CN116750715A - Oxygen permeable membrane hydrogen production method and application - Google Patents
Oxygen permeable membrane hydrogen production method and application Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 197
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 165
- 239000001301 oxygen Substances 0.000 title claims abstract description 165
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 165
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 137
- 239000001257 hydrogen Substances 0.000 title claims abstract description 131
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 131
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 50
- 239000007789 gas Substances 0.000 claims abstract description 76
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000012495 reaction gas Substances 0.000 claims abstract description 43
- 239000000446 fuel Substances 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims description 10
- 239000010410 layer Substances 0.000 claims description 7
- 239000011533 mixed conductor Substances 0.000 claims description 3
- 239000002356 single layer Substances 0.000 claims description 3
- 238000005265 energy consumption Methods 0.000 abstract description 7
- 239000000203 mixture Substances 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 7
- 238000000926 separation method Methods 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 239000005431 greenhouse gas Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
- C01B3/045—Decomposition of water in gaseous phase
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/506—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification at low temperatures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/0495—Composition of the impurity the impurity being water
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Hydrogen, Water And Hydrids (AREA)
Abstract
The invention belongs to the technical field of hydrogen production, and particularly relates to an oxygen permeable membrane hydrogen production method and application thereof, wherein the method comprises the following steps: (1) Introducing water vapor into a second oxygen-permeable membrane reactor R2 to generate high-temperature reaction gas I; (2) Mixing residual hydrogen-containing gas on the water vapor side of the second oxygen-permeable membrane reactor R2 with high-temperature reaction gas, and introducing the mixture into the first oxygen-permeable membrane reactor R1; (3) Introducing water vapor into a first oxygen permeable membrane reactor R1, and transferring oxygen to an oxygen side through an oxygen permeable membrane and reacting with mixed gas to generate high-temperature reaction gas II; (4) Introducing a second part of the high-temperature reaction gas into the second oxygen-permeable membrane reactor R2 as circulating gas and mixing the circulating gas with fuel; (5) The residual hydrogen-rich gas on the water vapor side of the first oxygen-permeable membrane reactor R1 is introduced into a first condenser C1 to obtain high-purity hydrogen. The invention further reduces the energy consumption while improving the speed, and conveniently, efficiently and economically prepares the hydrogen.
Description
Technical Field
The patent belongs to the technical field of hydrogen production, and in particular relates to an oxygen permeable membrane hydrogen production method and application.
Background
The global energy mainly comprises traditional fossil energy mainly comprising coal, petroleum, natural gas and the like and novel clean energy mainly comprising wind energy, water energy, solar energy, ocean energy, hydrogen energy and the like. Traditional fossil energy is not renewable, and toxic gases, greenhouse gases and the like generated by combustion of the traditional fossil energy seriously pollute the environment. With the industrial development, the energy demand is increasing, and in order to cope with the increasing energy demand and the low-carbon demand, the global transition from stone economy to low-carbon economy is quickened, and the development of clean and low-cost novel energy is urgent. Hydrogen is a highly efficient and ideal clean energy source. The energy source is considered to be one of the ideal energy sources for replacing the traditional fossil energy sources because of the advantages of no pollution in combustion, high energy density, high chemical activity, rich and renewable properties and the like.
At present, hydrogen production can be divided into four main flows in technology and technology: hydrogen production by electrolysis of water, fossil fuel, industrial by-products and biomass. The cost of hydrogen production by water electrolysis is high, and the hydrogen production method is limited to small-scale range use, so that the wide popularization of the technology is not facilitated. Fossil fuel hydrogen production raw materials belong to non-renewable energy sources, and the energy consumption in the hydrogen production process is high, the environment is influenced, and a large amount of discharged carbon dioxide can generate greenhouse effect. The purity of hydrogen produced by the industrial by-product hydrogen production is not high, a hydrogen purification system is needed later, the system is complex, the energy consumption is high, and greenhouse gases are produced. The purity of the hydrogen produced by the biomass hydrogen production is not high, the technology is not fully mature, and the investment cost is high.
