CN113526461A - Single selenium thermochemical cycle hydrogen production method - Google Patents
Single selenium thermochemical cycle hydrogen production method Download PDFInfo
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- CN113526461A CN113526461A CN202010331202.XA CN202010331202A CN113526461A CN 113526461 A CN113526461 A CN 113526461A CN 202010331202 A CN202010331202 A CN 202010331202A CN 113526461 A CN113526461 A CN 113526461A
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- 239000011669 selenium Substances 0.000 title claims abstract description 145
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 title claims abstract description 134
- 229910052711 selenium Inorganic materials 0.000 title claims abstract description 133
- 239000001257 hydrogen Substances 0.000 title claims abstract description 102
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 102
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 67
- 238000006243 chemical reaction Methods 0.000 claims abstract description 112
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 67
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 62
- 229940000207 selenious acid Drugs 0.000 claims abstract description 59
- MCAHWIHFGHIESP-UHFFFAOYSA-N selenous acid Chemical compound O[Se](O)=O MCAHWIHFGHIESP-UHFFFAOYSA-N 0.000 claims abstract description 59
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 49
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000002994 raw material Substances 0.000 claims abstract description 37
- 239000006227 byproduct Substances 0.000 claims abstract description 27
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000004064 recycling Methods 0.000 claims abstract description 17
- 239000000047 product Substances 0.000 claims abstract description 16
- 238000000926 separation method Methods 0.000 claims abstract description 16
- XDJWZONZDVNKDU-UHFFFAOYSA-N 1314-24-5 Chemical compound O=POP=O XDJWZONZDVNKDU-UHFFFAOYSA-N 0.000 claims abstract description 13
- VSAISIQCTGDGPU-UHFFFAOYSA-N phosphorus trioxide Inorganic materials O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000001816 cooling Methods 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 9
- OBSZRRSYVTXPNB-UHFFFAOYSA-N tetraphosphorus Chemical compound P12P3P1P32 OBSZRRSYVTXPNB-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000003054 catalyst Substances 0.000 claims abstract description 4
- 239000000376 reactant Substances 0.000 claims abstract description 4
- 239000004254 Ammonium phosphate Substances 0.000 claims abstract description 3
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims abstract description 3
- 235000019289 ammonium phosphates Nutrition 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims abstract description 3
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000003337 fertilizer Substances 0.000 claims abstract description 3
- 230000035484 reaction time Effects 0.000 claims description 53
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 46
- 229910052698 phosphorus Inorganic materials 0.000 claims description 42
- 239000011574 phosphorus Substances 0.000 claims description 42
- VFLXBUJKRRJAKY-UHFFFAOYSA-N 13768-86-0 Chemical compound O=[Se](=O)=O VFLXBUJKRRJAKY-UHFFFAOYSA-N 0.000 claims description 38
- QYHFIVBSNOWOCQ-UHFFFAOYSA-N selenic acid Chemical compound O[Se](O)(=O)=O QYHFIVBSNOWOCQ-UHFFFAOYSA-N 0.000 claims description 36
- 239000007788 liquid Substances 0.000 claims description 34
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 claims description 33
- 238000005868 electrolysis reaction Methods 0.000 claims description 26
- 229910003599 H2SeO4 Inorganic materials 0.000 claims description 20
- 238000006722 reduction reaction Methods 0.000 claims description 20
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 18
- 229910018143 SeO3 Inorganic materials 0.000 claims description 16
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- 229910018162 SeO2 Inorganic materials 0.000 claims description 11
- 229910003597 H2SeO3 Inorganic materials 0.000 claims description 10
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 10
- 238000002425 crystallisation Methods 0.000 claims description 9
- 230000008025 crystallization Effects 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 239000008247 solid mixture Substances 0.000 claims description 9
- 239000002244 precipitate Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000000197 pyrolysis Methods 0.000 claims description 7
- 239000003792 electrolyte Substances 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 230000001376 precipitating effect Effects 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 230000008878 coupling Effects 0.000 claims description 3
- 238000010168 coupling process Methods 0.000 claims description 3
