reaction that requires a significant amount of thermal energy and, therefore, is a less attractive method for the production of synthesis gas when the H2 / CO ratios are below 2. In the past, the development in the area of oxygen ion transport membrane system has included the combination of the membrane in conjunction with the gas turbines. U.S. Patent Nos. 5,516,359, 3,562,754, 5,565,017 and EPO Patent No. 0,658,366 describe the production of oxygen in a process that is integrated with a gas turbine system. U.S. Patent Application Serial No. 08 / 490,362 entitled "Method for Producing Oxygen and Generating Power Using a Solid Electrolyte Membrane Integrated with a Gas Turbine" is also directed to the production of oxygen using the gas transport membrane integrated with gas turbine and is incorporated herein by reference.

Oxygen ion transport membrane materials useful for the production of synthesis gas have been described by U. Balachandran et al. , in "Fabrication and Characterization of Dense Ceramic Membranes for Partial Oxidation of Methane", Proc. Of Coal Liquefaction and Gas Conversion Contractors' Review Conference, Pittsburgh, PA (August 29-21, 1995) and "Dense Ceramic Membranes for Converting Methane to Syngas", presented to the First International Conference on Ceramic Membranes, 188th Session for the Electrochemical Society, I nc. , Chicago, I L (Oct. 8- 1 3, 1995). U.S. Patent 5,306.41 1 (Mazanec et al.) Describes a process that integrates oxygen separation with partial oxidation (for gas production) or methane oxidant coupling. Despite recent technological advances involving ion transport membrane systems, the present inventors are not aware of any discovery of the practical integration of transport membrane systems based on the production of synthesis gas. and a hydrogen separation system using a solid electrolyte ion transport membrane and in addition, separating it into an individual unit.

OBJECTIVES OF THE I NVENC ION It is therefore an object of the invention to provide a process for the integration of synthesis gas production based on oxygen ion transport and hydrogen separation using hydrogen transport membranes, such as those based on palladium or palladium alloys. or proton transport membranes. It is a further object of this invention to provide such a process wherein partial oxidation and steam reforming reactions can occur together to achieve closeness to a neutral energy configuration. A further object is to provide an improved process for producing synthesis gas that is economically attractive, flexible and thermodynamically efficient. A further object of the invention is to balance the heats of reaction using a relatively large mass of the oxygen-containing gas (generally air) on the cathode side of the oxygen ion transport membrane as a "heat sink". It is a further object of the invention to achieve the gas inlet and outlet temperatures lower than the reaction temperatures by having reactive gases on the anode side flowing countercurrent to the oxygen-containing stream (generally air) on the cathode side. It is a further object of the invention to increase the conversion of the organic fuel to the synthesis gas on the anode side by removing hydrogen from the synthesis gas conversion zone using the ion transport membranes.

BRIEF DESCRIPTION OF THE INVENTION The present invention is directed to a process for producing hydrogen gas and synthesis gas. The process comprises passing a mixture of gas containing compressed and heated oxygen into an oxygen reactor having at least one solid electrolyte oxygen ion transport membrane. The reactor has a first zone and a second zone separated by the oxygen ion transport membrane. At least a portion of the oxygen in the mixture is transported through the oxygen ion transport membrane from the first zone to the second zone to react with a purge stream containing an organic gas phase fuel as long as produces a retention stream lacking oxygen from the first zone. The purge stream is passed into the second zone to react with the oxygen transported to produce the synthesis gas. The synthesis gas is directed to make contact with at least one hydrogen transport membrane to generate a high purity hydrogen infiltrate and a retentate of synthesis gas devoid of hydrogen. Subsequently, the high purity hydrogen infiltrate is removed as a product of hydrogen gas.

