Method for Separating Gases in an Oxy-Fuel Combustion Process by Using Oxygen-Permeable Membranes
20220001326 · 2022-01-06
Inventors
- José Manuel Serra Alfaro (Alaquàs (Valencia), ES)
- Isaac Herráiz Cardona (Alaquàs (Valencia), ES)
- David Catalán Martínez (Alaquàs (Valencia), ES)
Cpc classification
F23L7/00
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
B01D53/228
PERFORMING OPERATIONS; TRANSPORTING
F02C3/20
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
Y02E20/34
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
C01B3/34
CHEMISTRY; METALLURGY
C01B2203/041
CHEMISTRY; METALLURGY
C01B2203/0283
CHEMISTRY; METALLURGY
B01D53/265
PERFORMING OPERATIONS; TRANSPORTING
C01B2203/0233
CHEMISTRY; METALLURGY
Y02T50/60
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
F02C3/08
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
B01D53/229
PERFORMING OPERATIONS; TRANSPORTING
Y02P30/00
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
International classification
F02C3/20
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
Abstract
The invention relates to a method for separating gases which comprises: a first step in which a gas fuel stream comprising combustible substances that produce gas products when oxidised, and an oxygen-rich inlet stream are passed through at least two modules of oxygen-separating ceramic membranes, such that the two streams come into contact through the membranes and exchange heat; a second step of selective diffusion of oxygen from the oxygen-rich stream to the fuel stream, such that the outlet streams from the membrane modules are an oxygen-depleted or completely oxygen-free stream and a partially or completely oxidised stream; and a third step of recovery of at least two separate outlet streams of at least two gases selected from oxygen, nitrogen, carbon dioxide and hydrogen.
Claims
1. A process to selectively generate and separate gases, comprising: a first step in which a gas-phase fuel stream is passed, comprising combustible substances whose oxidation gives rise to gaseous products, and an oxygen-rich input stream through at least two oxygen separation ceramic membrane modules, such that the two streams come into contact through the membranes and a heat exchange takes place between them, a second step of selective oxygen diffusion from the oxygen-rich stream to the fuel stream, and such that the output streams from the membrane modules are, on the one hand, an oxygen-depleted or completely oxygen-free stream and, on the other hand, a partially oxidized or completely oxidized stream, and a third step of recovery of at least two separate outlet streams of at least two gases selected from oxygen, nitrogen, carbon dioxide and hydrogen.
2. The process according to claim 1, wherein the oxygen-rich input stream is selected from air, water vapor, and combinations thereof.
3. The process according to claim 1, wherein in the second step the oxidation of the fuel is complete.
4. The process according to claim 1, wherein the oxygen-rich input stream is air and the two separate output streams are nitrogen and carbon dioxide.
5. The process according to claim 1, wherein the oxygen-rich input stream is air and there are at least three separate output streams: oxygen, nitrogen, and carbon dioxide.
6. The process according to claim 1, wherein the oxygen-rich input stream is water vapor and the two separate outlet streams are hydrogen and carbon dioxide.
7. The process according to claim 1, wherein the oxygen-rich stream is water vapor and there are at least three separate output streams: they are oxygen, hydrogen and carbon dioxide.
8. The process according to claim 1, wherein the gas exchange between the two input streams to the membrane modules is carried out at a temperature between 600° C. and 1500° C.
9. The process according to claim 1, further comprising a pressurization step of the input streams in a first gas compressor device, at absolute pressures between 2 and 15 bar, obtaining pressurized input streams.
10. The process according to claim 1, further comprising a pre-heating step of the pressurized input streams, with heat given off by the output streams, obtaining pre-heated pressurized input streams.
11. The process according to claim 1, wherein the flows of the gaseous combustible stream and the oxygen-rich stream are arranged in countercurrent.
12.-13. (canceled)
14. The process according to claim 1, which is carried out on at least three modules selected from: a first membrane module in which the gasified combustible stream is partially oxidized, a second membrane module in which the gasified combustible stream is completely oxidized, a third membrane module in which the oxygen extraction is carried out.
