CN110467153B - Method for preparing hydrogen by high-temperature gas cooled reactor coupled iodine-selenium thermochemical cycle nitrogen reduction - Google Patents
Method for preparing hydrogen by high-temperature gas cooled reactor coupled iodine-selenium thermochemical cycle nitrogen reduction Download PDFInfo
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/02—Preparation of nitrogen
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- C—CHEMISTRY; METALLURGY
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- 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
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/068—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents the hydrogen being generated from the water as a result of a cyclus of reactions, not covered by groups C01B3/063 or C01B3/105
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention relates to a method for preparing hydrogen by iodine and selenium thermochemical cyclic nitrogen reduction, belonging to the technical field of hydrogen energy. Firstly, water is taken as a raw material, selenium and iodine are added, reaction is carried out under normal pressure to obtain selenious acid solution and hydroiodic acid, the hydroiodic acid is rectified and concentrated, the hydroiodic acid after rectification and concentration is decomposed, the decomposed hydrogen is taken as a product to be output, iodine is recycled, a reducing agent hydrazine hydrate or ammonia (ammonia water) is added into the obtained selenious acid solution to obtain selenium, nitrogen and water vapor, the nitrogen is dried and then is taken as a byproduct to be output, and the selenium is taken as a raw material to be recycled. The highest temperature required in the reaction process of the method is 400-. The reactants iodine and selenium in the method can be recycled, so that the production cost of hydrogen production is greatly reduced. The method can be well coupled with the latest clean energy high-temperature gas cooled reactor, and the heat energy, the electric energy and the mechanical energy of the high-temperature gas cooled reactor can be utilized by the iodine selenium thermochemical cycle hydrogen production process.
Description
Technical Field
The invention relates to a method for preparing hydrogen by high-temperature gas cooled reactor coupled iodine-selenium thermochemical cycle nitrogen reduction, belonging to the technical field of hydrogen energy.
Background
Hydrogen energy is an ideal clean secondary energy, is widely distributed, does not produce pollution when being combusted, is more convenient to store and transport compared with electric power, can be directly used as fuel, and is increasingly paid attention to energy systems taking hydrogen energy as a core. The thermochemical cycle of splitting water to produce hydrogen is one of the most promising methods. The currently common thermochemical cycle hydrogen production method is sulfur-iodine cycle hydrogen production, and for example, chinese patent application (application publication No. CN104817057) discloses a thermochemical cycle hydrogen production method, which includes 3 chemical reactions, as follows:
bunsen reaction:
SO2+I2+2H2O→2HI+H2SO4(T＝290-390K)
sulfuric acid decomposition reaction:
H2SO4→H2O+SO2+0.5O2(T＝970-1270K)
and (3) hydroiodic acid decomposition reaction:
2HI→H2+I2(T＝570-770K)
theoretically, water can be produced into hydrogen through thermal dissociation, but the reaction needs high temperature of more than 4000 ℃, the sulfur-iodine circulation hydrogen production method divides the decomposition reaction of water into a plurality of steps, so that the reaction temperature can be reduced, the problem of hydrogen-oxygen separation can be avoided, and sulfur dioxide and iodine used in circulation can be recycled. The disadvantage of the sulfur-iodine cycle hydrogen production method is that the decomposition reaction of sulfuric acid still needs higher temperature, and is still in laboratory scale, and the energy consumption and heat consumption are very high. If large-scale hydrogen production is carried out, a stable heat source capable of providing high temperature is needed, and the heat source meeting the condition and capable of providing high-temperature stable large-scale engineering above 970K does not exist.
Disclosure of Invention
The invention aims to provide a method for preparing hydrogen by coupling a high-temperature gas cooled reactor with iodoselenium thermochemical cycle nitrogen reduction, which improves the existing thermochemical sulfur-iodine cycle hydrogen preparation process, and realizes large-scale hydrogen preparation by coupling a high-temperature gas cooled reactor with a stable heat source capable of providing high temperature.
