A multi-effect synthesis apparatus and method for hydrogen sulfide synthesis
By designing a multi-effect synthesis device, the problems of low conversion rate, high energy consumption, and insufficient product purity in the direct synthesis of sulfur and hydrogen were solved, realizing efficient and low-energy hydrogen sulfide synthesis.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- YUNNAN TIN
- Filing Date
- 2026-05-22
- Publication Date
- 2026-06-26
AI Technical Summary
Existing direct sulfur-hydrogen synthesis technologies suffer from problems such as low reaction conversion rate, mismatch between mass and heat transfer efficiency, insufficient product purity, high energy consumption, and complex process flow.
The multi-effect synthesis device includes a vertical columnar liquid sulfur synthesis zone, a gas-liquid two-phase sulfur synthesis zone, and a compensation synthesis zone. Combined with electric heating, catalyst packing, and condenser coils, it realizes the segmented and directional reaction and cascade utilization of sulfur and hydrogen.
It improved the reaction conversion rate, reduced energy consumption, enhanced product purity, simplified the process flow, and achieved efficient hydrogen sulfide synthesis.
Smart Images
Figure CN122273464A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the technical field of hydrogen sulfide production equipment, specifically relating to a multi-effect synthesis device and method for hydrogen sulfide synthesis. Background Technology
[0002] Hydrogen sulfide (H2S) is an important basic chemical raw material, widely used in rubber vulcanization, pesticide synthesis, metal smelting, and the preparation of electronic-grade chemicals. Currently, the mainstream industrial methods for producing hydrogen sulfide include: the direct reaction of sulfur vapor with hydrogen, the byproduct recovery of hydrogen sulfide from thiols, and the purification of acidic gases from natural gas or refinery gas. Among these, the direct synthesis of hydrogen sulfide from elemental sulfur and hydrogen has attracted attention due to the readily available raw materials and relatively simple process.
[0003] However, existing direct sulfur-hydrogen synthesis technologies generally suffer from the following technical drawbacks:
[0004] Low reaction conversion rate: The reaction between sulfur and hydrogen is a reversible exothermic reaction. Due to thermodynamic equilibrium, the single-pass conversion rate of hydrogen in traditional single-stage reactors (such as tubular fixed bed or bubble column reactors) is usually only 60% to 75%. A large amount of unreacted hydrogen needs to be recycled, which increases compression energy consumption and equipment investment.
[0005] Mismatch between mass transfer and heat transfer efficiency: Sulfur exists in gaseous or liquid state under reaction conditions, and hydrogen has low solubility in the liquid sulfur phase, making gas-liquid (or gas-liquid-solid) phase mass transfer the rate-controlling step. Traditional reactors struggle to simultaneously accommodate high reaction rates at high temperatures and sulfur condensation and separation at low temperatures, often resulting in incomplete reactions or the inclusion of large amounts of sulfur vapor in the products.
[0006] Insufficient product purity: Due to the limited reaction conversion rate and sulfur entrainment, the hydrogen sulfide gas exiting the tower often contains unreacted hydrogen, sulfur vapor and a small amount of organic sulfur byproducts, with a purity generally below 95%. This requires subsequent multi-stage condensation, washing or distillation purification, which increases the length of the process and operating costs.
[0007] High energy consumption: In pursuit of higher conversion rates, existing technologies often use excessive amounts of hydrogen or excessively high reaction temperatures, resulting in a significant waste of thermal energy. At the same time, the cyclic compression of unreacted hydrogen and the repeated vaporization and condensation of sulfur also significantly increase the overall energy consumption of the device.
[0008] Therefore, how to provide a hydrogen sulfide synthesis device and method with high conversion rate, high product purity, low energy consumption, and the ability to achieve efficient segmented and directional reaction of sulfur and hydrogen is a problem that urgently needs to be solved by those skilled in the art. Summary of the Invention
[0009] In view of this, the present invention provides a multi-effect synthesis apparatus and method for hydrogen sulfide synthesis, which has high conversion rate, high product purity, low energy consumption, and can realize efficient segmented and directional reaction of sulfur and hydrogen.
