Apparatus and method for producing hydrogen sulfide using hydrogen and sulfur

Abstract

The application discloses a device and a production method for producing hydrogen sulfide by using hydrogen and sulfur, and the device comprises a molten sulfur tank, a liquid sulfur tank, a reactor, a sulfur trap, an absorption tower, a resolving tower, a methanol dehydration tower and a methanol recovery tower; hydrogen and liquid sulfur are bubbled to react to generate hydrogen sulfide. In the scheme, hydrogen and sulfur are bubbled to react, the reaction mode is mild, the reaction is easy to control, the whole reaction conversion rate is high, and energy utilization is good. The problems of violent reaction, difficult control and large energy consumption in the prior art are effectively solved.

Description

Technical Field

[0001] This invention belongs to the field of hydrogen sulfide preparation technology, specifically relating to a hydrogen sulfide production apparatus and a production method using the apparatus. Background Technology

[0002] Hydrogen sulfide, as a common raw material for the synthesis of sulfur-containing compounds, plays an important role in the production of pesticides, pharmaceuticals, cosmetics, and polymers. However, because hydrogen sulfide itself is a flammable and toxic gas, it is not conducive to transportation and storage. In large-scale industrial production, hydrogen sulfide is generally obtained by purifying hydrogen sulfide-containing tail gas or by producing hydrogen sulfide in its own form.

[0003] Hydrogen sulfide obtained by purifying synthesis tail gas often contains trace amounts of unidentified impurities. Some of these impurities can adversely affect the synthesis and purification of subsequent products. However, the method of generating hydrogen sulfide by reacting sulfur with hydrogen does not involve side reactions. After simple purification, pure hydrogen sulfide can be obtained, which meets the production requirements of fine chemicals.

[0004] The reaction between hydrogen and sulfur is a strongly exothermic reaction. The method of directly reacting hydrogen with sulfur vapor to produce hydrogen sulfide is a violent reaction, and the reaction temperature is difficult to control. It has disadvantages such as low conversion rate and incomplete utilization of reaction heat. In addition, this method requires the sulfur to be preheated and vaporized, which wastes energy and requires additional equipment. Summary of the Invention

[0005] The purpose of this invention is to provide an apparatus and method for producing hydrogen sulfide using hydrogen and sulfur, which produces hydrogen sulfide by bubbling and removes sulfur from the gas, thereby solving the problems in the prior art.

[0006] This invention is achieved through the following technical solution: an apparatus for producing hydrogen sulfide using hydrogen and sulfur, characterized in that it includes a reactor, an absorption tower, a stripping tower, and a methanol dehydration tower; the reactor includes a catalyst bed containing a catalyst for the decomposition of polysulfides and a catalyst containing a catalyst for the reaction of hydrogen and sulfur, with coils installed below both catalyst beds; an electric heater is installed inside the reactor, and a jacket is installed on the outer wall of the reactor; a lower hydrogen inlet and a middle hydrogen inlet are respectively provided at the bottom and middle of the reactor; a sulfur inlet is provided at the bottom of the reactor; a sulfur spraying device is provided in the middle of the two catalyst beds; it also includes a molten sulfur tank and a liquid sulfur tank, with a liquid sulfur feed pump installed on the liquid sulfur tank, the liquid sulfur feed pump being connected to the reactor through a pipeline; and a sulfur trap is also included. The inlet of the sulfur trap is connected to the top of the reactor, and the outlet of the sulfur trap is connected to the inlet of the absorption tower inlet buffer tank. A bag filter is installed at the outlet of the absorption tower inlet buffer tank. The lower inlet of the absorption tower is connected to the absorption tower inlet buffer tank, and a low-temperature methanol inlet is installed at the top. An internal heat exchanger is installed at the bottom of the tower body, and the outlet of the tower body is connected to the desorption tower via the bottom discharge pump of the absorption tower. The middle part of the desorption tower has a feed inlet connected to the outlet of the tower body. The lower part of the desorption tower is connected to the feed inlet of the desorption tower and the feed inlet of the methanol dehydration tower via pipelines. A desorption tower outlet cooler is installed at the top of the desorption tower. The bottom discharge pump is installed at the bottom of the methanol dehydration tower, and a top condenser is installed at the top. The top condenser is connected to the feed inlet of the desorption tower via a reflux pump.

