1. A sulfur-iodine circulating hydrogen production system utilizing a high-temperature gas cooled reactor is characterized by comprising a power generation part and a sulfur-iodine circulating hydrogen production part;

the power generation part adopts a helium gas cooled reactor as a high-temperature heat source and comprises a reactor (6), high-temperature high-pressure helium at the outlet of the reactor (6) passes through a helium-helium heat exchanger (7) and then enters a helium turbine (8) to do work, and the helium turbine (8) drives a power generator (9) to generate power and simultaneously drives a coaxial low-pressure compressor (2) and a coaxial high-pressure compressor (4) to compress working media; the exhaust of the helium turbine (8) passes through the low-pressure side of a heat regenerator (5) and then transmits heat to the helium at the high-pressure side, then the exhaust enters a precooler (1) to be reduced to low temperature, the low-temperature helium enters a compressor unit with an intercooler (3) and then is compressed into high-pressure helium, the high-pressure helium passes through the high-pressure side of the heat regenerator (5) and then is heated to be close to the exhaust temperature of the helium turbine (8), and then enters the reactor core of a reactor (6) to be heated repeatedly;

the part for circularly producing hydrogen by sulfur and iodine comprises a Bunsen premixing tank (17), wherein an initial material SO is put into the Bunsen premixing tank (17)₂、I₂And H₂O, the liquid outlet end of the Bunsen premixing tank (17) is connected with a Bunsen reaction tank (18), the liquid outlet end of the Bunsen reaction tank (18) is connected with a separator (19), and the lower layer of the separator (19) passes through HI_XThe phase control valve (29) is discharged to a HI tank (30), and the upper layer is passed through H₂SO₄Phase control valve (20) is discharged to H₂SO₄The output end of the tank (21) and the HI tank (30) is connected with HI_XPurification column (31), HI_XSO formed in the purification column (31)₂Is purged and returned to the Bunsen premix pot (17), HI_XHI of purification column (31)_XThe phase solution output end is pumped out to the EED (34) after passing through the buffer tank (33), and the I of the anode of the EED (34)₂The concentrated solution is returned to the Bunsen premix (17) via a scrubbing recycle tank (28), and the HI of the cathode_XThe concentrated solution is further concentrated by a HI rectifying tower (35), and then enters a HI decomposing bed (37) to be decomposed under the action of a catalyst to generate H₂And I₂The decomposed product is separated by a condenser (38) and H is removed₂Is led out to H₂The rest HI and I outside the storage tank₂And H₂All O flows back to a buffer tank (33), and H discharged from the middle upper part of the separator (19)₂SO₄The phase solution enters H₂SO₄In a purification column (22), the H₂SO₄The output end of the purification tower (22) is respectively connected with a Bunsen premixing tank (17) and an H₂SO₄A concentration column (24), said H₂SO₄H of the concentrating column (24)₂SO₄Output terminal is connected with H₂SO₄Decomposing bed (26), H₂SO₄H discharged from the concentration tower (24)₂O returns to the Bunsen premixing tank (17), and H is₂SO₄The output end of the decomposition bed (26) is respectively connected with a Bunsen premixing tank (17) and a washing gas recycling tank (28).

2. The system for producing hydrogen by sulfur-iodine cycle using high temperature gas cooled reactor as claimed in claim 1, wherein said H is hydrogen₂SO₄The concentrating tower (24) is connected with H₂SO₄The bottom of the decomposition bed (26).

3. The system for producing hydrogen by utilizing the sulfur-iodine cycle of the high-temperature gas cooled reactor according to claim 1, wherein an inlet at the low-pressure side of the heat regenerator (5) is connected with low-pressure exhaust gas at an outlet of a helium turbine (8), an outlet at the low-pressure side of the heat regenerator (5) is connected with a precooler (1), an inlet at the high-pressure side of the heat regenerator (5) is connected with high-pressure exhaust gas at an outlet of a high-pressure compressor (4), and an outlet at the high-pressure side of the heat regenerator (5) is connected with an inlet of a nuclear reactor (6).

4. The system for the cyclic production of hydrogen by sulfur and iodine using a high temperature gas cooled reactor according to claim 1, wherein an air storage tank (12) is arranged between a pipeline connected between the precooler (1) and the low pressure compressor (2) and a pipeline connected between the reheater (5) and the high pressure compressor (4).

5. The system for the cyclic production of hydrogen by sulfur and iodine using a high temperature gas cooled reactor as claimed in claim 1, wherein the gas storage tank (12) is connected with the pipeline between the precooler (1) and the low pressure compressor (2) through a gas storage tank low pressure compressor side valve (13), and the gas storage tank (12) is connected with the pipeline between the high pressure compressor (4) through a gas storage tank high pressure compressor side valve (11) and the reheater (5).

6. The system for producing hydrogen by using the sulfur-iodine cycle of the high-temperature gas cooled reactor according to claim 1, wherein a bypass valve (10) is connected between the outlet of the high-pressure compressor (4) and the exhaust end of the helium turbine (8).

7. The system for producing hydrogen by sulfur-iodine cycle using high temperature gas cooled reactor as claimed in claim 1, wherein the precooler (1) and the intercooler (3) are cooled by the feed water from the outlet of the feed water pump (41) of the heater, and the feed water is heated to about 200 ℃ for H supply₂SO₄Purification tower heater (23), H₂SO₄Concentration column heater (25), HI_XThe purification tower heater (32) and the HI rectifying tower heater (36) are used, return water passing through the heaters is converged to a buffer water tank (40), the buffer water tank (40) is connected with a heater water feeding pump (41) through a water feeding pipeline, and a heater water feeding and returning pipeline is connected through a heater water feeding and returning pipeline bypass valve (42) and pressure is adjusted.

