Hydrogen Sulfide Reactor

Abstract

To provide a hydrogen sulfide reactor in which molten sulfur supplied from a top of a tower can be prevented from flowing down along an inner wall surface of a quench column to a hydrogen sulfide reaction vessel without flowing down into fillers.SOLUTION: A hydrogen sulfide reactor 1 is composed of a hydrogen sulfide reaction vessel 10 for generating hydrogen sulfide gas by a reaction between high temperature molten sulfur and hydrogen gas in an uncatalyzed state, and a quench column 20, which is provided on a top of the hydrogen sulfide reaction vessel 10 and cools the generated hydrogen sulfide gas by countercurrent gas-liquid contact with low temperature molten sulfur. The quench column 20 is provided with sloping sections 28, 29, which incline diagonally downward toward a central axis O of the quench column 20, around inner peripheries of annular support rings 26, 27, which support inner parts such as a distributor 22 and a filler support 24.SELECTED DRAWING: Figure 3

Description

[Technical Field]

[0001] The present invention relates to a hydrogen sulfide reactor, and more particularly to a hydrogen sulfide reactor that produces hydrogen sulfide gas by reacting molten sulfur with hydrogen gas in the absence of a catalyst. [Background technology]

[0002] Hydrogen sulfide is used in various fields, such as non-ferrous metal smelting and pharmaceuticals. For example, hydrogen sulfide gas is used as a sulfiding agent in the field of hydrometallurgical nickel smelting. Specifically, in the HPAL (High Pressure Acid Leaching) process, in which low-grade nickel ore as a raw material is added with water to prepare an ore slurry, sulfuric acid is added to the slurry, and acid leaching is performed under high temperature and high pressure. Hydrogen sulfide gas is blown into the leachate containing valuable metals such as nickel and cobalt produced by the acid leaching process in a reaction vessel, and the valuable metals are recovered as sulfide products.

[0003] As described above, various methods for producing hydrogen sulfide gas for industrial use have been proposed, and for example, Patent Documents 1 to 3 disclose a method for producing hydrogen sulfide gas by reacting molten sulfur with hydrogen gas in the absence of a catalyst. This method produces hydrogen sulfide gas by blowing hydrogen gas produced in, for example, a hydrogen purification facility into high-temperature molten sulfur held under pressure in a hydrogen sulfide reaction vessel, and it is described that this method can produce hydrogen sulfide gas efficiently even in the absence of a catalyst. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2013-147364 [Patent Document 2] Japanese Patent Publication No. 2020-75822 [Patent Document 3] Japanese Patent Application Publication No. 2-55210 Summary of the Invention [Problem to be solved by the invention]

[0005] The hydrogen sulfide reactors disclosed in Patent Documents 1 and 2 are provided with a quench column at their top. High-temperature hydrogen sulfide gas produced in the hydrogen sulfide reactor enters the quench column from the bottom and rises toward the top. As the high-temperature hydrogen sulfide gas enters the quench column, it undergoes countercurrent gas-liquid contact with low-temperature molten sulfur flowing down from the top to the bottom. This cools the high-temperature hydrogen sulfide gas and condenses the sulfur vapor contained in the high-temperature hydrogen sulfide gas. As a result, low-temperature hydrogen sulfide gas from which the sulfur vapor has been removed is discharged from the top of the quench column.

[0006] The quench column is packed with random or structured packing to increase the contact area of ​​the countercurrent gas-liquid contact and thereby improve the efficiency of cooling and condensation. Furthermore, a distributor such as a trough-shaped distributor or a chimney tray is installed above the packing so that the low-temperature molten sulfur introduced from the top of the column is dispersed as uniformly as possible among the packing.

[0007] However, some of the low-temperature molten sulfur flowing down from the top of the column sometimes flows down along the inner wall surface of the quench column to the hydrogen sulfide reaction vessel without flowing down through the packing. In particular, when the low-temperature molten sulfur flows down only along a portion of the inner wall surface in the circumferential direction of the quench column, the temperature of the side wall of the quench column is partially cooled by the low-temperature molten sulfur flowing down along this portion of the inner wall surface, which causes a difference in thermal expansion of the side wall of the quench column, and the quench column may bend and tilt as a whole. When the quench column tilts in this way, excessive stress is applied to the connected piping system, which can cause problems such as bending of the piping or leakage from the flange surfaces.