[0007] This invention also discloses a method for producing hydrogen sulfide, characterized by comprising the following steps: S1: Sulfur is added to the molten sulfur tank and heated to melt. The molten sulfur is added to the liquid sulfur tank and pumped into the reactor by the liquid sulfur feed pump, forming a liquid sulfur pool below the reactor. S2: After heating, hydrogen is introduced into the reactor and bubbled with liquid sulfur in the liquid sulfur pool. After bubbling, the hydrogen carries sulfur upward and reacts at the catalyst bed to produce crude hydrogen sulfide. S3: Crude hydrogen sulfide is discharged from the top of the reactor and enters the inlet buffer tank of the absorption tower after passing through the sulfur precipitator and the crude hydrogen sulfide water cooler. After pressure stabilization, it enters the bag filter to remove the sulfur entrained in the gas. The resulting hydrogen sulfide containing hydrogen is sent to the purification section. The sulfur obtained from the sulfur precipitator and the crude hydrogen sulfide water cooler is returned to the sulfur melting tank for reuse. S4: Hydrogen sulfide containing hydrogen enters the absorption tower, and after separation, it forms hydrogen containing methanol and hydrogen sulfide containing methanol; the hydrogen containing methanol is recycled after recovering methanol in the methanol recovery tower. S5: Hydrogen sulfide containing methanol enters the stripping tower to remove methanol and form pure hydrogen sulfide; S6: Methanol at the bottom of the stripping column, part of which is cooled and enters the absorption column as absorbent; S7: The methanol at the bottom of the stripping tower is divided into two parts: one part enters the methanol dehydration tower, the methanol obtained at the top of the tower is cooled and enters the absorption tower as the absorbent, and the water-containing methanol at the bottom of the tower enters the wastewater system.

[0008] Furthermore: In the reactor, hydrogen gas is introduced from the middle of the reactor to control the temperature inside the reactor; sulfur is injected into the reactor from a sulfur spraying device to adjust the load.

[0009] Furthermore, a jacket is installed outside the reactor, which is connected to the molten salt tank. During shutdown or maintenance, the jacket serves to melt and remove residual sulfur from the reactor.

[0010] Furthermore: In S4, after the methanol-containing hydrogen is recovered by the methanol recovery tower, the hydrogen is introduced into the hydrogen buffer tank.

[0011] Further: In S2, the reactor is a fixed-bed reactor, with the bed divided into two parts. Both catalyst layers have coils for heat transfer. The bottom of the tower contains liquid sulfur, and an electric heater is installed inside the tower to control the sulfur temperature. A jacket is installed on the outer wall of the tower to increase the temperature of the tower and melt the sulfur during sulfur discharge. Hydrogen enters from the bottom of the tower and is bubbled through the liquid sulfur, so that the hydrogen carries the sulfur into the catalyst bed containing the catalyst for the reaction of hydrogen and sulfur. Subsequently, it enters the catalyst bed containing the catalyst for the decomposition of hydrogen polysulfides. The reaction temperature is 100-700℃, and the operating pressure is 0.1-2 MPaG.

[0012] Furthermore: In S1, raw sulfur enters the melting sulfur tank from the boundary area, melts, and then overflows into the liquid sulfur tank. After being filtered by the liquid sulfur feed pump, it enters the reactor.

