CN110407167B - Method for preparing hydrogen by high-temperature gas cooled reactor coupled iodine selenium thermochemical cycle phosphorus reduction - Google Patents
Method for preparing hydrogen by high-temperature gas cooled reactor coupled iodine selenium thermochemical cycle phosphorus reduction Download PDFInfo
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Abstract
The invention relates to a method for preparing hydrogen by thermochemically circulating phosphorus reduction of iodine and selenium, belonging to the technical field of hydrogen energy. Firstly, water is taken as a raw material, selenium and iodine are added to react 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 white phosphorus (yellow phosphorus) or red phosphorus or phosphorus trioxide is added to the obtained selenious acid solution to obtain selenium and 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 phosphorus 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+0.502(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 circulating hydrogen production method divides the decomposition reaction of the 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 high-temperature gas cooled reactor coupled iodine selenium thermochemical cycle phosphorus reduction hydrogen production method, which improves the existing thermochemical sulfur iodine cycle hydrogen production process to couple a high-temperature gas cooled reactor and a stable heat source capable of providing high temperature to realize large-scale hydrogen production.
The invention provides a method for producing hydrogen by high-temperature gas cooled reactor coupled iodine selenium thermochemical cycle phosphorus 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 are 1: (0.3-2): (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 white phosphorus (yellow phosphorus) into the selenious acid solution obtained in the step (1), wherein the molar ratio of the added reducing agent white phosphorus to the added selenious acid solution is as follows: selenious acid: reducing agent white phosphorus ═ 1: (3-8), reacting for 5-30min at 0-20 ℃ to obtain selenium and phosphorous acid, wherein the selenium is solid precipitate, the selenium is separated by a solid-liquid separator, the phosphorous acid is output as a byproduct, and the selenium returns to the step (1) to be recycled as a raw material, and the reaction equation is as follows:
P4+3H2SeO3+3H2O→4H3PO3+3Se
the step (4) in the above method for producing hydrogen by thermochemically cycling phosphorus reduction with iodine and selenium may also be: adding hydrogen peroxide into the selenious acid solution obtained in the step (1) according to the following molar ratio: selenious acid: hydrogen peroxide ═ 1: (1-4), reacting for 10-100min at 20-80 ℃ to obtain a selenic acid solution; heating the selenic acid solution for crystallization, wherein the reaction temperature is 40-160 ℃, and the reaction time is 10-100min, so as to obtain selenium trioxide; adding a reducing agent phosphorus into selenium trioxide, wherein the molar ratio of the selenium trioxide to the reducing agent phosphorus is as follows: selenium trioxide: reducing agent phosphorus 1: (1-3), the reaction temperature is 15-40 ℃, and the reaction time is as follows: reacting for 10-60min to generate selenium and tetraphosphorus decaoxide; adding water into the solid mixture, wherein the molar ratio of phosphorus to water is as follows: reducing agent phosphorus: water is 1 to (1-5), the reaction temperature is 10-100 ℃, and the reaction time is as follows: and (2) for 10-60min, generating phosphoric acid, precipitating without reacting selenium, performing solid-liquid separation on a solid-liquid mixture to obtain by-products of phosphoric acid and selenium, and recycling the selenium serving as a raw material in the step (1) according to the following reaction equation:
H2SeO3+H2O2→H2SeO4+H2O
H2SeO4→SeO3+H2O
10SeO3+12P→10Se+3P4O10
the step (4) in the above method for producing hydrogen by thermochemically cycling phosphorus reduction with iodine and selenium may also be: adding hydrogen peroxide into the selenious acid solution obtained in the step (1) according to the following molar ratio: selenious acid: hydrogen peroxide ═ 1: (1-4), reacting for 10-100min at 20-80 ℃ to obtain a selenic acid solution; heating the selenic acid solution for crystallization, wherein the reaction temperature is 40-160 ℃, and the reaction time is 10-100min, so as to obtain selenium trioxide; adding a reducing agent phosphorus trioxide into selenium trioxide, wherein the molar ratio of the selenium trioxide to the reducing agent phosphorus trioxide is as follows: selenium trioxide: reducing agent diphosphorus trioxide ═ 1: (1-5), the reaction temperature is 80-180 ℃, and the reaction time is as follows: reacting for 40-120min to generate selenium and tetraphosphorus decaoxide; adding water into the solid mixture, wherein the molar ratio of phosphorus to water is as follows: reducing agent phosphorus: water 1: (1-5), the reaction temperature is 10-100 ℃, and the reaction time is as follows: and (2) for 10-60min, generating phosphoric acid, precipitating without reacting selenium, performing solid-liquid separation on a solid-liquid mixture to obtain by-products of phosphoric acid and selenium, and recycling the selenium serving as a raw material in the step (1) according to the following reaction equation:
H2SeO3+H2O2→H2SeO4+H2O
H2SeO4→SeO3+H2O
4SeO3+6P2O3＝4Se+3P4O10
in the method for producing hydrogen by thermochemically circulating phosphorus reduction by iodine and selenium, the reaction temperature in the step (1) is 20-30 ℃.