Another embodiment comprises the steps of passing a mixture of gas containing heated and compressed oxygen into an oxygen reactor having at least one solid electrolyte oxygen ion transport membrane. The reactor has a first zone and a second zone separated by the first oxygen ion transport membrane. At least a portion of the oxygen in the mixture is transported through the oxygen ion transport membrane from the first zone to the second zone to generate a retentate stream devoid of oxygen from the first zone. An organic fuel of gas phase, and steam, and optionally C02, are passed into the second zone to react with the oxygen transported to produce the synthesis gas. The amount of steam and C02 injected into the second zone can be controlled to change the H2 / CO ratios of the synthesis gas stream produced. A stream of the synthesis gas from the second zone is removed and passed into a third zone in a hydrogen separator having at least one solid electrolyte hydrogen transport membrane. The hydrogen separator has a third and fourth zones separated by the hydrogen transport membrane. At least a portion of the hydrogen gas is transported through the hydrogen transport membrane from the third zone to the fourth zone to generate a hydrogen infiltrate in the fourth zone and a synthesis gas devoid of hydrogen in the third zone . The hydrogen infiltrate is removed from the fourth zone as a hydrogen product. The hydrogen separation is selected to operate at the same or at a moderately lower temperature than the oxygen ion transport membrane. In another embodiment, a gas mixture containing compressed and heated oxygen is passed into an oxygen reactor having at least one selective electrolyte oxygen ion transport membrane and at least one hydrogen transport membrane of solid electrolyte. The reactor has a first zone, second zone and third zone. At least a portion of the oxygen in the mixture is transported through the oxygen ion transport membrane from the first zone to the second zone to supply a first oxygen infiltration stream to react with a purge stream containing a Organic gas phase fuel while producing a retentate stream lacking oxygen. The purge stream is passed into the second zone to react with the oxygen transported to produce the synthesis gas. The synthesis gas is directed to make contact with at least one hydrogen transport membrane to generate a high purity hydrogen infiltrate in a third zone and a retentate of synthesis gas devoid of hydrogen remains in the second zone. The hydrogen infiltrate is then removed from the third zone as a hydrogen product. One of the advantages of removing hydrogen from the synthesis gas conversion zone is that it maintains a balance to drive the reaction to completion. In some of the embodiments, the gas mixture is heated at least in part by indirect heat exchange with at least one stream comprising the gas retained lacking oxygen from the first zone, the synthesis gas retained lacking oxygen and the gas infiltrated by hydrogen from the hydrogen separator. As used herein, the term "reactor" means a separator in which the transported oxygen supports a chemical reaction and oxygen is consumed thereby.

BRIEF DESCRIPTION OF THE DRAWINGS Other objects; features and advantages will be devised by those skilled in the art from the following description of the preferred embodiments and the following drawings, in which: Fig. 1 is a schematic representation of a system for producing hydrogen gas and hydrogen gas; synthesis according to this invention in the synthesis gas emerges from the transport of oxygen in the oxygen reactor and the hydrogen gas emerges from a hydrogen transport membrane in the hydrogen separator; and Fig. 2 is a schematic representation of a system for producing hydrogen gas and synthesis gas in accordance with this invention in which oxygen is filtered through an oxygen ion transport membrane that produces synthesis gas and , the hydrogen from the synthesis gas is infiltrated through the hydrogen transport membrane producing hydrogen, where both membranes are inside a reactor.

