CN115321479B - Method and device for producing hydrogen and co-producing sulfuric acid by thermochemical zinc-sulfur-iodine cycle decomposition of water - Google Patents
Method and device for producing hydrogen and co-producing sulfuric acid by thermochemical zinc-sulfur-iodine cycle decomposition of water Download PDFInfo
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/74—Preparation
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- 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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses a method and a device for producing hydrogen and co-producing sulfuric acid by thermochemical zinc-sulfur-iodine cycle decomposition of water. The method replenishes SO from outside 2 Water and system circulation I 2 Performing Bunsen reaction, reacting the reaction mixture with Zn and ZnO circulating in the system to prepare hydrogen, taking hydrogen as a product, removing water from the residual liquid mixture, then introducing the residual liquid mixture into a catalytic decomposition reactor for decomposition, cooling the catalytic decomposition reaction product by a primary cooler, returning molten Zn and solid ZnO to a hydrogen generator, and introducing the residual gas material into a secondary cooler for separation; obtained I 2 Returning to the Bunsen reactor, SO 3 Feeding into H 2 SO 4 The sulfuric acid is generated in the generator. The invention reduces the number of high-temperature reactors of the system; without excessive input of I 2 And water, the energy consumption of subsequent drying is reduced; the invention has simple reaction and high hydrogen production rate; the resulting product H 2 And the sulfuric acid has no separation problem.
Description
Technical Field
The invention relates to a technology for circularly producing hydrogen by zinc, sulfur and iodine, belongs to the related technical field of preparing hydrogen by thermal circulation, and particularly relates to a method and a device for producing hydrogen and co-producing sulfuric acid by circularly decomposing water by thermochemical zinc, sulfur and iodine.
Background
Hydrogen energy is considered as one of the most ideal clean energy sources, and the only product of combustion is water, so that the method has no problem of environmental pollution. The energy density of the hydrogen energy is large, and the conversion efficiency is high. Besides being used as an energy source, hydrogen is an important chemical raw material. More than half of the hydrogen is used in the important chemical processes of ammonia synthesis, petroleum cracking and the like in the world every year. At present, the hydrogen production method which is most widely used in the world is still hydrogen production by fossil fuel, but with the gradual exhaustion of fossil energy and the increasing severity of the pressure of carbon dioxide emission reduction, a large-scale, low-cost, sustainable and clean hydrogen production mode is urgently searched.
At the end of the last century, through series screening and evaluation by numerous researchers, the thermochemical sulfur-iodine cycle water decomposition hydrogen production technology is considered to be the most promising hydrogen production mode. It takes water as raw material, and decomposes the water into hydrogen and oxygen by a series of chemical reactions and using heat energy. The heat energy required by the whole system can be matched by solar energy or nuclear energy and the like. The traditional thermochemical sulfur-iodine closed cycle reaction is as follows:
SO 2 + 2H 2 O +I 2 = H 2 SO 4 + 2HI （85℃）
2H 2 SO 4 = 2SO 2 +2H 2 O + O 2 （850℃）
2HI = H 2 + I 2 (450℃)。
the temperature required for the metal oxide to achieve direct thermal decomposition is relatively high. To date, zn/ZnO is one of the most studied systems in a two-step thermochemical cycle, and this system has been intensively studied and developed. The whole process comprises the following steps:
2ZnO = 2Zn + O 2
Zn + H 2 O = ZnO + H 2
Zn + CO 2 = ZnO + CO。
the first step of ZnO pyrolysis is an endothermic process with the desired reaction temperature of 2058 c and the products of it are zinc vapour and oxygen, which eventually need to be separated or quenched to prevent recombination of the products. The second step is that: CO 2 2 And H 2 The decomposition reaction of O must be carried out at a temperature exceeding the melting point of zinc (420 ℃ C., 1 atm). However, when molten zinc reacts with water vapor or carbon dioxide, a layer of ZnO is formed to float on the melt, preventing further reaction.