The invention provides a method for preparing hydrogen by high-temperature gas cooled reactor coupled iodine-selenium thermochemical cycle nitrogen reduction, which comprises the following steps:
(1) taking water as a raw material, adding selenium and iodine, and reacting at normal pressure, wherein the molar ratio of the water to the selenium to the iodine is as follows: water, selenium and iodine, wherein the iodine is 1, (0.3-2) and (0.5-4), the reaction temperature is 15-80 ℃, the reaction time is 30-120min, selenious acid solution and hydroiodic acid are obtained by reaction, and the reaction equation is as follows:
3H2O+Se+2I2→H2SeO3+4HI
carrying out liquid-liquid separation on selenious acid solution and hydroiodic acid by using a liquid-liquid separation method to obtain selenious acid solution and hydroiodic acid;
(2) rectifying the hydroiodic acid obtained in the step (1), wherein the feeding temperature of a rectifying tower is the bubble point temperature, the pressure in the tower is 1.1-1.5MPa, and the reaction time is 10-50 min;
(3) decomposing the hydroiodic acid obtained in the step (2), wherein the pressure in a decomposition tower is 1.1-1.5MPa, the reaction temperature is 400-700 ℃, the reaction time is 30-120min, the products are hydrogen and iodine, the hydrogen is output as a product, the iodine is returned to the step (1) for recycling, and the chemical reaction equation is as follows:
2HI→H2+I2
(4) adding a reducing agent into the selenious acid solution obtained in the step (1) according to the following molar ratio: and (2) selenious acid, namely a reducing agent (1-10), reacting for 30-120min at the temperature of 100-400 ℃ to obtain selenium, nitrogen and water vapor, drying the nitrogen to be output as a byproduct, and returning the selenium to the step (1) to be recycled as a raw material, wherein the reaction equation is as follows:
H2SeO3+N2H4·H2O→Se+N2+4H2O
H2SeO3+4(NH2OH·H2O)→Se+2N2+11H2O
in the above method for producing hydrogen by nitrogen reduction, the reducing agent is hydrazine hydrate, hydrazine hydrate or ammonia gas (or ammonia water). When the reducing agent is hydrazine hydrate, the molar ratio of the selenious acid to the hydrazine hydrate is as follows: selenious acid, hydrazine hydrate, 1 (1-3). When the reducing agent is hydrazine hydrate, the molar ratio of the selenious acid to the hydrazine hydrate is as follows: selenious acid, hydrazine hydrate ═ 1 (4-6). When the reducing agent is ammonia (or ammonia water), the molar ratio of the selenious acid to the ammonia (or ammonia water) is as follows: selenious acid, ammonia (or ammonia water) ═ 1 (2-5).
In the above method for producing hydrogen by nitrogen reduction, the step (4) is: decomposing selenious acid solution at the reaction temperature of 100-200 ℃ to obtain selenium dioxide and water vapor, adding reducing agent hydrazine hydrate into the selenium dioxide, wherein the molar ratio of the selenium dioxide to the hydrazine hydrate is as follows: selenium dioxide, hydrazine hydrate 1 (1-3), and the reaction time is as follows: and (3) reacting for 30-120min till no gas is generated, completely reacting to generate selenium and nitrogen containing water vapor, returning the selenium to the step (1) to be recycled as a raw material, drying the nitrogen to be output as a byproduct, and performing a reaction equation as follows:
H2SeO3→SeO2+H2O
SeO2+N2H4·H2O→Se+N2+3H2O。
in the above method for producing hydrogen by nitrogen reduction, the step (4) may further include: decomposing selenious acid solution at the reaction temperature of 100-200 ℃ to obtain selenium dioxide and water vapor, adding a reducing agent hydrazine hydrate into the selenium dioxide, wherein the molar ratio of the selenium dioxide to the hydrazine hydrate is as follows: selenium dioxide and hydrazine hydrate (1-6), wherein the reaction time is as follows: and (3) reacting for 30-120min till no gas is generated, completely reacting to generate selenium and nitrogen containing water vapor, returning the selenium to the step (1) to be recycled as a raw material, drying the nitrogen to be output as a byproduct, and performing a reaction equation as follows:
H2SeO3→SeO2+H2O
SeO2+4(NH2OH·H2O)→Se+2N2+10H2O。
in the above method for producing hydrogen by nitrogen reduction, the step (4) may further include: decomposing the selenious acid solution obtained in the step (1) at the reaction temperature of 100-200 ℃ to obtain selenium dioxide and water vapor, adding a reducing agent ammonia (or ammonia water) into the obtained selenium dioxide, wherein the molar ratio of the selenium dioxide to the ammonia (or ammonia water) is as follows: selenium dioxide and ammonia (or ammonia water) ═ 1 (4-6), the reaction time is 30-120min, it is complete to react until no more gas is produced, produce selenium and aqueous vapor nitrogen, selenium will return to step (1) and use as raw materials to recycle, nitrogen is exported as the by-product after drying, the reaction equation is as follows:
H2SeO3→SeO2+H2O
3SeO2+4NH3→3Se+2N2+6H2O
in the method for preparing hydrogen by iodine-selenium thermochemical cycle nitrogen reduction, the reaction temperature in the step (1) is 20-30 ℃.