15. The process according to claim 14, wherein in the second membrane module, cross flows, co-current flows, or counter current flows are used.
16.-17. (canceled)
18. The process according to claim 1, wherein a first membrane module, a second membrane module, and a third membrane module are used, and wherein: the entire oxygen-rich input stream coming from the second heat exchanger is fed into the second membrane module, the oxygen-depleted stream leaving the second membrane is metered by a system of valves that partially circulate this stream: to the first membrane module as a stream supplying oxygen as an oxygen-depleted stream containing an amount of oxygen less than the stoichiometric amount to completely oxidize the gasified fuel stream, and to the third membrane module as a stream supplying oxygen to the third module and a turbine.
19. The process according to claim 18, wherein the second and third membrane modules are used, the entire heated pressurized, fuel gasified input stream coming from the first heat exchanger is fed into the second membrane module, and the entire oxygen-rich input stream coming from the second heat exchanger is fed into the second membrane module.
20. The process according to claim 18, wherein: only the first and second membrane modules are used, the oxygen depleted output stream from the second membrane module is recirculated to a turbine as the turbine input stream.
21. (canceled)
22. The process according to claim 18, wherein the first and third membrane modules are used, the partially oxidized fuel gas stream leaving the first membrane module and the oxygen depleted output stream from the third membrane module are introduced into a combustor to finish oxidizing the combustible material of the partially oxidized gas stream, and the output stream of the combustor is introduced into the turbine.
23. The process according to claim 18, wherein additional membrane modules are used, in addition to the first, second and third membrane modules, wherein the additional modules purify the gas streams produced in the first membrane module and the second membrane module by removing oxygen therefrom, and the combustible gaseous stream enters the additional modules as an entrainment stream.
24. The process according to claim 23, wherein the membrane modules have a countercurrent flow distribution to ensure the complete exchange of oxygen from the streams to be purified, to the fuel streams.
25. (canceled)
26. The process according to claim 1, wherein the source of the combustible gasified stream is biomass, which is gasified by a thermochemical reactor, the input streams to the thermochemical reactor being: biomass an entrainment stream consisting of an inert gas, and optionally water vapor, and, optionally, an oxygen-rich input stream.
27. The process according to claim 1, wherein the input stream, containing combustible materials, comprises one or more products selected from CO, H2, H2S, methane, liquefied petroleum gases, alcohols, olefins, peroxides, aromatic compounds, organic acids, organic amines, naphtha, asphalt, bituminous, diesel, vegetable, animal or mineral oils or fats, coals, and mixtures thereof.
28. An installation for carrying out a process to selectively generate and separate gases, wherein the process comprises: a first step in which a gas-phase fuel stream is passed, comprising combustible substances whose oxidation gives rise to gaseous products, and an oxygen-rich input stream through at least two oxygen separation ceramic membrane modules, such that the two streams come into contact through the membranes and a heat exchange takes place between them, a second step of selective oxygen diffusion from the oxygen-rich stream to the fuel stream, and such that the output streams from the membrane modules are, on the one hand, an oxygen-depleted or completely oxygen-free stream and, on the other hand, a partially oxidized or completely oxidized stream, and a third step of recovery of at least two separate outlet streams of at least two gases selected from oxygen, nitrogen, carbon dioxide and hydrogen, the installation comprising: two ceramic oxygen separation membrane modules, gas compressors that drive the input streams to the membrane modules, heat exchanger devices between incoming or outgoing gas streams in membrane modules, a turbine arranged to receive at least gas from one of the membrane modules and produce work, and at least two lines of separate individual output gas streams from the oxygen separation membrane modules, wherein each oxygen separation membrane module comprises a set of parallel flat ceramic membranes.