In order to avoid direct decomposition of metal oxides at high temperatures, thermochemical ZnSI circulation systems have been developed, which consist in particular of the following reactions:
I 2 + SO 2 + 2H 2 O = 2HI+H 2 SO 4
2HI = H 2 + I 2 （450℃）
2H 2 SO 4 = 2SO 2 + 2H 2 O + O 2 （850℃）
Zn + CO 2 = ZnO + CO（350-900℃）
ZnO + 2HI = ZnI 2 + H 2 O
ZnI 2 = Zn + I 2 （600-900℃）。
the zinc-sulfur-iodine circulating system has the following general reactions:
H 2 O + CO 2 = CO + H 2 +O 2 。
the traditional zinc-sulfur-iodine circulating hydrogen production system has complex reaction steps and needs to input excessive iodine and H 2 O to reach the HIx phase and H 2 SO 4 Phase separation increases the energy consumption of the subsequent concentration step; subject to HI-H 2 The azeotropic property of O can not obtain HI solution with high concentration under normal pressure (the azeotropic point of the HI solution is 57 percent under normal pressure), and the HI decomposition efficiency is low (only 22 percent under the existence of catalyst), thus seriously influencing the production rate of hydrogen; the sulfuric acid decomposition requires a high-temperature environment, so that the energy consumption is increased, and the requirement on equipment is high; zn and CO 2 The reaction belongs to gas-solid reaction, and the generated ZnO is attached to the surface of the zinc to block Zn and CO 2 Further reaction of (2); at present pure CO 2 The cost of complementation is high, and economic benefit is uncertain.
The existing SI systems are all circulating systems, i.e. the raw material is only water, I 2 And SO 2 Is recycledThe HI must be decomposed to produce hydrogen, and the decomposition of HI brings I 2 And (4) generating. But SO 2 Whether the cycle of (a) is necessary and reasonable or not still needs to be investigated. Need for sulfuric acid decomposition>The high temperature of 800 ℃ has considerable demand on heat, higher demand on catalyst and reactor materials, and the whole system can be greatly simplified if the sulfuric acid in the SI system is not decomposed any more. And carbon-free sulfur-containing raw materials can be selected to realize CO of the system 2 And (4) zero emission. Sulfuric acid has a huge market as product output, and is widely applied to industries such as chemical industry, national defense, metallurgy, pharmacy and the like.
Performing ring opening treatment on the ZnSI system, directly outputting sulfuric acid, and simultaneously generating HI and H by using Zn and Bunsen reaction 2 SO 4 The hydrogen is directly prepared by the reaction, the problems of low concentration (57%) of HI azeotropic solution, low HI decomposition rate (only 22% in the presence of a catalyst) and the like are avoided, and the generated ZnI 2 And ZnSO 4 Decomposition to form Zn, I 2 ZnO (into the next cycle) and SO 3 (reaction with water to form sulfuric acid) the chemical reaction is as follows:
SO 2 + 2H 2 O +I 2 = H 2 SO 4 + 2HI
2Zn + 2HI + H 2 SO 4 = ZnI 2 +ZnSO 4 + 2H 2
2ZnO + 2HI +H 2 SO 4 = ZnI 2 + ZnSO 4 + 2H 2 O
ZnI 2 = Zn + I 2 (600-1000℃）
ZnSO 4 = ZnO + SO 3 (>900℃）
SO 3 + H 2 O = H 2 SO 4 。
the overall reaction of the open-circuit ZnSI system is as follows:
2H 2 O + SO 2 = H 2 + H 2 SO 4 。
the technology and literature data disclosed at present are studied on the process for preparing hydrogen by thermochemical ZnSI cycle, wherein patent CN108821315A discloses thermochemical cycle mineralization of CO 2 Simultaneous decomposition of H 2 O system H 2 Method and apparatus for recycling hydrogen production with CO 2 Mineralization is organically combined, but the HI solution is concentrated by an electrodialysis method, so that the requirement on the corrosion resistance of an electrode material is extremely high, and the manufacturing cost is high; the electrolytic cell is limited in volume and difficult to realize large-scale industrial application. CN102583239B provides a thermochemical cyclic decomposition of CO 2 And H 2 O to CO and H 2 The method and the device realize CO 2 The objective of abatement and hydrogen production, but the problem of the HI solution being subject to azeotropic point and the hydrogen production rate being subject to low HI decomposition rate, is not yet solved. Patent CN108715438A discloses thermochemical cycle mineralization of CO 2 Simultaneous decomposition of H 2 Preparation of H from O 2 Coproduction of H 2 SO 4 Method of innovatively mixing CO 2 The mineralization technology is organically combined with the thermochemical sulfur-iodine open-circuit cycle decomposition of water to produce hydrogen, and CO is mineralized and fixed under mild reaction conditions 2 And simultaneously co-producing H with high added value 2 And H 2 SO 4 However, the problem that the hydrogen production rate is subject to a low decomposition rate of HI is not solved.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, provides a method and a device for producing hydrogen and sulfuric acid by thermochemically decomposing water by using zinc, sulfur and iodine, and can reduce the number of high-temperature equipment of the conventional system and improve the production rate of hydrogen.