In the method for preparing hydrogen by iodine-selenium thermochemical cycle nitrogen reduction, the reaction temperature in the step (3) is 400-500 ℃.
In the method for preparing hydrogen by iodine-selenium thermochemical cycle nitrogen reduction, the reaction temperature in the step (4) is 100-200 ℃.
The method for preparing hydrogen by high-temperature gas cooled reactor coupled iodine-selenium thermochemical cycle nitrogen reduction provided by the invention has the characteristics and advantages that:
1. the method for producing hydrogen by high-temperature gas cooled reactor coupled iodine selenium thermochemical cycle nitrogen reduction has the highest temperature of 400-500 ℃ required in the reaction process, and avoids the problem that large-scale hydrogen production cannot be carried out due to overhigh reaction temperature.
2. The method for producing hydrogen by nitrogen reduction has the advantages that the reactants iodine and selenium can be recycled, so the production cost of hydrogen production is greatly reduced.
3. The invention relates to a method for preparing hydrogen by coupling a high-temperature gas cooled reactor with iodine selenium thermochemical cycle nitrogen reduction, which utilizes the coupling of the high-temperature gas cooled reactor and various chemical equipment of an iodine selenium thermochemical cycle system, and because the reactant selenium, selenium dioxide, a reducing agent and intermediate products of selenious acid and hydroiodic acid belong to strong corrosivity or strong toxicity, the equipment, pipelines, pumps and the like need to resist corrosion and have zero leakage, and the zero leakage is realized by using torque magnetic transmission in the process.
4. The invention relates to a method for preparing hydrogen by coupling a high-temperature gas cooled reactor with iodine-selenium thermochemical cycle nitrogen reduction, which is used for coupling the high-temperature gas cooled reactor, wherein the high-temperature gas cooled reactor can provide three forms of energy, namely heat energy, electric energy and mechanical energy, which can be utilized by the iodine-selenium thermochemical cycle hydrogen preparation process. The heat energy generated by the high-temperature gas cooled reactor can be utilized in a gradient manner, the heat is transferred through the intermediate heat exchanger, the temperature gradients are set to be 700 ℃, 500 ℃, 300 ℃ and 100 ℃, the heat energy is fully utilized in such a manner, and the utilization rate of the heat energy can reach 99%. In addition, the electric energy generated by the high-temperature gas cooled reactor can be utilized in the subsequent iodine-selenium thermochemical cycle and used by electric equipment such as a motor, and the utilization rate of the electric energy can reach 30-50%. In addition, a large amount of steam generated by the high-temperature gas cooled reactor can also provide mechanical energy, and is directly coupled with a steam turbine in the iodine-selenium thermochemical circulating system, and the utilization efficiency can reach 90%.
5. The method for preparing hydrogen by the iodine selenium thermochemical cycle nitrogen reduction by coupling the high-temperature gas cooled reactor is not limited to coupling the high-temperature gas cooled reactor, and other high-temperature heat sources can be coupled with the method for preparing hydrogen by the iodine selenium thermochemical cycle nitrogen reduction.
Detailed Description
The invention provides a method for preparing hydrogen by high-temperature gas cooled reactor coupled iodine-selenium thermochemical cycle nitrogen reduction, which comprises the following steps:
(1) taking water as a raw material, adding selenium and iodine, and reacting at normal pressure, wherein the molar ratio of the water to the selenium to the iodine is as follows: water, selenium and iodine, wherein the ratio of iodine to water is 1 (0.3-2) to 0.5-4), the reaction temperature is 15-80 ℃, the reaction time is 30-120min, the mark of complete reaction is no longer gas, selenious acid solution and hydroiodic acid are obtained by reaction, and the reaction equation is as follows:
3H2O+Se+2I2→H2SeO3+4HI
the hydriodic acid and the selenious acid generated in the process are obviously layered due to different densities, wherein the hydriodic acid is on the upper layer, and the selenious acid solution is on the lower layer. And performing liquid-liquid separation on the selenious acid solution and the hydroiodic acid by using a liquid-liquid separation method to obtain the selenious acid solution and the hydroiodic acid.
