A reactor and method for producing hydrogen sulfide

Abstract

The application provides a reactor and a method for preparing hydrogen sulfide, and solves the technical problems of complex structure, low production efficiency and short service life of the catalyst of the existing equipment. The reactor is provided with a shell, an upper head and a lower head, an upper partition plate is arranged between the shell and the upper head, a lower partition plate is arranged between the shell and the lower head, at least one hydrogen gas feeding pipe and at least one sulfur feeding pipe are arranged on the reactor, at least one hydrogen gas discharging hole is arranged on the wall of the hydrogen gas feeding pipe, at least one sulfur discharging hole is arranged on the wall of the sulfur feeding pipe, a mixing pipe is arranged at the central axis of the reactor, at least one gas inlet hole is arranged on the wall of the mixing pipe, and at least one reaction pipe is arranged on the reactor. The application can be widely applied to the technical field of hydrogen sulfide reaction equipment.

Description

Technical Field

[0001] This application belongs to the field of sulfide synthesis technology, and more specifically, relates to a reactor and method for preparing hydrogen sulfide. Background Technology

[0002] Hydrogen sulfide is an important industrial intermediate, used in the synthesis of methanethiol, dimethyl sulfide, dimethyl disulfide, sulfonic acid, dimethyl sulfoxide, and in the reactions of many sulfides. The commonly used industrial preparation method involves the reaction of sulfur and hydrogen gas to obtain hydrogen sulfide. The preparation of hydrogen sulfide is characterized by high reaction temperatures, strong exothermic reactions, and highly corrosive raw materials, making industrial production of hydrogen sulfide subject to stringent requirements.

[0003] CN101583563A provides a method and apparatus for continuous production of hydrogen sulfide. The apparatus consists of a reactor, a cooler, and a container for collecting polysulfides. The reactor is a U-tube reactor. This method solves the heat exchange problem between polysulfides and materials. However, due to the U-tube design, it is difficult to remove liquid sulfur once it enters the system. At the same time, the U-tube design also means that the reactor is large in scale and expensive. The fixing of the U-tube also requires large flange components, and the equipment safety is low under high pressure.

[0004] US2214859A discloses a method for preparing hydrogen sulfide. Using a cobalt, nickel oxide, or sulfide catalyst, molybdenum deposited on a support evaporates excess sulfur from the catalyst using an excess of sulfur-averaged hydrogen, achieving high yields of hydrogen sulfide at temperatures between 500 and 800°C. However, the catalyst chamber temperature in this method approaches 800°C, necessitating the use of ceramic building materials. The heat of reaction is not economically viable because the gas is too corrosive at such high operating temperatures for use in the metal heat transfer equipment required for economical operation. Furthermore, the catalyst bed life is limited at these high temperatures, requiring frequent bed replacements, thus increasing operating costs. Since operation must be performed under conditions requiring a large excess of sulfur, a special condenser must be used to condense this excess free sulfur from the hydrogen sulfide gas as it exits the catalyst chamber, which is not economically viable.

[0005] US2863725A discloses a method for preparing hydrogen sulfide using a tubular reactor. Sulfur is introduced into a molten sulfur bath, and hydrogen is bubbled into the molten sulfur bath. The amount of hydrogen entering the sulfur bath and the temperature at the top of the bath are adjusted to maintain the correct ratio. Then, under pressure, the vapor mixture is forced into a filled catalytic reaction zone, and the catalyst bed is maintained at approximately 330°C. This allows for the continuous and high-yield direct recovery of homogeneous, essentially sulfur-free hydrogen sulfide directly from the catalytic reaction zone. However, in this device, due to the catalyst placement and feeding method, the most intense reaction occurs at the top of the reaction tubes, making the liquid sulfur level critical. If the level falls below the catalyst zone, it can cause catalyst overheating, affecting the reaction efficiency. Furthermore, the tubular installation of this equipment is not stable enough, and catalyst replacement is inconvenient.

[0006] CN104583116A discloses an apparatus and method for preparing hydrogen sulfide, which involves setting up multiple trays with different structures in a reactor, ultimately achieving a hydrogen conversion rate of 99.93%, a volume purity of 99.85%, and a product containing 400-600 ppm of polysulfides. However, this reaction equipment is difficult to prepare, has high process requirements, and the U-shaped tube setup in the reaction section requires a large tower diameter for a tower-type device, resulting in high equipment costs. Furthermore, if liquid sulfur is entrained in the gas within the U-shaped tube, the system must be shut down to remove the deposited sulfur.

