KR100982910B1 - Bunsen reactor comprising automatic separator for producing nuclear hydrogen and method of separating Sulfuric acid -Iodinic acid automatically using thereof - Google Patents

Abstract

The present invention relates to an integrated bunsen reactor having an automatic phase separator for nuclear hydrogen production and a method for automatically separating sulfuric acid and iodic acid, and more particularly, to an integrated bunsen reactor having an automatic phase separator, a converter and a valve.

The Bunsen reactor according to the present invention not only increases the efficiency of the Bunsen reaction by including a net packing, but also can produce sulfuric acid and iodine acid phases generated after the Bunsen reaction with high purity without a separate separation process. It can be useful for the hydrogen production of sulfur-iodine process.

Bunsen reactor, nuclear hydrogen production, sulfur-iodine thermochemical process

Description

Bunsen reactor comprising automatic separator for producing nuclear hydrogen and method of separating Sulfuric acid -Iodinic acid automatically using

The present invention relates to an integrated bunsen reactor having an automatic phase separator for nuclear hydrogen production and a method for automatically separating sulfuric acid and iodine acid.

As the Kyoto Protocol to prevent global warming came into force and oil prices continued to rise, hydrogen energy has been proposed as an alternative energy source as a measure to reduce carbon dioxide. Therefore, the development of economical hydrogen production process using high temperature nuclear thermal energy source has been conducted a lot of research around the world.

In the conventional hydrogen production process, U.S. General Atomic (GA) uses sulfur as a source of energy to produce hydrogen by decomposing water using a high-temperature heat source of more than 950 ° C of helium gas, a coolant of VHTR. -I have developed the Sulfur-Iodine Thermochemical Cycle Process (SI process). The SI process consists of the final chemical reaction as shown in the chemical scheme [J. H. Norman, G. E. Besenbruch, L. C. Brown, D. R. Okeefe, and C. L. Allen, Thermo-chemical Water-splitting Cycle, Bench-scale Investigations, and Process Engineering, General Atomic Company, GA-A16713, General Atomics, 1982.].

2H ₂ O + I ₂ + SO ₂ = 2HI + H ₂ SO ₄ (bunsen reaction, about 100 ℃, exothermic reaction) (1)

2HI = H ₂ + I ₂ (200 ~ 500 ℃, endothermic reaction) (2)

H ₂ SO ₄ = H ₂ O + SO ₂ + 0.5 O ₂ (about 850 ℃, endothermic reaction) (3)

The SI process consisting of the three chemical reactions is shown schematically based on the flow of chemical reaction participants.

Equation (1) named Bunsen Reaction is exothermic reaction (first unit process, see Fig. 1), and sulfuric acid decomposition reaction of formula (3) (second unit process, see Fig. 2) is 400-500 ° C. After primary decomposition into water and sulfur trioxide at, the decomposed sulfur trioxide (SO ₃ ) is secondary decomposition into sulfur dioxide and oxygen by solid catalysis above about 800 ℃. The iodide acid (HI) decomposition reaction of Formula (2) (third unit process, see FIG. 3) proceeds as a solid catalysis in the gas state or a homogeneous catalysis in the liquid state.

The first to third processes will be described in detail as follows.

The first step is a process of producing sulfuric acid (H ₂ SO ₄ ) and iodic acid (HI) by the reaction of water (H ₂ O), the sulfur dioxide (SO ₂ ), iodine (I ₂ ). This process not only promotes forward progress of Equation (1) by appropriately adding excessive amount of iodine, but also causes immiscibility so that the sulfuric acid phase and the iodic acid phase can be separated from each other. This reaction is a little exothermic and the reaction temperature is below 120 ° C. The solution discharged from the Bunsen reactor is a heavy phase in which HI / I ₂ / H ₂ O is the main component and a light phase in which H ₂ SO ₄ / H ₂ O is the main component in the phase separator. Are separated from each other.