(2) The hydroiodic acid obtained in the step (1) comprises the following components: i is2HI and H2O, mixed ternary solution is denoted as HIx solution. And (3) feeding the HIx solution into an HI rectification decomposition unit for rectification, wherein the feeding temperature of a rectification tower is the bubble point temperature, the pressure in the tower is 1.1-1.5MPa, and the reaction time is 10-50 min.
(3) Decomposing the hydroiodic acid obtained in the step (2), wherein the pressure in a decomposition tower is 1.1-1.5MPa, the reaction temperature is 400-700 ℃, the reaction time is 30-120min, and the product is H2And I2Hydrogen is output as a product, iodine is returned to the step (1) for recycling, and the chemical reaction equation is as follows:
2HI→H2+I2
the high-temperature environment in the step is provided by a high-temperature gas-cooled reactor, and high-temperature hot steam of the high-temperature gas-cooled reactor is transmitted into a hydroiodic acid decomposition tower through a heat exchanger.
(4) Adding a reducing agent into the selenious acid solution obtained in the step (1) according to the following molar ratio: and (2) selenious acid, namely a reducing agent, (1-10), reacting for 30-120min at 100-200 ℃ until no gas is generated, obtaining selenium, nitrogen and water vapor, drying the nitrogen to be output as a byproduct, and returning the selenium to the step (1) to be used as a raw material for recycling. The reaction principle equation is as follows:
H2SeO3+N2H4·H2O→Se+N2+4H2O
H2SeO3+4(NH2OH·H2O)→Se+2N2+11H2O
because the toxic substances selenium, selenious acid, selenium dioxide, reducing agent, strong corrosive substance hydroiodic acid and the like participate in the steps (1), (2), (3) and (4), the equipment, the pipeline, the pump and the like need to be resistant to corrosion and have zero leakage, and torque magnetic transmission is used in the process to realize zero leakage.
In the above method for producing hydrogen by nitrogen reduction, the reducing agent is hydrazine hydrate, hydrazine hydrate or ammonia gas (or ammonia water). When the reducing agent is hydrazine hydrate, the molar ratio of the selenious acid to the hydrazine hydrate is as follows: selenious acid, hydrazine hydrate, 1 (1-3). When the reducing agent is hydrazine hydrate, the molar ratio of the selenious acid to the hydrazine hydrate is as follows: selenious acid, hydrazine hydrate ═ 1 (4-6). When the reducing agent is ammonia gas (or ammonia water), the molar ratio of the selenious acid to the ammonia gas or the ammonia water is as follows: selenious acid, ammonia gas or ammonia water 1 (2-5).
In the above method for producing hydrogen by nitrogen reduction, the step (4) is: decomposing selenious acid solution at the reaction temperature of 100-200 ℃ to obtain selenium dioxide and water vapor, adding reducing agent hydrazine hydrate into the selenium dioxide, wherein the molar ratio of the selenium dioxide to the hydrazine hydrate is as follows: selenium dioxide, hydrazine hydrate 1 (1-3), and the reaction time is as follows: and (3) reacting for 30-120min till no gas is generated, completely reacting to generate selenium and nitrogen containing water vapor, returning the selenium to the step (1) to be recycled as a raw material, drying the nitrogen to be output as a byproduct, and performing a reaction equation as follows:
H2SeO3→SeO2+H2O
SeO2+N2H4·H2O→Se+N2+3H2O。
in the above method for producing hydrogen by nitrogen reduction, the step (4) may further include: decomposing selenious acid solution at the reaction temperature of 100-200 ℃ to obtain selenium dioxide and water vapor, adding a reducing agent hydrazine hydrate into the selenium dioxide, wherein the molar ratio of the selenium dioxide to the hydrazine hydrate is as follows: selenium dioxide and hydrazine hydrate (1-6), wherein the reaction time is as follows: and (3) reacting for 30-120min till no gas is generated, completely reacting to generate selenium and nitrogen containing water vapor, returning the selenium to the step (1) to be recycled as a raw material, drying the nitrogen to be output as a byproduct, and performing a reaction equation as follows:
H2SeO3→SeO2+H2O
SeO2+4(NH2OH·H2O)→Se+2N2+10H2O。
in the above method for producing hydrogen by nitrogen reduction, the step (4) may further include: decomposing the selenious acid solution obtained in the step (1) at the reaction temperature of 100-200 ℃ to obtain selenium dioxide and water vapor, adding a reducing agent ammonia (or ammonia water) into the obtained selenium dioxide, wherein the molar ratio of the selenium dioxide to the ammonia (or ammonia water) is as follows: and (2) selenium dioxide, namely ammonia gas (or ammonia water) ═ 1 (4-6), wherein the reaction time is 30-120min, the reaction is complete until no gas is generated any more, selenium and nitrogen containing water vapor are generated, the selenium returns to the step (1) to be used as raw materials for recycling, the nitrogen is dried and then is output as a byproduct, and the reaction equation is as follows:
H2SeO3→SeO2+H2O
3SeO2+4NH3→3Se+2N2+6H2O
in the method for preparing hydrogen by iodine-selenium thermochemical cycle nitrogen reduction, the reaction temperature in the step (1) is 20-30 ℃.