The oxygen permeable membrane is a new oxygen separation membrane, and the principle is that under a certain temperature, the oxygen partial pressure difference at two ends of the membrane is utilized to decompose the water vapor into oxygen and hydrogen under the separation action of the membrane, the oxygen diffuses and migrates from a high partial pressure side to a low partial pressure side, and the residual hydrogen-rich water vapor is condensed and separated to obtain the high-purity hydrogen. Compared with the conventional hydrogen production technology, the method has the advantages of simple system, low energy consumption, quick start, low cost, convenient operation and the like, and the economy and the system efficiency of the hydrogen production technology are greatly improved.
Chinese patent CN104163399B discloses a device for preparing hydrogen by alternately decomposing water with oxygen permeable membrane and hydrogen permeable membrane. The device comprises: the flat box body is internally divided into a plurality of oxygen permeation chambers and hydrogen permeation chambers which are arranged at intervals; and the inner pipelines extend in each oxygen permeation chamber and each hydrogen permeation chamber, the inner pipelines of the adjacent chambers are connected end to end through the outer pipelines, the inner pipelines and the outer pipelines jointly form a communicated snake-shaped steam channel, the inner pipelines in the oxygen permeation chambers are made of oxygen permeation membranes, the inner pipelines in the hydrogen permeation chambers are made of hydrogen permeation membranes, chemical potential differences are arranged on the inner side and the outer side of the hydrogen permeation membranes of the inner pipelines in the hydrogen permeation chambers and the inner side and the outer side of the oxygen permeation membranes of the inner pipelines in the oxygen permeation chambers, under the action of the chemical potential differences, oxygen permeates the oxygen permeation membranes, and hydrogen enters the areas between the inner pipelines and the inner walls of the corresponding chambers respectively through the hydrogen permeation membranes. In the invention, the steam passage is formed by alternately connecting the oxygen permeable membrane inner pipeline and the hydrogen permeable membrane inner pipeline, and the water vapor decomposition rate is much higher than that of the single oxygen permeable membrane or the single hydrogen permeable membrane.
However, the hydrogen production rate is difficult to be improved by the conventional oxygen permeable membrane hydrogen production technology, the requirements on the rate and the energy consumption are difficult to be met simultaneously, and the hydrogen can not be produced more conveniently, efficiently and economically.
Disclosure of Invention
The invention provides a hydrogen production method by an oxygen permeable membrane and application thereof, which effectively improves the hydrogen production rate, and simultaneously further reduces the energy consumption while improving the hydrogen production rate, thereby conveniently, efficiently and economically preparing hydrogen.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
an oxygen permeable membrane hydrogen production method comprises the following steps:
(1) Introducing water vapor into a second oxygen-permeable membrane reactor, and transferring oxygen to an oxygen side through an oxygen-permeable membrane to react with fuel to generate high-temperature reaction gas I;
(2) Mixing the residual hydrogen-containing gas on the water vapor side of the second oxygen-permeable membrane reactor with the first high-temperature reaction gas generated in the step (1) to obtain a first mixed gas, and introducing the first mixed gas into the first oxygen-permeable membrane reactor;
(3) Introducing water vapor into a first oxygen permeable membrane reactor, and transferring oxygen to an oxygen side through an oxygen permeable membrane and reacting with mixed gas to generate high-temperature reaction gas II;
(4) Part of the high-temperature reaction gas II obtained in the step (3) is used as an exhaust gas exhaust system, and the other part is used as circulating gas to be introduced into a second oxygen-permeable membrane reactor and mixed with fuel;
(5) Introducing the residual hydrogen-rich gas on the water vapor side of the first oxygen permeable membrane reactor in the step (3) into a first condenser to separate condensed water, and obtaining high-purity hydrogen.
Preferably, the structures of the first oxygen permeable membrane reactor and the second oxygen permeable membrane reactor are one or more selected from tube-plate structures and flat plate structures.
More preferably, the diameter of the oxygen permeable membrane tube of the tube plate type structure is 1-20 mm, the thickness of the membrane is 0.1-5 mm, and the tube spacing is 0.5-5 times of the tube diameter; the thickness of the oxygen permeable membrane of the flat plate structure is 0.1-5 mm, and the membrane spacing is 0.5-25 mm.