[0013] Compared with the prior art, the present invention has the following advantages: 1) The method of using hydrogen to bubble in sulfur allows the material to enter the catalyst layer, reducing the intensity of the reaction and making the reaction more controllable. 2) Adding a coil to the middle of the catalyst layer to control the reaction temperature prevents drastic temperature changes and thus extends the catalyst's lifespan; 3) Utilizing molten salt to absorb the heat of reaction and raise the temperature of the raw material hydrogen gas, the heat of reaction is used rationally and energy is saved; 4) Two different catalysts are packed at the top and bottom of the reactor to reduce the content of hydrogen polysulfide in the syngas at the reactor outlet, thereby reducing the sulfur content in the syngas. 5) By using a sulfur trap, a crude hydrogen sulfide water cooler, and a bag filter, sulfur is prevented from entering the subsequent hydrogen sulfide purification process, making the purification of hydrogen sulfide simpler. 6) The raw materials, sulfur and hydrogen, are equipped with multiple feed ports, which can be adjusted in a timely manner according to different working conditions, and have strong adaptability and adjustability. 7) The hydrogen sulfide can be automatically fed into subsequent stages by adjusting the pressure of the stripping tower, replacing the original compressor delivery method; 8) Compared with absorption methods using various water-containing absorbents, no additional dehydration and drying process is required; 9) Choosing methanol as the absorbent can avoid the equipment and pipeline corrosion problems caused by the absorbent and wet hydrogen sulfide; 10) The methanol used as the absorbent is recycled, saving methanol consumption and reducing costs; 11) The molecular sieve inside the methanol recovery tower can adsorb methanol in the recovered hydrogen, preventing methanol from entering the hydrogen sulfide reactor. This prevents methanol from entering the high-temperature hydrogen sulfide reactor and causing coking on the catalyst surface, which could reduce the catalyst's catalytic effect and service life. Attached Figure Description

[0014] Figure 1 This is a schematic diagram of the reaction process structure; Figure 2 This is a schematic diagram of the purification process; Figure 3 This is a schematic diagram of the regeneration process structure; Figure 4 It is a process flow diagram; Figure 5 This is a schematic diagram of the reactor structure.

[0015] Explanation of the numbers in the diagram: 1. Hydrogen 2. Hydrogen preheater 3. Syngas 4. Hydrogen heater 5. Molten salt 6. Reactor 7. Hydrogen electric heater 8. Sulfur 9. Molten sulfur tank 10. Liquid sulfur tank 11. Liquid sulfur feed pump 12. Filter 13. Sulfur catcher 14. Crude hydrogen sulfide water cooler 15. Absorber inlet buffer tank 16. Bag filter 17. Hydrogen sulfide containing hydrogen 18. Sulfur obtained from the sulfur catcher and crude hydrogen sulfide water cooler 19. Molten salt tank 20. Molten salt pump 21. Absorber 22. Low-temperature methanol 23. Hydrogen containing trace amounts of methanol 24. Mixture of methanol and hydrogen sulfide 25. Heat exchanger at the bottom of the tower 26. Absorber bottom discharge pump 27. Desorption tower preheater 28. Hot methanol at the bottom of the desorption tower 29. Desorption tower 30. Desorption tower 31. Filter tower discharge cooler, 32. Pure product hydrogen sulfide, 33. Reboiler, 34. Part of methanol, 35. Another part of methanol, 36. Methanol dehydration tower, 37. Top condenser, 38. Bottom reboiler, 39. Reflux tank, 40. Reflux pump, 41. Bottom discharge pump, 42. Bottom water-containing methanol, 43. First-stage methanol condenser, 44. Second-stage methanol condenser, 45. Third-stage methanol condenser, 46. Fresh methanol and methanol makeup liquid, 47. Hydrogen compressor, 48. Hydrogen compressor pre-buffer tank, 49. Hydrogen compressor post-buffer tank, 50. Methanol recovery tower, 51. Liquid methanol, 52. Pure hydrogen at the top outlet of the methanol recovery tower, 53. Methanol recovery tower regeneration preheater, 54. Hydrogen regenerated from the methanol recovery tower, 55. Hydrogen buffer tank, 56. Fresh hydrogen. The components include: coil 601, electric heater 602, jacket 603, catalyst bed 604 containing catalyst for the reaction of hydrogen and sulfur, catalyst bed 605 containing catalyst for the decomposition of hydrogen polysulfides, hydrogen inlet 606, hydrogen inlet 607, sulfur inlet 608, and sulfur spraying device 609. Detailed Implementation