8. The system for producing hydrogen by using the sulfur-iodine cycle of the high-temperature gas cooled reactor as claimed in claim 1, wherein the helium-helium heat exchanger (7), H₂SO₄Decomposition bed (26), HI decompositionThe bed (37) and the secondary loop main helium fan (39) are connected in series to form a secondary loop helium gas circulation, the secondary loop helium gas circulation is coupled with the primary loop high-temperature gas cooled reactor thermodynamic circulation through the helium-helium heat exchanger (7), and the high-temperature helium gas at the outlet of the helium-helium heat exchanger (7) sequentially passes through H₂SO₄Decomposing bed (26) and HI decomposing bed (37) for purified H₂SO₄And HI is subjected to pyrolysis under the action of a catalyst.

9. The operation method of the sulfur-iodine circulating hydrogen production system utilizing the high-temperature gas cooled reactor is characterized by comprising the following steps of;

in the starting stage of the power generation part, the bypass valve (10) is closed, the generator (9) is switched to operate in a motor mode through the static frequency conversion device, the helium turbine (8), the high-pressure air compressor (4) and the low-pressure air compressor (2) which are coaxially arranged with the generator (9) are driven by the static frequency conversion device to increase the speed, the output power of the reactor is gradually increased through a control rod controlling the nuclear reactor (6) in the speed increasing process, when the helium turbine generator set reaches the self-sustaining rotating speed, the static frequency conversion device quits operation, and the generator (9) is switched to operate in a generator mode;

when the helium turbine generator set reaches a rated rotating speed, checking whether the output power of the nuclear reactor (6) and the temperature and the pressure of helium working medium at an outlet are in a normal range, checking whether the running states of a shafting, a bearing bush and a sealing system of the helium turbine generator set are normal or not, and if no abnormality exists, connecting a generator (9) to the grid;

after the helium turbine generator set is connected to the grid, the output power of the nuclear reactor (6) is gradually improved, at the moment, the precooler (1) and the intercooler (3) are cooled by external cooling water, the overtemperature of a helium working medium is avoided, and in the normal operation stage of the helium turbine generator set, the output power of the system is adjusted through the following 3 modes:

1) and (3) reactivity adjustment: the reactivity of the reactor core is adjusted by controlling control rods of the nuclear reactor (6), the direct result is the rise or fall of the temperature at the outlet of the reactor, the reactivity adjustment can keep higher efficiency under the high-load working condition, but the efficiency is greatly reduced under the low-load working condition;

2) and (3) system pressure regulation: helium working medium in a loop flows out of or flows into the gas storage tank by adjusting the opening degree of a low-pressure gas compressor side valve (13) and a high-pressure gas compressor side valve (11) of the gas storage tank, the pressure in the loop rises or falls to realize the increase or reduction of the working capacity, the system pressure adjustment is a main means for adjusting the operation power, and the system still has higher circulation efficiency under partial load by synchronously adjusting the output power of the nuclear reactor (6);

3) bypass valve (10) regulation: the adjustment of the bypass valve (10) is usually used for emergency, the bypass valve (10) is opened, the helium turbine (8) is rapidly improved, the work-doing capability is rapidly reduced, the flow of the gas compressor is increased, the power consumption is increased, and the rotating speed of the helium turbine generator set can be rapidly reduced;

when the power generation part is started and operates normally, the sulfur-iodine circulating hydrogen production part is started, and SO is firstly added₂、I₂And H₂Adding O into a Bunsen premixing tank (17) in proportion as an initial material for maintaining the system to operate, allowing a reaction solution uniformly mixed in the Bunsen premixing tank (17) to enter a Bunsen reaction tank (18) through strict flow control, and allowing the material to fully react in the Bunsen reaction tank (18) to generate H₂SO₄And HI is discharged into a separator (19), excess I is discharged in the separator (19)₂Is divided into an upper layer and a lower layer, the lower layer is high-density HI_XPassing through HI via the lower part of separator (19)_XThe phase control valve (29) is discharged to a HI tank (30) with an upper layer of H₂SO₄Phase, passing through the middle upper part of the separator (19) by H₂SO₄Phase control valve (20) is discharged to H₂SO₄Tank (21), HI_XPhase solution in HI_XA purification reaction takes place in the purification column (31) to make the entrained H₂SO₄Conversion of impurities to SO₂And H₂O, SO formed₂Is purged and returned to the Bunsen premixing pot (17), and is subjected to I in the premixing pot (17)₂Absorbing to avoid S element loss, and purifying HI_XThe phase solution is pumped out to the EED (34) after entering the buffer tank (33), and under the electrolysis action, the cathode of the EED (34) realizes HI_XConcentration of the phase solution, anodic formation I₂Concentration of the solution, anodic I₂The concentrated solution is returned to the Bunsen premix (17) via a scrubbing recycle tank (28), and the HI of the cathode_XFurther concentrating the concentrated solution by HI rectifying tower (35), introducing into HI decomposition bed (37), adjusting outlet temperature of high temperature gas cooled reactor to make bed temperature of HI decomposition bed about 500 deg.C, decomposing HI under the action of catalyst to generate H₂And I₂The decomposed product is separated by a condenser (38) and H is removed₂Is led out to H₂The rest HI and I outside the storage tank₂And H₂All O flows back to a buffer tank (33), and H is discharged from the middle upper part of the separator₂SO₄The phase solution enters H₂SO₄In the purification tower (22), purification reaction is carried out to remove HI_XImpurities, purified H₂SO₄Part of the phase solution is returned to the Bunsen premix pot (17), and the rest solution is introduced into H₂SO₄In the concentration tower (24), the concentrated solution is sent to H after being subjected to flash evaporation concentration in the concentration tower (24)₂SO₄Decomposing bed (26), H₂SO₄H discharged from the concentration tower (24)₂Returning O to the Bunsen premixing tank (17), and concentrating H₂SO₄From bottom to top into H₂SO₄In the decomposing bed (26), the outlet temperature of the high temperature gas cooled reactor is adjusted to be H₂SO₄The bed temperature of the decomposing bed is about 800 ℃ at H₂SO₄The low temperature section of the decomposing bed (26) is rich in H₂SO₄Is decomposed into SO₃And H₂O, in H₂SO₄High temperature SO section of decomposition bed (26)₃Is decomposed into SO under the action of catalyst₂And O₂，H₂SO₄Cooling the decomposition product by a condenser (27), returning the cooled decomposition product to a Bunsen premixing tank (17) and continuing the next cycle, O₂Then the sulfur and iodine are collected and stored as the by-product of the sulfur and iodine cycle after being washed by the washing gas return tank (28).