DETAILED DESCRIPTION OF THE INVENTION This invention can be achieved by processes for the production of hydrogen using a solid oxygen ion transport membrane to separate oxygen from the oxygen-containing gas, i.e., air and to utilize the oxygen separated in the partial oxidation reactions and optionally in steam reforming reactions of carbonaceous supplies. Partial oxidation and / or steam reforming reactions produce synthesis gas that is used to produce hydrogen by means of a hydrogen transport membrane. Oxidation of the fuel on the anode side of the oxygen ion membrane reactor reduces the partial pressure of oxygen on that side of the membrane. This increases the driving force in the oxygen reactor, generating a high oxygen flow and a lower membrane area requirement. These benefits accumulate even when the oxygen-containing feed gas is at a relatively low pressure and the fuel side at a high temperature, thus requiring lower system energy demands. The partial oxidation reaction, an exothermic reaction and the steam reforming reaction, an endothermic reaction, can be carried out in the same reactor to obtain an almost neutral energy system. Furthermore, the heat sink in the form of a relatively large mass of the oxygen-containing gas (generally air) allows the reaction heats to be further balanced and the temperature of the reaction zone controlled. In another embodiment, the partial oxidation and steam reforming reactions take place in separate ion transport separators. The resulting synthesis gas produced by the oxygen ion transport reactor by partial oxidation and / or steam reforming reaction is then fed into a hydrogen membrane transport separator. Preferably the oxygen-containing gas and the reactive fuel flow concurrently. By introducing the fuel and gas stream containing oxygen at lower temperatures and depending on the internal heat transfer to the reactor, it is possible to keep critical reactor parts such as seals and structural components at the gas inlet and outlet ports of the reactor at intermediate temperatures for ease of mechanical design and reduction of manufacturing costs.

Oxygen ion transport membranes are used to separate oxygen from streams of oxygen-containing gas. Materials that can conduct oxygen ions as well as electrons are described herein as "mixed conductive oxides" or "mixed conductors". Currently, a number of potential mixed conductors have been identified in both fluorite and perovskite crystal structures. Table I is a partial list of mixed conductors of interest in oxygen production.

Unp of the materials of the family La? -? SrxCu.-yMy? 3-d, where M represents Fe or Co; x equal from zero to about 1; and equal from zero to about 1; d equals a number that satisfies the valences of La, Sr, Cu and M in formula 11 One of the materials of the family Ce.-xA ?? 2-or, where: A represents a lanthanide, Ru or Y; or a mixture of the same; x equal from zero to about 1; and equal from zero to about 1; d equals a number that satisfies the valences of Ce and A in a formula 12 One of the materials of the Sr?. XBixFe03.d family, where: A represents a lanthanide or Y, or a mixture thereof; x equal from zero to about 1; and equal from zero to about 1; d equals a number that satisfies the valences of Ce and A in a formula 13 One of the materials of the SrxFeyCozOw family, where: x equal from zero to approximately 1; and equal from zero to about 1; z equal from zero to about 1; w equal to a number that satisfies the valences of Sr, F e and Co in the formula 14 Mixed conductors of double phase (electronic / ionic). (Pd) os / (YSZ) or 5 (Pt) os / ((YSZ) 0 s (B-MgLaCrO?) Or 5 (YSZ) 0 s (In90% Pt10%) or ß / (YSZ) 0 s (ln90 % Pt? O%) os / (YSZ) os (ln_5% Pr25% Zr25%) os / (YSZ) or 5 Any of the materials described in 1-13, to which a metallic phase of high temperature is added (for example Pd, Pt, Ag, Au, T, Ta, W).

Although blended conductors or double phase conductors are preferred for the pressure driven ion transport separator, this invention also contemplates the use of electrically driven ion transport membranes. Typically, the ion transport membrane can be in the form of a dense film or a thin film supported on a porous substrate. The thickness of the membrane layer is less than about 5000 microns, preferably less than 1000 microns, and more preferably less than 100 microns. The ion transport membranes may be in tubular or flat form.