[0007] Based on existing hydrogen sulfide preparation equipment, three problems have been identified: 1) The hydrogen sulfide preparation process is highly sensitive to the sulfur liquid level, and a decrease in the sulfur liquid level can easily cause catalyst overheating; 2) The entrainment of liquid sulfur in the mixed gas, or the splashing of liquid sulfur, can contaminate the catalyst in the reaction, affecting reaction efficiency and production progress; 3) The structure of the equipment is crucial to whether the reaction can be used under high pressure, and most existing hydrogen sulfide pressurized equipment is very complex. Summary of the Invention

[0008] The present invention aims to overcome the shortcomings of the above-mentioned background technology by providing a reactor and method for preparing hydrogen sulfide that has a simple structure, high reaction efficiency, and long catalyst life.

[0009] Therefore, the present invention provides a reactor for preparing hydrogen sulfide, which includes a shell, an upper head, and a lower head. An upper partition is provided between the shell and the upper head, and a lower partition is provided between the shell and the lower head. The reactor is provided with at least one hydrogen feed pipe and at least one sulfur feed pipe. At least one hydrogen outlet hole is provided on the wall of the hydrogen feed pipe, and at least one sulfur outlet hole is provided on the wall of the sulfur feed pipe. A mixing pipe is provided at the central axis of the reactor, and at least one air inlet hole is provided at the upper end of the wall of the mixing pipe. The reactor is also provided with at least one reaction pipe.

[0010] Preferably, both the hydrogen feed pipe and the sulfur feed pipe are vertical tubes that are open at the top and closed at the bottom. The upper ends of the hydrogen feed pipe and the sulfur feed pipe pass through the upper partition and the upper end cap, respectively, and the lower ends of the hydrogen feed pipe and the sulfur feed pipe pass through the lower partition, respectively.

[0011] Preferably, the mixing tube is a vertical tube with openings at both the upper and lower ends, the upper end of the mixing tube extending to the upper end cap region, and the lower end of the mixing tube extending to the lower end cap region.

[0012] Preferably, the reaction tube is a vertical tube with openings at both the upper and lower ends, and the upper and lower ends of the reaction tube pass through an upper partition and a lower partition, respectively.

[0013] Preferably, the reaction tube contains a catalyst, and the bottom of the reaction tube is provided with a mesh support.

[0014] Preferably, a distribution plate is provided below the shell, the distribution plate is located above the hydrogen outlet and parallel to the lower partition plate, and the distribution plate is provided with channel holes.

[0015] Preferably, the upper head of the reactor is provided with a discharge port, and the bottom of the lower head of the reactor is provided with a discharge port for heavy components.

[0016] Meanwhile, the present invention provides a method for preparing hydrogen sulfide, which utilizes the above-mentioned reactor for preparing hydrogen sulfide, including the following steps: sulfur enters the shell through the sulfur inlet of the sulfur inlet pipe to form sulfur melt, and hydrogen enters the shell through the hydrogen outlet of the hydrogen inlet pipe, where it gathers into hydrogen bubbles in the sulfur melt below the distribution plate. The hydrogen bubbles mix with the rising sulfur vapor in the vapor zone to form a mixed gas, and the mixed gas enters the lower head area through the mixing pipe, and then enters the reaction tube to be converted into hydrogen sulfide.

[0017] Preferably, the liquid level of the sulfur melt is maintained at 1 / 2 to 4 / 5 of the reactor volume, and the distance between the sulfur melt phase boundary and the air inlet of the mixing pipe is 0.5m to 2m.

[0018] The preferred hydrogen flow rate is controlled at 100-280 m / s. The sulfur feed temperature is 100-150℃, the temperature inside the shell is 280-350℃, the pressure is 5-10 bar, the temperature inside the reaction tube is 325-425℃, and the pressure inside the reaction tube is 5-10 bar.