[0010] To achieve the above objectives, the present invention adopts the following technical solution: a multi-effect synthesis device for hydrogen sulfide synthesis, wherein the device has a vertical columnar structure, and its interior is arranged from bottom to top as follows: a first-effect liquid sulfur synthesis zone, a second-effect gas-liquid two-phase sulfur synthesis zone, a third-effect compensation synthesis zone, and a condensation and sulfur replenishment zone. The first-effect liquid sulfur synthesis zone is equipped with an electric heating component and a baffle plate for enhancing gas-liquid contact. The device is equipped with a hydrogen inlet and a liquid sulfur inlet corresponding to the first-effect liquid sulfur synthesis zone. The first-effect liquid sulfur synthesis zone is used for the main reaction of molten sulfur and hydrogen. Both the two-phase gas-liquid sulfur synthesis zone and the three-phase compensation synthesis zone are filled with catalyst packing. The two-phase gas-liquid sulfur synthesis zone is used for the deep reaction of residual sulfur vapor and hydrogen. The three-phase compensation synthesis zone is used for the compensation catalytic synthesis of unconverted hydrogen and uses the temperature drop to condense and reflux the gas phase sulfur. The condensation and sulfur replenishment zone is equipped with a condensation coil for gradient cooling of the rising gas, causing gaseous sulfur to condense into liquid and fall for reuse. The device is equipped with a hydrogen sulfide gas outlet at the top of the condensation and sulfur replenishment zone.
[0011] The beneficial technical effects of this invention are as follows: This device has an extremely high reaction conversion rate. Through the main reaction in the first-effect liquid sulfur synthesis zone, the deep reaction in the second-effect gas-liquid two-phase sulfur synthesis zone, and the compensating catalytic synthesis in the third-effect compensating synthesis zone, hydrogen gas is converted in a segmented gradient. There is no need for hydrogen gas circulation compression, which significantly reduces energy consumption and improves the purity of hydrogen sulfide products. The high-temperature gas after the third-effect reaction enters the condensation and sulfur replenishment zone. After gradient cooling by the condensation coil, the gaseous sulfur is condensed and precipitated and returned to the reaction zone, effectively removing sulfur vapor from the product gas. The energy consumption is low, and thermal energy is utilized in stages. The second-effect zone uses its own reaction exothermic heat (temperature up to 350°C) to heat and replenish liquid sulfur, without the need for external additional heating, achieving self-heating balance. The coils in the condensation and sulfur replenishment zone not only cool and separate sulfur, but also recover waste heat for preheating the feed or for insulation, achieving cascaded energy utilization. The temperature and pressure of each effect zone are independently controllable: the high temperature (300~500℃) in the first effect zone promotes the main reaction kinetics; the medium temperature (330±20℃) in the second effect zone matches the optimal catalyst activity; and the lower temperature (270~300℃) in the third effect zone facilitates a rightward shift of equilibrium while suppressing the formation of side reactions such as organic sulfur. This avoids side reactions or reaction stagnation caused by excessively high or low temperatures in traditional single reactors.
[0012] Preferably, the first-effect liquid sulfur synthesis zone is provided with: a heating component support plate, a hydrogen supply pipe, and a first liquid sulfur replenishment pipe. The heating component support plate is fixed inside the device and is used to support the electric heating component. The side wall of the hydrogen supply pipe and the area below the liquid sulfur immersion zone are provided with multiple gas outlet holes. The first liquid sulfur replenishment pipe is connected to and communicates with the side wall of the device and is used for first-effect sulfur replenishment. The bottom of the device corresponding to the first-effect liquid sulfur synthesis zone is connected to and communicates with the liquid sulfur supply pipe. The bottom of the device is provided with a sulfur discharge pipe.
[0013] The resulting technical effects are as follows: The hydrogen supply pipe has multiple vent holes on its sidewall, located below the liquid sulfur immersion zone. Hydrogen gas is evenly dispersed into the liquid sulfur layer through these small holes, forming a cluster of tiny bubbles. This significantly increases the gas-liquid contact area, enhances mass transfer efficiency, and promotes the dissolution and reaction of hydrogen in the liquid sulfur, thereby improving the main reaction conversion rate of the first-effect zone. The heating component support plate fixes the electric heating component, ensuring stable positioning of the electric heating element within the reaction zone and uniform heat distribution. This prevents localized overheating or carbonization of the liquid sulfur due to heater shaking or localized accumulation, extending equipment life and ensuring reaction stability. Combined with the gas distribution from the multiple vent holes, the entire liquid sulfur bed reacts uniformly, suppressing side reactions. The first liquid sulfur replenishment pipe (used for first-effect sulfur replenishment) can replenish molten sulfur to the first-effect zone as needed during the reaction, maintaining liquid level and reaction activity, adapting to fluctuations in hydrogen feed, and achieving continuous and stable production. The bottom liquid sulfur supply pipe is used for initial or continuous injection of liquid sulfur into the first-effect zone, forming a dual-sugar supply system in conjunction with the replenishment pipe to meet sulfur requirements under different operating conditions.