In a similar manner, the hydrogen transport membranes are used to separate the hydrogen from the synthesis gas stream. Several hydrogen separation units are possible using any of several high temperature hydrogen technologies, for example, solid permeable hydrogen membranes, such as those based on palladium or palladium alloy or proton conductors. Preferably, the proton conductors are used. Table II is a partial list of hydrogen conductors of interest for the separation of hydrogen The process of this invention can be described by the schematic representation of the system 50, Fig. 1, in which a process configuration for employing the ion transport technology for the production of synthesis gas and hydrogen gas is provided. The gas stream containing oxygen 1 (preferably air) is compressed to a low pressure using a blower 2 and then heating it against the oxygen-free holding stream 8 in the heat exchanger 3, and is then directed to the oxygen reactor 6. , by means of an optional heater 4 to emerge as a stream of gas containing compressed and heated oxygen 5. Stream 8 in one embodiment is discarded as waste and in another embodiment is used as a stream of nitrogen product. The gas stream 5 is fed into the first zone 40 of the oxygen ion transport membrane reactor 6, the reactor having been divided into the first zone 40 and the second zone 41 by the oxygen ion transport membrane 7. As used herein, first zone 40 is where the oxygen containing gas 5 is fed and is referred to as the cathode side or retained. Typically, the pressure in the first zone 40 is 1 to 40 atm, preferably 1 to 10 atm. In reactor 6, a portion of the oxygen in the oxygen-containing gas stream 5 in the first zone 40 is removed and the outflow 8 is a current devoid of oxygen. The oxygen ion conductivity of the membrane is typically in the range of 0.01 to 100 S / cm, where "S" is 1 / ohm. The oxygen is transported through the membrane 7 within the second zone 41, referred to as the infiltrate or anode side, where it is respectively purged using the gas mixture 9 containing organic fuel 10. If a liquid carbonaceous fuel is used for The production of hydrogen must evaporate before entering or evaporating inside the reactor. The pressure of the second zone 41 is typically from 1 to 100 atm, preferably from 1 to 40 atm. The organic fuel in one embodiment is a carbonaceous fuel, preferably methane or a natural gas with no combustion residues, which has optionally been pressurized in the compressor 1 1 and preferably further heated in the heater 12, mixed with steam or atomized water. and a stream of recycled infiltrate 14 from the hydrogen transport membrane separator 16. Although hydrogen-permeable membranes are used here to effect separation of the hydrogen, other separation schemes known to those skilled in the art would also be applicable, for example, pressure twist adsorption, temperature twist adsorption, cryogenic gas separation, polymer membranes for gas separation. The vapor or atomized water added to the fuel stream favors the steam reforming process and increases the concentration of hydrogen in the synthesis gas 1 5. This is because steam reforming generally produces a hugely larger amount of hydrogen that the process of partial oxidation. For example, if methane is used as a fuel, steam reforming provides 50% more hydrogen than the partial oxidation process. The process of steam reforming is generally endothermic while the partial oxidation process of a hydrogen fuel is exothermic. Depending on the heat requirement and heat transfer of the system, any of the partial oxidation and heat reforming reactions can be carried out using a suitable catalyst. As a result, the use of oxidation and the steam reforming process favor obtaining a "neutral energy" ion transport system, where the exothermic nature of the partial oxidation process provides the efficient energy for the reforming process steam. This also favors obtaining a thermally self-sustaining process. As discussed above, the reaction temperatures can be further suppressed by the heat sink in the form of a relatively large mass of the oxygen-containing gas (generally air). At typical ion transport membrane operating temperatures, the partial pressure of oxygen in the gas stream that consumes oxygen is low. The low partial pressure facilitates the rapid transport of oxygen through the oxygen ion transport membrane, even when the pressure of the oxygen-containing gas is relatively lower since oxygen transport is driven by the difference in oxygen activity. oxygen on opposite sides of the membrane. This aspect of the reactor allows oxygen to be transported with a