The technical scheme of the invention is as follows:
the invention firstly provides a method for producing hydrogen and co-producing sulfuric acid by thermochemical zinc-sulfur-iodine cycle decomposition of water, which comprises the following steps:
s1: external supplemental SO 2 Water in the Bunsen reactor with I from the secondary desuperheater 2 The reaction is carried out, and the liquid mixture after the reaction enters H 2 A generator;
S2：H 2 in the generator, HI and sulfuric acid in the liquid mixture react with Zn and ZnO from the primary desuperheater to generate ZnI 2 、ZnSO 4 Water and H 2 Hydrogen leaves as product H 2 Generator, remainsDrying and dewatering the rest liquid mixture, and then feeding the liquid mixture into a catalytic decomposition reactor;
s3: in a catalytic decomposition reactor, znI 2 Decomposition reaction is carried out at high temperature to generate Zn and I 2 ，ZnSO 4 Decomposition reaction is carried out to generate SO 3 And ZnO; cooling the product of the catalytic decomposition reactor by a primary cooler, and returning molten Zn and solid ZnO to H 2 The generator enters the next cycle, and the rest materials enter a secondary cooler in a gas form;
s4: the material is cooled by a secondary cooler I 2 Cooling to obtain liquid I 2 Returning to the Bunsen reactor for the next cycle, and collecting the residual SO 3 Feeding into H 2 SO 4 The generator reacts with water to generate sulfuric acid.
As a preferred embodiment of the invention, the Bunsen reactor, H 2 The generator, the first-stage cooler, the second-stage cooler and the catalytic decomposition reactor are operated under normal pressure.
As a preferred embodiment of the present invention, the temperature of the Bunsen reactor is 70 to 90 ℃. H 2 The generator operating temperature is 70-90 ℃. The operating temperature of the catalytic decomposition reactor is 900-1000 ℃. The operation temperature of the first-stage cooler is 450-600 ℃. The operating temperature of the secondary cooler is 120-160 ℃.
The invention also provides a device for producing hydrogen and co-producing sulfuric acid by thermochemical zinc-sulfur-iodine cycle decomposition of water, which comprises:
bunsen reactor as a reaction device for generating Bunsen reaction, which has several raw material inlets for adding externally supplemented SO 2 Water, and has I connected to a secondary cooler 2 Inlet and H 2 A product outlet connected to the generator;
H 2 a generator connected with the product outlet of the Bunsen reactor, a Zn and ZnO inlet connected with the first-stage cooler, a hydrogen outlet and a liquid outlet, and H 2 The generator is used for producing hydrogen;
dryer for removing H 2 Water in the material flowing out of the liquid outlet of the generator;
the catalytic decomposition reactor is connected with the dryer and is used for decomposing the dried material;
a primary cooler connected with the catalytic decomposition reactor for cooling and separating decomposition products of the catalytic decomposition reactor, and conveying molten Zn and solid ZnO obtained by separation to H 2 Zn and ZnO inlets of the generator; the gas-phase material obtained by separation is discharged from a gas-phase outlet of the separator;
a second-stage cooler for cooling and separating the material discharged from the gas-phase outlet of the first-stage cooler to obtain I 2 Transferring to a Bunsen reactor to obtain SO 3 Feeding into H 2 SO 4 A generator;
H 2 SO 4 generator of SO 3 Reacting with water to form sulfuric acid.
Compared with the traditional process and device for preparing hydrogen by thermochemical iodine-sulfur circulation, the invention reduces the number of high-temperature reactors of the system; the traditional thermochemical sulfur iodine cycle needs at least 2 high-temperature reactors (one is used for HI decomposition and one is used for sulfuric acid decomposition), the traditional zinc sulfur iodine cycle needs at least 3 high-temperature reactors, and only 1 catalytic decomposition reactor is high-temperature equipment.