[0019] The beneficial effects of this invention are as follows:

[0020] (1) The reactor for preparing hydrogen sulfide of the present invention is provided with a hydrogen feed pipe, a sulfur feed pipe, a mixing pipe, and a reaction pipe. This allows a mixture of hydrogen and sulfur vapor to enter the reaction pipe from the lower head region and pass through the reactor from bottom to top. This ensures that the exothermic reaction occurs in the lower section of the shell, guaranteeing the effective contact area between the reaction pipe and the molten sulfur. This reduces the sensitivity of the reaction process to the molten sulfur level and prevents catalyst overheating in the event of uncontrolled sulfur level. It also improves catalyst lifespan and increases hydrogen conversion rate, reaching 99.97%-99.99%, and the purity of hydrogen sulfide reaches 99.95%-99.99%.

[0021] (2) In the reactor for preparing hydrogen sulfide of the present invention, the hydrogen feed pipe, the sulfur feed pipe and the reaction pipe are all vertical tubes and are fixed by upper and lower partitions. No special components are needed for fixing, which enhances the pressure carrying capacity and is suitable for hydrogen sulfide preparation under high pressure and low pressure.

[0022] (3) In the reactor for preparing hydrogen sulfide of the present invention, the upper and lower ends of the reaction tube are open to avoid the possibility of liquid sulfur accumulating in the tube. At the same time, the lower end is provided with a heavy component discharge port. When the sulfur liquid level exceeds the upper limit or other impurities enter the mixing tube together with the mixed gas, the other impurities or excess sulfur can be discharged out of the reactor directly through the heavy component discharge port, thereby ensuring the purity of sulfur vapor and hydrogen entering the reaction tube. Attached Figure Description

[0023] To more clearly illustrate the technical solutions in the embodiments of this application, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0024] Figure 1 This is a front view of the reactor used to prepare hydrogen sulfide according to the present invention.

[0025] Figure 2 A top view of the reactor for preparing hydrogen sulfide according to the present invention;

[0026] Explanation of symbols in the diagram:

[0027] 1. Sulfur feed pipe; 2. Hydrogen feed pipe; 3. Gas inlet; 4. Mixing pipe; 5. Upper end cap; 6. Upper baffle plate; 7. Catalyst; 8. Reaction tube; 9. Sulfur outlet; 10. Mesh support; 11. Hydrogen outlet; 12. Heavy component outlet; 13. Lower end cap; 14. Lower baffle plate; 15. Distribution plate; 16. Hydrogen sulfide outlet; 17. Shell. Detailed Implementation

[0028] To make the technical problems, technical solutions, and beneficial effects to be solved by this application clearer, the following detailed description is provided in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative and are not intended to limit the scope of this application.

[0029] Example 1: A reactor for preparing hydrogen sulfide

[0030] A reactor for the continuous production of hydrogen sulfide from hydrogen and sulfur, specifically a vertical tubular reactor, such as... Figure 1-2 As shown, it has a shell 17, an upper end cap 5 and a lower end cap 13. An upper partition 6 is provided between the shell 17 and the upper end cap 5, and a lower partition 14 is provided between the shell 17 and the lower end cap 13. By setting the upper partition 6 and the lower partition 14, there is no space flow between the inside of the shell 17 and the upper end cap 5 and the lower end cap 13, thus preventing the reactants inside the shell 17 from flowing into the area of ​​the upper end cap 5 and the area of ​​the lower end cap 13.

[0031] The reactor is equipped with at least one hydrogen feed pipe 2 and at least one sulfur feed pipe 1. Both the hydrogen feed pipe 2 and the sulfur feed pipe 1 are vertical tubes that are open at the top and closed at the bottom. The upper ends of the hydrogen feed pipe 2 and the sulfur feed pipe 1 pass through the upper partition 6 and the upper end cap 5, respectively, and extend out of the reactor for feeding the reaction materials. The lower ends of the hydrogen feed pipe 2 and the sulfur feed pipe 1 pass through the lower partition 14, respectively, and extend out 8-10 cm.