low pressure requirement. The partial pressure of oxygen can be increased to improve oxygen flow through the oxygen transport membrane. For example, if air is used as the feed gas containing oxygen and nitrogen, it is necessary at high pressure, then pressurization of the air would be beneficial. Analogously, air compression may not be desirable if nitrogen is not necessary as a product at a high pressure. The retentate stream can be expanded to recover part of the compression work or, burned in a gas turbine to generate power. If the production of energy is desirable, then the oxygen-containing gas (usually air) must be pressurized at the typical gas turbine inlet pressures (7.03-17.57 kg / cm2). Also, if nitrogen is not necessary as a product, it may be beneficial to compress the oxygen-containing gas (usually air) only to a pressure required to offset the change in pressure loss in the reactor. Under the typical operating conditions in the oxygen ion transport membrane reactor, the fuel gas undergoes the partial oxidation reaction to produce the synthesis gas (hydrogen and carbon monoxide) and a variety of other components including carbon dioxide , water and other minor components such as higher hydrocarbons. A catalyst can be used in the second reactor zone to improve the desired partial oxidation and steam reforming reactions. The external catalyst used to promote the partial oxidation / steam reforming reactions can be deployed in various ways including depositing it on the transport membrane, a fixed bed, a fluidized bed, rods or catalyst tubes. For example, it is likely that the partial oxidation catalyst is used on the surface of the oxygen ion transport membrane and the steam reforming catalyst in the form of a fixed bed. Different catalysts may be necessary for the partial oxidation and steam reforming reactions, the degree of which can be controlled by mixing the respective catalysts in suitable proportions appreciated by the person skilled in the art. For example, a bed of partial oxidation layers and steam reforming catalyst (eg, Nio-based catalysts) can be used to control the ratio of carbon monoxide / hydrogen in the synthesis gas. The vapor and C02 concentrations in the purge gas phase can also be used to control the carbon monoxide / hydrogen ratio in the synthesis gas. As shown additionally in Fig. 1, the synthesis gas 15 emerging from the oxygen reactor 6 through the partial oxidation reaction of the fuel 10 in the second zone 41 of the reactor 6. Optionally, the synthesis gas stream 15 can then be fed within the second downstream hydrogen membrane separator 16. It may be necessary to moderate the temperature of the synthesis gas stream if the operating temperature of the hydrogen transport membrane is lower than the operating temperature of the hydrogen membrane. oxygen ion. As in the oxygen ion membrane reactor, the hydrogen separator 16 is also separated from the third zone 42, referred to as the retentate side of hydrogen or cathode side, and the fourth zone 43, referred to as the permeable side to hydrogen or anode side. The third zone 42 and the fourth zone 43 are separated by at least one hydrogen transport membrane 30. The hydrogen gas is infiltrated through at least one hydrogen transport membrane 30 of the hydrogen separator 16. The current of resulting hydrogen gas 17 emerging from the fourth zone 16 can enter the heat exchanger 3 to transfer the heat to the gas stream containing upstream oxygen 1. It is important that the high pressure of the synthesis gas be maintained in order to hold the differential pressure differential of hydrogen needed through the hydrogen transport membrane. In this embodiment, the compressor 11 can compress the fuel gas to provide the desired conditions for the reaction in the second zone 41 and the partial pressure of hydrogen needed in the second zone 41 for effective downstream hydrogen transport. Preferably, a pressure of about 10 to 50 atm is provided. The carbon monoxide-rich stream 18 emerging from the third zone 42 is preferably used to heat the stream of oxygen-containing gas 1 in the heat exchanger 3. Further recovery of the hydrogen from the retentate stream 18 can be achieved in another separator 19, leaving behind a stream rich in carbon monoxide 21. The separation thereby provides the hydrogen stream 20 for the addition to the stream of hydrogen gas 17. This process of recovering hydrogen in the separator 19 can be carried to either at low temperature according to conventional methods known in the art, for example, such as pressure twist adsorption, thermal swirl adsorption, polymer membranes and cryogenic