- 238000005859 coupling reaction Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 239000002028 Biomass Substances 0.000 claims description 2
- 238000002485 combustion reaction Methods 0.000 claims description 2
- 230000002860 competitive effect Effects 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 229940082569 selenite Drugs 0.000 claims description 2
- MCAHWIHFGHIESP-UHFFFAOYSA-L selenite(2-) Chemical compound [O-][Se]([O-])=O MCAHWIHFGHIESP-UHFFFAOYSA-L 0.000 claims description 2
- 239000002918 waste heat Substances 0.000 claims description 2
- 238000004056 waste incineration Methods 0.000 claims description 2
- 230000009286 beneficial effect Effects 0.000 claims 1
- 125000004122 cyclic group Chemical group 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 7
- JIKZEPRTARLVKA-UHFFFAOYSA-N [Se].[I] Chemical compound [Se].[I] JIKZEPRTARLVKA-UHFFFAOYSA-N 0.000 description 6
- GOIGHUHRYZUEOM-UHFFFAOYSA-N [S].[I] Chemical group [S].[I] GOIGHUHRYZUEOM-UHFFFAOYSA-N 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 4
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 4
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 4
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 229910000043 hydrogen iodide Inorganic materials 0.000 description 2
- 229940071870 hydroiodic acid Drugs 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 238000004174 sulfur cycle Methods 0.000 description 2
- 238000007132 Bunsen reaction Methods 0.000 description 1
- VUGLMIODQKHJFB-UHFFFAOYSA-L Cl[Cu](Cl)O[Cu] Chemical compound Cl[Cu](Cl)O[Cu] VUGLMIODQKHJFB-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
Classifications
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention relates to a method for producing hydrogen by single selenium thermochemical cycle, belonging to the technical field of hydrogen energy. Taking water as a hydrogen production raw material, adding a reactant selenium, reacting at normal pressure, wherein the reaction temperature is 150-200 ℃, and hydrogen is taken as a leading product for separation and output; reducing agent white phosphorus (yellow phosphorus) or red phosphorus or phosphorus trioxide is added into selenious acid solution obtained by cooling to normal temperature or an electrolytic reduction method is utilized to obtain selenium and simultaneously generate a byproduct, the selenium is used as a catalyst for recycling, and the byproduct phosphoric acid can be used as a compound fertilizer ammonium phosphate raw material and has commercial value. The highest temperature required in the reaction process is 150-. The method only relates to the thermochemical cycle of a single substance selenium, and the reactant selenium is also used as a catalyst for cyclic utilization, so that the reaction process is simplified and shortened, the stability and reliability of the system are improved, the heat efficiency and the heat utilization rate are improved, and the large-scale high-efficiency low-cost hydrogen production can be supported.
Description
(I) technical field
The invention relates to a method for producing hydrogen by single selenium thermochemical cycle, belonging to the technical field of hydrogen energy.
(II) background of the invention
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. Four methods for thermochemical cycle hydrogen production are currently common.
The first is a sulfur iodine cycle hydrogen production, 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)
the second is a hybrid sulfur recycle HyS hydrogen production process, developed by Western House, USA, which includes two steps, as follows:
electrolysis: SO (SO)2+2H2O→H2+H2SO4(T＝353K)
High temperature: h2SO4→H2O+SO2+0.5O2(T＞1123K)
The sulfur-iodine cycle hydrogen production method and the mixed sulfur cycle HyS hydrogen production method have the disadvantages that the decomposition reaction of sulfuric acid still needs higher temperature and is still in laboratory scale, and the energy consumption and the 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 number and resources of the heat source which can provide high-temperature stable large-scale engineering above 970K according with the condition are limited.
The third is the Cu-Cl cycle for hydrogen production, and the most prevalent method is a four-step Cu-Cl cycle, which includes four steps, as follows:
electrolysis: 2CuCl (aq) +2HCl → 2CuCl2(aq)+H2(g)(T＝353K-373K，P＝2.4MPa)
And (3) drying: CuCl2(aq)→CuCl2(s)(T＜373K，P＝0.1MPa)
Hydrolysis: CuCl2(s)+H2O(g)→Cu2OCl2(s)+2HCl(g)(T＝613K-673K，P＝0.1MPa)
Pyrolysis: cu2OCl2(s)→2CuCl(l)+0.5O2(g)(T＝723K-803K，P＝0.1MPa)
The Cu-Cl circulation hydrogen production has the advantages of reducing the reaction temperature and has the disadvantages of complicated reaction conditions, more byproducts, complicated devices and larger distance from the large-scale production of industrial hydrogen production.