Preferably, the oxygen permeable membrane is one or more selected from a single layer membrane, a double layer membrane and a mixed conductor oxygen permeable membrane.
Preferably, the oxygen permeable membrane is one or more selected from perovskite, fluorite-metal, perovskite-metal structures.
Preferably, the working temperature of the first oxygen permeable membrane reactor and the second oxygen permeable membrane reactor is 400-1000 ℃; the pressure difference of the two sides of the oxygen permeable membrane is 0-9 MPa, and the pressure of the inner side of the membrane cavity is not lower than the pressure of the outer side of the membrane cavity.
Preferably, the circulating gas in the step (4) accounts for 10-90% of the two volumes of the high-temperature reaction gas.
Preferably, the hydrogen volume concentration of the residual hydrogen-containing gas at the water vapor side of the second oxygen permeable membrane reactor in the step (2) is 0-40%, and the hydrogen volume concentration of the residual hydrogen-rich gas at the water vapor side of the first oxygen permeable membrane reactor in the step (5) is 0-95%.
More preferably, the hydrogen volume concentration of the residual hydrogen-containing gas on the water vapor side of the second oxygen-permeable membrane reactor in the step (2) is 5 to 20%, and the hydrogen volume concentration of the residual hydrogen-rich gas on the water vapor side of the first oxygen-permeable membrane reactor in the step (5) is 50 to 80%.
The invention also claims an application in the field of hydrogen production using the above method.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the oxygen permeable membrane hydrogen production method provided by the invention, fuel enters the second oxygen permeable membrane reactor R2 to perform incomplete combustion reaction with oxygen to generate high-temperature reaction gas I containing CO, so that heat is provided for migration of oxygen in the second oxygen permeable membrane reactor R2 while oxygen is consumed, and the migration rate is improved; the mixed gas enters the first oxygen-permeable membrane reactor R1, can quickly react with oxygen separated from water vapor, accelerates the hydrogen production rate by water vapor decomposition, and simultaneously the heat released by the reaction is used for maintaining the reaction temperature of hydrogen separation, so that the hydrogen preparation speed is ensured; the invention improves the hydrogen production rate and simultaneously fully utilizes the heat in the reaction, and the two complement each other.
(2) The high-temperature reaction gas II in the first oxygen-permeable membrane reactor R1 can be further utilized and used as a part of fuel for circulation, so that the utilization rate of raw materials is greatly improved, meanwhile, condensed water generated by the system can be recycled, the internal circulation of the system is increased, and the production cost is further reduced.
(3) The process of the invention utilizes the oxygen enrichment characteristic of the oxygen permeable membrane, under the separation action of the membrane, the vapor is decomposed into oxygen and hydrogen, and after condensation and separation, the hydrogen with the purity of more than 99% can be prepared, the system is simple and convenient, the hydrogen purity is high, and the hydrogen can be directly used for hydrogen fuel cells; the oxygen permeable membrane hydrogen production method has the advantages of low energy consumption, low running cost and convenient operation.
Drawings
FIG. 1 is a schematic flow chart of a method for producing hydrogen by using an oxygen permeable membrane according to the invention.
In the figure, R1 is the first oxygen permeable membrane reactor; r2-a second oxygen permeable membrane reactor; c1-a first condenser.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the following examples. Of course, the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Although the steps of the present invention are arranged by reference numerals, the order of the steps is not limited, and the relative order of the steps may be adjusted unless the order of the steps is explicitly stated or the execution of a step requires other steps as a basis. It is to be understood that the term "and/or" as used herein relates to and encompasses any and all possible combinations of one or more of the associated listed items.
The invention discloses a hydrogen production method by an oxygen permeable membrane, which comprises the following steps:
(1) Introducing water vapor into a second oxygen permeable membrane reactor R2, and transferring oxygen to an oxygen side through an oxygen permeable membrane to react with fuel to generate high-temperature reaction gas I; the fuel enters the second oxygen-permeable membrane reactor and is subjected to incomplete combustion reaction with oxygen transferred by water vapor decomposition to generate mixed gas containing CO, and the heat is provided for the migration of the oxygen of the second oxygen-permeable membrane reactor while consuming the oxygen and releasing heat.