distillation; or at elevated temperatures, for example, using solid hydrogen transport membranes such as those based on palladium or palladium alloy or electrically driven or pressure driven proton conductive membranes. It should be noted that if a proton-conducting membrane is used for the separation of hydrogen, electrodes and external circuits are required for the electrically driven process. If the hydrogen transport membrane has sufficient electronic conductivity, pressure-driven hydrogen separation can be carried out in situ. The choice of the hydrogen separation process downstream depends on the pressure and purity at which hydrogen and carbon dioxide are needed. For example, a polymer membrane process will give a slightly impure hydrogen current (90-96%) at a low pressure and a relatively pure carbon dioxide at a high pressure, considering that a pressure twist adsorption separation of a mixture Synthetic gas at high temperature will give a stream of purer hydrogen (96-99.9%) at a high pressure and an impure carbon dioxide at a low pressure. The membranes based on palladium or proton conductors allow the production of a stream of H2 of very high quality by virtue of its infinite selectivity for the transport of hydrogen. The concentration of hydrogen in the carbon monoxide rich stream can be adjusted using a number of operating parameters, for example, by varying the partial pressure differential of hydrogen through the hydrogen transport membrane. Similarly, various parameters associated with the hydrogen transport membrane can be adjusted, such as varying the thickness and area of the membrane. Carbon monoxide in the carbon monoxide-rich stream 21 can be recovered by a separator 22, producing an enriched carbon monoxide stream 23. The remnant waste carbon monoxide stream 14 can be optionally discarded as a stream of carbon monoxide. scrap 24 or recycled to be combined with the organic fuel stream 10 to the oxygen ion transport reactor 6. If carbon monoxide is not desired as a product, it can be used as a fuel to provide heat input in several stages of this process. For example, it can be used in the waste boiler to generate the steam needed for this process. In addition, if carbon monoxide is not desired as a product, it can be converted to carbon dioxide as well as to increase the yield of hydrogen by carrying out the water-gas displacement reaction. Optionally, carbon monoxide can also be burned to provide the necessary heat at various points in the system. The carbon monoxide can also be burned in a gas turbine integrated with the present system to generate energy. Another embodiment of this invention is presented in system 250, Fig. 2. In this embodiment, an oxygen ion transport membrane reactor is combined with a hydrogen separator in a single unit. This system allows the separation of oxygen, the production of synthesis gas and the separation of hydrogen in the same membrane unit providing improved equilibrium conditions in the reactor. The gas stream containing oxygen (preferably air) 201 is compressed at high pressure using the blower 202 and then heated against the waste stream (or nitrogen product) 208 in the heat exchanger 203 and then to an optional heater 204, emerging as the stream of gas containing compressed and heated oxygen 205. The gas stream 205 is fed into the first zone 240 of the oxygen ion transport membrane reactor 206, the reactor having been divided into first zone 240. and second zone 241 by the oxygen transport membrane 207. As used herein, the first zone is where the oxygen-containing gas 205 is fed, or alternatively, it is referred to as the oxygen cathode or the oxygen retentate side. In reactor 206, a portion of the oxygen-containing gas in the first zone 24o is removed and the exiting stream 208 is a stream enriched with nitrogen. Oxygen is transported through a membrane 207 within the second zone 241 or alternatively referred to as the permeate side or anode side, where it is purged using the gas mixture 209 containing the organic fuel 210. Under the operating conditions Typical in the ion transport membrane reactor, the fuel gas supports partial oxidation to produce the synthesis gas and a variety of other components that include carbon dioxide, water and other hydrocarbons. A catalyst may be incorporated in the second zone 241 of the reactor 206. The purge gas 209 is a carbonaceous fuel, preferably methane or natural gas. The purge gas 209 is preferably pressurized in the compressor 212, mixed with steam or atomized water 213 and a stream of recycled expelled synthesis gas 214. At the typical membrane operating temperatures of the ion, the partial