In the method for producing hydrogen by thermochemically circulating phosphorus reduction by iodine and selenium, the reaction temperature in the step (3) is 400-500 ℃.
The method for preparing hydrogen by high-temperature gas cooled reactor coupled iodine-selenium thermochemical cycle phosphorus reduction provided by the invention has the characteristics and advantages that:
1. the method for producing hydrogen by thermo-chemical circulation of phosphorus reduction by coupling the iodine selenium with the high-temperature gas cooled reactor 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 reactants iodine and selenium in the method for producing hydrogen by reducing phosphorus can be recycled, so that the production cost of producing hydrogen 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 phosphorus reduction, which couples various chemical equipment of an iodine-selenium thermochemical cycle system by using the high-temperature gas cooled reactor, and because selenium reactant, selenium trioxide, reducing agent and intermediate products of selenious acid, selenic 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 high-temperature gas cooled reactor with iodine selenium thermochemical cycle phosphorus reduction, which is used for coupling with 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. According to the method for preparing hydrogen by the thermochemical cycle phosphorus reduction of iodine selenium through coupling of the high-temperature gas cooled reactor, the byproduct is phosphoric acid, the phosphoric acid is an important raw material for agricultural production and chemical production, the phosphoric acid can be sold as a product, and the method has great economical efficiency.
6. The method for preparing hydrogen by the thermochemical cycle phosphorus reduction of the high-temperature gas cooled reactor coupled with the iodine selenium is not limited to the coupling of the high-temperature gas cooled reactor, and other high-temperature heat sources can be coupled with the method for preparing hydrogen by the thermochemical cycle phosphorus reduction of the iodine selenium.
Detailed Description
The invention provides a method for producing hydrogen by high-temperature gas cooled reactor coupled iodine selenium thermochemical cycle phosphorus 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 are 1: (0.3-2): (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 white phosphorus into the selenious acid solution obtained in the step (1), wherein the adding molar ratio is as follows: selenious acid: reducing agent white phosphorus ═ 1: (3-8), reacting for 5-30min at 0-20 ℃ to obtain selenium and phosphorous acid, wherein the selenium is solid precipitate, the selenium is separated by a solid-liquid separator, the phosphorous acid is output as a byproduct, and the selenium returns to the step (1) to be recycled as a raw material, and the reaction equation is as follows:
P4+3H2SeO3+3H2O→4H3PO3+3Se
the step (4) in the above method for producing hydrogen by thermochemically cycling phosphorus reduction with iodine and selenium may also be: adding hydrogen peroxide into the selenious acid solution obtained in the step (1) according to the following molar ratio: selenious acid: reacting hydrogen peroxide in the ratio of 1 to (1-4) at 20-80 deg.c for 10-100min to obtain selenic acid solution; heating the selenic acid solution for crystallization, wherein the reaction temperature is 40-160 ℃, and the reaction time is 10-100min, so as to obtain selenium trioxide; adding a reducing agent phosphorus into selenium trioxide, wherein the molar ratio of the selenium trioxide to the reducing agent phosphorus is as follows: selenium trioxide: reducing agent phosphorus 1: (1-3), the reaction temperature is 15-40 ℃, and the reaction time is as follows: reacting for 10-60min to generate selenium and tetraphosphorus decaoxide; adding water into the solid mixture, wherein the molar ratio of phosphorus to water is as follows: reducing agent phosphorus: water 1: (1-5), the reaction temperature is 10-100 ℃, and the reaction time is as follows: and (2) for 10-60min, generating phosphoric acid, precipitating without reacting selenium, performing solid-liquid separation on a solid-liquid mixture to obtain by-products of phosphoric acid and selenium, and recycling the selenium serving as a raw material in the step (1) according to the following reaction equation:
