METHOD AND ARRANGEMENT FOR THE PRODUCTION AND THERMAL COMPRESSION OF OXYGEN

Abstract

The invention relates to a method and an arrangement for the continuous production of compressed oxygen from air using mixed conducting ceramic membranes. The aim of the invention is to provide a way of isolating pure oxygen from the air and compressing said oxygen to pressures above the ambient pressure, without using mechanical or electromechanical compression of air or oxygen. To achieve this aim, according to the invention water in various aggregate states is conducted in a circuit and the configuration of the equipment is designed such that the desired high oxygen pressure is produced in a separate area from the membrane module and the oxygen produced is prevented from mixing with the freshly produced water vapour.

Claims

1.-8. (canceled)

9. A method for generating compressed oxygen, wherein the method uses one or more mixed-conduction MIEC membranes, each having a sweep gas side and a feed gas side, and wherein (a) water is evaporated in an evaporator and passed in the form of steam to a heated MIEC membrane on the sweep gas side, (b) uncompressed air is passed to the feed gas side of the MIEC membrane, whereby oxygen from air permeates through the MIEC membrane into the steam, forming a gas mixture of steam and oxygen, (c) the gas mixture of steam and oxygen, after passing through a nonreturn valve is supplied to a condenser, whereby steam largely condenses out again to form water, which water is supplied to the evaporator, and liberated oxygen is supplied via a pressure control valve to a gas reservoir, (d) establishment of an equilibrium of oxygen partial pressures is prevented by setting steam volume flow at levels ranging from 0.1 to 3 times air volume flow,

10. The method of claim 9, wherein the MIEC membrane is heated by waste heat.

11. The method of claim 9, wherein a flow rate of the gas mixture through the nonreturn valve is set at a level of greater than 0.2 m/s.

12. The method of claim 9, wherein electrical energy is generated from the gas mixture under pressure.

13. The method of claim 9, wherein the MIEC membrane is a BSCF (Ba.sub.0.5Sr.sub.0.5Co.sub.0.8Fe.sub.0.2O.sub.3-δ) membrane.

14. The method of claim 9, wherein the MIEC membrane is present in the form of a pressure-tight shell.

15. An arrangement for generating compressed oxygen, wherein the arrangement comprises a mixed-conduction MIEC membrane module which on a sweep gas side comprises an inlet and an outlet and on a feed gas side comprises an air supply inlet and an air outlet, the inlet communicating with an evaporator, and the outlet communicating with an evaporator via a nonreturn valve, a condenser, and a condensate collector.

16. The arrangement of claim 15, wherein the condenser comprises a siphon.

17. The arrangement of claim 15, wherein the arrangement further comprises a siphon located downstream of the condenser.

18. The arrangement of claim 15, wherein fresh air which is supplied to the condenser for cooling, after passing through the condenser, is passed via a conduit system to a first heat exchanger and subsequently to a second heat exchanger to be further passed to the air supply inlet.

19. The arrangement of claim 15, wherein the arrangement further comprises a steam turbine located downstream of the nonreturn valve.

20. The arrangement of claim 15, wherein the arrangement further comprises a third heat exchanger and a superheater arranged between the evaporator and the inlet.

21. The arrangement of claim 15, wherein the MIEC membrane is a BSCF (Ba.sub.0.5Sr.sub.0.5Co.sub.0.8Fe.sub.0.20.sub.3-δ) membrane.

22. The arrangement of claim 15, wherein the MIEC membrane is present in the form of a pressure-tight shell.

23. The arrangement of claim 15, wherein in operation (a) water is evaporated in the evaporator and passed in the form of steam to the heated MIEC membrane on the sweep gas side, (b) uncompressed air is passed to the feed gas side of the MIEC membrane, whereby oxygen from air permeates through the MIEC membrane into the steam, forming a gas mixture of steam and oxygen, (c) the gas mixture of steam and oxygen, after passing through the nonreturn valve is supplied to the condenser, whereby steam largely condenses out again to form water, which water is supplied to the evaporator, and liberated oxygen is supplied via a pressure control valve to a gas reservoir.

24. The arrangement of claim 23, wherein the MIEC membrane is heated by waste heat.

Description

[0020] The invention is to be elucidated in more detail below by means of exemplary embodiments. For this purpose

[0021] FIG. 1 shows a method scheme for generation of compressed oxygen,

[0022] FIG. 2 shows a method scheme for generation of compressed oxygen with improved energy efficiency,

[0023] FIG. 3 shows a method scheme for combined generation of oxygen and electricity, and

[0024] FIG. 4 shows a membrane module with steam purging for generating oxygen with superatmospheric pressure.