pressure of oxygen in the Purge gas stream is lower, typically less than 10-10 atm, which facilitates the rapid transport of oxygen through the oxygen gas transport membrane and allows low compression of the oxygen-containing gas stream. This aspect of the reactor allows oxygen to be transported with a low energy requirement. The reactor 206 also presents the hydrogen transport membrane 225, and where the transport of hydrogen through the membrane 225 emerges as a high purity hydrogen infiltrate within the third zone 242, or alternatively referred to as the oxygen infiltrate or side of the anode. The removal of the hydrogen changes the equilibrium conditions in the second zone 21 favorably to increase the yield of hydrogen. Another purge gas 226 is optionally used to remove the highly pure hydrogen gas infiltrated from the third zone 242. The purge gas 226 may be a gas that is easily separated from H2, such as steam or N2. Preferably, the pure gas 225 is pressurized in the compressor 227 and optionally heated in the heater 228. Emerging from the reactor 206 through the partial oxidation reaction of the fuel 210 in the second zone 241 is the stream rich in carbon monoxide 21. 8, which can be removed and recovered. The stream 218 can be used to provide heat against the stream of oxygen-containing gas 201 in the heat exchanger 203. Recovery of additional hydrogen can be provided as the stream 218 passes through the separator 219, which arises as the stream rich in carbon monoxide 221 and the separated hydrogen stream 220. Recovery of the carbon monoxide stream 221 takes place in the carbon monoxide separation unit 222 as pure or nearly pure carbon monoxide 223. The ejected waste stream 214 emerges from the carbon monoxide separation unit 222 and is optionally discarded as the waste stream 224. The hydrogen-rich stream 217 emerging from the third zone 242 of the reactor 206 passes through the heat exchanger 203. Separately , the hydrogen-rich stream 220 separated from the carbon dioxide-rich stream 218 in the separator 219 can be combined with in the hydrogen-rich stream 217 which forms the hydrogen-rich stream 229. The system provided by the embodiment of Fig. 2 also favors the greater production of synthesis gas. Because the hydrogen is separated in situ, the partial pressure of hydrogen is reduced in the partial oxidation reaction. Consequently, the principle of Le Chatelier's favors the synthesis gas formation even displacing the partial oxidation / steam reforming reactions more towards the side of the product. Introducing organic fuel into the second zone at high temperature, hydrogen is generated at sufficiently high pressure to push it through the hydrogen transport membrane. Alternatively, a purge gas can be used to effect the separation of hydrogen in the mode employing an independent oxygen separator and hydrogen separator. For example, steam could be used as a purge gas in the hydrogen separator since the vapor can be easily separated from the hydrogen by condensation. If the conversion to the reactor is complete, the purge stream will contain unreacted fuel, where at least a portion of the stream can be recycled to the reactor, preferably after the hydrogen and carbon monoxide have been removed. . Several other aspects of the embodiment of Fig. 1 as described above are also applicable to the embodiment of Fig. 2 and would be appreciated by those skilled in the art. Various functions such as heat exchange in exchangers 3 or 203 can be integrated into reactor 6 or 206 as described in United States Patent Application No. from Series entitled "SELIC Reactor Design", which is incorporated herein by reference. It is contemplated that this invention may be further extended using the products derived from this invention. For example, the separate hydrogen-rich and nitrogen-rich streams produced from this invention can be used in the production of ammonia. Additionally, the synthesis gas as produced by this invention is a valuable commercial product that can be used in fuel cells or for the production of chemical products such as methanol, acetic acid, dimethyl ether, acetonitrile and formaldehyde. Accordingly, synthesis gas production can be integrated with the downstream process, optionally with adjustment of the hydrogen / carbon monoxide ratio. The specific features of the invention are shown in one or more of the drawings for convenience only, since each feature can be combined with other features in accordance with the invention. Alternative embodiments of the invention will be recognized by those skilled in the art and are intended to be included within the scope of the claims.