[0008] The present invention has been proposed in view of the problems inherent in the above-mentioned hydrogen sulfide reaction apparatus, which is composed of a reaction vessel for producing hydrogen sulfide gas and a quench column provided above the reaction vessel, and has as its object to provide a hydrogen sulfide reaction apparatus that can suppress the problem of low-temperature molten sulfur introduced from the top of the quench column flowing down along the inner wall surface of the quench column without flowing down through the packing. [Means for solving the problem]

[0009] As a result of extensive research to solve the above-mentioned problems, the present inventors have concluded that, because the inner wall of the quench column is provided with an annular support ring that supports, at its periphery, so-called internal components (internals), such as packing supports that support the packing and dispersion plates that distribute the low-temperature molten sulfur as uniformly as possible, some of the molten sulfur flows down the inner wall surface of the quench column, starting from this support ring. Therefore, the present inventors modified the shape of this support ring to make it more difficult for the molten sulfur to flow down, and found that this could suppress the problem of the quench column tilting due to differential thermal expansion, which led to the completion of the present invention.

[0010] That is, the hydrogen sulfide reaction apparatus of the present invention is a hydrogen sulfide reaction apparatus comprising a hydrogen sulfide reaction vessel for generating hydrogen sulfide gas by a reaction between high-temperature molten sulfur and hydrogen gas in a non-catalytic state, and a quench column provided above the hydrogen sulfide reaction vessel for cooling the generated hydrogen sulfide gas by countercurrent gas-liquid contact with low-temperature molten sulfur, wherein the quench column is characterized in that an inclined portion inclined obliquely downward toward the central axis of the quench column is provided around the inner peripheral edge of an annular support ring that supports the internal parts of the quench column. [Effects of the Invention]

[0011] According to the present invention, it is possible to suppress the problem that low-temperature molten sulfur introduced from the top of a quench column packed with packings flows down along the inner wall surface of the quench column without flowing down through the packings. [Brief explanation of the drawings]

[0012] [Figure 1] FIG. 1 is a process flow diagram showing a specific example of a hydrogen sulfide gas production plant in which a hydrogen sulfide reaction facility according to an embodiment of the present invention is suitably employed. [Figure 2] FIG. 1 is a front view of a hydrogen sulfide reaction apparatus according to an embodiment of the present invention. [Figure 3] FIG. 2 is a longitudinal cross-sectional view of a quench column of the hydrogen sulfide reaction apparatus according to the embodiment of the present invention. [Figure 4] FIG. 4 is a partially cutaway perspective view of a support ring provided inside the quench column of FIG. 3. [Figure 5] FIG. 1 is a vertical cross-sectional view of a quench column of a conventional hydrogen sulfide reaction apparatus. [Figure 6] FIG. 6 is a vertical cross-sectional view schematically illustrating a state in which the quench column of FIG. 5 is tilted due to a difference in thermal expansion caused by low-temperature molten sulfur flowing down along part of the inner wall surface of the quench column. [Figure 7] 5 is a cross-sectional view of one side of the support ring of FIG. 4 when cut by a plane including the central axis thereof. DETAILED DESCRIPTION OF THE INVENTION

[0013] Hereinafter, embodiments of the hydrogen sulfide reaction apparatus of the present invention will be described in detail with reference to the drawings. Note that the hydrogen sulfide reaction apparatus of the present invention is not limited to the following embodiments, and various modifications and alternatives can be included within the scope of the present invention. In other words, the rights of the present invention are within the scope of the claims and their equivalents.

[0014] ≪1. Hydrogen sulfide gas production plant≫ First, a specific example of a hydrogen sulfide gas production plant suitable for employing a hydrogen sulfide reaction apparatus according to an embodiment of the present invention will be described with reference to the process flow diagram shown in Fig. 1. The hydrogen sulfide gas production plant shown in Fig. 1 has a hydrogen sulfide reaction apparatus 1 maintained under a pressurized state of approximately 700 kPaG to 900 kPaG, in which hydrogen gas is blown from below into high-temperature molten sulfur maintained at a temperature of 400°C to 500°C, and the high-temperature molten sulfur and hydrogen gas are reacted in the absence of a catalyst to produce hydrogen sulfide gas.