In the method for preparing hydrogen by iodine-selenium thermochemical cycle nitrogen reduction, the reaction temperature in the step (3) is 400-500 ℃.
In the method for preparing hydrogen by iodine-selenium thermochemical cycle nitrogen reduction, the reaction temperature in the step (4) is 100-200 ℃.
The following describes embodiments of the method of the invention:
example one
(1) Taking water as a raw material, adding selenium and iodine, and reacting at normal pressure, wherein the molar ratio of the water to the selenium to the iodine is as follows: selenium and iodine in water are 1:0.4:1, the reaction temperature is 25 ℃, the reaction time is 60min, the complete reaction mark is that no gas is generated, selenious acid solution and hydroiodic acid are obtained by reaction, and the reaction equation is as follows:
3H2O+Se+2I2→H2SeO3+4HI
the hydriodic acid and the selenious acid generated in the process are obviously layered due to different densities, wherein the hydriodic acid is on the upper layer, and the selenious acid solution is on the lower layer. Carrying out liquid-liquid separation on selenious acid solution and hydroiodic acid by using a liquid-liquid separation method to obtain selenious acid solution and hydroiodic acid;
(2) the hydroiodic acid obtained in the step (1) comprises the following components: i is2HI and H2O, mixed ternary solution is denoted as HIx solution. And (3) feeding the HIx solution into an HI rectification decomposition unit for rectification, wherein the feeding temperature of a rectification tower is the bubble point temperature, the pressure in the tower is 1.17MPa, and the reaction time is 30 min.
(3) Decomposing the hydroiodic acid rectified in the step (2), wherein the pressure in a decomposition tower is 1.17MPa, the reaction temperature is 480 ℃, the reaction time is 60min, and the product is H2And I2Outputting hydrogen as a product, and returning iodine to the step (1) for recycling; the chemical reaction principle of the process is shown as the following chemical reaction equation:
2HI→H2+I2
the high temperature environment in the step is provided by a high temperature gas cooled reactor, and high temperature steam of the high temperature gas cooled reactor is transmitted into a hydroiodic acid decomposition tower through a heat exchanger.
(4) Adding a reducing agent hydrazine hydrate into the selenious acid solution obtained in the step (1), wherein the adding molar ratio is as follows: and (2) reacting selenious acid and a reducing agent at 120 ℃ for 120min until no gas is generated, so as to obtain selenium, nitrogen and water vapor, drying the nitrogen to be output as a byproduct, and returning the selenium to the step (1) to be used as a raw material for recycling. The reaction principle equation is shown below.
H2SeO3+N2H4·H2O→Se+N2+4H2O
Because the toxic substances selenium, selenious acid, selenium dioxide, reducing agent, strong corrosive substance hydroiodic acid and the like participate in the steps (1), (2), (3) and (4), the equipment, the pipeline, the pump and the like need to be resistant to corrosion and have zero leakage, and torque magnetic transmission is used in the process to realize zero leakage.