The molar ratio of sulfuric acid to water discharged from the phase separator is about 1: 5, which is finally increased to about 1: 4 while passing through the second Bunsen reactor, which is injected into the second unit process. On the other hand, the heavy phase is gas-liquid contact using oxygen gas generated in the sulfuric acid decomposition reactor of the second unit process to vaporize sulfur dioxide remaining in the heavy phase, and the chemical equilibrium disturbance caused by this results in decomposition of sulfuric acid remaining in the solution. After the reaction, the sulfuric acid concentration in the HIx solution is minimized, and then injected into the third unit process. The HI: I ₂ : H ₂ O molar concentration ratio of the fluid is designed to maintain about 1: 4: 5.

As shown in FIG. 2, the sulfuric acid solution (57 wt%) generated from the first unit process is supplied to the sulfuric acid solution concentrator of the second unit process in the form of a small amount of SO ₂ . In this unit process, a large number of heat recovery heat exchangers (Recuperators) were installed to maximize the heat utilization efficiency. Concentrate to wt% and pressurize to about 7.6kg / cm ² G to evaporate in sulfuric acid evaporator, some vaporized sulfuric acid gas is decomposed into SO ₃ and water, and finally re-decomposed into SO ₂ , oxygen by SO ₃ decomposer This is composed.

FIG. 3 shows a third unit process of the HI _x solution concentration / decomposition process employing a high pressure reaction distillation technique proposed in Germany, excluding HI _x solution concentration technology using phosphoric acid as an extraction solvent, which was introduced in GA in 1982. As shown in FIG. 3, the third unit process includes three heat recovery heat exchangers, one high-pressure reaction distillation tower, a hydrogen gas scrubber tower, and a HI / I ₂ / H ₂ O phase separator. It is characterized by being injected into the washing liquid of the hydrogen washing tower of the process.

As shown in the SI process conceptual diagram, the entire SI process for hydrogen production is organically connected, and in order to increase the overall yield, not only each process should be operated under optimum conditions, but also the result of the previous process is It is required to be produced to be optimal for the next process.

In order to solve the above requirement, Japanese Laid-Open Patent Publication No. 2005-41735 discloses a method for separating a sulfuric acid phase and an iodine acid phase produced through a Bunsen reaction in a Bunsen reactor.

The Bunsen reactor includes only a sulfuric acid discharge pipe and an iodine acid discharge pipe, respectively, in the upper and lower portions of the conventional reactor (see FIG. 1). It may take a long time to form a phase separation layer, or only an iodic acid phase may be prepared, whereby separation of the sulfuric acid phase and the iodic acid phase is virtually impossible.

Further, the published patent has a problem in that contact efficiency with iodine and water injected into the liquid phase is lowered by buoyancy of the injected gas when gaseous sulfur dioxide is injected during the Bunsen reaction.

Thus, the present inventors not only increased the reaction efficiency by removing the drift phenomenon regardless of the phase type of the reactants including the filler of the net in the Bunsen reactor, but also provided an automatic phase separator on the top of the Bunsen reactor to separate sulfuric acid phase and iodine High purity sulfuric acid phase and iodine acid were prepared without the acid phase separation process to complete the present invention.

It is an object of the present invention to provide an integrated bunsen reactor with an automatic phase separator for nuclear hydrogen production.

Another object of the present invention is to provide a method for automatically separating sulfuric acid and iodic acid for producing nuclear hydrogen.

In order to achieve the above object, the present invention provides an integrated Bunsen reactor having an automatic phase separator for nuclear hydrogen production.

In addition, the present invention provides a method for automatically separating sulfuric acid and iodic acid for the production of nuclear hydrogen.

The integrated Bunsen reactor according to the present invention not only increases the efficiency of the Bunsen reaction by including a net packing, but also can produce sulfuric acid and iodine acid phases generated after the Bunsen reaction with high purity without a separate separation process. It can be useful for hydrogen production.

The present invention will be described in detail.

The present invention provides a bunsen reactor for nuclear hydrogen production, which is an integrated bunsen reactor having an automatic phase separator, a converter and a valve.

The Bunsen reactor comprises a charge. The filling may prevent channeling of the fluid injected into the Bunsen reactor and maintain a uniform concentration of the fluid in the radial direction of the reactor. Furthermore, even when the phase of the reactant is a gas, the same effects as described above may be applied.