The invention does not need to input excessive I 2 And water, the energy consumption of subsequent drying is reduced; solves the problem that the prior art is limited by HI-H 2 O azeotropy (57% at normal pressure) and low HI decomposition rate (22% in the presence of catalyst), zn and HI and H are used 2 SO 4 The hydrogen is produced by direct reaction, and the hydrogen production rate is high due to simple reaction; product H formed 2 And the sulfuric acid has no separation problem. All parts of the system belong to chemical processes, and the reaction temperature is appropriate, so that the system has a prospect of wide application on a large scale. Incorporating solid ZnI 2 ，ZnSO 4 Zn and ZnO are produced by decomposition, and the Zn and ZnO are further reacted with HI and H 2 SO 4 Reaction to form ZnI 2 And ZnSO 4 Realize ZnI 2 And ZnSO 4 And (4) internal circulation. The iodine recovered in the system is returned to the Bunsen reactor again for reuse.
Drawings
FIG. 1 is a schematic diagram of the process flow of the zinc-sulfur-iodine cycle hydrogen production and sulfuric acid co-production.
Wherein: 1-Bunsen reactor, 2-H 2 A generator, a 3-dryer, a 4-catalytic decomposition reactor, a 5-first cooler, a 6-second cooler and a 7-H 2 SO 4 A generator; a-water, B-SO 2 C-HI and H 2 SO 4 Mixed solution, D-product H 2 E-mixed solution, F-dry solid, G-Zn, znO, I 2 And SO 3 Mixture of H-I 2 And SO 3 Mixture of I-SO 3 J-Zn and ZnO mixture, K-product sulfuric acid, L-I 2 。
Detailed Description
The technical solutions of the present invention are described in detail below with reference to the drawings and specific embodiments, and the specific embodiments described herein are only used to explain the present invention, but the scope of the present invention is not limited to the embodiments.
As shown in FIG. 1, the thermochemical Zn-S-I cycle decomposition H provided in this example 2 O system H 2 The method and the device for coproducing the sulfuric acid mainly comprise a Bunsen reactor 1, H 2 A generator 2, a dryer 3, a catalytic decomposition reactor 4, a first-stage cooler 5, a second-stage cooler 6 and H 2 SO 4 A generator 7.
I in the Bunsen reactor 1 2 From the secondary cooler 6, the reactant SO 2 And H 2 O is directly supplemented by the outside. The operating environment of the Bunsen reactor 1 is normal pressure of 70-90 ℃, the reaction is spontaneous exothermic reaction, and H is remained after the reaction is finished 2 SO 4 HI and H 2 A liquid phase mixture of O. In one embodiment, the Bunsen reactor of the present invention is provided with at least three inlets and one liquid outlet; the liquid outlet of the Bunsen reactor is connected with the inlet of the hydrogen generator, one inlet is supplemented with water, one inlet receives iodine from the secondary cooler, and the other inlet is supplemented with SO 2 。
The reaction liquid after the reaction in the Bunsen reactor 1 enters H 2 A generator 2, wherein the operating environment is normal pressure of 70-90 ℃, and HI and sulfuric acid react with Zn and ZnO from the primary cooler 5 to prepare hydrogen; in one embodiment, H 2 The generator has an inlet connected to the Bunsen reactor 1, a Zn and ZnO inlet connected to the primary desuperheater, a gas outlet for discharging the product hydrogen, and a liquid outlet connected to the dryer.
Liquid mixture after the end of the reaction (ZnI) 2 ,ZnSO 4 ) Removing H by a drier 3 2 The O enters a catalytic decomposition reactor 4 under the normal pressure of 900-1000 ℃ and ZnI 2 Decomposition reaction is carried out to generate Zn, znO and ZnSO 4 Decomposition reaction takes place to generate I 2 And SO 3 The mixture is sent into a primary cooler 5, the operating environment is normal pressure of 450-600 ℃, znO (solid) and Zn (molten) leave the primary cooler 5 and return to H 2 The generator 2 is recycled; in one embodiment, the primary desuperheater has an inlet connected to the catalytic reactor and an outlet connected to the Bunsen reactor output Zn and ZnO, and an outlet connected to the secondary desuperheater output I 2 And SO 3 And (4) mixing the gases.