[0025] The method principle of the invention is to be elucidated using FIG. 1. First of all, liquid water is evaporated in an evaporator 1 and is passed within a membrane module 2 to the MIEC membrane (sweepgas side), which is heated by waste heat or otherwise. The oxygen permeates from the uncompressed feed gas air through the membrane into the steam, since its oxygen partial pressure (p.sub.1) is initially much lower than the oxygen partial pressure (p.sub.h) on the air side, especially close to the steam entry. Along the membrane surface receiving steam flow, the steam becomes increasingly rich in oxygen, and the pressure remains virtually the same but there is an expansion in volume. The gas mixture of steam and oxygen, after contact with the membrane, is supplied to a condenser 3, which very largely condenses steam out again and supplies the water in liquid form to the evaporator 1 again.

[0026] In accordance with the invention, the establishment of an equilibrium of the oxygen partial pressures is prevented by setting the steam volume flow at levels from 0.1 times up to 3 times the air volume flow. As a result, oxygen is carried continually out of the membrane module 2, and new, virtually oxygen-free steam is introduced into the membrane module 2. At the same, the flow rate of the steam/oxygen mixture is adjusted, through reduction in the free flow cross sections, in such a way that the flow rate exceeds 0.2 m/s during and, in particular, after membrane contact, but at least within a nonreturn valve 4. Consequently, return flow of the generated oxygen to the membrane, the corresponding reduction in the driving force In(p.sub.h/p.sub.1), and the establishment of the equilibrium of the oxygen partial pressures are avoided.

[0027] Within the condenser 3, the gas mixture is introduced into liquid water, and consequently cooled, and the steam is very largely separated in the forth of liquid water, which runs downward. The introduction is accomplished such that the oxygen ascending in gaseous form within the water passes into a separate gas reservoir, and therefore is separated by liquid water in the condenser 3 from the inflowing gas mixture of steam and oxygen. This can be realized in a simple manner by means of a siphon 5 and/or by a submerged siphon (not shown) at the point of entry of the gas mixture into the condenser 3. The liquid water then passes into a liquid separator or condensate collector 6, in which finely divided oxygen bubbles that have still remained are separated off by calming of the liquid. To improve pressure equalization in the gas phase, an equalization line can be taken, starting from the gas space of the condensate collector 6, to the top of the condenser 3 and/or to the oxygen line that goes off there. Oxygen collecting in the upper, gas phase of the condenser 3 is pure but moist. The moisture content of the oxygen can be adjusted ahead of the pressure control valve 7 by condensation at defined temperature, with the condensate advantageously being returned to the water circuit. The system pressure and the oxygen pressure are mandated at the pressure reducer and/or at the pressure control valve 7.

[0028] The liquid water is passed back from the condensate collector 6 into the evaporator 1; a sufficiently high fill level of the liquid water in condensate collector 6 and evaporator 1 prevents contact between oxygen and freshly generated steam in the gas phase. Since water at close to its boiling point contains only small amounts of dissolved gases, steam with only a low oxygen fraction is always generated in the evaporator 1, and so the low oxygen partial pressure (p.sub.1) that is needed for oxygen permeation is obtained in turn at the MIEC membrane.

[0029] Oxygen compression is therefore accomplished primarily through the pressure of the steam. Furthermore, there is an automatic compression through the oxygen which enters the half-open system via the membrane. This takes place not only at ambient pressure, i.e., at approximately 1 bar, but also at high superatmospheric pressure of the steam, since nonreturn valve 4 and liquid-phase barrier separate the isolated gaseous oxygen from the mixed-conduction membrane.

[0030] Even without opposing pressure at the gas outlet of the system, in other words at ambient pressure of the steam, therefore, the overall pressure in the system is increased. In the equilibrium case, a system pressure of around 1.2 bar can be achieved even in the first evaporation and condensation cycle. If an opposing pressure is deliberately set at the pressure control valve 7, and if, moreover, the evaporator 1 is supplied with more heat energy than is taken off at the condenser 3, then, in the same way as in a conventional steam generator, the pressure in the system gradually rises until it reaches this set opposing pressure. On account of the circuit, which is virtually a closed circuit in terms of the water, this pressure increase is transferred to the oxygen. Accordingly, there are no fundamental limits, but instead only technical limits, of the kind which also apply to technical steam generation, on the thermal compression of the oxygen.