Preferably, the filler is in the form of a mesh made of a ceramic material of a ceramic material which is not modified even when contacted with a reactive reactant such as a strong acid or a strong base (see FIG. 5).

At this time, the filling is Berl saddle (Inrlax saddle), Intalax saddle (Intalax saddle), Raschig ring (Raschig ring), Lessing ring (Lessing ring), Cross-partition ring, Single- Single-spiral ring, double-spiral ring, triple-spiral ring, etc. may be used.

The automatic phase separator may be located at the top of the Bunsen reactor, and may include two dip tubes, a pressure control valve, a differential pressure sensor, and an sulfuric acid discharge tube.

The valve is located at the bottom of the Bunsen reactor and may comprise a current pressure transducer in a pneumatic actuated valve.

In this case, the differential pressure sensor and the current-voltage transformer may be connected to a PID controller.

The automatic phase separator is equipped with a dip tube on the sulfuric acid phase and the iodine acid produced in the Bunsen reactor located at the bottom, and using the differential pressure sensor connected thereto to measure the interface position of the sulfuric acid phase and the iodine acid phase separated by the specific gravity difference. The position of the interface measured as described above is maintained through the PID.

At this time, PID controls the discharge of the mixed solution of iodine acid through a pneumatic valve connected to the current-voltage device, and discharges the sulfuric acid solution through the sulfuric acid discharge pipe mounted in the automatic phase separator to separate the sulfuric acid phase and the iodine acid phase. Can be separated automatically.

In addition, in the present invention, the iodine mixed solution is injected into the upper part through the iodine mixed solution inlet tube 9 and flows from the upper part of the Bunsen reactor 1 to the lower part, and sulfur dioxide is injected into the lower part through the sulfur dioxide inlet tube 10 and the Bunsen reactor ( Flowing from the lower part to the upper part of 1) to react the iodine mixed solution with sulfur dioxide to produce a sulfuric acid phase and an iodine acid phase (step 1); The sulfuric acid phase and iodine acid prepared in step 1 are separated in the phase separator to form an interface, and measuring the position of the interface formed through the dip tube 3 and the differential pressure sensor 4 inserted into each phase. (Step 2): and discharging the sulfuric acid phase and the iodide phase while maintaining the interface position measured in the step 2 through the PID controller 5 and the pneumatic automatic valve 7 (step 3) Provides automatic separation of sulfuric acid and iodine acid for hydrogen production.

The invention is described in detail step by step.

In the method for automatically separating sulfuric acid and iodic acid according to the present invention, step 1 is an iodine mixed solution is injected into the upper part through the iodine mixed solution inlet tube 9 and flows from the upper part of the Bunsen reactor 1 to the lower part, and sulfur dioxide is injected into the sulfur dioxide. It is injected into the lower portion through the tube 10 and flows from the lower portion of the Bunsen reactor 1 to the upper portion to react the iodine mixed solution with sulfur dioxide to prepare a sulfuric acid phase and an iodine acid phase.

At this time, it is preferable that the specific gravity difference of the sulfuric acid phase and the iodic acid phase of step 1 is 0.9-1.3. If the difference in specific gravity is less than 0.9, there is a problem in that the separation of the sulfuric acid phase and the iodine phase is difficult, and it is difficult to exceed 1.3 due to the original specific gravity of the sulfuric acid phase and the iodine phase itself.

In step 2 according to the present invention, the sulfuric acid phase and the iodine acid prepared in step 1 are separated in the phase separator to form an interface, and through the dip tube 3 and the differential pressure sensor 4 inserted into each phase. It is a step of measuring the position of the formed interface.

At this time, the dip tube measures the water pressure of each of the sulfuric acid phase, the iodine acid phase and the interface position of the sulfuric acid phase and the iodine acid phase through the differential pressure sensor. The differential pressure sensor converts the position of the measured interface into a current and sends it to the PID controller.

The position of the interface is measured by the following calculation (see FIG. 6).