Background

The use of traditional fossil energy can release a large amount of pollutants such as carbon dioxide, sulfide, nitrogen oxide and dust particles, and causes serious problems such as global warming effect aggravation and environmental pollution. Hydrogen is a clean energy source, and only water is generated after the hydrogen is utilized. The fuel can be stored and transported in various forms such as gas state, liquid state, solid oxide and the like, can be suitable for various application conditions, and has wide application prospect in the aspects of clean combustion, hydrogen fuel cells and the like.

At present, the main hydrogen production method is the hydrogen production by fossil fuel: 48% from natural gas, 30% from oil, 18% from coal; the remaining 4% comes from the electrolysis of water to produce hydrogen. The hydrogen production process of fossil fuel can release a large amount of greenhouse gases and pollutants, the hydrogen production by water electrolysis consumes a large amount of electric energy, the conversion efficiency is low, and the cost is high, which is inconsistent with the concept of efficient, clean and low-cost hydrogen energy development in the future.

Disclosure of Invention

In order to overcome the defects of the prior art, the invention aims to provide a sulfur-iodine circulating hydrogen production system and a method by using a high-temperature gas-cooled reactor, wherein a high-temperature gas-cooled reactor power generation system is coupled with a thermochemical sulfur-iodine circulating hydrogen production system, and high-temperature helium gas at the outlet of the high-temperature gas-cooled reactor is used as a heat source to catalyze and thermally decompose water at 800-1000 ℃ so as to prepare hydrogen and oxygen. The principle of hydrogen production by the high-temperature gas cooled reactor is as follows: high-grade heat energy at the outlet of the high-temperature gas-cooled reactor is used in the hydrogen production process, low-grade heat energy after heat exchange through the helium-helium heat exchanger is used for power generation, electric energy obtained by power generation is supplied to the hydrogen production process, and the rest electric energy is output to a power grid, so that gradient utilization of the high-temperature gas-cooled reactor energy and hydrogen-electricity cogeneration with zero carbon emission are realized.

In order to achieve the purpose, the invention adopts the technical scheme that:

a sulfur-iodine circulating hydrogen production system utilizing a high-temperature gas cooled reactor comprises a power generation part and a sulfur-iodine circulating hydrogen production part;

the power generation part adopts a helium gas cooled reactor as a high-temperature heat source and comprises a reactor 6, high-temperature high-pressure helium gas at the outlet of the reactor 6 passes through a helium-helium heat exchanger 7 and then enters a helium turbine 8 to do work, and the helium turbine 8 drives a generator 9 to generate power and simultaneously drives a coaxial low-pressure compressor 2 and a coaxial high-pressure compressor 4 to compress working media; the exhaust of the helium turbine 8 is transmitted to the helium at the high-pressure side after passing through the low-pressure side of the heat regenerator 5, then the exhaust enters the precooler 1 to be reduced to low temperature, the low-temperature helium enters the compressor unit with the intercooler 3 and then is compressed into high-pressure helium, the high-pressure helium passes through the high-pressure side of the heat regenerator 5 and then is heated to be close to the exhaust temperature of the helium turbine 8, and then enters the reactor core of the reactor 6 to be heated repeatedly;

the part for circularly producing hydrogen by sulfur and iodine comprises a Bunsen premixing tank 17, wherein an initial material SO is put into the Bunsen premixing tank 17₂、I₂And H₂O, the liquid outlet end of the Bunsen premixing tank 17 is connected with a Bunsen reaction tank 18, the liquid outlet end of the Bunsen reaction tank 18 is connected with a separator 19, and the lower layer of the separator 19 passes through HI_XPhase control valve 29 discharges to HI tank 30 and the upper layer passes through H₂SO₄Phase control valve 20 exhaust to H₂SO₄The output ends of the tank 21 and the HI tank 30 are connected with HI_XPurification column 31, HI_XSO produced in the purification column 31₂Is purged and returned to the Bunsen premix 17, HI_XHI of purification column 31_XThe phase solution output end is pumped out to the EED34 after passing through the buffer tank 33, the I of the anode of the EED34₂The concentrated solution is returned to the Bunsen premix 17 via a purge recycle tank 28, the HI of the cathode_XThe concentrated solution is further concentrated by a HI rectifying tower 35, and then enters a HI decomposing bed 37 to be decomposed under the action of a catalyst to generate H₂And I₂The decomposed product is separated by a condenser 38 and H is removed₂Is led out to H₂The rest HI and I outside the storage tank₂And H₂All O flows back to the buffer tank 33, and H is discharged from the upper middle part of the separator 19₂SO₄The phase solution enters H₂SO₄In the purification column 22, the H₂SO₄The output end of the purifying tower 22 is respectively connected with a Bunsen premixing tank 17 and a H₂SO₄A concentration column 24, said H₂SO₄H of the concentrating column 24₂SO₄Output terminal is connected with H₂SO₄Decomposing bed 26, H₂SO₄H from the concentrating column 24₂O returns to the Bunsen premix tank 17, and H is₂SO₄The output end of the decomposition bed 26 is respectively connected with the Bunsen premixing tank 17 and the washing gas recycling tank 28.