The fourth method is a high-temperature gas cooled reactor coupled iodine selenium thermochemical cycle phosphorus reduction hydrogen production method, and the chinese patent application (application No. 201910768263.X) is a thermochemical cycle hydrogen production method, which includes three reaction units, as follows:
iodine selenium reaction unit: 3H2O+Se+2I2→H2SeO3+4HI (about 30 ℃ T)
A hydroiodic acid separation and decomposition circulating unit: 2HI → H2+I2(T about 500 ℃ C.)
Selenious acid separation decomposition circulating unit: h2SeO3+H2O2→H2SeO4+H2O (Normal temperature)
H2SeO4→SeO3+H2O (T about 100 deg.C)
10SeO3+12P→10Se+3P4O10(T about 25 ℃ C.)
The method has the advantages of greatly reducing the reaction temperature, having higher thermal efficiency, being capable of coupling with a high-temperature gas cooled reactor to carry out large-scale hydrogen production, and having the defects of two independent cycles of iodine and selenium, long concentration, separation and reduction process, more complex reaction, difficult inhibition and separation of side reaction, and difficult control of intermediate products and byproducts.
Disclosure of the invention
The invention provides a single selenium thermochemical cycle hydrogen production method, which optimizes and improves the applied iodine selenium thermochemical cycle phosphorus reduction hydrogen production method and the applied electric reduction hydrogen production method, cancels iodine cycle, achieves the purpose of hydrogen production only through simple selenium thermochemical cycle, simplifies and shortens reaction flow, greatly reduces reaction temperature, reduces intermediate products and by-products in the reaction process, avoids excessive concentration, separation and reduction, and improves heat efficiency and total heat utilization rate, thereby realizing large-scale low-cost high-efficiency hydrogen production.
The invention provides a method for producing hydrogen by single selenium thermochemical cycle, which comprises the following steps:
(1) taking water as a raw material, adding selenium, and reacting at normal pressure, wherein the molar ratio of the water to the selenium is as follows: the reaction temperature is 150-200 ℃, the reaction time is 30-120min, selenium dioxide and hydrogen are obtained by reaction, and the reaction equation is as follows:
2H2O+Se→SeO2+2H2
separating out hydrogen as a product;
(2) cooling the liquid obtained in the step (1) to normal temperature to obtain selenious acid solution;
(3) adding a reducing agent white phosphorus (yellow phosphorus) into the selenious acid solution obtained in the step (2), wherein the molar ratio of the added reducing agent white phosphorus to the added selenious acid solution is as follows: reacting selenious acid and reducing agent white phosphorus (1: 3-8) at 0-20 ℃ for 5-30min to obtain selenium and phosphorous acid, wherein the selenium is solid precipitate and 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 (3) in the method for producing hydrogen by thermochemical circulation of selenium can also be: adding hydrogen peroxide into the selenious acid solution obtained in the step (2) according to the following molar ratio: reacting selenious acid and hydrogen peroxide 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 (red phosphorus) into selenium trioxide, wherein the molar ratio of the selenium trioxide to the reducing agent phosphorus (red phosphorus) is as follows: selenium trioxide, reducing agent phosphorus, wherein the ratio of phosphorus to selenium trioxide to reducing agent phosphorus is 1 to (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: the reducing agent phosphorus and water are 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 method for producing hydrogen by thermochemical circulation of selenium can also be: adding hydrogen peroxide into the selenious acid solution obtained in the step (2) according to the following molar ratio: reacting selenious acid and hydrogen peroxide 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, phosphorus trioxide, 1 to (1 to 5), the reaction temperature is 80 to 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: the reducing agent phosphorus and water are 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
the step (4) in the method for producing hydrogen by thermochemical circulation of selenium can also be: and (3) carrying out electrolytic reduction on the selenious acid solution in the step (2), taking the selenious acid solution as an electrolyte, taking an electrolytic cathode and an electrolytic anode as nickel sheets, carrying out the electrolytic reduction at the reaction temperature of 10-210 ℃, the electrolytic voltage of 0.10-10V and the reaction time of 10-120min under normal pressure, separating out the selenium obtained by electrolytic reduction at the cathode, and returning the selenium to the step (1) to be used as a raw material for recycling.