Residual I of the primary cooler 5 2 And SO 3 Entering a secondary cooler 6 in a gas form, wherein the operating environment is normal pressure of 120-160 ℃, I 2 Melting point 113 ℃ and boiling point 184 ℃; SO (SO) 3 Melting point 16.8 ℃ and boiling point 44.8 ℃. I is 2 Cooling and returning the liquid to the Bunsen reactor 1 3 Is sent to H 2 SO 4 Generator 7 (Normal temperature and pressure), and H 2 And (4) concentrating the sulfuric acid solution generated by the O reaction to output as a product. In one embodiment, the inlet of the secondary desuperheater is connected to the primary desuperheater, and one outlet of the secondary desuperheater is connected to the Bunsen reactor output I 2 One outlet is connected to H 2 SO 4 And a generator.
The process steps for preparing hydrogen and co-producing sulfuric acid in the zinc-sulfur-iodine cycle by adopting the device are as follows:
external supplementary SO 2 And H 2 O as reactant enters the Bunsen reactor 1, with I circulating internally 2 The exothermic reaction which spontaneously proceeds at 70-90 ℃ takes place as follows:
SO 2 + 2H 2 O + I 2 = 2HI+ H 2 SO 4 。
after the reaction is finished, the mixture enters H 2 The generator 2, in the environment of normal pressure 70-90 ℃, performs spontaneous exothermic reaction with Zn and ZnO from the primary cooler 5, as follows:
2Zn + 2HI + H 2 SO 4 = ZnI 2 +ZnSO 4 + 2H 2
2ZnO + 2HI +H 2 SO 4 = ZnI 2 + ZnSO 4 + 2H 2 O。
hydrogen as product output, znI 2 And ZnSO 4 After passing through a dryer 3, the liquid mixture enters a catalytic decomposer 4, the operation environment is normal pressure 900-1000 ℃, and the chemical reaction is as follows:
ZnI 2 = Zn + I 2
ZnSO 4 = ZnO + SO 3 。
the mixture after the reaction enters a first-stage cooler 5, the operating environment is normal pressure of 450-600 ℃, znO (solid) and Zn (molten) leave the first-stage cooler 5 and enter H 2 A generator 2, entering the next cycle;
residual I of primary cooler 5 2 And SO 3 Entering a secondary cooler 6 in a gas form, wherein the operating environment is normal pressure of 120-160 ℃, I 2 Cooled to become liquid and returned to the Bunsen reactor 1 3 Is sent to H 2 SO 4 Generator 7 (ambient temperature and pressure), the following reaction occurs:
SO 3 + H 2 O = H 2 SO 4
the generated sulfuric acid solution is output as a product after being concentrated.
The invention reduces the number of high temperature reactors in the system, does not need HI and H 2 SO 4 Separation apparatus, without HI and H 2 SO 4 Pyrolysis apparatus, without HI and H 2 SO 4 The concentrating device simplifies the flow.
Compared with the traditional thermochemical hydrogen preparation process and device, the invention reduces the number of high-temperature reactors of the system; without input of excessive I 2 And water, reducing subsequent dryingEnergy consumption; solves the problem that the strain is restricted by HI-H 2 O azeotropy (57% at normal pressure) and low HI decomposition rate (22% in the presence of catalyst), zn and HI and H are used 2 SO 4 Hydrogen is produced by direct reaction, the reaction condition is simple, and the hydrogen production rate is high; the resulting product H 2 And the sulfuric acid has no separation problem. All parts of the system belong to chemical processes, and the reaction temperature is appropriate, so that the system has a prospect of wide application on a large scale. Introduction of solid ZnI 2 And ZnSO 4 Zn and ZnO are produced by decomposition, zn and ZnO are further reacted with HI and H, respectively 2 SO 4 Reaction to form ZnI 2 And ZnSO 4 Realize ZnI 2 And ZnSO 4 And (4) internal circulation. The iodine recovered in the system is returned to the Bunsen reactor again for reuse.