[0031] In order to improve the energy efficiency of the method, the media flows are passed advantageously via various heat exchangers, as is shown schematically in FIG. 2. Because the heat capacities of air and steam differ considerably, the heat contained in the corresponding gas flows is preferably recovered within the respective gas flows. As a result, their volume flows can be varied largely independently of one another without greatly affecting heat recovery. Accordingly, the fresh air is initially utilized for condensing the steam in the condenser 3, and is subsequently passed via the first heat exchanger 11, so that the fresh air is further preheated by the hot waste air. The pressure losses, which are higher in comparison to the process according to FIG. 1, are overcome by means of an extractor fan 12 on the waste air side.

[0032] Afterheating in the second heat exchanger 10 is accomplished ahead of the membrane module 2 by means of high-temperature waste heat or through external heat input; the second heat exchanger 10 may also be integrated into the membrane module 2. Given that small leakage flows between incoming and outgoing air stream are not critical to the operating regime, preference is given here to using inexpensive regenerative heat exchangers with high heat recovery. After the second heat exchanger 10, the waste heat stream is used first to heat steam in the superheater 9 and thereafter to evaporate the water in the evaporator 1. The evaporator 1 is also supplied, furthermore, according to FIG. 2 with the residual heat of the waste air coming from the extractor fan 12.

[0033] The hot H.sub.2O(g)/O.sub.2 gas mixture emerging from the membrane module 2 is guided via the nonreturn valve 4 and used subsequently to heat the entering steam in the third heat exchanger 8. Thereafter it is supplied to the condenser 3 for the separation of the water. In the condenser 3, the water is largely condensed out and is introduced via the siphon 5 into the condensate collector 6. As in the embodiment according to FIG. 1, the system pressure and hence also the oxygen pressure are set on the pressure control valve 7.

[0034] The automatic compression of the gas mixture through the entry of the oxygen into the steam may be utilized not only for generating compressed oxygen but also for the combined generation of electricity. The process depicted in FIG. 3, accordingly, contains a conventional steam turbine 13 for power generation, instead of the third heat exchanger 8 and the condenser 3.

[0035] Since a major part of the generated pressure of the H.sub.2O(g)/O.sub.2 gas mixture declines over the steam turbine 13, the hydrostatic pressure difference between condensate collector 6 and evaporator 1 is no longer sufficient to fill the evaporator 1 in the case of energy utilization. Additionally, therefore, a pump 14 is used in order to bring liquid water into the evaporator 1.

[0036] Relative to conventional energy generation via steam generation and turbine, the process of the invention offers the advantage that not only power but also superatmospheric-pressure oxygen are generated. Furthermore, because of the additional self-compression of the oxygen, the system pressure is typically slightly above the pressure which in the case of a conventional steam power plant would be achieved for the same temperature level and/or for comparable heat input.

[0037] According to FIG. 4, a module for thermal generation and compression of oxygen in a pressure vessel 16 is shown, allowing 1 m.sup.3/h oxygen with 7 bar superatmospheric pressure to be generated.

[0038] The schematic construction is shown in accordance with FIG. 4. 400 membrane tubes 15 made of the BSCF material are used, with a length of 500 mm, an external diameter of 10 mm, and a wall thickness of 1 mm, in a temperature-stable and pressure-stable pressure vessel 16, which contains the majority of the process engineering components, such as membrane module 2, evaporator 1, condensate collector 6, siphon 5, nonreturn valve 4. The pressure vessel 16 is in turn introduced into a combustion chamber or flue gas channel (not shown) or is contacted therewith in such a way that a temperature of approximately 850° C. is attained in the pressure vessel 16. For this purpose, it is also possible for waste heat to be coupled otherwise into the pressure vessel 16. The membrane tubes 15 installed in the pressure vessel 16 are thereby heated to a temperature of around 850° C. over a length of at least 20 cm.

[0039] The open ends of the membrane tubes 15 are sealed in a gastight manner into a baseplate 17; sealing 18 may take place by means of conventional polymer seals or welding. Baseplate 17 and housing are designed so that the thermal stability of the seal 18 is not jeopardized and so that effective separation is ensured between the steam superatmospheric pressure region 19 and the waste air region 20.

[0040] Temperature-resistant air introduction tubes 21 made from scale-resistant steel or ceramic are inserted into the membrane tubes 15. in the hot region of the pressure vessel 16, the air introduction tubes 21 end in each case about 2 cm before the inner end of the single-sidedly closed membrane tube 15. The air introduction tubes 21 are passed through the waste air region 20 in a gastight manner The air introduction tubes 21 guide fresh air via the air introduction openings 22 at room temperature into the membrane tubes 15. Following the emergence of the fresh air from the air introduction tube 21 at the hot membrane end, the fresh air has already been preheated to around 850° C.