[0015] The hydrogen sulfide gas thus produced leaves the hydrogen sulfide reactor 1 and is introduced into one of two parallel cooling units 2A and 2B, where it is cooled to about 50°C using, for example, cooling water. It is then introduced into a sulfur removal unit 3, which is comprised of a knockout drum or the like, where the mist-like sulfur contained in the hydrogen sulfide gas is separated and removed, and the hydrogen sulfide gas is then supplied to a sulfurization treatment plant as nearly pure hydrogen sulfide gas. The sulfur separated and removed in the sulfur removal unit 3 is recovered in a blowdown unit 4, where it is temporarily stored and then supplied to a sulfur treatment plant.

[0016] A portion of the high-temperature molten sulfur is extracted from the bottom of the hydrogen sulfide reactor 1 and introduced into the sulfur cooler 5, where it is cooled to approximately 130°C to 140°C to adjust the heat balance. The molten sulfur is then pressurized by the pump 7 and returned to the hydrogen sulfide reactor 1 via the circulation pipe 6 as low-temperature molten sulfur. A sulfur supply pipe is connected to the discharge side of the pump 7 to replenish the molten sulfur in the system, which gradually decreases due to the generation of hydrogen sulfide gas. Two parallel solid-liquid separators 8A and 8B, such as strainers, are installed on the suction side of the pump 7, where solid impurities are removed. Nitrogen gas is introduced into the hydrogen sulfide reactor 1, sulfur cooler 5, and other devices as needed from a nitrogen gas supply facility (not shown).

[0017] ≪2. Hydrogen sulfide reaction device≫ Next, the hydrogen sulfide reactor 1 included in the hydrogen sulfide gas production plant will be described with reference to Figure 2. The hydrogen sulfide reactor 1 is mainly composed of a substantially cylindrical hydrogen sulfide reactor vessel 10 that holds high-temperature molten sulfur under pressurized conditions as described above, and a quench column 20 that is attached to the upper discharge nozzle of the hydrogen sulfide reactor vessel 10 by a flange connection.

[0018] The hydrogen sulfide reactor 10 has a supply nozzle for hydrogen gas injected into the high-temperature molten sulfur at the bottom of its sidewall, and a lower discharge nozzle at the bottom through which the high-temperature molten sulfur is extracted. The hydrogen sulfide reactor 10 is further equipped with a heater 11 at a position immersed in the high-temperature molten sulfur. This configuration allows the molten sulfur held in the hydrogen sulfide reactor 10 to be constantly maintained at a high temperature of preferably 400°C to 500°C, more preferably about 450°C, by the heater 11. The hydrogen gas injected into the high-temperature molten sulfur rises within the high-temperature molten sulfur due to buoyancy, and reacts with the surrounding high-temperature molten sulfur to produce high-temperature hydrogen sulfide gas at approximately the same temperature as the high-temperature molten sulfur.

[0019] The high-temperature hydrogen sulfide gas produced in the hydrogen sulfide reactor 10 is discharged from the top discharge nozzle of the hydrogen sulfide reactor 10 together with sulfur vapor, enters the quench column 20, which is flange-connected to the top discharge nozzle, from the bottom, and rises through the column. As described above, low-temperature molten sulfur, preferably cooled to 138°C, is supplied to the quench column 20 from the top. Therefore, the high-temperature hydrogen sulfide gas rising through the column and the accompanying sulfur vapor are in countercurrent gas-liquid contact with the low-temperature molten sulfur flowing downward through the column. As a result, the high-temperature hydrogen sulfide gas is cooled to approximately the same temperature as the low-temperature molten sulfur, exits the quench column 20 from the top, and is sent to a downstream device. Meanwhile, the sulfur vapor is condensed and separated from the hydrogen sulfide gas, and then flows downward through the column together with the low-temperature molten sulfur supplied from the top.