H2SeO3+H2O2→H2SeO4+H2O
H2SeO4→SeO3+H2O
10SeO3+12P→10Se+3P4O10
the step (4) in the above method for producing hydrogen by thermochemically cycling phosphorus reduction with iodine and selenium may also be: adding hydrogen peroxide into the selenious acid solution obtained in the step (1) according to the following molar ratio: selenious acid and hydrogen peroxide, 1: (1-4), reacting for 10-100min at 20-80 ℃ to obtain a selenic acid solution; heating the selenic acid solution for crystallization, wherein the reaction temperature is 40-160 ℃, and the reaction time is 10-100min, so as to obtain selenium trioxide; adding a reducing agent phosphorus trioxide into selenium trioxide, wherein the molar ratio of the selenium trioxide to the reducing agent phosphorus trioxide is as follows: selenium trioxide, reducing agent diphosphorus trioxide is 1: (1-5), the reaction temperature is 80-180 ℃, and the reaction time is as follows: reacting for 40-120min to generate selenium and tetraphosphorus decaoxide; adding water into the solid mixture, wherein the molar ratio of phosphorus to water is as follows: reducing agent phosphorus: water is 1 to (1-5), the reaction temperature is 10-100 ℃, and the reaction time is as follows: and (2) for 10-60min, generating phosphoric acid, precipitating without reacting selenium, performing solid-liquid separation on a solid-liquid mixture to obtain by-products of phosphoric acid and selenium, and recycling the selenium serving as a raw material in the step (1) according to the following reaction equation:
H2SeO3+H2O2→H2SeO4+H2O
H2SeO4→SeO3+H2O
4SeO3+6P2O3＝4Se+3P4O10
in the method for producing hydrogen by thermochemically circulating phosphorus reduction by iodine and selenium, the reaction temperature in the step (1) is 20-30 ℃.
In the method for producing hydrogen by thermochemically circulating phosphorus reduction by iodine and selenium, the reaction temperature in the step (3) is 400-500 ℃.
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: water: selenium: iodine is 1: 0.4: 1, the reaction temperature is 25 ℃, the reaction time is 60min, the sign of complete reaction is no longer generating 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. 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 H20, the 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 white phosphorus (yellow phosphorus) into the selenious acid solution obtained in the step (1), wherein the molar ratio of the added reducing agent white phosphorus to the added selenious acid solution is as follows: selenious acid: reducing agent white phosphorus is 1: 5, reacting for 30min at 0 ℃ to obtain selenium and phosphorous acid, wherein the selenium is solid precipitate, the selenium is separated by a solid-liquid separator, the phosphorous acid is output as a byproduct, the selenium returns to the step (1) to be used as a raw material for recycling, and the reaction equation is as follows:
P4+3H2SeO3+3H2O→4H3PO3+3Se
because the toxic substances selenium, selenious acid, the strong corrosive substances 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 the zero leakage is realized by using torque magnetic transmission in the process.
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: the reaction temperature is 28 ℃, the reaction time is 50min, 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 1.2MPa, 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 white phosphorus (yellow phosphorus) into the selenious acid solution obtained in the step (1), wherein the molar ratio of the added reducing agent white phosphorus to the added selenious acid solution is as follows: selenious acid: reducing agent white phosphorus is 1: 3.5, reacting for 10min at 16 ℃ to obtain selenium and phosphorous acid, wherein the selenium is solid precipitate, the selenium is separated by a solid-liquid separator, the phosphorous acid is output as a byproduct, the selenium returns to the step (1) to be recycled as a raw material, and the reaction equation is as follows:
P4+3H2SeO3+3H2O→4H3PO3+3Se
because the toxic substances selenium, selenious acid, the strong corrosive substances 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 the zero leakage is realized by using torque magnetic transmission in the process.