[0016] Reference Appendix Figure 1-5As shown. This invention discloses a hydrogen sulfide production apparatus, which includes a reactor, an absorption tower, a stripping tower, and a methanol dehydration tower; the reactor includes a catalyst bed 605 containing a catalyst for the decomposition of polysulfides and a catalyst bed 604 containing a catalyst for the reaction of hydrogen and sulfur, with coils 601 installed below both catalyst beds, an electric heater 602 installed inside the reactor, and a jacket 603 installed on the outer wall of the reactor; a lower hydrogen inlet 606 and a middle hydrogen inlet 607 are respectively installed at the bottom and middle of the reactor, a sulfur inlet 608 is installed at the bottom of the reactor, and a sulfur spraying device 609 is installed in the middle of the two catalyst beds, i.e., a nozzle is installed in the inlet; it also includes a molten sulfur tank 9 and a liquid sulfur tank 10, with a liquid sulfur feed pump 11 installed on the liquid sulfur tank 10, and the liquid sulfur feed pump 11 is connected to the reactor through a pipeline; it also includes a sulfur trap 13, the inlet of which is connected to The reactor is connected at the top, and the outlet of the sulfur trap 13 is connected to the inlet of the absorption tower inlet buffer tank 15. A bag filter 16 is installed at the outlet of the absorption tower inlet buffer tank 15. The lower inlet of the absorption tower 21 is connected to the absorption tower inlet buffer tank 15, and a low-temperature methanol 22 inlet is provided at the top. A bottom heat exchanger 25 is installed in the lower part of the reactor. The reactor outlet is connected to the desorption tower 29 through the absorption tower bottom discharge pump 26. The middle part of the desorption tower 29 is provided with a feed inlet connected to the reactor outlet. The lower part of the desorption tower 29 is connected to the desorption tower 29 inlet and the methanol dehydration tower 36 inlet through pipelines. A desorption tower outlet cooler 31 is provided at the top of the desorption tower 29. A bottom discharge pump 41 is provided at the bottom of the methanol dehydration tower 36, and a top condenser 37 is provided at the top. The top condenser 37 is connected to the desorption tower 29 inlet through a reflux pump 40.

[0017] This invention also discloses a method for producing hydrogen sulfide, which includes the following steps: S1: Sulfur is added to the molten sulfur tank and heated to melt. The molten sulfur is added to the liquid sulfur tank and pumped into the reactor by the liquid sulfur feed pump, forming a liquid sulfur pool below the reactor. S2: After heating, hydrogen is introduced into the reactor and bubbled with liquid sulfur in the liquid sulfur pool. After bubbling, the hydrogen carries sulfur upward and reacts at the catalyst bed to produce crude hydrogen sulfide. S3: Crude hydrogen sulfide is discharged from the top of the reactor and enters the inlet buffer tank of the absorption tower after passing through the sulfur precipitator and the crude hydrogen sulfide water cooler. After pressure stabilization, it enters the bag filter to remove the sulfur entrained in the gas. The resulting hydrogen sulfide containing hydrogen is sent to the purification section. The sulfur obtained from the sulfur precipitator and the crude hydrogen sulfide water cooler is returned to the sulfur melting tank for reuse. S4: Hydrogen sulfide containing hydrogen enters the absorption tower, and after separation, it forms hydrogen containing methanol and hydrogen sulfide containing methanol; the hydrogen containing methanol is recycled after recovering methanol in the methanol recovery tower. S5: Hydrogen sulfide containing methanol enters the stripping tower to remove methanol and form pure hydrogen sulfide; S6: Methanol at the bottom of the stripping column, part of which is cooled and enters the absorption column as absorbent; S7: The methanol at the bottom of the stripping tower is divided into two parts: one part enters the methanol dehydration tower, the methanol obtained at the top of the tower is cooled and enters the absorption tower as the absorbent, and the water-containing methanol at the bottom of the tower enters the wastewater system.

[0018] Preferred: In S1, raw material sulfur 8 enters the sulfur melting tank 9 from the boundary area, melts and then flows into the liquid sulfur tank 10 through overflow, and then enters the reactor after being filtered by the liquid sulfur feed pump 11 and filtered.

[0019] Preferably, in S2, the reactor is a fixed-bed reactor, with the bed divided into two parts. Both catalyst layers have coils 601 for heat transfer. The bottom of the tower contains liquid sulfur, and an electric heater 602 is installed inside the tower to control the sulfur temperature. A jacket 603 is installed on the outer wall of the tower to increase the temperature of the tower and melt the sulfur during sulfur discharge. Hydrogen enters from the bottom of the tower and is bubbled through the liquid sulfur, so that the hydrogen carries the sulfur into the catalyst bed 604 containing the catalyst for the reaction of hydrogen and sulfur, and then enters the catalyst bed 605 containing the catalyst for the decomposition of hydrogen polysulfides. The reaction temperature is 100-700℃, and the operating pressure is 0.1-2 MPaG.