The method for preparing hydrogen by single selenium thermochemical cycle has the characteristics and advantages that:
1. the method for producing hydrogen by single selenium thermochemical cycle has the advantages that the highest temperature required in the reaction process is 150-200 ℃, the reaction temperature is greatly reduced, and the method is favorable for coupling various ready-made heat sources, such as waste heat utilization of boilers, kilns and blast furnaces; the method is also suitable for hydrogen production by new energy sources, such as solar photo-thermal hydrogen production, wind power electro-reduction hydrogen production, biomass combustion hydrogen production or waste incineration hydrogen production.
2. The single selenium thermochemical cycle hydrogen production method has the advantages that the reactant, namely the single selenium, can be recycled without loss, the single selenium can be also used as a catalyst in the whole cycle process, and the material cost for hydrogen production is greatly reduced.
3. The single selenium thermochemical cycle hydrogen production method only has single selenium cycle, simplifies and shortens the reaction process, increases the stability of the system, greatly reduces the generation of intermediate substances and byproducts in the reaction process, and ensures the quality of hydrogen products.
4. The sulfur-iodine cycle requires high-temperature pyrolysis to open chemical bonds of sulfur trioxide and hydrogen iodide so that the sulfur-iodine is recycled after reduction, the mixed sulfur cycle requires high-temperature pyrolysis to open sulfur trioxide so that the sulfur-iodine is recycled after reduction, the Cu-C1 cycle requires high-temperature pyrolysis to open a copper oxide-copper chloride complex so that the copper chloride is recycled after reduction, and the iodine-selenium cycle requires high-temperature pyrolysis of hydrogen iodide and high-temperature electrolysis of selenious acid so that the iodine-selenium is recycled after reduction. According to the single selenium thermochemical cycle hydrogen production method, high-energy chemical bonds do not need to be opened in a pyrolysis mode, the single selenium is reduced and then recycled to produce hydrogen only through a phosphorus chemical reduction or electrolytic reduction method, and energy (heat energy, electric energy and mechanical energy) input required in the reaction process is greatly reduced, so that the heat efficiency and the total heat utilization rate are improved.
5. The hydrogen production is more economical and cheaper than normal-temperature water electrolysis and high-temperature water electrolysis by taking water as a hydrogen production raw material, and the single-selenium thermochemical hydrogen production technical route has more competitive advantages compared with normal-temperature water electrolysis and high-temperature water electrolysis; the main product of the mono-selenium thermochemical hydrogen production is hydrogen, and the byproduct of the phosphorus reduction selenite method is phosphoric acid, so that the phosphoric acid can be sold as a compound fertilizer ammonium phosphate raw material, the income can be used as a subsidy, and the hydrogen production cost is reduced; the byproduct of the method for electrically reducing selenium is oxygen, and the purpose of the byproduct oxygen can be developed.
(IV) detailed description of the preferred embodiments
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 reacting at normal pressure, wherein the molar ratio of the water to the selenium is as follows: the reaction temperature is 150-200 ℃, the reaction time is 30-120min, selenium dioxide and hydrogen are obtained by reaction, and the reaction equation is as follows:
2H2O+Se→SeO2+2H2
separating out hydrogen as a product;
(2) cooling the liquid obtained in the step (1) to normal temperature to obtain selenious acid solution;
(3) adding a reducing agent white phosphorus (yellow phosphorus) into the selenious acid solution obtained in the step (2), wherein the molar ratio of the added reducing agent white phosphorus to the added selenious acid solution is as follows: reacting selenious acid and reducing agent white phosphorus (1: 3-8) at 0-20 ℃ for 5-30min to obtain selenium and phosphorous acid, wherein the selenium is solid precipitate and 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 (3) in the method for producing hydrogen by thermochemical circulation of selenium can also be: adding hydrogen peroxide into the selenious acid solution obtained in the step (2) according to the following molar ratio: reacting selenious acid and hydrogen peroxide 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, wherein the ratio of phosphorus to selenium trioxide to reducing agent phosphorus is 1 to (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: the reducing agent phosphorus and water are 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 method for producing hydrogen by thermochemical circulation of selenium can also be: adding hydrogen peroxide into the selenious acid solution obtained in the step (2) according to the following molar ratio: reacting selenious acid and hydrogen peroxide 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, phosphorus trioxide, 1 to (1 to 5), the reaction temperature is 80 to 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: the reducing agent phosphorus and water are 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
the step (4) in the method for producing hydrogen by thermochemical circulation of selenium can also be: and (3) electrolyzing the selenious acid solution in the step (2), taking the selenious acid solution as an electrolyte, taking the cathode and the anode of electrolysis as nickel sheets, and under the normal pressure, the reaction temperature is 10-210 ℃, the electrolysis voltage is 0.10-10V, the reaction time is 10-120min, separating out the selenium obtained by electrolysis at the cathode, and returning the selenium to the step (1) to be used as a raw material for recycling.