(2) Mixing the residual hydrogen-containing gas on the water vapor side of the second oxygen-permeable membrane reactor R2 with the first high-temperature reaction gas generated in the step (1) to obtain a first mixed gas, and introducing the first mixed gas into the first oxygen-permeable membrane reactor R1; the volume concentration of hydrogen in the hydrogen-containing gas is 0-40%, which can be 0%, 10%, 20%, 30%, 40%, preferably 5-20%;
(3) And introducing water vapor into the first oxygen permeable membrane reactor R1, and transferring oxygen to the oxygen side through the oxygen permeable membrane and reacting with the mixed gas to generate high-temperature reaction gas II.
(4) And (3) taking part of the high-temperature reaction gas II obtained in the step (3) as an exhaust gas discharge system, and taking the other part of the high-temperature reaction gas II as a circulating gas to be introduced into the second oxygen-permeable membrane reactor R2 and mixed with fuel. The circulating gas accounts for 10-90% of the volume of the high-temperature reaction gas, and can be 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80% and 90%.
(5) Introducing residual hydrogen-rich gas on the water vapor side of the first oxygen permeable membrane reactor R1 in the step (3) into a first condenser C1 to separate condensed water, and obtaining high-purity hydrogen; the hydrogen gas in the hydrogen-rich gas may have a volume concentration of 0 to 95%, preferably 0%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, and more preferably 50 to 80%.
Preferably, the structures of the first oxygen permeable membrane reactor R1 and the second oxygen permeable membrane reactor R2 are one or more selected from tube-plate structures and plate structures.
Specifically, the diameter of the oxygen permeable membrane tube with the tube plate structure is 1-20 mm, which can be 1mm, 5mm, 10mm, 15mm and 20mm; the film thickness is 0.1-5 mm, and can be 0.1mm, 0.5mm, 1mm, 2mm, 3mm, 4mm, 5mm; the pipe spacing is 0.5-5 times of pipe diameter, which can be 0.5 times of pipe diameter, 1 time of pipe diameter, 2 times of pipe diameter, 3 times of pipe diameter, 4 times of pipe diameter and 5 times of pipe diameter; the thickness of the oxygen permeable membrane of the flat plate structure is 0.1-5 mm, which can be 0.1mm, 0.5mm, 1mm, 2mm, 3mm, 4mm and 5mm; the film spacing is 0.5-25 mm, and can be 0.5mm, 1mm, 5mm, 10mm, 15mm, 20mm, 25mm.
Specifically, the oxygen permeable membrane is one or more selected from a single-layer membrane, a double-layer membrane and a mixed conductor oxygen permeable membrane.
Specifically, the oxygen permeable membrane is one or more selected from perovskite, fluorite-metal and perovskite-metal structures.
Specifically, the working temperature of the first oxygen permeation membrane reactor R1 and the second oxygen permeation membrane reactor R2 is 400-1000 ℃, which can be 400 ℃, 500 ℃, 600 ℃, 700 ℃, 800 ℃, 900 ℃ and 1000 ℃; the pressure difference between two sides of the oxygen permeable membrane is 0-9 MPa, and can be 0MPa, 1MPa, 3MPa, 6MPa and 9MPa, and the pressure of the inner side of the membrane cavity is not lower than the pressure of the outer side of the membrane cavity.
The invention will be further illustrated by the following examples.
Example 1
An oxygen permeable membrane hydrogen production method comprises the following steps:
(1) Introducing water vapor into a second oxygen-permeable membrane reactor R2, and transferring oxygen to an oxygen side through an oxygen-permeable membrane to react with fuel, wherein the working temperature of the second oxygen-permeable membrane reactor R2 is 900 ℃ to generate high-temperature reaction gas I;
(2) Mixing the residual hydrogen-containing gas on the water vapor side of the second oxygen-permeable membrane reactor R2 with the first high-temperature reaction gas generated in the step (1) to obtain a first mixed gas, and introducing the first mixed gas into the first oxygen-permeable membrane reactor R1; the hydrogen gas was present in the hydrogen-containing gas at a volume concentration of 15%.