29. The installation according to claim 28, further including at least one membrane module based on ceramic electronic and ionic conductors, and composed of parallel and flat channels that facilitate contact between gaseous currents isolated by the membrane and whose sole input is a stream rich in oxygen, and as outputs (i) a rejection stream, depleted in oxygen with respect to the input stream, and (ii) an oxygen rich stream with purity greater than 95% and which is under vacuum between 1 and 750 mbar-
30. The installation according to claim 28, wherein the membrane modules comprise separation membranes based on ceramic ionic and electronic conductors, and porous ceramic supports.
31. The installation according to claim 28, wherein the membrane modules comprise a catalyst for the effective oxidation of the combustible components with the oxygen diffusing through the membrane.
32. The installation according to claim 28, wherein the flow of the two streams, which facilitates the exchange of matter and heat, in the membrane modules is countercurrent flow and sufficient length is provided for effective exchange.
33. The installation according to claim 28, further comprising at least one separation module based on porous polymeric or inorganic membranes selective to nitrogen diffusion and allowing to obtain at temperatures below 400° C. a nitrogen enriched stream from a pressurized air supply.
34. (canceled)
35. The installation according to claim 28 comprising at least: a first oxygen separation membrane module, which has two inlets for a first gasified combustible stream and an oxygen rich input stream. a first gas compressor allowing the combustible gaseous stream to be pressurized, and that leaves the compressor as a pressurized combustible gaseous stream, towards a first heat exchanger device that allows the pressurized fuel gas stream to be heated and that leaves the exchanger as a preheated pressurized fuel gas stream a second gas compressor that allows the oxygen-rich input stream to be pressurized, leaving the compressor as a pressurized oxygen-rich input stream, a turbine arranged to receive at least gas from one of the membrane modules and produce work a countercurrent gas heat exchanger device that allows heating: the oxygen-rich input stream pressurized to the input temperature to the first membrane module, and exiting the heat exchanger as a heated pressurized oxygen-rich input stream, and an oxygen-depleted stream coming from a turbine at least two separate individual gas output streamlines from a second and a third oxygen separation membrane modules and wherein each oxygen separating membrane module comprises a set of parallel planar membranes.
36. The installation according to claim 28, wherein at least one compressor and one turbine are axially coupled to use the mechanical energy of the expansion in the compression of a gaseous stream.
37. (canceled)
38. The installation according to claim 28, comprising three membrane modules and wherein the output stream from the second membrane module is separated into three streamlines, each comprising a metering valve, and two out of the three streamlines lead to the first or second module allowing gas recirculation, and the third stream line leads to the third membrane module, allowing the process to advance.
39.-40. (canceled)
Description
BRIEF DESCRIPTION OF THE FIGURES
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Results for a membrane module of a total membrane area of 380 cm.sup.2 and a supply of CO and CO.sub.2 (57.1% CO) for stream (5) with the input streams at 700° C.
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[0202] Light gas oil is defined as a by-product obtained from atmospheric distillation of petroleum that starts boiling between 175 and 200° C. and ends between 320 and 350° C.
[0203] Medium gas oil: intermediate is defined as a by-product obtained from the distillation of petroleum, which boils within a range comprised between the boiling point of light gas oil and the boiling point of heavy gas oil.
[0204] Heavy gas oil is defined as the residual product of petroleum distillation, whose boiling range is between 423 and 600° C.
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EXAMPLES
[0220]
[0221] All embodiments of the installation of the invention use the same references for the elements common to all of them, which are detailed below:
[0222] The installation has two main conduits or input streamlines: an input material stream—combustible gaseous stream—(C1) and an oxygen rich stream (C2).
[0223] The installation has several outlet conduits or lines: the oxygen-depleted stream (C3) and each of the gaseous streams that are obtained depending on the process application.
[0224] The combustible gaseous stream (C1) is driven by a first gas compressor (2).
[0225] The input stream to the first compressor (2) is the input combustible gaseous stream (1). The output stream of the first compressor (2) is the pressurized fuel gas phase stream (3).
[0226] The pressurized combustible gaseous stream (3) is heated until the input temperature, to the membrane modules by means of a first heat exchanger device (4).
[0227] The input stream to the first heat exchanger (4) is the combustible gaseous stream (3) coming from the first compressor (2).