Example two
(1) Taking water as a raw material, adding selenium and iodine, and reacting at normal pressure, wherein the molar ratio of the water to the selenium to the iodine is as follows: selenium and iodine are mixed together at the ratio of 1:0.5:1.2, the reaction temperature is 28 ℃, the reaction time is 50min, the sign of complete reaction is that no gas is generated, selenious acid solution and hydroiodic acid are obtained by reaction, and the reaction equation is as follows:
3H2O+Se+2I2→H2SeO3+4HI
the hydriodic acid and the selenious acid generated in the process are obviously layered due to different densities, wherein the hydriodic acid is on the upper layer, and the selenious acid solution is on the lower layer. Carrying out liquid-liquid separation on selenious acid solution and hydroiodic acid by using a liquid-liquid separation method to obtain selenious acid solution and hydroiodic acid;
(2) the hydroiodic acid obtained in the step (1) comprises the following components: i is2HI and H2O, mixed ternary solution is denoted as HIx solution. And (3) feeding the HIx solution into an HI rectification decomposition unit for rectification, wherein the feeding temperature of a rectification tower is the bubble point temperature, the pressure in the tower is 1.2MPa, and the reaction time is 23 min.
(3) Decomposing the hydroiodic acid rectified in the step (2), wherein the pressure in a decomposition tower is 1.2MPa, the reaction temperature is 450 ℃, the reaction time is 55min, and the product is H2And I2Outputting hydrogen as a product, and returning iodine to the step (1) for recycling; the chemical reaction principle of the process is shown as the following chemical reaction equation:
2HI→H2+I2
the high temperature environment in the step is provided by a high temperature gas cooled reactor, and high temperature steam of the high temperature gas cooled reactor is transmitted into a hydroiodic acid decomposition tower through a heat exchanger.
(4) Adding a reducing agent hydrazine hydrate into the selenious acid solution obtained in the step (1), wherein the adding molar ratio is as follows: and (3) reacting selenious acid and a reducing agent at 150 ℃ for 110min until no gas is generated, so as to obtain selenium, nitrogen and water vapor, drying the nitrogen to be output as a byproduct, and returning the selenium to the step (1) to be recycled as a raw material. The reaction principle equation is as follows:
H2SeO3+N2H4·H2O→Se+N2+4H2O
because the toxic substances selenium, selenious acid, selenium dioxide, reducing agent, strong corrosive substance hydroiodic acid and the like participate in the steps (1), (2), (3) and (4), the equipment, the pipeline, the pump and the like need to be resistant to corrosion and have zero leakage, and torque magnetic transmission is used in the process to realize zero leakage.
EXAMPLE III
(1) Taking water as a raw material, adding selenium and iodine, and reacting at normal pressure, wherein the molar ratio of the water to the selenium to the iodine is as follows: selenium and iodine in water are 1:1:2, the reaction temperature is 28 ℃, the reaction time is 48min, the complete reaction mark is that no gas is generated, selenious acid solution and hydroiodic acid are obtained by reaction, and the reaction equation is as follows:
3H2O+Se+2I2→H2SeO3+4HI
the hydriodic acid and the selenious acid generated in the process are obviously layered due to different densities, wherein the hydriodic acid is on the upper layer, and the selenious acid solution is on the lower layer. Carrying out liquid-liquid separation on selenious acid solution and hydroiodic acid by using a liquid-liquid separation method to obtain selenious acid solution and hydroiodic acid;
(2) the hydroiodic acid obtained in the step (1) comprises the following components: i is2HI and H2O, mixed ternary solution is denoted as HIx solution. And (3) feeding the HIx solution into an HI rectification decomposition unit for rectification, wherein the feeding temperature of a rectification tower is the bubble point temperature, the pressure in the tower is 1.3MPa, and the reaction time is 20 min.
(3) Decomposing the hydroiodic acid rectified in the step (2), wherein the pressure in a decomposition tower is 1.3MPa, the reaction temperature is 450 ℃, the reaction time is 57min, and the product is H2And I2Outputting hydrogen as a product, and returning iodine to the step (1) for recycling; the chemical reaction principle of the process is shown as the following chemical reaction equation:
2HI→H2+I2
the high temperature environment in the step is provided by a high temperature gas cooled reactor, and high temperature steam of the high temperature gas cooled reactor is transmitted into a hydroiodic acid decomposition tower through a heat exchanger.