(3) Introducing water vapor into a first oxygen permeation membrane reactor R1, transferring oxygen to an oxygen side through an oxygen permeation membrane and reacting with mixed gas, wherein the working temperature of the first oxygen permeation membrane reactor R1 is 900 ℃, and generating high-temperature reaction gas II.
(4) And (3) taking 30% of the high-temperature reaction gas II obtained in the step (3) as an exhaust gas discharge system, and introducing the other part of the high-temperature reaction gas II into the second oxygen-permeable membrane reactor R2 as circulating gas and mixing the circulating gas with fuel. The recycle gas accounts for 70% of the volume of the high temperature reaction gas.
(5) And (3) introducing the residual hydrogen-rich gas on the water vapor side of the first oxygen permeable membrane reactor R1 in the step (3) into a first condenser C1 to separate condensed water, and obtaining high-purity hydrogen. The volume concentration of hydrogen in the hydrogen-rich gas is 95%.
Specifically, the oxygen permeable membranes of the first oxygen permeable membrane reactor R1 and the second oxygen permeable membrane reactor R2 are double-layer oxygen permeable membranes of perovskite-metal structures, and adopt a tube plate structure, wherein the diameter of a membrane tube is 10mm, the thickness of the membrane is 2mm, the distance between the tubes is 1.5 times of the diameter of the tubes, and the pressure difference between two sides of the oxygen permeable membrane tubes is 3MPa.
In the embodiment, condensed water can be recycled to generate water vapor, heat required by the water vapor generation can be obtained by optimizing a condensation cooling process of hydrogen-rich gas, and the heat exchange process can be arbitrarily combined and optimized according to a temperature gradient, so that the method is not limited to the enumerated heat exchange mode.
Example 2
An oxygen permeable membrane hydrogen production method comprises the following steps:
(1) Introducing water vapor into a second oxygen-permeable membrane reactor R2, and transferring oxygen to an oxygen side through an oxygen-permeable membrane to react with fuel, wherein the working temperature of the second oxygen-permeable membrane reactor R2 is 500 ℃ to generate high-temperature reaction gas I;
(2) Mixing the residual hydrogen-containing gas on the water vapor side of the second oxygen-permeable membrane reactor R2 with the first high-temperature reaction gas generated in the step (1) to obtain a first mixed gas, and introducing the first mixed gas into the first oxygen-permeable membrane reactor R1; the hydrogen gas was present in the hydrogen-containing gas at a volume concentration of 10%.
(3) Introducing water vapor into a first oxygen permeation membrane reactor R1, transferring oxygen to the oxygen side through an oxygen permeation membrane and reacting with mixed gas, wherein the working temperature of the first oxygen permeation membrane reactor R1 is 500 ℃, and generating high-temperature reaction gas II.
(4) And (3) taking 40% of the high-temperature reaction gas II obtained in the step (3) as an exhaust gas discharge system, and introducing the other part of the high-temperature reaction gas II into the second oxygen-permeable membrane reactor R2 as circulating gas and mixing the circulating gas with fuel. The recycle gas accounts for 60% of the volume of the high temperature reaction gas.
(5) And (3) introducing the residual hydrogen-rich gas on the water vapor side of the first oxygen permeable membrane reactor R1 in the step (3) into a first condenser C1 to separate condensed water, and obtaining high-purity hydrogen. The volume concentration of hydrogen in the hydrogen-rich gas is 90%.
Specifically, the oxygen permeable membranes of the first oxygen permeable membrane reactor R1 and the second oxygen permeable membrane reactor R2 are double-layer oxygen permeable membranes of perovskite-metal structures, and adopt a tube plate structure, wherein the diameter of a membrane tube is 5mm, the thickness of the membrane is 1mm, the distance between the tubes is 1 time of the diameter of the tubes, and the pressure difference between two sides of the oxygen permeable membrane tubes is 1.5MPa.