[0228] The output stream of the first heat exchanger system (4) is the preheated pressurized combustible gaseous stream (5).
[0229] The oxygen-rich stream (C2) (27) is driven by a second gas compressor (28).
[0230] The input stream to the second compressor (28) is the oxygen rich input stream (27).
[0231] The output stream from the second compressor (28) is the pressurized oxygen-rich input stream (30).
[0232] The pressurized oxygen-rich stream (30) is heated until the input temperature of the membrane modules by means of a gas heat exchanger (31).
[0233] The input streams to the heat exchanger device (31) are the oxygen-rich stream (30) coming from the compressor (28) and an oxygen-depleted stream (32) coming from the turbine (33).
[0234] One of the output streams of the heat exchanger system (31) is the oxygen-depleted stream (C3), which reaches the outlet through streamline (35). One of the output streams of the heat exchanger system (31) is the oxygen-rich stream (34) To optimize the pressurization (and depressurization) of the oxygen-rich line, the compressor (28) and the turbine (33) can be connected to the same shaft (29).
Example 1
[0235]
[0236] The installation has in this particular case three main oxygen permeation ceramic membrane modules (M.sub.1, M.sub.2 and M.sub.3), also designated as (6), (10) and (15). These modules have parallel flat membranes whose total area is distributed in different sections within each module. The arrangement of the streams, the geometry of the module, and the trajectory of the streams of each module are focused to optimize the process it houses and to optimize the heat transfer between the different streams that pass through it.
[0237] The input material stream (C1) (gasified stream, or fuel gas phase stream) contains combustible substances whose complete oxidation by reaction with oxygen produces gaseous compounds. The oxygen-rich input stream (C2) is composed primarily of O.sub.2 and N.sub.2.
[0238] The combustible gaseous stream (3) is heated until the input temperature to the first membrane module (6) by the first heat exchanger device (4). The input stream to the heat exchanger (4) is the combustible gaseous stream (3) coming from the compressor (2). The output stream of the heat exchanger (4) is the heated pressurized combustible gaseous stream (5).
[0239] The oxygen-rich stream (C2) (30) is heated until the input temperature of the M.sub.1 module by means of a second heat exchanger (31). The input streams to the heat exchanger (31) are the oxygen-rich stream (30) coming from the compressor (28) and the oxygen-depleted stream (32) coming from the turbine (33). In this case there are two output streams from the second heat exchanger system (31), which are an oxygen-rich stream (34) and the oxygen-depleted output stream (35).
[0240] The metering or control of the volumetric flow of the incoming and outgoing gaseous streams to the oxygen permeation membrane modules (6) and (10) is carried out by means of a valve system (38 and 39). This dosage must be carried out considering that a quantity of air containing oxygen quantities less than the stoichiometric quantity is introduced to the first membrane module (6) to completely oxidize the fuel gas, while a quantity of air containing an excess of oxygen with respect to the stoichiometric quantity is introduced to the second membrane module (10). Consequently, the heated oxygen-rich stream (34) is divided into two streams (36 and 37). The input stream to the metering valve (38) of the first membrane module (6) is an oxygen-rich stream (36). The output stream from the metering valve (38) of the first membrane module is an oxygen-rich stream (7). The input stream (37) to the metering valve (39) of the second membrane module (10) is an oxygen-rich stream (37). The output stream from the metering valve (39) of the second membrane module (10) is an oxygen-rich stream (11).