Example 1
The operating environment in the Bunsen reactor is 75 ℃, the temperature is normal, the charging in the reactor is 100mol of SO 2 ,100mol I 2 400mol of water. After the reaction is fully stirred, SO 2 The conversion rate reaches more than 98 percent, and HI and H are remained in the reactor 2 SO 4 The liquid composition of the mixed acid solution of (1) HI 65.6 wt%, H 2 SO 4 25.1 wt %。
The mixed acid solution leaves the Bunsen reactor and enters H 2 The generator, which spontaneously evolves exothermic reaction at 80 ℃, is as follows:
2Zn + 2HI + H 2 SO 4 = ZnI 2 +ZnSO 4 + 2H 2
2ZnO + 2HI +H 2 SO 4 = ZnI 2 + ZnSO 4 + 2H 2 O。
zn and ZnO react fully, and hydrogen is output as a product (98 mol), H 2 Generator remaining HI 0.9wt%, H 2 SO 4 0.4 wt %，ZnI 2 58.9wt% and ZnSO 4 29.7wt% mixed solution. The mixed salt solution is dried and then enters a catalytic decomposition reactor, and the decomposition reaction is carried out under the action of a catalyst at the normal pressure of 1000 ℃ as follows:
ZnI 2 = Zn + I 2
ZnSO 4 = ZnO + SO 3 。
the mixture after the end of the reaction had a composition of Zn 13.3% by weight 2 51.9 wt %，ZnO 16.5 wt %，SO 3 16.3 wt %，ZnI 2 1.3 wt %，ZnSO 4 0.7 And wt%. The mixture is sent to a primary desuperheater where Zn and ZnO are returned to H at 450 deg.C 2 The generator continues with the next cycle, I 2 And SO 3 And enters the secondary cooler in a gas form. The temperature in the secondary cooler is 120 ℃, I 2 Returned to the Bunsen reactor in liquid form into the next cycle, SO 3 In gaseous form into H 2 SO 4 The generator reacts as follows:
SO 3 + H 2 O = H 2 SO 4
the system outputs 98mol H to the outside 2 SO 4 。
In the traditional sulfur iodine circulation, the high-temperature HI part is concentrated and decomposed with energy consumption of 33kw x h/m 3 H 2 。H 2 SO 4 The energy consumption of the pyrolysis part is 2.3kw x h/m 3 H 2 . The high-temperature part of the invention only stores ZnI 2 With ZnSO 4 Decomposition (hydrogen generator) with an energy consumption of 11.2 kw h/m 3 H 2 And the energy consumption is only 31.7 percent of that of the high-temperature reactor in the traditional route.
Example 2
The operating environment in the Bunsen reactor is 90 ℃, the temperature is normal pressure, and the feeding in the tower is 200mol SO 2 ,200mol I 2 600mol of water. After stirring the reaction well, SO 2 The conversion rate reaches more than 98 percent, and HI and H are remained in the reactor 2 SO 4 With a composition of HI 68.8 wt.% and H 2 SO 4 26.3 wt %。
The mixed acid solution leaves the Bunsen reactor and enters H 2 The generator, which spontaneously evolves exothermic reaction at 80 ℃, is as follows:
2Zn + 2HI + H 2 SO 4 = ZnI 2 +ZnSO 4 + 2H 2
2ZnO + 2HI +H 2 SO 4 = ZnI 2 + ZnSO 4 + 2H 2 O。
Znfully reacting with ZnO, outputting hydrogen as a product (190 mol), and H 2 Generator residual HI 2.5wt%, H 2 SO 4 1.0 wt %，ZnI 2 59.6wt% and ZnSO 4 30.1wt% of the mixed solution. The mixed salt solution is dried and then enters a catalytic decomposition reactor, and the decomposition reaction is carried out under the action of a catalyst at the normal pressure of 900 ℃ as follows:
ZnI 2 = Zn + I 2
ZnSO 4 = ZnO + SO 3 。
the mixture after the reaction is sent to a first-stage cooler, and Zn and ZnO are returned to H at 500 DEG C 2 The generator continues with the next cycle, I 2 And SO 3 And enters the secondary cooler in a gas form. The temperature in the secondary cooler is 140 ℃, I 2 Returned to the Bunsen reactor in liquid form into the next cycle, SO 3 In gaseous form into H 2 SO 4 The generator reacts as follows:
SO 3 + H 2 O = H 2 SO 4
190mol H is output externally by the system 2 SO 4 . The energy consumption of the example 2 is equivalent to that of the example 1 and is far lower than that of a high-temperature reactor of a traditional route.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present invention should be subject to the appended claims.