[0032] The sulfur feed pipe 1 is preferably located at both ends of the reactor. At least one sulfur outlet hole 9 is formed on the pipe wall of the sulfur feed pipe 1. Liquid sulfur is fed through the sulfur feed pipe 1 at a feed temperature of 100-150℃ and enters the interior of the shell 17 through the sulfur outlet hole 9. The internal temperature of the shell 17 is 280℃-350℃, and the liquid sulfur transitions into sulfur melt. The shell 17 is divided into a sulfur melt zone and a steam zone. The liquid level in the sulfur melt zone is maintained at 1 / 2-4 / 5 of the reactor volume, and the steam zone is located above the sulfur melt zone.

[0033] Furthermore, the sulfur outlet hole 9 is preferably circular, arranged vertically, and its diameter is 1 / 6 to 1 / 2 of the diameter of the sulfur feed pipe 1.

[0034] The hydrogen feed pipe 2 is preferably located adjacent to the sulfur feed pipe 1 and close to the center of the reactor to facilitate uniform hydrogen dispersion. At least one hydrogen outlet hole 11 is provided at the lower end of the pipe wall of the hydrogen feed pipe 2 and above the lower partition plate 14 for hydrogen to enter the interior of the shell 17.

[0035] Furthermore, the hydrogen outlet hole 11 is preferably circular, and the hydrogen outlet hole 11 is arranged around the hydrogen inlet pipe 2. The diameter of the hydrogen outlet hole 11 is 1 / 5 to 1 / 2 of the diameter of the hydrogen inlet pipe 2.

[0036] A distribution plate 15 is located below the reactor. Specifically, the distribution plate 15 is positioned above the hydrogen outlet 11 and parallel to the lower partition plate 14, with a distance of 10-30 cm between the distribution plate 15 and the lower partition plate 14. The distribution plate 15 has channel holes. Hydrogen enters through the hydrogen feed pipe 2, escapes through the hydrogen outlet 11, and then enters the sulfur melt through the channel holes on the distribution plate 15. The hydrogen flow rate is controlled at 100-280 m / s. The hydrogen gathers into uniformly distributed hydrogen bubbles in the sulfur melt. These hydrogen bubbles pass through the sulfur melt and enter the upper steam zone. Simultaneously, the sulfur vapor generated by the sulfur melt also rises to the steam zone and mixes with the hydrogen bubbles to form a mixed gas.

[0037] A mixing tube 4 is located at the central axis of the reactor. The mixing tube 4 is a vertical tube with openings at both the upper and lower ends. The upper end of the mixing tube 4 extends into the interior of the upper head 5, and the lower end of the mixing tube 4 extends into the interior of the lower head 13. At least one air inlet 3 is provided at the upper end of the mixing tube 4, arranged around the circumference of the mixing tube 4. To prevent the entry of sulfur melt into the reactor, the distance between the air inlet 3 and the boundary of the sulfur melt phase is 0.5m-2m.

[0038] The reactor is also equipped with at least one reaction tube 8, such as Figure 1-2 As shown, the reaction tube 8 is a vertical tube with openings at both the upper and lower ends. The upper end of the reaction tube 8 passes through the upper partition 6 and the lower partition 14, respectively. The distance between the upper opening of the reaction tube 8 and the upper partition 6 is 0-10cm, and the distance between the lower opening of the reaction tube 8 and the lower partition 14 is 0-10cm.

[0039] Furthermore, the reaction tube 8 is a fixed-bed reaction tube, which contains a catalyst 7, including but not limited to cobalt-molybdenum catalysts. A mesh support 10 is provided at the bottom of the reaction tube 8 to support the catalyst.

[0040] When sulfur vapor and hydrogen are mixed, the resulting gas mixture enters the lower head 13 region of the reactor through the inlet 3 of the mixing tube 4, and then flows upwards into the reaction tube 8. The temperature inside the reaction tube 8 is 325℃-425℃, and the pressure is 5-10 bar. Under the action of the catalyst inside the reaction tube 8, the sulfur vapor and hydrogen are converted into hydrogen sulfide. The hydrogen conversion rate can reach 99.97%-99.99%, and the purity of the hydrogen sulfide can reach 99.95%-99.99%. During this process, the heat of reaction in the reaction tube 8 that generates hydrogen sulfide is transferred to the sulfur melt through the tube wall, which is used to evaporate the sulfur present therein. This utilization of the heat not only saves energy but also avoids catalyst overheating, thus improving catalyst lifespan. Simultaneously, the sulfur vapor and hydrogen mixture enters from the lower end of the reaction tube 8 and flows upwards, meaning the heat release during the reaction is most significant in the early stages of the reaction. By setting the direction in which the sulfur vapor and hydrogen mixture enters the reaction tube 8, the effective contact area between the reaction tube 8 and the sulfur melt can be effectively guaranteed, reducing the sensitivity of the reaction process to the sulfur melt level and preventing catalyst overheating in the event of uncontrolled sulfur melt level.