(4) Decomposing selenious acid solution at the reaction temperature of 110 ℃ to obtain selenium dioxide and water vapor, adding reducing agent hydrazine hydrate into the selenium dioxide, wherein the molar ratio of the selenium dioxide to the hydrazine hydrate is as follows: and (3) selenium dioxide and hydrazine hydrate are 1:1, the reaction time is 120min, the reaction is complete until no gas is generated, selenium and nitrogen containing water vapor are generated, the selenium returns to the step (1) and is recycled as a raw material, and the nitrogen is dried and then is output as a byproduct. The reaction principle equation is as follows:
H2SeO3→SeO2+H2O
SeO2+N2H4·H2O→Se+N2+3H2O。
because the toxic substances selenium, selenious acid, selenium dioxide, reducing agent, strong corrosive substance hydroiodic acid and the like participate in the steps (1), (2), (3) and (4), the equipment, the pipeline, the pump and the like need to be resistant to corrosion and have zero leakage, and torque magnetic transmission is used in the process to realize zero leakage.
Example four
(1) Taking water as a raw material, adding selenium and iodine, and reacting at normal pressure, wherein the molar ratio of the water to the selenium to the iodine is as follows: selenium and iodine are mixed together at the ratio of 1:1.3:2.7, the reaction temperature is 28 ℃, the reaction time is 40min, the sign of complete reaction is that no gas is generated, selenious acid solution and hydroiodic acid are obtained by reaction, and the reaction equation is as follows:
3H2O+Se+2I2→H2SeO3+4HI
the hydriodic acid and the selenious acid generated in the process are obviously layered due to different densities, wherein the hydriodic acid is on the upper layer, and the selenious acid solution is on the lower layer. Carrying out liquid-liquid separation on selenious acid solution and hydroiodic acid by using a liquid-liquid separation method to obtain selenious acid solution and hydroiodic acid;
(2) the hydroiodic acid obtained in the step (1) comprises the following components: i is2HI and H2O, mixed ternary solution is denoted as HIx solution. And (3) feeding the HIx solution into an HI rectification decomposition unit for rectification, wherein the feeding temperature of a rectification tower is the bubble point temperature, the pressure in the tower is 1.17MPa, and the reaction time is 30 min. (ii) a
(3) Decomposing the hydroiodic acid rectified in the step (2), wherein the pressure in a decomposition tower is 1.17MPa, the reaction temperature is 450 ℃, the reaction time is 65min, and the product is H2And I2Outputting hydrogen as a product, and returning iodine to the step (1) for recycling; the chemical reaction principle of the process is shown as the following chemical reaction equation:
2HI→H2+I2
the high temperature environment in the step is provided by a high temperature gas cooled reactor, and high temperature steam of the high temperature gas cooled reactor is transmitted into a hydroiodic acid decomposition tower through a heat exchanger.
(4) Decomposing selenious acid solution at the reaction temperature of 150 ℃ to obtain selenium dioxide and water vapor, adding reducing agent hydrazine hydrate into the selenium dioxide, wherein the molar ratio of the selenium dioxide to the hydrazine hydrate is as follows: and (3) selenium dioxide and hydrazine hydrate are 1:4.5, the reaction time is 110min, the reaction is complete until no gas is generated, selenium and nitrogen containing water vapor are generated, the selenium returns to the step (1) and is recycled as a raw material, and the nitrogen is dried and then is output as a byproduct. The reaction principle equation is as follows:
H2SeO3→SeO2+H2O
SeO2+4(NH2OH·H2O)→Se+2N2+10H2O
because the toxic substances selenium, selenious acid, selenium dioxide, reducing agent, strong corrosive substance hydroiodic acid and the like participate in the steps (1), (2), (3) and (4), the equipment, the pipeline, the pump and the like need to be resistant to corrosion and have zero leakage, and torque magnetic transmission is used in the process to realize zero leakage.