(V) example of the method of the invention:
example one
(1) Taking water as a raw material, adding selenium, and reacting at normal pressure, wherein the molar ratio of the water to the selenium is as follows: the reaction temperature is 150 ℃, the reaction time is 120min, the complete reaction mark is that no gas is generated, selenium dioxide and hydrogen are obtained by reaction, and the reaction equation is as follows:
2H2O+Se→SeO2+2H2
hydrogen is separated off as product.
(2) And (3) cooling the liquid obtained in the step (1) to normal temperature to obtain a selenious acid solution, wherein the reaction time is 30 min.
(3) Adding a reducing agent white phosphorus (yellow phosphorus) into the selenious acid solution obtained in the step (2), wherein the molar ratio of the added reducing agent white phosphorus to the added selenious acid solution is as follows: selenious acid and a reducing agent white phosphorus are 1: 5, the reaction time is 30min at the temperature of 0 ℃, selenium and phosphorous acid are obtained, 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
example two
(1) Taking water as a raw material, adding selenium, and reacting at normal pressure, wherein the molar ratio of the water to the selenium is as follows: the reaction temperature is 160 ℃, the reaction time is 90min, the complete reaction mark is no longer gas, selenium dioxide and hydrogen are obtained by reaction, and the reaction equation is as follows:
2H2O+Se→SeO2+2H2
hydrogen is separated off as product.
(2) And (3) cooling the liquid obtained in the step (1) to normal temperature to obtain a selenious acid solution, wherein the reaction time is 30 min.
(3) Adding a reducing agent white phosphorus (yellow phosphorus) into the selenious acid solution obtained in the step (2), wherein the molar ratio of the added reducing agent white phosphorus to the added selenious acid solution is as follows: selenious acid and a reducing agent white phosphorus are 1: 3.5, the reaction time is 10min at 16 ℃, selenium and phosphorous acid are obtained, the selenium is solid precipitate, the solid precipitate 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
EXAMPLE III
(1) Taking water as a raw material, adding selenium, and reacting at normal pressure, wherein the molar ratio of the water to the selenium is as follows: the reaction temperature is 180 ℃, the reaction time is 50min, the complete reaction mark is that no gas is generated, selenium dioxide and hydrogen are obtained by reaction, and the reaction equation is as follows:
2H2O+Se→SeO2+2H2
hydrogen is separated off as product.
(2) And (3) cooling the liquid obtained in the step (1) to normal temperature to obtain a selenious acid solution, wherein the reaction time is 30 min.
(3) Adding hydrogen peroxide into the selenious acid solution obtained in the step (2) according to the following molar ratio: selenious acid and hydrogen peroxide in the ratio of 1 to 2.5, and through reaction at 30 deg.c for 50min to obtain 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 and phosphorus are 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 and water are 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。
example four
(1) Taking water as a raw material, adding selenium, and reacting at normal pressure, wherein the molar ratio of the water to the selenium is as follows: the reaction temperature is 180 ℃, the reaction time is 40min, the complete reaction mark is that no gas is generated, selenium dioxide and hydrogen are obtained by reaction, and the reaction equation is as follows:
2H2O+Se→SeO2+2H2
hydrogen is separated off as product.
(2) And (3) cooling the liquid obtained in the step (1) to normal temperature to obtain a selenious acid solution, wherein the reaction time is 30 min.
(3) Adding hydrogen peroxide into the selenious acid solution obtained in the step (2) according to the following molar ratio: selenious acid and hydrogen peroxide in the ratio of 1 to 3, and through reaction at 40 deg.c for 20min to obtain 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 and phosphorus in a ratio of 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 and water are 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
EXAMPLE five
(1) Taking water as a raw material, adding selenium, and reacting at normal pressure, wherein the molar ratio of the water to the selenium is as follows: the reaction temperature is 190 ℃, the reaction time is 35min, the complete reaction mark is no longer gas, selenium dioxide and hydrogen are obtained by reaction, and the reaction equation is as follows:
2H2O+Se→SeO2+2H2
hydrogen is separated off as product.