[0020] 3. Quench column Next, the quench column 20 constituting the hydrogen sulfide reaction apparatus 1 will be described in detail with reference to Fig. 3. As illustrated in Fig. 3, the quench column 20 is composed of a vertically long cylindrical body 21, the lower end flange of which is connected to the flange of the upper discharge nozzle of the hydrogen sulfide reaction vessel 10. A nozzle for introducing low-temperature molten sulfur is provided at the upper part of the side wall of this cylindrical body 21, and a distributor 22 consisting of a trough with a sawtooth upper end arranged in a cross shape in plan view is attached to the tip of this nozzle in order to distribute the low-temperature molten sulfur as uniformly as possible and supply it to a distribution plate described below.

[0021] The inside of the cylindrical body 21 is packed with packings 23 in multiple stages (two stages of packings 23 are shown in FIG. 3 ) that serve to increase the contact area in the countercurrent gas-liquid contact between the high-temperature hydrogen sulfide gas rising inside the column and the low-temperature molten sulfur flowing down inside the column, thereby enhancing the cooling effect. Below the packings 23 in each stage, slit- or grid-shaped packing supports 24 are provided to support the packings 23 while allowing the rising hydrogen sulfide gas to pass through. Furthermore, above the packings 23 in each stage, distribution plates 25 are provided to allow the low-temperature molten sulfur to flow down in a state as uniformly dispersed as possible.

[0022] Various shapes have been proposed for the above-mentioned distribution plate 25, and Fig. 3 shows an example of a so-called chimney tray type distribution plate 25, in which a plurality of cylindrical bodies are provided on a circular plate having a plurality of through holes through which the ascending hydrogen sulfide gas passes, and each of the cylindrical bodies is connected to the plurality of through holes. Each of the plurality of cylindrical bodies has a V-shaped notch formed at the upper end, and the low-temperature molten sulfur temporarily retained on the distribution plate 25 overflows the V-shaped notch and flows down through the inside of the cylindrical body while the flow rate is controlled to some extent, thereby making it possible to uniformly distribute the low-temperature molten sulfur.

[0023] As described above, the quench column 20 is provided with so-called internal components, such as the packing support 24 that supports the packing 23 and the distribution plate 25 that distributes low-temperature molten sulfur. Annular support rings 26, 27 that support each of these internal components at their peripheries are attached to the inner wall surface of the cylindrical body 21. Therefore, some of the molten sulfur may flow downward along the inner wall surface of the quench column 20, originating from the support rings 26, 27. In this case, since the distribution plate 25 allows the low-temperature molten sulfur to flow downward from the inside of the multiple cylindrical bodies as described above, it is unlikely that the low-temperature molten sulfur will flow along the support ring 27 of the distribution plate 25 and reach the inner wall surface of the quench column 20. However, since the packing support 24 is open over almost the entire surface so as not to obstruct the passage of the ascending hydrogen sulfide gas, the low-temperature molten sulfur is likely to flow along the lower surface of the support ring 26 and reach the inner wall surface of the quench column 20.

[0024] Therefore, in the hydrogen sulfide reaction apparatus 1 according to an embodiment of the present invention, as shown in Fig. 4, inclined portions 28, 29 that slope obliquely downward toward the central axis O of the quench column 20 are provided around the entire inner peripheral edge of the annular support rings 26, 27 that support the internal components of the quench column 20. This allows the low-temperature molten sulfur that has flowed into the upper surface sides of the support rings 26, 27 to flow downward along the inclined portions 28, 29 toward the central axis O of the quench column 20. As a result, it is possible to more effectively bring the low-temperature molten sulfur into countercurrent gas-liquid contact with the high-temperature hydrogen sulfide gas rising inside the column, and the high-temperature hydrogen sulfide gas can be efficiently cooled.

[0025] Furthermore, since low-temperature molten sulfur is almost never allowed to flow down the support rings 26, 27 and reach the inner wall surface of the quench column 20, it is possible to prevent the problem of tilting of the quench column 20, which occurs when low-temperature molten sulfur flows down along part of the wall surface of the quench column 20. That is, as shown in Fig. 5, in the quench column 120 of a conventional hydrogen sulfide reaction apparatus, low-temperature molten sulfur easily flows down along the lower surface sides of the support rings 126, 127 and reaches the inner wall portion of the cylindrical main body 121 of the quench column 120. In particular, when the low-temperature molten sulfur flows down only part of the inner wall surface of the cylindrical main body 121 in the circumferential direction, the side wall of the cylindrical main body 121 of the quench column 120 is partially cooled, and the resulting difference in thermal expansion causes the problem of the quench column 120 tilting overall, as shown in Fig. 6.