[0020] Preferably, in step S4, after methanol is recovered by the methanol recovery tower, the hydrogen containing methanol is introduced into the hydrogen buffer tank.

[0021] Preferably, hydrogen gas is introduced into the reactor from the middle of the reactor to control the temperature inside the reactor; sulfur is injected into the reactor from the sulfur spraying device 609 to adjust the load.

[0022] Preferably, a jacket 603 is provided outside the reactor, and the jacket 603 is connected to the molten salt tank to control the reactor temperature.

[0023] The following examples further illustrate this solution.

[0024] Example: A hydrogen sulfide production apparatus and production method, wherein the hydrogen sulfide production apparatus includes a hydrogen preheater, a hydrogen heater, a hydrogen electric heater, a hydrogen sulfide reactor, a molten sulfur tank, a liquid sulfur tank, a liquid sulfur feed pump, a liquid sulfur collection tank, a molten salt tank, a molten salt feed pump, a filter, a sulfur trap, a crude hydrogen sulfide water cooler and a bag filter, and an absorption tower inlet buffer tank.

[0025] The production method includes the following steps: Hydrogen 1 from the hydrogen buffer tank exchanges heat with syngas 3 through hydrogen preheater 2 and then enters hydrogen heater 4 to exchange heat with molten salt 5. The raw material is preheated by the heat absorbed by the molten salt from reactor 6, and then enters the reactor after passing through hydrogen electric heater 7; raw material sulfur 8 enters the sulfur melting tank 9 from the boundary area, melts and then enters the liquid sulfur tank 10 by overflow, and then enters the reactor after being filtered by filter 12 through liquid sulfur feed pump 11. The hydrogen sulfide generated in the reaction passes through a sulfur trap 13 and a crude hydrogen sulfide water cooler 14, then enters the inlet buffer tank 15 of the absorption tower for pressure stabilization before entering a bag filter 16 to remove sulfur entrained in the gas. The resulting hydrogen-containing hydrogen sulfide 17 is sent to the purification section. The sulfur 18 obtained from the sulfur trap and crude hydrogen sulfide water cooler is returned to the molten sulfur tank for reuse. The reactor is a fixed-bed reactor, with the bed divided into two parts. Both catalyst layers have coils 601 for heat transfer. The bottom of the tower contains liquid sulfur, and an electric heater 602 is installed inside the tower to control the sulfur temperature. A jacket 603 is installed on the outer wall of the tower to increase the bottom temperature during sulfur discharge. The reactor melts sulfur; hydrogen enters from the bottom of the tower and is bubbled through liquid sulfur, allowing the hydrogen to carry the sulfur into the catalyst bed 604 containing the catalyst for the reaction of hydrogen and sulfur, and then into the catalyst bed 605 containing the catalyst for the decomposition of hydrogen polysulfides; operating temperature: 100-700℃; operating pressure: 0.1-2MPaG; 4. In addition to the hydrogen inlet 606 at the bottom, the reactor also has a hydrogen inlet 607 below each catalyst section. When the temperature of the reaction section exceeds a predetermined value, this hydrogen can be used to lower the temperature of the reaction section, ensuring the stable progress of the reaction.

[0026] In addition to the sulfur inlet 608 at the bottom, the reactor is also equipped with a sulfur spraying device 609 between the two catalyst sections. This device is used to adjust the load. When the demand for hydrogen sulfide is high, the spraying device can be turned on intermittently to increase the sulfur feed rate and increase the hydrogen sulfide production.

[0027] The molten salt enters the reactor and hydrogen heater in the molten salt tank 19 via the molten salt pump 20 to participate in heat exchange. The temperature of the molten salt is controlled by electric heating rods: 100-700℃, and the pressure of the molten salt is 0.1-2MPaG.

[0028] The sulfur melting and liquid sulfur tank is equipped with a steam coil to control the temperature of the sulfur melting and liquid sulfur tank: 100-400℃, and the pressure of the sulfur melting and liquid sulfur tank: 0.1-2MPaG.