Example 3
An oxygen permeable membrane hydrogen production method comprises the following steps:
(1) Introducing water vapor into a second oxygen-permeable membrane reactor R2, and transferring oxygen to an oxygen side through an oxygen-permeable membrane to react with fuel, wherein the working temperature of the second oxygen-permeable membrane reactor R2 is 750 ℃, so as to generate high-temperature reaction gas I;
(2) Mixing the residual hydrogen-containing gas on the water vapor side of the second oxygen-permeable membrane reactor R2 with the first high-temperature reaction gas generated in the step (1) to obtain a first mixed gas, and introducing the first mixed gas into the first oxygen-permeable membrane reactor R1; the hydrogen gas was present in the hydrogen-containing gas at a volume concentration of 12%.
(3) Introducing water vapor into a first oxygen permeation membrane reactor R1, transferring oxygen to an oxygen side through an oxygen permeation membrane and reacting with mixed gas, wherein the working temperature of the first oxygen permeation membrane reactor R1 is 750 ℃, and generating high-temperature reaction gas II.
(4) And (3) taking 35% of the high-temperature reaction gas II obtained in the step (3) as an exhaust gas discharge system, and taking the other part of the high-temperature reaction gas II as a circulating gas to be introduced into the second oxygen-permeable membrane reactor R2 and mixed with fuel. The recycle gas accounts for 65% of the volume of the high temperature reaction gas.
(5) And (3) introducing the residual hydrogen-rich gas on the water vapor side of the first oxygen permeable membrane reactor R1 in the step (3) into a first condenser C1 to separate condensed water, and obtaining high-purity hydrogen. The hydrogen concentration in the hydrogen-rich gas was 92% by volume.
Specifically, the oxygen permeable membranes of the first oxygen permeable membrane reactor R1 and the second oxygen permeable membrane reactor R2 are double-layer oxygen permeable membranes of perovskite-metal structures, and adopt a tube plate structure, wherein the diameter of a membrane tube is 7mm, the thickness of the membrane is 1.5mm, the distance between the tubes is 1.2 times of the diameter of the tubes, and the pressure difference at two sides of the oxygen permeable membrane tube is 2MPa.
Comparative example 1
An oxygen permeable membrane hydrogen production method comprises the following steps:
introducing water vapor into a first oxygen-permeable membrane reactor R1, and transferring oxygen to an oxygen side through an oxygen-permeable membrane to react with fuel, wherein the working temperature of the first oxygen-permeable membrane reactor R1 is 900 ℃ to generate high-temperature reaction gas I; 30% of the high-temperature reaction gas is discharged out of the system, and 70% of the high-temperature reaction gas is used as circulating gas to be mixed with fuel; the hydrogen-rich gas with the residual volume concentration of 95% on the water vapor side of the first oxygen-permeable membrane reactor R1 is introduced into the first condenser C1 to obtain high-purity hydrogen and condensed water.
Specifically, the oxygen permeable membrane of the first oxygen permeable membrane reactor R1 is a double-layer oxygen permeable membrane with a perovskite-metal structure, a tube plate structure is adopted, the diameter of a membrane tube is 10mm, the thickness of the membrane is 2mm, the distance between the tubes is 1.5 times of the diameter of the tube, and the pressure difference at two sides of the oxygen permeable membrane tube is 3MPa.
The hydrogen production rates and the product conditions of examples 1 to 3 and comparative example 1 are shown in Table 1, and the hydrogen production rates are calculated as the oxygen permeable membrane area and the water vapor side area.
TABLE 1 Hydrogen production Rate and product
| Hydrogen production rate/[ mL/(cm) 2 ·min)] | Product(s) | |
| Example 1 | 30 | Hydrogen gas |
| Example 2 | 27.8 | Hydrogen gas |
| Example 3 | 26.5 | Hydrogen gas |
| Comparative example 1 | 15.6 | Hydrogen gas |
As can be seen from Table 1, the hydrogen production rates using the hydrogen production methods of examples 1-3 of the present invention were faster than those of comparative example 1.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that modifications and changes can be made by those skilled in the art without departing from the inventive concept and remain within the scope of the invention.