Claims (9)
1. A method for thermochemically decomposing water to produce hydrogen and co-produce sulfuric acid by using zinc, sulfur and iodine is characterized by comprising the following steps:
s1: external supplemental SO 2 Water in the Bunsen reactor with I from the secondary desuperheater 2 The reaction is carried out, and the liquid mixture after the reaction enters H 2 A generator;
S2：H 2 in the generator, HI and sulfuric acid in the liquid mixture react with Zn and ZnO from the primary desuperheater to generate ZnI 2 、ZnSO 4 Water and H 2 Hydrogen leaves as product H 2 The generator is used for drying and dewatering the residual liquid mixture and then feeding the dried liquid mixture into a catalytic decomposition reactor;
s3: in a catalytic decomposition reactor, znI 2 Decomposition reaction is carried out at high temperature to generate Zn and I 2 ，ZnSO 4 Decomposition reaction is carried out to generate SO 3 And ZnO; cooling the product of the catalytic decomposition reactor by a primary cooler, and returning molten Zn and solid ZnO to H 2 The generator enters the next cycle, and the rest materials enter a secondary cooler in a gas form;
s4: the material is cooled by a secondary cooler I 2 Cooling to obtain liquid I 2 Returning the obtained product to the Bunsen reactor for the next circulation, and obtaining the residual SO 3 Feeding into H 2 SO 4 The generator reacts with water to generate sulfuric acid.
2. The method for hydrogen production and sulfuric acid coproduction through thermochemical zinc-sulfur-iodine cycle decomposition of water according to claim 1, wherein the operating environment of the Bunsen reactor is normal pressure and the temperature is 70-90 ℃.
3. The method for producing hydrogen and sulfuric acid by thermochemical zinc-sulfur-iodine cycle decomposition of water according to claim 1, wherein H is H 2 The generator operating environment is normal pressure, and the temperature is 70-90 ℃.
4. The method for hydrogen production and sulfuric acid coproduction by thermochemical zinc-sulfur-iodine cycle decomposition of water according to claim 1, wherein the operating environment of the catalytic decomposition reactor is normal pressure and the temperature is 900-1000 ℃.
5. The method for hydrogen production and sulfuric acid coproduction by thermochemical zinc-sulfur-iodine cycle decomposition of water according to claim 1, wherein the operating environment of the primary cooler is normal pressure and the temperature is 450-600 ℃.
6. The method for hydrogen production and sulfuric acid coproduction by thermochemical zinc-sulfur-iodine cycle decomposition of water according to claim 1, wherein the operating environment of the secondary cooler is normal pressure and the temperature is 120-160 ℃.
7. The method for producing hydrogen and sulfuric acid by thermochemical zinc-sulfur-iodine cycle decomposition of water according to claim 1, wherein H is H 2 SO 4 The generator operates in normal temperature and pressure, SO 3 And H 2 And (4) carrying out O reaction to generate a sulfuric acid solution, and concentrating the obtained sulfuric acid solution according to the concentration requirement of a downstream process or the concentration requirement of the product sulfuric acid.
8. An apparatus for producing hydrogen and sulfuric acid by thermochemical zinc-sulfur-iodine cycle decomposition of water by implementing the method of any of claims 1 to 7, characterized by comprising:
bunsen reactor as a reaction device for generating Bunsen reaction, which has several raw material inlets for adding externally supplemented SO 2 Water, and has I connected to a secondary cooler 2 Inlet and H 2 A product outlet connected to the generator;
H 2 a generator connected with the product outlet of the Bunsen reactor, a Zn and ZnO inlet connected with the first-stage cooler, a hydrogen outlet and a liquid outlet, and H 2 The generator is used for producing hydrogen;
dryer for removing H 2 Water in the material flowing out of the liquid outlet of the generator;
the catalytic decomposition reactor is connected with the dryer and is used for decomposing the dried material;
a primary cooler connected with the catalytic decomposition reactor for cooling and separating decomposition products of the catalytic decomposition reactor, and conveying molten Zn and solid ZnO obtained by separation to H 2 Zn and ZnO inlets of the generator; the gas-phase material obtained by separation is discharged from a gas-phase outlet of the separator;
a second-stage cooler for feeding the material discharged from the gas-phase outlet of the first-stage coolerCooling and separating to obtain I 2 Transferring to a Bunsen reactor to obtain SO 3 Feeding H 2 SO 4 A generator;
H 2 SO 4 generator of SO 3 Reacting with water to form sulfuric acid.
9. The device for hydrogen production and sulfuric acid coproduction through thermochemical zinc-sulfur-iodine cycle decomposition of water according to claim 8, wherein the H is H 2 SO 4 The product outlet of the generator is connected with H 2 SO 4 Concentration device for H according to demand 2 SO 4 Concentration of, to H 2 SO 4 H of the generator output 2 SO 4 The product is concentrated.
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