Claims (10)

1. A process for pro-d cir g_aa of hydrogena and. from. The synthesis comprises the steps of: (a) containing gas compressed and heated within an oxygen reactor which comprises at least one oxygen transport medium of oxygen d.sub.s. solid catalyst, the reactor having a first zone and a second separated zone, by oxygen membrane, in which at least a portion of the oxygen from said mixture is transported through the membrane of the membrane. Oxygen ion is poured from the first zone into the second zone to generate a first stream of infiltrate from the second carrot to react with a purge stream containing an organic fuel from the faease while a retentate stream is produced. lacking oxygen from the first zone, (b) passing the purge runner into the second zone to react with the oxygen transported to produce the synthesis gas, in the first infiltrating stream; c) directing the first infiltrating stream or to make contact with at least one membrane, transporting hydrogen to generate a high purity hydrogen infiltrate and a retentate of synthesis lacking hydrogen; and (d) removing the high purity hydrogen infiltrate as a product of hydrogen gas stream.

2. The process of claim 1, further comprising a hydrogen separator and qua having, the membrane provides hydrogen transport and a conduit for directing the first infiltrating stream towards. to the separator, it gives hydrogena.

3. The process of claim 2, wherein the gas mixture qua t-tiana. Ax is heated at least partially by heat exchange with at least one of the gas retained lacking oxygen from the first. zanar to ratenida gives gas. gives synthesis lacking hydrogen and hydrogen infiltrated gas from the hydrogen separator.

4. The process of the. claim 1, wherein the gas phase organic fuel is comprised of organic fuel tied to steam or atomized water.

5. A process for producing hydrogen gas comprising the steps of: (a), passing na. mix of. gas containing oxygen compressed and heated inside an oxygen reactor comprising by the hands a transport membrane gives oxygen ion gives solidAltralite, the reactor having a first zone and a second zone separated by the first transport membrane of. oxygen, wherein at least a portion of the oxygen from said mixture is conveyed through the oxygen transport membrane from the first zone to the next zone to supply a first, oxygen infiltrate stream to react with a pu rga stream containing an organic gas-phase fuel while a retentate stream devoid of oxygen is produced from the first zone; (b) passing the purge stream into the second zone to react with the axirang. transported to produce the synthesis gas; (a) withdrawing and passing the second zone the first runner of infiltration of the synthesis gas into a third zone in a hydrogen separator which comprises one hand. mamhrana of hydrogen transport of solid electrolyte, the separator of 0_ hydrogen, which tiana la-tarcara zone y. a fourth zone spaced from one another by the hydrogen transport membrane, wherein at least a portion of the gas. of synthesis is transported ,. through the hydrogen membrane from the third zone towards the fourth carrot to generate an infiltrate of hydrogen in the fourth carrot and a synthesis gas devoid of hydrogen in the third zone; and (d) removing the infiltrate. d_a hydrogen of the fourth carrot a product of hydrogen gas stream.

6- The process gives the claim 5, wherein the temperature of the synthesis gas stream is optionally reduced before passing into the hydrogen separator.

7. The process of claim 5, wherein the mixture is heated at least in part by indirect heat exchange with at least one of the oxygen-free retentate of the first zone, the retentate synthesis gas devoid of hydrogen. from the third zone and the hydrogen infiltrate of the fourth zone.

8. A process for producing hydrogen gas comprising the steps of: (a) passing a mixture of compressed and heated oxygenated gas contained within a membrane reactor comprising at least one selective electrolyte oxygen ion-transporting membrane and at least one ion transport membrane gives solid electrolyte hydrogen, the reactor having a first zone, second zone and a third zone, wherein at least a portion of the oxygen from said mixture is conveyed through, from the oxygen ion transport membrane from the first zone to the second zone to generate a retention stream lacking oxygen from the first zone; (b) passing an organic gaseous phase cambifibt within the second zone to react with the transported oxygen to produce the synthesis gas; (c) directing the synthesis gas to contact at least one hydrogen transport membrane to generate a high purity hydrogen infiltrate in a third carrot and a retentate of synthesis gas devoid of hydrogen in the second zone; and (d) removing the hydrogen infiltrate from the third bed zone a product of hydrogen gas stream.

The process of claim 8, wherein the mixture is heated at least in part by indirect heat exchange with at least one of the oxygen retentate from the first zone, the synthesis gas lacking hydrogen from the second zone and the hydrogen infiltrate of the third zone.

10. The process of claim 8, wherein the gasanase phase organic fuel is comprised of combusiih. The organic treated with steam or atomized water.