[0029] The sulfur trap is equipped with a steam coil. When the sulfur inside the sulfur trap accumulates to a certain level, the steam coil is turned on to melt the sulfur in the sulfur trap. The sulfur trap temperature is 20-700℃ and the sulfur trap pressure is 0.1-2MPaG.

[0030] The shell side of the crude hydrogen sulfide water cooler can be circulated with a low-temperature fluid to cool the crude hydrogen sulfide and cause it to precipitate sulfur. Steam can also be circulated through the shell side and the lower head jacket to liquefy the precipitated sulfur. There are two crude hydrogen sulfide water coolers, ensuring that one can regenerate while the other operates normally. Crude hydrogen sulfide water cooler temperature: 20-700℃; Crude hydrogen sulfide water cooler pressure: 0.1-2 MPaG.

[0031] The cryogenic fluid includes, but is not limited to, circulating water, cryogenic water, and chilled water.

[0032] The liquid sulfur collection tank is the endpoint for sulfur removal and discharge from all the above-mentioned equipment. After passing through the liquid sulfur collection tank, the free hydrogen sulfide in the sulfur containing hydrogen sulfide in all the above-mentioned equipment is discharged and then enters the liquid sulfur tank for reuse.

[0033] There are two bag filters and two buffer tanks at the inlet of the absorption tower, ensuring that one of them is being regenerated while the other is still operating normally.

[0034] The absorption tower 21 is connected to the hydrogen sulfide outlet of the bag filter. Hydrogen sulfide containing hydrogen from the bag filter enters from the bottom of the tower, while low-temperature methanol 22 enters from the top of the tower. The two are in countercurrent contact. Hydrogen gas 23 containing trace amounts of methanol is obtained at the top of the tower, and a mixture 24 of methanol and hydrogen sulfide is obtained at the bottom of the tower. After being cooled by the heat exchanger 25 at the bottom of the tower, the mixture enters the bottom discharge pump 26 of the absorption tower, is pressurized, and then enters the preheater 27 of the desorption tower to exchange heat with the hot methanol 28 at the bottom of the desorption tower before entering the desorption tower 29. The temperature of the absorption tower is -10℃ to 50℃, and the pressure is 0.1 to 2 MPaG.

[0035] The stripping tower is equipped with a methanol-rich inlet and an upper built-in condenser 30 connected to the stripping tower outlet cooler 31. The top component of the tower after cooling by the cooler is pure product hydrogen sulfide 32. The lower part is equipped with a reboiler 33 and a methanol outlet. This methanol contains trace amounts of water brought into the reaction system from the raw materials. In order to prevent the accumulation of water in the system, part of the methanol 34 directly enters the stripping tower preheater, while another part of the methanol 35 enters the methanol dehydration tower 36 for dehydration. The stripping tower temperature is 20℃-150℃ and the pressure is 0.1-2MPaG.

[0036] The methanol dehydration tower is equipped with a top condenser 37, a bottom reboiler 38, a reflux tank 39, a reflux pump 40, and a bottom discharge pump 41. The methanol recovered from the top of the methanol dehydration tower and another part of the methanol from the bottom of the stripping tower are combined and enter the stripping tower preheater. The water-containing methanol 42 from the bottom of the tower enters the wastewater treatment system. The temperature of the methanol dehydration tower is 20℃-150℃ and the pressure is 0.1-2MPaG.

[0037] The hot methanol at the bottom of the analytical column exchanges heat with the methanol and hydrogen sulfide mixture obtained at the bottom of the absorption column, and then sequentially enters the methanol primary condenser 43, the methanol secondary condenser 44, and the methanol tertiary condenser 45. Fresh methanol and methanol makeup liquid 46 enter the absorption column from the methanol tertiary condenser. The temperature of the methanol primary to tertiary condensers is -5℃ to 70℃, and the pressure is 0.1-2MPaG.

[0038] The hydrogen gas containing trace amounts of methanol obtained at the top of the absorption tower enters the hydrogen compressor pre-buffer tank 48 before entering the hydrogen compressor 47. After being pressurized by the hydrogen compressor, it enters the hydrogen compressor post-buffer tank 49 to stabilize the pressure and flow rate and perform gas-liquid separation before entering the methanol recovery tower 50. The liquid methanol 51 obtained after gas-liquid separation is returned to the bottom of the absorption tower. The temperature of the hydrogen compressor system is -5℃ to 50℃, and the pressure is 0.1-2MPaG.