Step 3 according to the present invention is a step of discharging the iodine acid mixture solution, sulfuric acid phase or iodic acid phase to the PID controller 5 and the pneumatic automatic valve 7 to maintain the interface position measured in the step 2 constant. .

The PID controller may control the discharge of the mixed solution of iodine acid through a pneumatic automatic valve connected to the current-voltage conversion when the position of the interface received from the differential pressure sensor of step 2 is different from the position of the pre-input interface.

At this time, the sulfuric acid phase may be discharged through the sulfuric acid discharge pipe (11) mounted in the automatic phase separator (2), the iodine acid phase is iodic acid by a pneumatic automatic valve (7) located below the Bunsen reactor (1) The mixed solution discharge pipe 12 may be discharged.

As described above, the integrated Bunsen reactor equipped with an automatic phase separator not only increases the efficiency of the Bunsen reaction by including a net-shaped filler, but also manufactures the sulfuric acid phase and the iodine acid phase generated after the Bunsen reaction without high separation process. can do.

1 is a sulfur-iodine production process;

2 is a sulfate decomposition reaction process;

3 is an iodide acid (HI) decomposition reaction process;

4 is an embodiment of a filler according to the present invention;

5 is a simplified diagram of an embodiment according to the present invention; And

6 is a simplified diagram of an embodiment according to the present invention.

<Explanation of symbols for the main parts of the drawings>

1: Bunsen reactor, 2: Phase separator,

3: dip tube, 4: differential pressure sensor,

5: PID controller, 6: current-voltage converter,

7: pneumatic valve, 8: pressure regulating valve,

9: iodine mixed solution injection tube, 10: sulfur dioxide injection tube,

11: sulfuric acid discharge pipe 12: iodine acid mixed solution discharge pipe,

13: compressed air engine.

Claims (11)

In the Bunsen reactor for nuclear hydrogen production, The lower end of the Bunsen reactor includes an iodine acid discharge pipe and a sulfur dioxide injection pipe including a pneumatic valve, The upper part includes an iodine mixed solution inlet tube and an automatic phase separator, The automatic phase separator includes a dip tube for measuring the pressure of each separated phase; A differential pressure sensor for detecting a difference in measured pressure; A PID controller for controlling opening and closing of the pneumatic valve by a difference in pressure sensed by a differential pressure sensor; And a sulfuric acid discharge tube. 2. The integrated Bunsen reactor according to claim 1, wherein the Bunsen reactor comprises a charge. 3. The integrated Bunsen reactor according to claim 2, wherein the filler is in the form of a mesh made of a ceramic material or a corrosion resistant metal material. The method of claim 2, wherein the filler material is Berl saddle, Intalax saddle, Raschig ring, Lessing ring, Cross-partition ring ), Single-spiral ring (Single-spiral ring), Double-spiral ring (Double-spiral ring) and triple-spiral ring (Triple-spiral ring), characterized in that any one selected from the group consisting of or a mixture thereof Integral Bunsen reactor. delete delete delete The iodine mixed solution is injected into the upper part through the iodine mixed solution injection pipe and flows from the upper part of the Bunsen reactor to the lower part. Preparing a sulfuric acid phase and an iodine acid phase (step 1); The sulfuric acid phase and iodine acid prepared in step 1 is separated in the phase separator to form an interface, and measuring the position of the interface formed through the dip tube and the differential pressure sensor inserted in each phase (step 2): And A sulfuric acid and iodine automatic separation method comprising the step of discharging the sulfuric acid phase and iodine phase acid while maintaining the interface position measured in the step 2 through the PID controller and the pneumatic automatic valve (step 3). 9. The method of claim 8, wherein the difference in specific gravity between the sulfuric acid phase and the iodine phase of step 1 is 0.9-1.3. 9. The method of claim 8, wherein the sulfuric acid phase of step 3 is discharged through the sulfuric acid discharge pipe in the phase separator. 9. The method of claim 8, wherein the iodine acid phase of step 3 is discharged to the iodine acid mixture solution discharge pipe by a pneumatic automatic valve located at the bottom of the Bunsen reactor.

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