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: water: selenium: iodine is 1: 2, the reaction temperature is 28 ℃, the reaction time is 48min, the sign of complete reaction is no longer generating 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. 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) Adding hydrogen peroxide into the selenious acid solution obtained in the step (1) according to the following molar ratio: selenious acid: hydrogen peroxide is 1: 2.5, and the reaction lasts for 50min at the temperature of 30 ℃, and the product of the reaction is selenic acid solution. And introducing the dilute acid solution into a distillation tower for evaporation and crystallization, wherein the reaction temperature is 40 ℃, and the reaction time is 100min, so as to obtain the selenium trioxide. Adding a reducing agent red phosphorus into selenium trioxide, wherein the molar ratio of selenium trioxide to phosphorus is as follows: selenium trioxide: phosphorus is 1: 1.5, the reaction temperature is 15 ℃, and the reaction time is as follows: reacting for 60min to generate selenium and tetraphosphorus decaoxide. Adding water into the solid mixture, wherein the molar ratio of phosphorus to water is as follows: phosphorus: water is 1: 3, the reaction temperature is 20 ℃, and the reaction time is as follows: after 45min, phosphoric acid is generated, selenium does not react and precipitates. And (3) introducing the solid-liquid mixture into a solid-liquid separator for separation to obtain by-products of phosphoric acid and selenium, wherein the selenium is returned to the step (1) and used as a raw material for recycling, and the reaction equation is as follows:
H2SeO3+H2O2→H2SeO4+H2O
H2SeO4→SeO3+H2O
10SeO3+12P→10Se+3P4O10。
because the toxic substances selenium, selenious acid, selenium trioxide, the strong corrosive substances 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 the torque magnetic transmission is used in the process to realize the 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: water, selenium and iodine are equal to 1: 1.3: 2.7, the reaction temperature is 28 ℃, the reaction time is 40min, the sign of complete reaction is no longer generating gas, selenious acid solution and hydroiodic acid are obtained by reaction, and the reaction equation is as follows:
3H20+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 H20, the 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) Adding hydrogen peroxide into the selenious acid solution obtained in the step (1) according to the following molar ratio: selenious acid: hydrogen peroxide is 1: 3, and the reaction lasts for 20min at the temperature of 40 ℃, and the product of the reaction is selenic acid solution. And introducing the dilute acid solution into a distillation tower for evaporation and crystallization, wherein the reaction temperature is 80 ℃, and the reaction time is 20min, so as to obtain the selenium trioxide. Adding a reducing agent red phosphorus into selenium trioxide, wherein the molar ratio of selenium trioxide to phosphorus is as follows: selenium trioxide: phosphorus is 1: 1.3, the reaction temperature is 35 ℃, and the reaction time is as follows: reacting for 20min to generate selenium and tetraphosphorus decaoxide. Adding water into the solid mixture, wherein the molar ratio of phosphorus to water is as follows: phosphorus: water is 1: 2.5, the reaction temperature is 80 ℃, and the reaction time is as follows: 20min, phosphoric acid is generated, selenium does not react, and precipitates. And (3) introducing the solid-liquid mixture into a solid-liquid separator for separation to obtain by-products of phosphoric acid and selenium, wherein the selenium is returned to the step (1) and used as a raw material for recycling, and the reaction equation is as follows:
H2SeO3+H2O2→H2SeO4+H2O
H2SeO4→SeO3+H2O
10SeO3+12P→10Se+3P4O10
because the toxic substances selenium, selenious acid, selenium trioxide, the strong corrosive substances 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 the torque magnetic transmission is used in the process to realize the 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: 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. Feeding the HIx solution into a HI rectification decomposition unit for rectification, wherein the feeding temperature of a rectification tower isThe bubble point temperature, the pressure in the tower are 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) Adding hydrogen peroxide into the selenious acid solution obtained in the step (1) according to the following molar ratio: selenious acid: reacting hydrogen peroxide at a ratio of 1: 3 at 40 ℃ for 50min to obtain a selenic acid solution; heating a selenic acid solution for crystallization at 40 ℃ for 100min to obtain selenium trioxide; adding a reducing agent phosphorus trioxide into selenium trioxide, wherein the molar ratio of the selenium trioxide to the reducing agent phosphorus trioxide is as follows: selenium trioxide: reducing agent phosphorus trioxide is 1: 2, the reaction temperature is 120 ℃, and the reaction time is as follows: reacting for 80min to generate selenium and tetraphosphorus decaoxide; adding water into the solid mixture, wherein the molar ratio of phosphorus to water is as follows: phosphorus and water are mixed at the ratio of 1: 3, the reaction temperature is 20 ℃, the reaction time is 45min, phosphoric acid is generated, selenium does not react, and the selenium is precipitated. Introducing the solid-liquid mixture into a solid-liquid separator for separation to obtain by-products of phosphoric acid and selenium, and recycling the selenium serving as a raw material in the step (1) according to the following reaction equation
H2SeO3+H2O2→H2SeO4+H2O
H2SeO4→SeO3+H2O
4SeO3+6P2O3＝4Se+3P4O10
Because the toxic substances selenium, selenious acid, selenium trioxide, the strong corrosive substances 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 the torque magnetic transmission is used in the process to realize the zero leakage.