[0041] In practice, the molar ratio of sulfur vapor to hydrogen is adjusted by controlling the temperature, pressure, and liquid level of the sulfur melt inside the reactor shell. Preferably, the molar ratio of sulfur vapor to hydrogen is 1.01-1.2:1. The slight excess sulfur in the final reaction product can be recovered by condensation and then reintroduced into the reactor.

[0042] Furthermore, the upper head 5 of the reactor is provided with a hydrogen sulfide outlet 16 for exporting and collecting the hydrogen sulfide converted in the reaction tube 8. The bottom of the lower head 13 of the reactor is provided with a heavy component outlet 12. When liquid sulfur or other impurities enter the mixing tube 8 together with sulfur vapor and hydrogen, the liquid sulfur and other impurities can be directly discharged out of the reactor through the heavy component outlet 12, thereby ensuring the purity of the sulfur vapor and hydrogen entering the reaction tube 8.

[0043] Example 2: A method for preparing hydrogen sulfide using the above-described reactor for preparing hydrogen sulfide, the specific steps of which are as follows:

[0044] The reactor tower diameter is set to 1 meter; there are 4 sulfur feed pipes 1 with a diameter of 8 cm and a sulfur outlet hole diameter of 2.5 cm; there are 2 hydrogen feed pipes 2 with a diameter of 10 cm and a hydrogen outlet hole diameter of 2 cm; the mixing pipe 8 has a diameter of 15 cm; and there are 50 reaction pipes 8 with a diameter of 5 cm.

[0045] Liquid sulfur is preheated to 100°C and enters the shell 17 through sulfur feed pipe 1, ensuring the sulfur melt level is 2 / 3 full. The distance between the sulfur melt phase boundary and the air inlet 3 of mixing pipe 4 is 1m. Hydrogen enters the shell 17 through hydrogen feed pipe 2, passes through hydrogen outlet 11, and enters the sulfur melt zone via distribution plate 15. The flow rate of hydrogen through distribution plate 15 is 240m / s. The temperature inside shell 17 is 375°C, and the pressure is 6 bar. Sulfur vapor mixes with hydrogen in the sulfur melt zone and enters mixing pipe 4. After passing through the lower head 13 area, it enters reaction pipe 8. The temperature inside reaction pipe 8 is 425°C, and the pressure is 7 bar. The mixed gas is converted into hydrogen sulfide and collected from hydrogen sulfide outlet 16 via the upper head 5 area. The hydrogen conversion rate is 99.97%, and the purity of hydrogen sulfide is 99.99%.

[0046] In summary, the reactor for preparing hydrogen sulfide of the present invention includes a hydrogen feed pipe 2, a sulfur feed pipe 1, and a mixing pipe 4. This allows the mixed gas to enter the reaction tube 8 from the lower end cap 13 region and flow upwards through the reactor. This ensures the exothermic reaction occurs in the lower section of the shell 17, guaranteeing the effective contact area between the reaction tube 8 and the molten sulfur. This reduces the sensitivity of the reaction process to the molten sulfur level and prevents catalyst overheating in case of uncontrolled sulfur level. It also improves catalyst lifespan and hydrogen conversion rate, reaching 99.97%-99.99%, and hydrogen sulfide purity, reaching 99.95%-99.99%. Furthermore, the hydrogen feed pipe 2, sulfur feed pipe 1, and reaction tube 8 are all vertically arranged tubes, fixed by the upper baffle 6 and lower baffle 14, eliminating the need for special components for fixation. This enhances the pressure-bearing capacity and makes it suitable for hydrogen sulfide preparation under both high and low pressure conditions. In addition, the upper and lower ends of the reaction tube 8 are open to avoid the possibility of liquid sulfur accumulating in the tube. At the same time, the lower end cap 13 is provided with a heavy component discharge port 12. When the sulfur liquid level exceeds the upper limit or other impurities enter the mixing tube 4 together with the mixed gas, the other impurities or excess sulfur can be discharged directly through the heavy component discharge port 12, thereby ensuring the purity of sulfur vapor and hydrogen entering the reaction tube 8.