[0241] The first membrane module (6) is intended to produce—according to this particular embodiment—nitrogen from the combustible gaseous stream and an oxygen-rich stream. The input streams to the membrane module (6) are the combustible gaseous stream (5), which comes from the exchanger (4) and the oxygen-rich stream (7) which comes from the metering valve (38). The output streams from the membrane module (6) are the partially oxidized combustible gasified stream (8) and the oxygen-depleted stream (9) whose composition is practically pure N.sub.2. In this embodiment of the process, the oxygen-rich stream (7) is introduced in an amount less than the minimum amount to oxidize all the combustible material carried by the combustible gaseous stream (5). Considering that an amount of oxygen less than the stoichiometric amount of the combustible gaseous stream (5) has been introduced, the chamber of the combustible gaseous stream will maintain a very low oxygen pressure (of the order of mbar) and, therefore, the driving force of the oxygen transport process will be very high. In this module (6) it must be ensured that the outgoing oxygen-depleted stream (9) is practically pure nitrogen and that the heat transfer between the streams that pass through the module is efficient. For this purpose, the input streams to the M.sub.1 module (6) (the combustible gaseous stream (5) and the air stream (7)) are arranged in counter-current. The oxygen exchanged through the membrane reacts with the combustible material by increasing the temperature, thereby improving the oxygen transport properties of the material. If necessary and in order to avoid excessive heating due to the oxidation of combustible gases, it is possible, optionally, to recirculate part of the carbon dioxide or nitrogen obtained in the process and thus dilute the combustible gaseous stream (5) and absorb the oxidation heat. Considering that the combustible material of the combustible gaseous stream (5) has a composition of CxHyOz, the maximum nitrogen production that could be achieved is
mole of N.sub.2 for each mole of combustible material. The variables x, y, z can take any value that is technically possible.
[0242] The second membrane module (10) is intended to completely oxidize the combustible gaseous stream (8) that leaves the first membrane module (6) partially oxidized. For this purpose, an excess (in flow rate) of the oxygen rich stream with respect to the minimum amount to oxidize all the combustible material carried by the combustible gaseous stream (8), is introduced into the process. The input streams to the second membrane module (10) are the combustible gaseous stream (8), which comes from the outlet of the first membrane module (6), and the oxygen-rich stream (11). The output streams from the second membrane module (10) are the combustible gaseous stream (13), which is mainly composed of CO.sub.2 and water vapor (unless the combustible material of the gasified stream be CO, in which case the output combustible gaseous stream will be composed mostly of CO.sub.2), and the oxygen stream (14), depleted in oxygen with respect to C2. The oxygen exchanged through the membrane reacts with the combustible material increasing the temperature, thereby improving the oxygen transport properties of the material. The amount of air introduced into the second module (10) M.sub.2 must be high enough to ensure that the exchanged oxygen causes complete combustion of all the combustible material contained in the combustible gaseous stream (i.e., that at the outlet of M.sub.2 the hydrocarbon and carbon monoxide content of this stream is negligible) and to avoid excessive heating of the module due to combustion processes, through a dilution effect and heat distribution in a large volumetric flow rate. Finally, for this module (10) the gases can be distributed in cross flows, in co-current flows or in countercurrent flows. The final choice of the module is subject to the needs: for example, considering that oxidation processes can generate excessive temperatures within the module, a co-current distribution may be necessary to allow a more gradual dosage of the oxygen exchanged by the membranes of the module and, in this way, reduce and control the progress of oxidation reactions to avoid excessive temperature increases.
[0243] The third membrane module (15) is intended to extract oxygen from an oxygen-rich stream. The input stream to the membrane module (15) is the oxygen-depleted stream (14) relative to the stream (C2) coming from the second membrane module (10). The output streams from the third membrane module (15) are the oxygen-depleted stream (16) and the extracted oxygen (17). The oxygen is extracted by imposing a vacuum in the entrainment chamber and thus achieving a high driving force. As no additional phenomena occur, this module works isothermally as long as it is well thermally insulated.
[0244] The completely oxidized combustible gaseous stream (13) coming from the second membrane module (10) is mainly composed of carbon dioxide and water vapor. For the separation thereof, the water vapor is condensed by cooling the stream to room temperature (15-25° C.). A heat exchanger device (22) is used for this purpose. The input stream to the heat exchanger system (22) is the completely oxidized combustible gaseous stream (13) coming from the second membrane module (10). The output stream to the heat exchanger system (22) is the completely oxidized combustible gaseous stream (23).