The temperature of the high-temperature high-pressure helium gas at the outlet of the reactor 6 is reduced from about 1000 ℃ to about 600 ℃ after passing through the helium-helium heat exchanger 7.

Said H₂SO₄The concentrating tower 24 is connected with H₂SO₄The bottom of the decomposition bed 26.

The low-pressure side inlet of the heat regenerator 5 is connected with low-pressure exhaust at the outlet of the helium turbine 8, the low-pressure side outlet of the heat regenerator 5 is connected with the precooler 1, the high-pressure side inlet of the heat regenerator 5 is connected with high-pressure exhaust at the outlet of the high-pressure compressor 4, and the high-pressure side outlet of the heat regenerator 5 is connected with the inlet of the nuclear reactor 6.

And an air storage tank 12 is arranged between a pipeline connected between the precooler 1 and the low-pressure compressor 2 and a pipeline connected between the heat regenerator 5 and the high-pressure compressor 4.

The air storage tank 12 is connected with a pipeline between the precooler 1 and the low-pressure compressor 2 through an air storage tank low-pressure compressor side valve 13, and the air storage tank 12 is connected with a pipeline between the heat regenerator 5 and the high-pressure compressor 4 through an air storage tank high-pressure compressor side valve 11.

A bypass valve 10 is connected between the outlet of the high-pressure compressor 4 and the exhaust end of the helium turbine 8.

The precooler 1 and the intercooler 3 adopt the feed water at the outlet of the heater feed pump 41 for cooling, and simultaneously heat the feed water to about 200 ℃ for H supply₂SO₄Purification column heaters 23, H₂SO₄Concentration column heater 25, HI_XThe purification tower heater 32 and the HI distillation tower heater 36 are used, the return water passing through the heaters is converged into a buffer water tank 40, and the buffer water tank 40 and a heater water-feeding pump 41 are connected through a water supply pipelineThe heater water supply and return line is connected to and pressure-adjusted by a heater water supply and return line bypass valve 42.

The helium-helium heat exchanger 7, H₂SO₄The decomposition bed 26, the HI decomposition bed 37 and the secondary loop main helium fan 39 are connected in series to form a secondary loop helium gas circulation, the secondary loop helium gas circulation is coupled with the primary loop high-temperature gas cooled reactor thermodynamic circulation through the helium-helium heat exchanger 7, and the high-temperature helium gas at the outlet of the helium-helium heat exchanger 7 sequentially passes through H₂SO₄Decomposing bed 26 and HI decomposing bed 37 for purified H₂SO₄And HI is subjected to pyrolysis under the action of a catalyst.

An operation method of a sulfur-iodine circulating hydrogen production system utilizing a high-temperature gas cooled reactor comprises the following steps;

in the starting stage of the power generation part, the bypass valve 10 is closed, the generator 9 is switched to operate in a motor mode through the static frequency conversion device, the helium turbine 8, the high-pressure compressor 4 and the low-pressure compressor 2 which are coaxially arranged with the generator 9 are driven by the static frequency conversion device to increase the speed, the output power of the reactor is gradually increased through controlling a control rod of the nuclear reactor 6 in the speed increasing process, when the helium turbine generator set reaches the self-sustaining rotating speed, the static frequency conversion device quits operating, and the generator 9 is switched to operate in a generator mode;

when the helium turbine generator set reaches a rated rotating speed, checking whether the output power of the nuclear reactor 6 and the temperature and the pressure of an outlet helium working medium are in a normal range, checking whether the running states of a shafting, a bearing bush and a sealing system of the helium turbine generator set are normal or not, and if no abnormity exists, connecting a generator 9 in a grid mode;

after the helium turbine generator set is connected to the grid, the output power of the nuclear reactor 6 is gradually improved, at the moment, the precooler 1 and the intercooler 3 are cooled by external cooling water, the overtemperature of a helium working medium is avoided, and in the normal operation stage of the helium turbine generator set, the output power of the system is adjusted by the following 3 modes:

1) and (3) reactivity adjustment: the reactivity of the reactor core is adjusted by controlling control rods of the nuclear reactor 6, the direct result is the rise or fall of the temperature at the outlet of the reactor, the reactivity adjustment can keep higher efficiency under the high-load working condition, but the efficiency is greatly reduced under the low-load working condition;

2) and (3) system pressure regulation: the helium working medium in the loop flows out of or flows into the gas storage tank by adjusting the opening degrees of a low-pressure gas compressor side valve 13 and a high-pressure gas compressor side valve 11 of the gas storage tank, the pressure in the loop rises or falls to realize the increase or reduction of the working capacity, the system pressure adjustment is a main means for adjusting the operating power, and the system still has higher circulation efficiency under partial load by synchronously adjusting the output power of the nuclear reactor 6;