[0039] The methanol recovery tower consists of two units. When one unit is in use, the other unit is used for regeneration. During regeneration, a portion of the pure hydrogen gas 52 from the top outlet of the methanol recovery tower is taken, heated by the methanol recovery tower regeneration preheater 53, and then purged to desorb the methanol in the methanol recovery tower. The hydrogen gas 54 used for the regeneration of the methanol recovery tower enters the buffer tank before the hydrogen compressor. After being pressurized by the hydrogen compressor to remove most of the methanol, it re-enters the methanol recovery tower to obtain pure hydrogen gas. The temperature of the methanol recovery tower is 20℃-150℃, and the pressure is 0.1-2MPaG.

[0040] The pure hydrogen obtained from the methanol recovery tower is combined with fresh hydrogen 56 in the hydrogen buffer tank 55, and after pressure stabilization, it enters the reactor. The temperature of the hydrogen buffer tank is 20℃-50℃ and the pressure is 0.1-2MPaG.

[0041] It should be noted that in the attached diagram, some serial numbers corresponding to the name of a medium refer to the medium being stored or transported in the corresponding pipeline or container. For example, "Hydrogen 1" means that hydrogen is stored or transported in the pipeline below serial number 1. Furthermore, in this design, control valves are installed at the inlet and outlet of each pipeline and / or tower body to control the flow of the medium as needed.

[0042] In this scheme, hydrogen and sulfur react via a bubbling reaction, which is a mild and easily controlled process with high overall conversion rate and good energy utilization. This effectively solves the problems in existing technologies.

Claims

1. An apparatus for producing hydrogen sulfide using hydrogen and sulfur, characterized in that: It includes a sulfur melting tank (9), a liquid sulfur tank (10), a reactor (6), a sulfur trap (13), an absorption tower (21), a stripping tower (29), a methanol dehydration tower (36), and a methanol recovery tower (50). The sulfur melting tank (9) is connected to the liquid sulfur tank (10) via a pipeline; the methanol recovery tower (50) is connected to the absorption tower via a hydrogen compressor; The reactor (6) has two catalyst beds at the top, and coils (601) are installed below each catalyst bed. An electric heater (602) is installed at the bottom of the reactor (6), and a jacket (603) is installed on the lower outer wall of the reactor (6). A lower hydrogen inlet (606) and a middle hydrogen inlet (607) are installed at the bottom and middle of the reactor, respectively. A sulfur inlet (608) is also installed at the bottom of the reactor. A sulfur spraying device (609) is installed in the middle of the two catalyst beds. The liquid sulfur tank (10) is equipped with... A liquid sulfur feed pump (11) is connected to the lower part of the reactor via a pipeline; the inlet of the sulfur trap (13) is connected to the upper part of the reactor, and the outlet of the sulfur trap (13) is connected to the inlet of the absorption tower inlet buffer tank (15), and a bag filter (16) is installed at the outlet of the absorption tower inlet buffer tank (15); the lower inlet of the absorption tower (21) is connected to the absorption tower inlet buffer tank (15), and a low-temperature methanol (22) inlet is installed at the upper part of the absorption tower (21), and a vessel is installed at the lower part of the absorption tower. An internal heat exchanger (25) is installed at the bottom of the tower. The outlet of the absorption tower is connected to the desorption tower (29) via a bottom discharge pump (26). The middle part of the desorption tower (29) is provided with an inlet connected to the outlet of the absorption tower. The lower part of the desorption tower (29) is connected to the inlet of the absorption tower (21) and the inlet of the methanol dehydration tower (36) via pipelines. The upper part of the desorption tower (29) is provided with a desorption tower outlet cooler (31) and a pure product hydrogen sulfide discharge pipeline. The lower part of the methanol dehydration tower (36) is provided with a bottom outlet. The feed pump (41) is equipped with a tower top condenser (37) at the top. The tower top condenser (37) is connected to the feed inlet of the absorption tower (21) through a reflux pump (40). The methanol recovery tower (50) has a pure hydrogen outlet at the top connected to a hydrogen buffer tank (55). A branch line is provided on the pure hydrogen outlet pipeline connected to the methanol recovery tower regeneration preheater (53). The methanol recovery tower has a hydrogen inlet at the bottom connected to a hydrogen compressor rear buffer tank (49). The methanol recovery tower has a regeneration gas outlet at the bottom connected to a hydrogen compressor front buffer tank (48).