[0245] A condenser-separator (24) is optionally used to evacuate the condensed liquid water from the completely oxidized combustible gaseous stream (23) coming from the third module (15) and which has passed through the heat exchanger (22). The input stream to the condenser-separator (24) is the completely oxidized combustible gaseous stream (23) that comes from the heat exchanger device (22). The output streams of the condenser-separator (24) are the completely oxidized combustible gaseous stream (25), mainly composed of CO.sub.2, and a liquid water stream (26).
[0246] Alternatively, in the case where the starting combustible gaseous stream (C1) is a mixture of CO and CO.sub.2, the completely oxidized combustible gaseous stream (13) coming from the second membrane module (10) will be composed mainly of CO.sub.2, thus that the separator condenser (24) is not needed and the output stream (23) of the heat exchanger device (22) would be the final CO.sub.2 stream.
[0247] The oxygen stream (17) extracted from the third module (15) must be cooled before being introduced into a vacuum generation system (20). For this purpose, a device with at least one heat exchanger (18) is required to lower the temperature of the oxygen stream to approximately room temperature. The input stream to the heat exchanger device (18) is the oxygen stream (17) that comes from the outlet of the third membrane module (15). The output stream of the heat exchanger device (18) is an oxygen stream (19). Finally, the vacuum generation unit (20) drives the oxygen and pressurizes it, inducing a depression or vacuum upstream. The input stream for the vacuum generation system (20) is the oxygen stream (19) that comes from the heat exchanger device (18). The output stream for the vacuum unit (20) is the oxygen stream at the required service pressure.
[0248] Finally, the oxygen-depleted stream (16) is introduced into a turbine (33) for its energy upgrading. The outlet stream from the turbine (33) is the oxygen-depleted stream (32) that comes from the third membrane module (15). To optimize the pressurization (and depressurization) of the oxygen-rich line, the compressor (28) and the turbine (33) can be connected to the same shaft (29).
[0249]
[0250] This means that the hottest areas and the areas with the greatest driving force are in the same area of the module. Consequently, for countercurrent distribution, the oxygen transport phenomena through the membrane are activated as the driving force increases.
[0251]
[0252]
Example 2
[0253] A second alternative of the process according to the invention is shown in
[0254] This variant of the process presents an alternative in terms of the dosage of the oxygen rich stream in the modules M.sub.1 and M.sub.2. In this case, the oxygen-rich stream (11) in the heat exchanger device (31) is introduced into the second membrane module (10). The oxygen-depleted stream (14) leaving the second membrane module (10) is metered by a metering valve system (44, 45 and 46) to recirculate this stream from the first membrane module (6), to the third module membrane (15) and the turbine (33). So, the depleted oxygen stream (14) that comes from the second membrane module (10) is divided into three streams (41, 42 and 43) that are introduced into the metering valves. The input stream to the first metering valve (44) is a fraction of the depleted air stream (41). The input stream to the second metering valve (45) is a fraction of the depleted oxygen stream (42) with respect to (C2) and the output stream is the oxygen-rich stream (48) entering the third membrane module (15). The oxygen-depleted stream (16) coming from the third membrane module (15) and the output stream from the first metering valve (47) are joined and introduced into an oxygen-depleted stream (40) that is introduced into the turbine (33). The input stream to the third metering valve (46) is a fraction of the oxygen-depleted stream (43) coming from the second membrane module (10). The output stream from the third metering valve is the oxygen-rich stream (7) entering the first membrane module. This stream (7), as in the case of example 1, must contain an amount of oxygen less than the stoichiometric amount to completely oxidize the combustible stream (5), it is supplied to the third membrane module (15) as stream (48) which supplies oxygen to the module (15) and to the turbine (33). In this way, the metering of the metering valves (44, 45, and 46) is carried out considering that the depleted oxygen output stream (9) must be practically pure N.sub.2 and the amount of oxygen (21) that is desired to be produced.