(2) And (3) cooling the liquid obtained in the step (1) to normal temperature to obtain a selenious acid solution, wherein the reaction time is 30 min.
(3) Adding hydrogen peroxide into the selenious acid solution obtained in the step (1) according to the following molar ratio: reacting selenious acid and hydrogen peroxide at a ratio of 1: 3 at 40 deg.C for 50min to obtain 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
EXAMPLE six
(1) Taking water as a raw material, adding selenium, and reacting at normal pressure, wherein the molar ratio of the water to the selenium is as follows: the reaction temperature is 150 ℃, the reaction time is 120min, the complete reaction mark is that no gas is generated, selenium dioxide and hydrogen are obtained by reaction, and the reaction equation is as follows:
2H2O+Se→SeO2+2H2
hydrogen is separated off as product.
(2) And (3) cooling the liquid obtained in the step (1) to normal temperature to obtain a selenious acid solution, wherein the reaction time is 30 min.
(3) And (3) electrolyzing the selenious acid solution in the step (2), taking the selenious acid solution as an electrolyte, taking the cathode and the anode of electrolysis as nickel sheets, and separating out the selenium obtained by electrolysis at the cathode under the conditions of normal pressure, reaction temperature of 25 ℃, electrolysis voltage of 0.9V and reaction time of 100 min. The selenium is returned to the step (1) to be used as a raw material for recycling.
EXAMPLE seven
(1) Taking water as a raw material, adding selenium, and reacting at normal pressure, wherein the molar ratio of the water to the selenium is as follows: water to selenium ratio is 1: 3, reaction temperature is 160 ° (C, reaction time is 90min, the sign of complete reaction is no longer gas, selenium dioxide and hydrogen are obtained by reaction, the reaction equation is as follows:
2H2O+Se→SeO2+2H2
hydrogen is separated off as product.
(2) And (3) cooling the liquid obtained in the step (1) to normal temperature to obtain a selenious acid solution, wherein the reaction time is 30 min.
(3) And (2) electrolyzing the selenious acid solution in the step (1), taking the selenious acid solution as an electrolyte, taking the cathode and the anode of electrolysis as nickel sheets, and separating out the selenium obtained by electrolysis at the cathode under normal pressure at the reaction temperature of 200 ℃, the electrolysis voltage of 5V and the reaction time of 30 min. The selenium is returned to the step (1) to be used as a raw material for recycling.
Example eight
(1) Taking water as a raw material, adding selenium, and reacting at normal pressure, wherein the molar ratio of the water to the selenium is as follows: the reaction temperature is 180 ℃, the reaction time is 50min, the complete reaction mark is that no gas is generated, selenium dioxide and hydrogen are obtained by reaction, and the reaction equation is as follows:
2H2O+Se→SeO2+2H2
hydrogen is separated off as product.
(2) And (3) cooling the liquid obtained in the step (1) to normal temperature to obtain a selenious acid solution, wherein the reaction time is 30 min.
(3) And (3) electrolyzing the selenious acid solution in the step (2), taking the selenious acid solution as an electrolyte, taking the cathode and the anode of electrolysis as nickel sheets, and separating out the selenium obtained by electrolysis at the cathode under normal pressure at the reaction temperature of 100 ℃, the electrolysis voltage of 8V and the reaction time of 40 min. The selenium is returned to the step (1) to be used as a raw material for recycling.