[0041] Located on the baseplate 17 in the pressure vessel 16 is a water reservoir with a height of around 2 cm that constitutes an evaporator 1 integrated into the pressure vessel 16. From the hot region of the pressure vessel 16, heat conduction and radiation heat the water reservoir, and the water evaporates. The steam passes into the hot module region and acts as a low-oxygen sweep gas.

[0042] The oxygen partial pressure ratio between the inside of the membrane tube (about 21% O.sub.2) and the steam superatmospheric pressure region 19, with about 0% O.sub.2, and also the high temperatures, result in permeation of the oxygen through the membrane wall into the steam. The oxygen-depleted air in the membrane tube 15 is passed into the waste air region 20 in the gap between the membrane tube 15 and the air introduction tube 21, and leaves the pressure vessel 16 at the waste air outlet 23. The steam becomes enriched with the permeated oxygen, and an H.sub.2O(g)/O.sub.2 mixture 24 is formed in the top part of the pressure vessel 16. This mixture 24 is guided through the nonreturn valve 4 into the outer region of the pressure vessel 16 and subsequently through a submersion (siphon 5) within the condensate collector 6. The nonreturn valve 4 consists of a simple narrowing of an open cross section in the gas space, which for the throughputs specified below produces a flow rate of not less than 0.3 m/s. The gas stream composed of water and oxygen, after the submersion in hot liquid water, passes to the air-cooled condenser 3, where water is predominantly condensed out. Together with the water reservoir and/or the evaporator 1, the condensate collector 6 forms a common liquid container, with the component containers being connected to one another via a further submerged siphon within the liquid phase.

[0043] Excess liquid water from the condenser 3 flows back into the water reservoir. The gaseous oxygen can be taken off with superatmospheric pressure after the pressure control valve 7, at the oxygen withdrawal port 25.

[0044] In order to increase the rate of evaporation of the water, a capillary-active wick 26 can be used, which by capillary suction transports water from the water reservoir into the hot region of the module. The transfer of heat from the hot region of the module to the liquid water in the region of the evaporation zone may be additionally improved by means of a heat exchanger 27. If the heat exchanger 27 is configured, for example, as a heat pipe, substantially higher evaporation rates and higher oxygen production rates can be achieved as a result.

[0045] Further heat exchangers 28 may be used in order to transfer the heat of condensation from the hot H.sub.2O(g)/O.sub.2 mixture 24 from the steam into liquid water. As a result, a major part of the heat of condensation can be recovered and used for evaporation of the water, thereby improving the energy efficiency of the separation process.

[0046] Initial operation is accomplished by setting the pressure control valve 7 to 7 bar, reducing the air cooling of the condenser 3 by lining it with insulating material, and starting to heat the module. In the pressure vessel 16, the pressure of the resultant steam rises until it reaches the set superatmospheric pressure of 7 bar; in the water reservoir and/or in the evaporator 1, the evaporation temperature rises to about 170° C. When the operating temperature of 850° C. is reached in the hot reactor zone, the further supply of heat and the air cooling at the condenser 3 are set such that around 35 liters of liquid water evaporate per hour, meaning that around 45 standard m.sup.3 of steam per hour are passed in the circuit. Moreover, the membrane reactor is supplied with around 45 standard m.sup.3 of fresh air per hour.

[0047] After the initial operation time, the absolute pressure in the system is about 8 bar. Over the length of the membrane tubes 15, about 1 standard in.sup.3 of oxygen per hour transfers from the air into the steam. The partial pressure of the oxygen in the steam after membrane contact reaches about 180 mbar. After the pressure control valve, 1 standard m.sup.3 of oxygen per hour with a superatmospheric pressure of 7 bar is available.

LIST OF REFERENCE NUMERALS

[0048] 1 evaporator [0049] 2 membrane module [0050] 3 condenser [0051] 4 nonreturn valve [0052] 5 siphon [0053] 6 condensate collector [0054] 7 pressure control valve [0055] 8 third heat exchanger [0056] 9 superheater [0057] 10 second heat exchanger [0058] 11 first heat exchanger [0059] 12 extractor fan [0060] 13 steam turbine [0061] 14 pump [0062] 15 membrane tubes [0063] 16 pressure vessel [0064] 17 baseplate [0065] 18 seal [0066] 19 steam superatmospheric pressure region [0067] 20 waste air region [0068] 21 air introduction tube [0069] 22 air introduction openings [0070] 23 waste air exit [0071] 24 H.sub.2O(g)/O.sub.2 mixture [0072] 25 oxygen withdrawal port [0073] 26 capillary-active wick [0074] 27 heat exchanger [0075] 28 further heat exchangers