[0026] In contrast, in the hydrogen sulfide reaction apparatus 1 according to an embodiment of the present invention, the inclined portions 28, 29 are provided around the entire inner peripheral edge of the annular support rings 26, 27, as described above. Therefore, even if low-temperature molten sulfur flows into the upper surface side of the support rings 26, 27, it is virtually impossible for the flowing low-temperature molten sulfur to rise against gravity along the lower surface sides of the inclined portions 28, 29. This makes it difficult for the low-temperature molten sulfur to reach the inner wall surface of the quench column 20 along the lower surface sides of the support rings 26, 27 of the quench column 20. This prevents the above-described problem of the quench column 20 tilting overall due to a difference in thermal expansion.

[0027] 7, in the hydrogen sulfide reaction apparatus 1 according to the embodiment of the present invention, the inclined length L of the inclined portions 28, 29 is preferably 30 mm or more and 70 mm or less. If the inclined length L is less than 30 mm, the effect of providing the inclined portions 28, 29 is less likely to be achieved, and the low-temperature molten sulfur tends to flow along the inner wall surface of the quench column 20. Conversely, if the inclined length L exceeds 70 mm, the inclined portions 28, 29 may obstruct the flow of the low-temperature molten sulfur flowing down inside the quench column 20 and the flow of the hydrogen sulfide gas rising inside the column.

[0028] The inclination angle α of the inclined portions 28, 29 relative to the horizontal plane is preferably 50 degrees or more and 70 degrees or less. If the inclination angle α is less than 50 degrees, the flow of low-temperature molten sulfur flowing down the inside of the quench column 20 and the flow of hydrogen sulfide gas rising up the inside of the column may be obstructed. Conversely, if the inclination angle exceeds 70 degrees, the effect of the inclined portions 28, 29 is less pronounced, and the low-temperature molten sulfur tends to flow along the inner wall surface of the quench column 20. As shown in FIG. 3 , the support ring 26 of the packing support 24 supporting the lowest packing 23 among the multiple packing stages 23 has a short distance to the bottom flange. Therefore, even if the low-temperature molten sulfur flows along the underside of the support ring 26 and reaches the inner wall surface of the quench column 20, there is almost no adverse effect, and therefore the inclined portion 28 may not be provided. [Explanation of symbols]

[0029] 1 Hydrogen sulfide reactor 2A, 2B Cooling device 3 Sulfur removal equipment 4 Blowdown equipment 5 Sulfur cooling device 6 Circulation piping 7. Pump 8 Solid-liquid separation equipment 10 Hydrogen sulfide reaction vessel 11 Heater 20, 120 Quench column 21, 121 Cylindrical body 22, 122 Distributor 23, 123 filling 24, 124 Filler support 25, 125 Dispersion plate 26, 27, 126, 127 Support Rings 28, 29 Slope section

Claims

1. A hydrogen sulfide reaction apparatus comprising a hydrogen sulfide reaction vessel for generating hydrogen sulfide gas by a reaction between high-temperature molten sulfur and hydrogen gas in a non-catalytic state, and a quench column provided above the hydrogen sulfide reaction vessel for cooling the generated hydrogen sulfide gas by countercurrent gas-liquid contact with low-temperature molten sulfur, A hydrogen sulfide reaction apparatus characterized in that the quench column has an inclined portion that slopes obliquely downward toward the central axis of the quench column, the inclined portion being provided around the entire inner peripheral edge of an annular support ring that supports the internal components of the quench column.

2. 2. The hydrogen sulfide reaction device according to claim 1, wherein the inclined portion has an inclination length of 30 mm or more and 70 mm or less, and an inclination angle with respect to a horizontal plane of 50 degrees or more and 70 degrees or less.

3. 3. The hydrogen sulfide reaction apparatus according to claim 1, wherein the high-temperature molten sulfur has a temperature of 400°C or higher and 500°C or lower, and the high-temperature molten sulfur is held in the hydrogen sulfide reaction vessel pressurized to a pressure of 700 kPaG or higher and 900 kPaG or lower, and the hydrogen sulfide gas is generated by blowing the hydrogen gas into the high-temperature molten sulfur.

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