Example 3
[0255]
Example 4
[0256]
[0257] Additionally, depending on the final application of the gaseous streams obtained, the process can optionally incorporate a pressurization system for the different streams that are produced as shown in the figure. Therefore, a variant of this embodiment would be an embodiment in which the nitrogen and carbon dioxide streams obtained are not pressurized and therefore the compressors (49) and (51) would not be present.
[0258] In the case that the stream is pressurized, for the CO.sub.2 pressurization system (49), the input stream is the CO.sub.2 stream (25) that comes from the condenser-separator (24) and the output stream is a CO.sub.2 stream (50) at the required operating pressure. The nitrogen (9) (oxygen depleted stream) that leaves the first membrane module (6) is cooled to practically room temperature by means of a heat exchanger (73), from which it leaves as an N.sub.2 stream (74). Finally, a N.sub.2 pressurization system (51) is provided. The input stream to this pressurization system (51) is the N.sub.2 stream (74) leaving the heat exchanger (73). The output stream of the N.sub.2 pressurization system (51) is the N.sub.2 stream (52) at the required operating pressure.
[0259] Dosing or volumetric flow control of the incoming and outgoing gaseous streams to the oxygen permeation membrane modules (6) M.sub.1 and M.sub.2 (10) is carried out by means of a system of valves (38 and 39) as in Example 1.
Example 5
[0260]
[0261] Dosing or volumetric flow control of the incoming and outgoing gaseous streams to the oxygen permeation membrane modules M.sub.1 and M.sub.2 is carried out by means of a system of valves (38 and 39) as in the case of example 1.
[0262] The nitrogen (9) (oxygen-depleted stream) that leaves the first membrane module (6) is cooled and pressurized in the same way and with the same components that are used in example 4, shown in
Example 6
[0263]
[0264] According to a further alternative, another way of purifying the CO.sub.2 and/or N.sub.2 streams can be the use of polymeric oxygen permeation membranes. In this case, the streams to be purified must be cooled to atmospheric temperature and pressurized in order to carry out the process.
[0265] The completely oxidized combustible gaseous stream (13) that comes from the second membrane module (10) is mainly composed of carbon dioxide and water vapor, as in the case of example 1. The same components and procedure are used for its separation as in the case of example 1.
[0266] Dosing or volumetric flow control of the incoming and outgoing gaseous streams to the oxygen permeation membrane modules M.sub.1 and M.sub.2 is carried out by means of a system of valves (38 and 39) as in the case of example 1.
Example 7
[0267]
Example 8
[0268] Membrane module to produce N.sub.2 (not shown in the figures) from air as an oxygen-rich stream and a combustible gaseous stream composed of CO and CO.sub.2. The initial input fuel gas stream is composed of 57.10% CO in CO.sub.2. The initial input combustible gaseous stream is diluted with CO.sub.2 to reduce the increase in temperature due to oxidation reactions such that
where r is the molar ratio between the input flow rate of diluted CO.sub.2 (F.sub.CO2) and the initial fuel gaseous input flow rate (F.sub.i). Different dilutions from r=2.5 to r=10 have been tested. All the streams enter at 700° C. The airline is pressurized to 2.5 bar absolute pressure. Amounts of air at 25%, 50% and 75% of the stoichiometric amount of air have been used. The considered membrane module has 5 membranes of 380 cm.sup.2 per membrane. Co-current and counter-current flow distribution has been considered. The longitudinal distance between the inlet of the module chambers and the outlet of each chamber is 20 cm. The transport of oxygen through the membrane has been simulated from the following equation:
wherein J.sub.O2 is the molar flow of oxygen per unit area, K is the permeability constant, pair is the total pressure in the air chamber, p.sub.entrainment is the pressure in the entrainment chamber and x.sub.O2, is the mole fraction of oxygen in chamber i (i is general and indicates the chamber in question, it can be air or entrainment.), T is the temperature, x is the longitudinal coordinate and tol is a parameter to avoid indeterminates in the calculation set at 10.sup.−5. K is calculated as a function of temperature to be able to predict the improvement in permeation as the temperature increases.