3) the bypass valve 10 regulates: the adjustment of the bypass valve 10 is usually used for emergency, the bypass valve 10 is opened, the helium turbine 8 is rapidly improved, the work-doing capability is rapidly reduced, the flow of the gas compressor is increased, the power consumption is increased, and the rotating speed of the helium turbine generator set can be rapidly reduced;

when the power generation part is started and operates normally, the sulfur-iodine circulating hydrogen production part is started, and SO is firstly added₂、I₂And H₂Adding O into a Bunsen premixing tank 17 in proportion as an initial material for maintaining the operation of the system, allowing a reaction solution uniformly mixed in the Bunsen premixing tank 17 to enter a Bunsen reaction tank 18 through strict flow control, and allowing the material to fully react in the Bunsen reaction tank 18 to generate H₂SO₄And HI are discharged into a separator 19, and excess I is discharged into the separator 19₂Is divided into an upper layer and a lower layer, the lower layer is high-density HI_XThe phase passes through HI via the lower part of the separator 19_XPhase control valve 29 discharges to HI tank 30 with the upper layer H₂SO₄The phases pass through the separator 19 at the upper middle part by H₂SO₄Phase control valve 20 exhaust to H₂SO₄And a tank 21. HI (high-intensity)_XPhase solution in HI_XA purification reaction takes place in the purification column 31 to make entrained H₂SO₄Conversion of impurities to SO₂And H₂O, SO formed₂Is purged back to the Bunsen premix tank 17, is fed into the premix tank 17 by I₂Absorbing to avoid S element loss, and purifying HI_XThe phase solution is drawn out to an EED (electrodialysis device) 34 after entering a buffer tank 33, and under the electrolysis action, the EED34 cathode realizes HI_XConcentration of the phase solution, anodic formation I₂Concentration of the solution, anodic I₂The concentrated solution is returned to the Bunsen premix 17 via a purge recycle tank 28, the HI of the cathode_XFurther concentrating the concentrated solution by HI rectifying tower 35, introducing into HI decomposition bed 37, adjusting outlet temperature of high temperature gas cooled reactor to make bed temperature of HI decomposition bed about 500 deg.C, decomposing HI under the action of catalyst to generate H₂And I₂The decomposed product is separated by a condenser 38 and H is removed₂Is led out to H₂The rest HI and I outside the storage tank₂And H₂All O flows back to the buffer tank 33, and H is discharged from the middle upper part of the separator₂SO₄The phase solution enters H₂SO₄In the purification tower 22, purification reaction takes place to remove HI_XAnd the like. Purified H₂SO₄Part of the phase solution is returned to the Bunsen premix 17, and the rest solution is fed to H₂SO₄In the concentration tower 24, the concentrated solution is sent to H after being subjected to flash evaporation concentration in the concentration tower 24₂SO₄Decomposing bed 26, H₂SO₄H from the concentrating column 24₂Returning O to the Bunsen premixing tank 17, and concentrating H₂SO₄From bottom to top into H₂SO₄In the decomposing bed 26, the outlet temperature of the high temperature gas cooled reactor is adjusted to be H₂SO₄The bed temperature of the decomposing bed is about 800 ℃ at H₂SO₄Dense H in low temperature section of decomposing bed 26₂SO₄Is decomposed into SO₃And H₂O, in H₂SO₄High temperature SO section of decomposition bed 26₃Is decomposed into SO under the action of catalyst₂And O₂，H₂SO₄The decomposition product is cooled by a condenser 27 and returned to the Bunsen premixing pot 17 to continue the next cycle, O₂The sulfur and iodine is collected and stored as a byproduct of the sulfur and iodine cycle after being washed by the washing gas recycling tank 28.

The invention has the beneficial effects that:

the high-temperature gas cooled reactor power generation system is coupled with the thermochemical sulfur-iodine cycle hydrogen production system, and the high-temperature helium gas at the outlet of the high-temperature gas cooled reactor is used as a heat source to catalyze and thermally decompose water at 800-1000 ℃, so that hydrogen and oxygen are efficiently prepared. High-grade heat energy at the outlet of the high-temperature gas-cooled reactor is used in the hydrogen production process, low-grade heat energy after heat exchange through the helium-helium heat exchanger is used for power generation, electric energy obtained by power generation is supplied to the hydrogen production process, and the rest electric energy is output to a power grid, so that gradient utilization of the high-temperature gas-cooled reactor energy and hydrogen-electricity cogeneration with zero carbon emission are realized.

In the operation process of the system, the output power of the power generation part and the temperature of the outlet of the reactor can be adjusted by respectively or comprehensively utilizing methods of adjusting the output power of the nuclear reactor, the helium working medium conductivity, the loop system pressure and the like, so that different operation requirements are met.

The system operation mode provided by the invention can realize cascade utilization of high-temperature gas cooled reactor energy and hydrogen-electricity cogeneration without carbon emission. Zero carbon emission is realized in the power and heat production process, so that the situation that power enterprises occupy favorable positions in future energy market competition is favorably improved, and the competitive capacity of power generation enterprises is improved.

The invention is suitable for a sulfur-iodine circulating hydrogen production system using a high-temperature gas cooled reactor and has popularization conditions.

Drawings

FIG. 1 is a schematic diagram of a thermodynamic system of the invention.

Wherein 1-precooler, 2-low pressure compressor, 3-intercooler, 4-high pressure compressor, 5-heat regenerator, 6-reactor, 7-helium heat exchanger, 8-helium turbine, 9-generator, 10-by-pass valve, 11-gas storage tank high pressure compressor side valve, 12-gas storage tank, 13-gas storage tank low pressure compressor side valve, 14-precooler circulating cooling water backwater side valve, 15-precooler circulating cooling water by-pass valve, 16-precooler circulating cooling water supply side valve, 17-Bunsen pre-mixing tank, 18-Bunsen reaction tank, 19-separator, 20-H-reactor₂SO₄Phase control valve, 21-H₂SO₄Pot, 22-H₂SO₄Purification column, 23-H₂SO₄Purification column Heater, 24-H₂SO₄Concentration column, 25-H₂SO₄Concentrator column heater, 26-H₂SO₄Decomposition bed, 27-condenser, 28-purge recycle tank, 29-HI_XPhase control valve, 30-HI_XTank, 31-HI_XPurification column, 32-HI_XPurification column heater, 33-buffer tank, 34-EED, 35-HI rectifying tower, 36-HI rectifying tower heater, 37-HI decomposition bed, 38-condenser, 39-two-loop helium main blower, 40-buffer water tank, 41-heater water feeding pump and 42-heater water supply return pipeline bypass valve.