Claims (4)
1. A method for producing hydrogen by single selenium thermochemical cycle, which is characterized by comprising the following steps:
(1) taking water as a raw material, adding selenium, and reacting at normal pressure, wherein the molar ratio of the water to the selenium is as follows: the reaction temperature is 150-200 ℃, the reaction time is 30-120min, selenium dioxide and hydrogen are obtained by reaction, and the reaction equation is as follows:
2H2O+Se→SeO2+2H2
hydrogen is taken as a leading product for separation and output;
(2) cooling the liquid obtained in the step (1) to normal temperature to obtain selenious acid solution;
(3) adding a reducing agent white phosphorus (yellow phosphorus) into the selenious acid solution obtained in the step (2), wherein the molar ratio of the added reducing agent white phosphorus to the added selenious acid solution is as follows: reacting selenious acid and reducing agent white phosphorus (1: 3-8) at 0-20 ℃ for 5-30min to obtain selenium and phosphorous acid, wherein the selenium is solid precipitate and 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 method for producing hydrogen by single selenium thermochemical cycle has the advantages and characteristics that:
the single selenium thermochemical cycle hydrogen production method has the highest temperature of 150-200 ℃ required in the reaction process, greatly reduces the reaction temperature, and is beneficial to coupling various ready-made heat sources, such as a boiler, a kiln and a blast furnace, and recovering the waste heat utilization energy; the method is also suitable for hydrogen production by new energy sources, such as solar photo-thermal hydrogen production, wind power electro-reduction hydrogen production, biomass combustion hydrogen production or waste incineration hydrogen production.
The single selenium thermo-chemical circulation hydrogen production method has the advantages that the reactant, the single substance selenium, can be recycled without loss, the single substance selenium can also be used as a catalyst in the whole circulation process, the material variety is few, the price is low, and the material cost for hydrogen production is greatly reduced.
The single selenium thermochemical cycle hydrogen production method has the advantages that only single selenium is circulated, the reaction process is simplified and shortened, the stability and reliability of the system are improved, the generation of intermediate substances and byproducts in the reaction process is greatly reduced, and the quality of hydrogen products is ensured.
The single selenium thermochemical cycle hydrogen production method does not need to open a high-energy chemical bond in a pyrolysis mode, and can produce hydrogen only by recycling the reduced single selenium through a phosphorus chemical reduction or electrolytic reduction method, so that the energy (heat energy, electric energy and mechanical energy) input required in the reaction process is greatly reduced, and the heat efficiency and the total heat utilization rate are improved.
The hydrogen production method by single selenium thermochemical cycle takes water as a hydrogen production raw material, is more economical and cheaper than the hydrogen production by normal-temperature water electrolysis and high-temperature water electrolysis, and has more competitive advantages compared with the hydrogen production by normal-temperature water electrolysis and high-temperature water electrolysis; the main product of the mono-selenium thermochemical hydrogen production is hydrogen, and the byproduct of the phosphorus reduction selenite method is phosphoric acid, so that the phosphoric acid can be sold as a compound fertilizer ammonium phosphate raw material, the income can be used as a subsidy, and the hydrogen production cost is reduced; the byproduct of the method for electrically reducing selenium is oxygen, and the purpose of the byproduct oxygen can be developed.
2. The method for producing hydrogen by single selenium thermochemical cycle as set forth in claim 1, wherein said step (3) is: adding hydrogen peroxide into the selenious acid solution obtained in the step (2) according to the following molar ratio: reacting selenious acid and hydrogen peroxide 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 (red phosphorus) into selenium trioxide, wherein the molar ratio of the selenium trioxide to the reducing agent phosphorus (red phosphorus) is as follows: selenium trioxide, reducing agent phosphorus (red phosphorus) is 1 to (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 (red phosphorus) and 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
3. the method for producing hydrogen by single selenium thermochemical cycle as set forth in claim 1, wherein said step (3) is: adding hydrogen peroxide into the selenious acid solution obtained in the step (2) according to the following molar ratio: reacting selenious acid and hydrogen peroxide 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, phosphorus trioxide, 1 to (1 to 5), the reaction temperature is 80 to 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: the reducing agent phosphorus and water are 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
4. the method for producing hydrogen by single selenium thermochemical cycle as set forth in claim 1, wherein said step (3) is: and (3) electrolyzing the selenious acid solution in the step (2), taking the selenious acid solution as an electrolyte, taking the cathode and the anode of electrolysis as nickel sheets, and under the normal pressure, the reaction temperature is 10-210 ℃, the electrolysis voltage is 0.10-10V, the reaction time is 10-120min, separating out the selenium obtained by electrolysis at the cathode, and returning the selenium to the step (1) to be used as a raw material for recycling.
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| CN116812865A (en) * | 2023-08-29 | 2023-09-29 | 浙江百能科技有限公司 | System and process for thermochemical selenium-iodine cyclic hydrogen production and simultaneous removal of CO in flue gas |
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