Claims (10)
1. The oxygen permeable membrane hydrogen production method is characterized by comprising the following steps:
(1) Introducing water vapor into a second oxygen permeable membrane reactor (R2), and transferring oxygen to an oxygen side through an oxygen permeable membrane to react with fuel to generate high-temperature reaction gas I;
(2) Mixing the residual hydrogen-containing gas at the water vapor side of the second oxygen-permeable membrane reactor (R2) with the first high-temperature reaction gas generated in the step (1) to obtain a first mixed gas, and introducing the first mixed gas into the first oxygen-permeable membrane reactor (R1);
(3) Introducing water vapor into a first oxygen permeable membrane reactor (R1), and transferring oxygen to an oxygen side through an oxygen permeable membrane and reacting with mixed gas to generate high-temperature reaction gas II;
(4) Part of the high-temperature reaction gas II obtained in the step (3) is used as an exhaust gas exhaust system, and the other part is used as circulating gas to be introduced into a second oxygen-permeable membrane reactor (R2) and mixed with fuel;
(5) Introducing the residual hydrogen-rich gas on the water vapor side of the first oxygen permeable membrane reactor (R1) in the step (3) into a first condenser (C1) to separate condensed water, and obtaining high-purity hydrogen.
2. The method for producing hydrogen by oxygen permeable membrane according to claim 1, wherein the first oxygen permeable membrane reactor (R1) and the second oxygen permeable membrane reactor (R2) have one or more structures selected from the group consisting of a tube-sheet structure and a flat-sheet structure.
3. The method for producing hydrogen by using oxygen permeable membrane according to claim 2, wherein the diameter of the oxygen permeable membrane tube of the tube plate type structure is 1-20 mm, the thickness of the membrane is 0.1-5 mm, and the distance between the tubes is 0.5-5 times of the diameter of the tube; the thickness of the oxygen permeable membrane of the flat plate structure is 0.1-5 mm, and the membrane spacing is 0.5-25 mm.
4. The method for producing hydrogen by using an oxygen permeable membrane according to claim 1, wherein the oxygen permeable membrane is one or more selected from the group consisting of a single layer membrane, a double layer membrane, and a mixed conductor oxygen permeable membrane.
5. The method for producing hydrogen by using an oxygen permeable membrane according to claim 1, wherein the oxygen permeable membrane is one or more selected from the group consisting of perovskite type, fluorite-metal type, and perovskite-metal type structures.
6. The oxygen permeable membrane hydrogen production method according to claim 1, wherein the operating temperature of the first oxygen permeable membrane reactor (R1) and the second oxygen permeable membrane reactor (R2) is 400-1000 ℃; the pressure difference of the two sides of the oxygen permeable membrane is 0-9 MPa, and the pressure of the inner side of the membrane cavity is not lower than the pressure of the outer side of the membrane cavity.
7. The method for producing hydrogen by oxygen permeable membrane according to claim 1, wherein the circulating gas in the step (4) occupies 10 to 90% of the two volumes of the high temperature reaction gas.
8. The method for producing hydrogen by oxygen permeable membrane according to claim 1, wherein the hydrogen volume concentration of the residual hydrogen-containing gas on the water vapor side of the second oxygen permeable membrane reactor (R2) in the step (2) is 0 to 40%, and the hydrogen volume concentration of the residual hydrogen-rich gas on the water vapor side of the first oxygen permeable membrane reactor (R1) in the step (5) is 0 to 95%.
9. The method for producing hydrogen by oxygen permeable membrane according to claim 8, wherein the hydrogen volume concentration of the residual hydrogen-containing gas on the water vapor side of the second oxygen permeable membrane reactor (R2) in step (2) is 5 to 20%, and the hydrogen volume concentration of the residual hydrogen-rich gas on the water vapor side of the first oxygen permeable membrane reactor (R1) in step (5) is 50 to 80%.
10. Use in the field of hydrogen production of a method according to any one of claims 1 to 9.
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