Detailed Description

The present invention will be described in further detail with reference to the accompanying drawings.

Referring to fig. 1, the present invention is a system for producing hydrogen by sulfur-iodine cycle using high temperature gas cooled reactor, including a power generation part and a sulfur-iodine cycle hydrogen production part.

The first part is a power generation part, a helium gas cold stack is used as a high-temperature heat source, when high-temperature high-pressure helium gas at the outlet of a reactor 6 passes through a helium-helium heat exchanger 7, the temperature is reduced from about 1000 ℃ to about 600 ℃, the helium gas still with high energy enters a helium turbine 8 to do work, and the helium turbine 8 drives a generator 9 to generate power and simultaneously drives a coaxial low-pressure compressor 2 and a coaxial high-pressure compressor 4 to compress working media. The exhaust of helium turbine 8, which is still at a higher temperature, passes through the low pressure side of regenerator 5 and transfers heat to the high pressure side helium before entering precooler 1 to cool. The low temperature helium gas enters the compressor block with intercooler 3 and is then compressed to high pressure helium gas. The high-pressure helium passes through the high-pressure side of the regenerator 5 and is heated to the exhaust temperature close to the exhaust temperature of the helium turbine 8, and then enters the reactor core 6 to be heated repeatedly.

The second part is a sulfur iodine circulation hydrogen production part which comprises a Bunsen reaction, a hydroiodic acid decomposition reaction and a sulfuric acid decomposition reaction. First SO₂、I₂And H₂Adding O into a Bunsen premixing tank 17 in proportion as an initial material for maintaining the operation of the system, allowing a reaction solution uniformly mixed in the Bunsen premixing tank 17 to enter a Bunsen reaction tank 18 through strict flow control, and allowing the material to fully react in the Bunsen reaction tank 18 to generate H₂SO₄And HI to separator 19. Excess I in separator 19₂Is divided into an upper layer and a lower layer, the lower layer is high-density HI_XThe phase passes through HI via the lower part of the separator 19_XPhase control valve 29 discharges to HI tank 30 with the upper layer H₂SO₄The phases pass through the separator 19 at the upper middle part by H₂SO₄Phase controlValve 20 exhaust to H₂SO₄And a tank 21. HI (high-intensity)_XPhase solution in HI_XA purification reaction takes place in the purification column 31 to make entrained H₂SO₄Conversion of impurities to SO₂And H₂O, SO formed₂Is purged back to the Bunsen premix tank 17, is fed into the premix tank 17 by I₂Absorbing and avoiding the loss of S element. Purified HI_XThe phase solution is drawn out to an EED (electrodialysis device) 34 after entering a buffer tank 33, and under the electrolysis action, the EED34 cathode realizes HI_XConcentration of the phase solution, anodic formation I₂And (4) concentrating the solution. Of the anode I₂The concentrated solution is returned to the Bunsen premix 17 via a purge recycle tank 28, the HI of the cathode_XThe concentrated solution is further concentrated by a HI rectifying tower 35, and then enters a HI decomposing bed 37 to be decomposed under the action of a catalyst to generate H₂And I₂The decomposed product is separated by a condenser 38 and H is removed₂Is led out to H₂The rest HI and I outside the storage tank₂And H₂All of the O flows back to the buffer tank 33. H discharged from the middle upper part of the separator₂SO₄The phase solution enters H₂SO₄In the purification tower 22, purification reaction takes place to remove HI_XAnd the like. Purified H₂SO₄Part of the phase solution is returned to the Bunsen premix 17, and the rest solution is fed to H₂SO₄In the concentration tower 24, the concentrated solution is sent to H after being subjected to flash evaporation concentration in the concentration tower 24₂SO₄Decomposing bed 26, H₂SO₄H from the concentrating column 24₂O is returned to the Bunsen premix tank 17. Concentrated H₂SO₄From bottom to top into H₂SO₄In the decomposing bed 26, in H₂SO₄Dense H in low temperature section of decomposing bed 26₂SO₄Is decomposed into SO₃And H₂O, in H₂SO₄High temperature SO section of decomposition bed 26₃Is decomposed into SO under the action of catalyst₂And O₂，H₂SO₄The decomposition product is cooled by a condenser 27 and returned to the Bunsen premixing pot 17 to continue the next cycle, O₂The sulfur and iodine is collected and stored as a byproduct of the sulfur and iodine cycle after being washed by the washing gas recycling tank 28. Thus H in the whole process₂Decomposition of O to H₂And O₂And I is₂And SO₂And the intermediate product is continuously circulated in the whole system.

The low-pressure compressor 2, the high-pressure compressor 4, the helium turbine 8 and the generator 9 are coaxially arranged.

The low-pressure side inlet of the heat regenerator 5 is connected with low-pressure exhaust at the outlet of the helium turbine 8, the low-pressure side outlet of the heat regenerator 5 is connected with the precooler 1, the high-pressure side inlet of the heat regenerator 5 is connected with high-pressure exhaust at the outlet of the high-pressure compressor 4, and the high-pressure side outlet of the heat regenerator 5 is connected with the inlet of the nuclear reactor 6.