EXAMPLE five
(1) Taking water as a raw material, adding selenium and iodine, and reacting at normal pressure, wherein the molar ratio of the water to the selenium to the iodine is as follows: selenium and iodine are added into water, wherein the ratio of the selenium to the iodine is 1:1.6:3.7, the reaction temperature is 25 ℃, the reaction time is 60min, the sign of complete reaction is that no gas is generated, selenious acid solution and hydroiodic acid are obtained through reaction, and the reaction equation is as follows:
3H2O+Se+2I2→H2SeO3+4HI
the hydriodic acid and the selenious acid generated in the process are obviously layered due to different densities, wherein the hydriodic acid is on the upper layer, and the selenious acid solution is on the lower layer. Carrying out liquid-liquid separation on selenious acid solution and hydroiodic acid by using a liquid-liquid separation method to obtain selenious acid solution and hydroiodic acid;
(2) the hydroiodic acid obtained in the step (1) comprises the following components: i is2HI and H2O, mixed ternary solution is denoted as HIx solution. And (3) feeding the HIx solution into an HI rectification decomposition unit for rectification, wherein the feeding temperature of a rectification tower is the bubble point temperature, the pressure in the tower is 1.4MPa, and the reaction time is 15 min.
(3) Decomposing the hydroiodic acid rectified in the step (2), wherein the pressure in a decomposition tower is 1.4MPa, the reaction temperature is 410 ℃, the reaction time is 54min, and the product is H2And I2Outputting hydrogen as a product, and returning iodine to the step (1) for recycling; the chemical reaction principle of the process is shown as the following chemical reaction equation:
2HI→H2+I2
the high temperature environment in the step is provided by a high temperature gas cooled reactor, and high temperature steam of the high temperature gas cooled reactor is transmitted into a hydroiodic acid decomposition tower through a heat exchanger.
(4) Decomposing selenious acid solution at the reaction temperature of 180 ℃ to obtain selenium dioxide and water vapor, adding reducing agent hydrazine hydrate into the selenium dioxide, wherein the molar ratio of the selenium dioxide to the hydrazine hydrate is as follows: and (3) selenium dioxide and hydrazine hydrate are 1:5, the reaction time is 100min, the reaction is complete until no gas is generated, selenium and nitrogen containing water vapor are generated, the selenium returns to the step (1) to be used as a raw material for recycling, and the nitrogen is dried and then is output as a byproduct. The reaction principle equation is as follows:
H2SeO3→SeO2+H2O
3SeO2+4NH3→3Se+2N2+6H2O。
because the toxic substances selenium, selenious acid, selenium dioxide, reducing agent, strong corrosive substance hydroiodic acid and the like participate in the steps (1), (2), (3) and (4), the equipment, the pipeline, the pump and the like need to be resistant to corrosion and have zero leakage, and torque magnetic transmission is used in the process to realize zero leakage.
Claims (1)
1. A method for preparing hydrogen by high-temperature gas cooled reactor coupled iodine selenium thermochemical cycle nitrogen reduction is characterized by comprising the following steps:
(1) taking water as a raw material, adding selenium and iodine, and reacting at normal pressure, wherein the molar ratio of the water to the selenium to the iodine is as follows: water, selenium and iodine, wherein the iodine is 1, (0.3-2) and (0.5-4), the reaction temperature is 15-80 ℃, the reaction time is 30-120min, selenious acid solution and hydroiodic acid are obtained by reaction, and the reaction equation is as follows:
3H2O+Se+2I2→H2SeO3+4HI
carrying out liquid-liquid separation on selenious acid solution and hydroiodic acid by using a liquid-liquid separation method to obtain selenious acid solution and hydroiodic acid;
(2) rectifying the hydroiodic acid obtained in the step (1), wherein the feeding temperature of a rectifying tower is the bubble point temperature, the pressure in the tower is 1.1-1.5MPa, and the reaction time is 10-50 min;
(3) decomposing the hydroiodic acid obtained in the step (2), wherein the pressure in a decomposition tower is 1.1-1.5MPa, the reaction temperature is 400-700 ℃, the reaction time is 30-120min, and the product is H2And I2Hydrogen is output as a product, iodine is returned to the step (1) for recycling, and the chemical reaction equation is as follows:
2HI→H2+I2；
(4) adding a reducing agent hydrazine hydrate into the selenious acid solution obtained in the step (1), wherein the adding molar ratio is as follows: selenious acid, hydrazine hydrate, 1 (10), reacting at 100-400 ℃ for 30-120min to obtain selenium, nitrogen and water vapor, drying the nitrogen to be output as a byproduct, returning the selenium to the step (1) to be recycled as a raw material, wherein the reaction equation is as follows:
H2SeO3+N2H4·H2O→Se+N2+4H2O。
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