[0047] The above description is merely a preferred embodiment of this application and is not intended to limit this application. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of this application should be included within the protection scope of this application.

Claims

1. A reactor for producing hydrogen sulfide, provided with a shell, an upper head and a lower head, an upper partition being provided between the shell and the upper head, and a lower partition being provided between the shell and the lower head, characterized in that, The reactor is provided with at least one hydrogen feeding pipe and at least one sulfur feeding pipe, the hydrogen feeding pipe is provided with at least one hydrogen outlet hole on the pipe wall, the sulfur feeding pipe is provided with at least one sulfur outlet hole on the pipe wall, the reactor is provided with a mixing pipe at the central axis, the mixing pipe is provided with at least one gas inlet hole on the upper end of the pipe wall, and the reactor is further provided with at least one reaction pipe; the mixing pipe is a vertical column pipe with open upper and lower ends, the upper end of the mixing pipe extends to the upper head area, and the lower end of the mixing pipe extends to the lower head area; the reaction pipe is a vertical column pipe with open upper and lower ends, and the upper end and the lower end of the reaction pipe respectively pass through the upper baffle and the lower baffle; the upper head of the reactor is provided with an outlet, and the bottom of the lower head of the reactor is provided with a heavy component outlet; the sulfur enters the inside of the shell through the sulfur feeding pipe to form a sulfur melt, the hydrogen enters the inside of the shell through the hydrogen feeding pipe to gather into hydrogen bubbles in the sulfur melt below the distribution plate, the hydrogen bubbles and the sulfur vapor rising to the vapor area are mixed to form mixed gas, the mixed gas enters the lower head area through the mixing pipe, and the mixed gas is converted into hydrogen sulfide in the reaction pipe from bottom to top.

2. The reactor for producing hydrogen sulfide according to claim 1, wherein The hydrogen feeding pipe and the sulfur feeding pipe are vertical column pipes with open upper ends and closed lower ends, and the upper ends of the hydrogen feeding pipe and the sulfur feeding pipe respectively pass through the upper baffle and the upper head, and the lower ends of the hydrogen feeding pipe and the sulfur feeding pipe respectively pass through the lower baffle.

3. The reactor for producing hydrogen sulfide according to claim 1, wherein The reaction pipe is provided with a catalyst, and the bottom of the reaction pipe is provided with a net support.

4. The hydrogen sulfide producing reactor of claim 1, wherein, The shell is provided with a distribution plate below the hydrogen outlet hole, the distribution plate is parallel to the lower baffle, and the distribution plate is provided with a passage hole.

5. A method for producing hydrogen sulfide using the reactor for producing hydrogen sulfide according to any one of claims 1 to 4, characterized by, The method comprises the following steps: the sulfur enters the inside of the shell through the sulfur feeding pipe to form a sulfur melt, the hydrogen enters the inside of the shell through the hydrogen feeding pipe to gather into hydrogen bubbles in the sulfur melt below the distribution plate, the hydrogen bubbles and the sulfur vapor rising to the vapor area are mixed to form mixed gas, the mixed gas enters the lower head area through the mixing pipe, and the mixed gas is converted into hydrogen sulfide in the reaction pipe from bottom to top.

6. The method of claim 5, wherein the hydrogen sulfide is produced by the reaction of the hydrogen and the sulfur compound. The liquid level of the sulfur melt is maintained at 1 / 2-4 / 5 of the volume of the reactor, and the distance between the phase boundary of the sulfur melt and the gas inlet hole of the mixing pipe is 0.5-2 m.

7. The method of claim 6, wherein the hydrogen sulfide is produced by the reaction of the hydrogen and the sulfur compound. The flow rate of the hydrogen is controlled at 100-280 m / s, the sulfur feeding temperature is 100-150 DEG C, the temperature in the shell is 280-350 DEG C, the pressure is 5-10 bar, the temperature in the reaction pipe is 325-425 DEG C, and the pressure in the reaction pipe is 5-10 bar.

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