An air storage tank 12 is arranged between a pipeline connected between the precooler 1 and the low-pressure compressor 2 and a pipeline connected between the heat regenerator 5 and the high-pressure compressor 4.

The air storage tank 12 is connected with a pipeline between the precooler 1 and the low-pressure compressor 2 through an air storage tank low-pressure compressor side valve 13, and the air storage tank 12 is connected with a pipeline between the heat regenerator 5 and the high-pressure compressor 4 through an air storage tank high-pressure compressor side valve 11.

A bypass valve 10 is connected between the outlet of the high-pressure compressor 4 and the exhaust end of the helium turbine 8.

The precooler 1 and the intercooler 3 adopt the feed water at the outlet of the heater feed pump 41 for cooling, and simultaneously heat the feed water to about 200 ℃ for H supply₂SO₄Purification column heaters 23, H₂SO₄Concentration column heater 25, HI_XThe purification tower heater 32 and the HI rectifying tower heater 36 are used, return water passing through the above heaters is collected to a buffer water tank 40, the buffer water tank 40 is connected to a heater water feed pump 41 through a water supply pipe, and a heater water supply/return pipe is connected to and pressure-regulated by a heater water supply/return pipe bypass valve 42.

The two-loop helium gas circulation is composed of a helium-helium heat exchanger 7 and H₂SO₄The decomposition bed 26, the HI decomposition bed 37 and the secondary loop main helium fan 39 are connected in series, the secondary loop helium gas is circularly coupled with the thermodynamic cycle of the primary loop high-temperature gas cooled reactor through the helium-helium heat exchanger 7, and the high-temperature helium gas at the outlet of the helium-helium heat exchanger 7 sequentially passes through H₂SO₄Decomposing bed 26 and HI decomposing bed 37 for purified H₂SO₄And HI is subjected to pyrolysis under the action of a catalyst.

The Bunsen reaction device consists of a Bunsen premixing tank 17, a Bunsen reaction tank 18 and a separator 19, and SO is added₂、I₂And H₂And proportionally adding O into the Bunsen premixing tank 17 to serve as an initial material for maintaining the operation of the system. The well mixed material enters the Bunsen reaction tank 18 where excess I is present due to the Bunsen reaction₂And H₂In the presence of O, SO₂Can be considered as being completely absorbed. Materials HI and I generated by Bunsen reaction₂、H₂SO₄And H₂O enters a separator 19 where the solution will be separated into HI in separator 19_XPhase sum H₂SO₄And (4) phase(s).

The HI_XThe phases are collected in the lower part of the separator 19 and passed through HI_XPhase control valve 29 into HI_XTank 30, slightly left to enter HI_XPurification column 31, HI_XPurification column 31 from HI_XThe purification column heater 32 maintains the temperature at about 150 deg.C, and the purification reaction allows HI to react_XH contained in the phase solution₂SO₄Conversion to SO₂And H₂O, SO formed₂Is discharged to a Bunsen premixing tank 17 through a purging pipeline from the part I₂Absorbing, purifying the reacted HI_XThe phase solution enters a buffer tank 33 and is then pumped out to an EED34, and under the action of electrolysis, the cathode of the EED34 realizes HI_XConcentration of the phase solution, anodic formation I₂And (4) concentrating the solution. Of the anode I₂The concentrated solution is returned to the Bunsen premix 17 via a purge recycle tank 28, the HI of the cathode_XThe concentrated solution is further concentrated by a HI rectifying tower 35, and then enters a HI decomposing bed 37 to be decomposed under the action of a catalyst to generate H₂And I₂The decomposed product is separated by a condenser 38 and H is removed₂Is led out to H₂The rest HI and I outside the storage tank₂And H₂All of the O flows back to the buffer tank 33.

Said H₂SO₄The phases are collected in the upper part of the separator 19 and pass through H₂SO₄Phase control valve 20 goes to H₂SO₄The tank enters H after slightly staying₂SO₄Purification ofColumn 22, in which HI impurities are reacted with H₂SO₄The Bunsen reverse reaction is removed, part of the purified sulfuric acid phase solution is sent back to the Bunsen premixing tank 17, and the rest solution is sent to the H₂SO₄Thickener column 24, H₂SO₄The concentration tower is composed of₂SO₄The concentrating tower heater 25 provides a heating source, H₂SO₄At H₂SO₄Feeding the concentrated solution into a concentration tower for flash evaporation and concentration₂SO₄The bed 26 is decomposed and the vented water vapor is returned to the Bunsen premix 17. H₂SO₄The decomposing bed 26 adopts a bottom feeding mode and is divided into H₂SO₄Decomposition section and SO₃Decomposition section, H₂SO₄The decomposition section reacts H at about 450 DEG C₂SO₄Decomposition to SO₃And H₂O，SO₃The decomposition section reacts SO under the action of a catalyst at about 800 DEG C₃Decomposition to SO₂And H₂O，H₂SO₄Decomposition product SO₂Condensed by the condenser 27 and returned to the Bunsen premix 17 for the next cycle, O₂The sulfur and iodine is collected and stored as a byproduct of the sulfur and iodine cycle after being washed by the washing gas recycling tank 28.