[0269] The heat transmission has been carried out considering the thermal conduction between the two membrane walls, using the equation:
wherein k.sub.MEMB is the thermal conductivity of the membrane, dA is the membrane area differential, dx is the length differential, T.sub.i(x) is the temperature in chamber i (air or entrainment) at position x, and x represents the longitudinal position.
[0270] The oxidation reaction that takes place in the entrainment chamber (69) is: CO+0.5O.sub.2.fwdarw.CO.sub.2. The heat of reaction has been calculated using the reaction enthalpy of the combustion reaction. Results are shown in
Example 9
[0271] Membrane module for complete oxidation of a stream with combustible material from air as an oxygen-rich stream and a combustible gaseous stream composed of CO and CO.sub.2. The gaseous combustible stream is made up of 9.5% CO in CO.sub.2. The temperature of the input streams was varied such that the air stream was introduced at temperatures from 600° C. to 815° C. and the entrainment current was introduced at 600° C. and 700° C. The airline was pressurized at 2.5 bar absolute pressure. Air is introduced in excess, where A is the molar ratio between the input air molar flow rate (F.sub.air) and the stoichiometric air molar flow rate (F.sub.stoichiometric air), such that
Different air excesses were tested, from A=5 to A=20. The considered membrane module has 5 membranes of 380 cm.sup.2 per membrane. Co-current and countercurrent distribution has been considered. The output temperatures of the air stream and the maximum temperature the system reaches were measured. The longitudinal distance between the inlet of the module chambers and the outlet of each chamber is 20 cm. The transport of oxygen through the membrane was simulated using the following equation:
wherein J.sub.O2 is the molar flow of oxygen per unit area, K is the permeability constant, p.sub.air is the total pressure in the air chamber, p.sub.entrainment is the pressure in the entrainment chamber and x.sub.O2, is the mole fraction of oxygen in chamber i (air or drag), T is the temperature, x is the longitudinal coordinate and tol is a parameter to avoid indeterminates in the calculation, set at 10.sup.−5. K is calculated as a function of temperature to be able to predict the improvement in permeation as the temperature increases.
[0272] The heat transmission was carried out considering the thermal conduction between the two membrane walls, using the equation:
where k.sub.MEMB is the thermal conductivity of the membrane, dA is the membrane area differential, dx is the differential length, T.sub.i(x) is the temperature in chamber i (air or entrainment) at position x and x represents the longitudinal position. The oxidation reaction that occurs in the entrainment chamber (69) is: CO+0.5O.sub.2.fwdarw.CO.sub.2. The reaction heat was calculated using the reaction enthalpy of the combustion reaction. The results are shown in
Example 10
[0273] Membrane module for obtaining oxygen from air as an oxygen rich stream and imposing a vacuum.
[0274] This example is intended to illustrate the third membrane module of Examples 1, 2, 3, 5, 6, and 7. In these cases, it is an O.sub.2 permeation from an O.sub.2 rich stream.
[0275] The temperature of the input stream was varied from 900° C. to 1050° C. Different pressurizations of the airline were tested from 1 bar to 5 bar absolute pressure.
[0276] Two vacuum pressures have been tested: 50 mbar and 100 mbar. Different membrane areas were studied (from 0.5 m.sup.3 to 10 m.sup.3). The equivalence between membrane area and number of membranes was carried out considering 380 cm.sup.2 membranes. The oxygen transport through the membrane was simulated using the following equation:
wherein J.sub.O2 is the molar flow of oxygen per unit area, K is the permeability constant, pair is the total pressure in the air chamber, p.sub.vacuum is the pressure in the entrainment chamber and x.sub.O2, is the mole fraction of oxygen in chamber i (air or vacuum), T is the temperature, and x is the longitudinal coordinate. K is calculated as a function of temperature to be able to predict the improvement in permeation as the temperature increases. The results are shown in
Example 11
[0277] Flat oxygen permeation membrane modules were designed with various configurations shown in
[0278]
[0279]
[0280]
[0281]