2. A method for producing hydrogen sulfide, using the apparatus as described in claim 1, characterized in that: Includes the following steps: S1: Sulfur is added to the molten sulfur tank and heated to melt. The molten sulfur overflows into the liquid sulfur tank and is pumped into the reactor by the liquid sulfur feed pump, forming a liquid sulfur pool below the reactor. S2: After heating, hydrogen is introduced into the reactor and bubbled with liquid sulfur in the liquid sulfur tank. After bubbling, the hydrogen carries sulfur upward and reacts at the catalyst bed to generate crude hydrogen sulfide. S3: The crude hydrogen sulfide is discharged from the top of the reactor and enters the inlet buffer tank (15) of the absorption tower after passing through the sulfur trap (13) and the crude hydrogen sulfide water cooler (14). After pressure stabilization, it enters the bag filter (16) to remove the sulfur carried in the gas. The resulting hydrogen sulfide (17) containing hydrogen is sent to the purification section. The sulfur (18) obtained from the sulfur trap and the crude hydrogen sulfide water cooler is returned to the liquid sulfur tank for reuse. S4: Hydrogen sulfide containing hydrogen (17) enters the absorption tower, and after separation, it forms hydrogen containing methanol and methanol containing hydrogen sulfide; the hydrogen containing methanol is recycled after recovering methanol in the methanol recovery tower (50); S5: Methanol containing hydrogen sulfide enters the stripping column (29), and the hydrogen sulfide obtained at the top of the column is cooled by the stripping column outlet cooler (31) to obtain pure hydrogen sulfide. S6: Methanol at the bottom of the stripping tower is partially fed directly into the stripping tower preheater (27), cooled down and then passed through the methanol primary condenser (43), methanol secondary condenser (44), methanol tertiary condenser (45), and then entered the absorption tower (21) as the absorbent. S7: The methanol at the bottom of the stripping tower, after removing a portion of S6, enters the methanol dehydration tower (36). The methanol obtained at the top of the tower enters the stripping tower preheater (27), and after cooling, it passes through the methanol primary condenser (43), methanol secondary condenser (44), and methanol tertiary condenser (45), and then enters the absorption tower (21) as the absorbent. The water-containing methanol at the bottom of the tower enters the wastewater system.

3. The method for producing hydrogen sulfide according to claim 2, characterized in that: In the reactor, hydrogen gas is introduced from the middle of the reactor to control the temperature inside the reactor; sulfur is injected into the reactor from the sulfur spraying device (609) to adjust the load inside the reactor.

4. The method for producing hydrogen sulfide according to claim 2, characterized in that: The jacket (603) is connected to the molten salt tank.

5. The method for producing hydrogen sulfide according to claim 2, characterized in that: In S4, after the methanol-containing hydrogen is recovered by the methanol recovery tower, the remaining hydrogen is fed into the hydrogen buffer tank.

6. The method for producing hydrogen sulfide according to claim 2, characterized in that: In S2, the reactor is a fixed-bed reactor; the lower part of the reactor contains liquid sulfur, and an electric heater (602) is provided inside the reactor (6) at the bottom to control the temperature of the sulfur in the lower part of the reactor; hydrogen enters from the lower part of the reactor and is bubbled by the liquid sulfur, so that the hydrogen carries the sulfur into the catalyst bed (604) containing the catalyst for the reaction of hydrogen and sulfur, and then enters the catalyst bed (605) containing the catalyst for the decomposition of hydrogen polysulfides; wherein: reaction temperature: 100-700℃; operating pressure: 0.1-2MPaG.

7. The method for producing hydrogen sulfide according to claim 2, characterized in that: In S1, raw sulfur (8) enters the sulfur melting tank (9) from the outside. After melting, it enters the liquid sulfur tank (10) by overflow. Then, it enters the filter (12) through the liquid sulfur feed pump (11) and enters the reactor after filtration.

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