The HI decomposition bed 37 is heated by two-loop high-temperature helium gas, and HI from the HI rectifying tower 35 is heated and gasified at the bottom of the cracker and then decomposed in a catalytic bed to generate H₂And I₂。

Said H₂SO₄The decomposition bed 26 is heated by two circuits of high temperature helium gas from H₂SO₄H from the concentrating column 24₂SO₄By H₂SO₄Decomposition section and SO₃The decomposition section is decomposed into SO₂And H₂O。

The working principle of the invention is as follows:

in the starting stage of the power generation part, the bypass valve 10 is closed, the generator 9 is switched to operate in a motor mode through the static frequency conversion device, the helium turbine 8, the high-pressure compressor 4 and the low-pressure compressor 2 which are coaxially arranged with the generator 9 are driven by the static frequency conversion device to increase the speed, the output power of the reactor is gradually increased through controlling a control rod of the nuclear reactor 6 in the speed increasing process, when the helium turbine generator set reaches the self-sustaining rotating speed, the static frequency conversion device quits operating, and the generator 9 is switched to operate in a generator mode;

when the helium turbine generator set reaches a rated rotating speed, checking whether the output power of the nuclear reactor 6 and the temperature and the pressure of an outlet helium working medium are in a normal range, checking whether the running states of a shafting, a bearing bush and a sealing system of the helium turbine generator set are normal or not, and if no abnormity exists, connecting a generator 9 in a grid mode;

after the helium turbine generator set is connected to the grid, the output power of the nuclear reactor 6 is gradually increased, and at the moment, the precooler 1 and the intercooler 3 are cooled by external cooling water, so that the helium working medium is prevented from being over-heated. During the normal operation stage of the helium turbine generator set, the output power of the system can be regulated in the following 3 ways:

1) and (3) reactivity adjustment: the reactivity of the reactor core is adjusted by controlling control rods of the nuclear reactor 6, the direct result is the rise or fall of the temperature at the outlet of the reactor, the reactivity adjustment can keep higher efficiency under the high-load working condition, but the efficiency is greatly reduced under the low-load working condition;

2) and (3) system pressure regulation: the helium working medium in the loop flows out of or flows into the gas storage tank by adjusting the opening degrees of a low-pressure gas compressor side valve 13 and a high-pressure gas compressor side valve 11 of the gas storage tank, the pressure in the loop rises or falls to realize the increase or reduction of the working capacity, the system pressure adjustment is a main means for adjusting the operating power, and the system still has higher circulation efficiency under partial load by synchronously adjusting the output power of the nuclear reactor 6;

3) the bypass valve 10 regulates: the adjustment of the bypass valve 10 is usually used for emergency needs, the bypass valve 10 is opened, the helium turbine 8 is rapidly improved, the work capacity is rapidly reduced, meanwhile, the flow of the air compressor is increased, the power consumption is increased, and the rotating speed of the helium turbine generator set can be rapidly reduced.

When the power generation part is started up and operates normally, the sulfur-iodine circulation hydrogen production part can be started up. First SO₂、I₂And H₂Adding O into the Bunsen premixing tank 17 in proportion as an initial material for maintaining the operation of the systemThe reaction solution which is uniformly mixed in the Bunsen premixing tank 17 enters the Bunsen reaction tank 18 through strict flow control, and materials are fully reacted in the Bunsen reaction tank 18 to generate H₂SO₄And HI to separator 19. Excess I in separator 19₂Is divided into an upper layer and a lower layer, the lower layer is high-density HI_XThe phase passes through HI via the lower part of the separator 19_XPhase control valve 29 discharges to HI tank 30 with the upper layer H₂SO₄The phases pass through the separator 19 at the upper middle part by H₂SO₄Phase control valve 20 exhaust to H₂SO₄And a tank 21. HI (high-intensity)_XPhase solution in HI_XA purification reaction takes place in the purification column 31 to make entrained H₂SO₄Conversion of impurities to SO₂And H₂O, SO formed₂Is purged back to the Bunsen premix tank 17, is fed into the premix tank 17 by I₂Absorbing and avoiding the loss of S element. Purified HI_XThe phase solution is drawn out to an EED (electrodialysis device) 34 after entering a buffer tank 33, and under the electrolysis action, the EED34 cathode realizes HI_XConcentration of the phase solution, anodic formation I₂And (4) concentrating the solution. Of the anode I₂The concentrated solution is returned to the Bunsen premix 17 via a purge recycle tank 28, the HI of the cathode_XFurther concentrating the concentrated solution by HI rectifying tower 35, introducing into HI decomposition bed 37, adjusting outlet temperature of high temperature gas cooled reactor to make bed temperature of HI decomposition bed about 500 deg.C, decomposing HI under the action of catalyst to generate H₂And I₂The decomposed product is separated by a condenser 38 and H is removed₂Is led out to H₂The rest HI and I outside the storage tank₂And H₂All of the O flows back to the buffer tank 33. H discharged from the middle upper part of the separator₂SO₄The phase solution enters H₂SO₄In the purification tower 22, purification reaction takes place to remove HI_XAnd the like. Purified H₂SO₄Part of the phase solution is returned to the Bunsen premix 17, and the rest solution is fed to H₂SO₄In the concentration tower 24, the concentrated solution is sent to H after being subjected to flash evaporation concentration in the concentration tower 24₂SO₄Decomposing bed 26, H₂SO₄H from the concentrating column 24₂O is returned to the Bunsen premix tank 17. Concentrated H₂SO₄From bottom to top into H₂SO₄In the decomposing bed 26, the outlet temperature of the high temperature gas cooled reactor is adjusted to be H₂SO₄The bed temperature of the decomposing bed is about 800 ℃ at H₂SO₄Dense H in low temperature section of decomposing bed 26₂SO₄Is decomposed into SO₃And H₂O, in H₂SO₄High temperature SO section of decomposition bed 26₃Is decomposed into SO under the action of catalyst₂And O₂，H₂SO₄The decomposition product is cooled by a condenser 27 and returned to the Bunsen premixing pot 17 to continue the next cycle, O₂The sulfur and iodine is collected and stored as a byproduct of the sulfur and iodine cycle after being washed by the washing gas recycling tank 28.