Claims (5)
1. A method for producing hydrogen by high-temperature gas cooled reactor coupled iodine selenium thermochemical cycle phosphorus 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 white phosphorus into the selenious acid solution obtained in the step (1), wherein the adding molar ratio is as follows: selenious acid, namely reducing agent white phosphorus ═ 1, (3-8), reacting for 5-30min at 0-20 ℃ to obtain selenium and phosphorous acid, wherein the selenium is solid precipitate, the selenium is separated by a solid-liquid separator, the phosphorous acid is output as a byproduct, the selenium returns to the step (1) to be recycled as a raw material, and the reaction equation is as follows:
P4+3H2SeO3+3H2O→4H3PO3+3Se。
2. a method for producing hydrogen by high-temperature gas cooled reactor coupled iodine selenium thermochemical cycle phosphorus 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 hydrogen peroxide into the selenious acid solution obtained in the step (1) according to the following molar ratio: selenious acid, hydrogen peroxide (1-4), reacting at 20-80 deg.C for 10-100min to obtain selenic acid solution; heating the selenic acid solution for crystallization, wherein the reaction temperature is 40-160 ℃, and the reaction time is 10-100min, so as to obtain selenium trioxide; adding a reducing agent red phosphorus into selenium trioxide, wherein the molar ratio of the selenium trioxide to the reducing agent red phosphorus is as follows: selenium trioxide, reducing agent phosphorus ═ 1 (1-3), the reaction temperature is 15-40 ℃, and the reaction time is as follows: reacting for 10-60min to generate selenium and tetraphosphorus decaoxide; adding water into the solid mixture, wherein the molar ratio of phosphorus to water is as follows: reducing agent phosphorus: water is 1, (1-5), the reaction temperature is 10-100 ℃, and the reaction time is as follows: and (2) for 10-60min, generating phosphoric acid, precipitating without reacting selenium, performing solid-liquid separation on a solid-liquid mixture to obtain by-products of phosphoric acid and selenium, and recycling the selenium serving as a raw material in the step (1) according to the following reaction equation:
H2SeO3+H2O2→H2SeO4+H2O
H2SeO4→SeO3+H2O
10SeO3+12P→10Se+3P4O10。
3. a method for producing hydrogen by high-temperature gas cooled reactor coupled iodine selenium thermochemical cycle phosphorus 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 hydrogen peroxide into the selenious acid solution obtained in the step (1) according to the following molar ratio: selenious acid, hydrogen peroxide (1-4), reacting at 20-80 deg.C for 10-100min to obtain selenic acid solution; heating the selenic acid solution for crystallization, wherein the reaction temperature is 40-160 ℃, and the reaction time is 10-100min, so as to obtain selenium trioxide; adding a reducing agent phosphorus trioxide into selenium trioxide, wherein the molar ratio of the selenium trioxide to the reducing agent phosphorus trioxide is as follows: selenium trioxide, reducing agent diphosphorus trioxide-1 (1-5), the reaction temperature is 80-180 ℃, and the reaction time is as follows: reacting for 40-120min to generate selenium and tetraphosphorus decaoxide; adding water into the solid mixture, wherein the molar ratio of phosphorus to water is as follows: reducing agent phosphorus: water is 1, (1-5), the reaction temperature is 10-100 ℃, and the reaction time is as follows: and (2) for 10-60min, generating phosphoric acid, precipitating without reacting selenium, performing solid-liquid separation on a solid-liquid mixture to obtain by-products of phosphoric acid and selenium, and recycling the selenium serving as a raw material in the step (1) according to the following reaction equation:
H2SeO3+H2O2→H2SeO4+H2O
H2SeO4→SeO3+H2O
4SeO3+6P2O3＝4Se+3P4O10。
4. the method for producing hydrogen by thermochemically cycling phosphorus reduction through iodine selenium as claimed in claim 1, 2 or 3, wherein the reaction temperature in step (1) is 20 ℃ to 30 ℃.
5. The method for producing hydrogen by thermochemically cycling phosphorus reduction through iodine selenium as recited in claim 1, 2 or 3, wherein the reaction temperature in step (3) is 400 ℃ to 500 ℃.
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