[0014] Preferably, the device is equipped with a steam jacket corresponding to the first-effect liquid sulfur synthesis zone.
[0015] The resulting technical effect is that the steam jacket can preheat, maintain, and control the temperature.
[0016] Preferably, the device is provided with a packing support assembly and a packing discharge port assembly for both the two-effect gas-liquid two-phase sulfur synthesis zone and the three-effect compensation synthesis zone. The packing support assembly is used to support the catalyst packing, and the packing discharge port assembly is located on the side wall of the device in the corresponding zone. The device is provided with a heat-insulating inner lining for both the two-effect gas-liquid two-phase sulfur synthesis zone and the three-effect compensation synthesis zone.
[0017] The resulting technical effects are: the loading and unloading of the corresponding effective zone is realized through the packing discharge port assembly, the catalyst loading is stable and the operation is reliable, the heat insulation lining can reduce heat loss, prevent the shell from overheating, and inhibit sulfur condensation corrosion.
[0018] Preferably, the condenser coil is provided with a medium inlet and a medium outlet on both sides of the corresponding device; the top of the condensation and sulfur replenishment zone is provided with a hydrogen sulfide outlet pipe, which is connected to the hydrogen sulfide gas outlet.
[0019] The resulting technical effect is that the condenser coil, used for heat exchange, can condense the sulfur vapor mixed in with hydrogen sulfide gas, which can be recycled and reused on the one hand, and improve the purity of hydrogen sulfide products on the other.
[0020] Preferably, a nitrogen inlet assembly is provided between the first-effect liquid sulfur synthesis zone and the second-effect gas-liquid two-phase sulfur synthesis zone of the device, for emptying residual gas and liquid in the entire device during maintenance.
[0021] The resulting technical effect is that the nitrogen inlet component facilitates the removal of residual gas and liquid from the entire device during subsequent maintenance.
[0022] Preferably, a second liquid sulfur inlet pipe and a manhole are provided between the two-effect gas-liquid two-phase sulfur synthesis zone and the three-effect compensation synthesis zone corresponding to the device; the part of the second liquid sulfur inlet pipe located inside the device is a liquid sulfur distributor, which is used to evenly distribute the liquid sulfur into the two-effect gas-liquid two-phase sulfur synthesis zone.
[0023] The resulting technical advantages are: independent sulfur replenishment in the second-effect zone, optimized temperature gradient control and utilization; the liquid sulfur distributor, located above the packing layer in the second-effect zone, can uniformly disperse the replenished liquid sulfur into fine droplets or liquid films, allowing it to permeate evenly along the packing cross-section. Rising hydrogen gas and the uniformly distributed liquid sulfur come into counter-current contact within the packing layer, significantly improving the gas-liquid-solid (catalyst) three-phase mass transfer efficiency, avoiding uneven reaction or penetration caused by localized excess or deficiency of liquid sulfur; and the manhole is flush with the distributor for easy installation and maintenance.
[0024] Preferably, the main body of the device is made of stainless steel, and each effect zone of the device is equipped with a temperature sensor and a pressure sensor for real-time monitoring of the reaction conditions in each effect zone; the temperature sensor and the pressure sensor are both electrically connected to an external DCS system.
[0025] The resulting technical advantages are: by using a stainless steel body and equipping it with temperature and pressure sensors for each effect zone and a DCS system, not only is the cleanliness of the high-purity products and the durability of the equipment guaranteed at the material level, but also the precise coordination of gradient temperature and pressure in multiple effect zones and fully automated and safe operation are achieved at the control level. These features collectively enhance the product quality, operational stability, safety, and intelligence level of the equipment.
[0026] This invention also discloses a method for preparing high-purity hydrogen sulfide using the above-mentioned multi-effect synthesis apparatus, which includes the following steps: S1 Preheating and Feeding Saturated steam at 0.2~0.3MPa is introduced into the steam jacket of the first-effect liquid sulfur synthesis zone of the device to preheat to 135°C, and the electric heating components are turned on simultaneously to raise the temperature of the first-effect zone to 145°C; after injecting molten sulfur into the first-effect zone to 3 / 4 of its volume through the liquid sulfur supply pipe at the bottom of the device, the electric heating power is increased to raise the temperature of the liquid sulfur in the first-effect zone to 300~500°C. S2 main reaction and deep reaction Hydrogen gas at 300~500℃ is introduced through the hydrogen inlet. Under the synergistic disturbance of the baffle and the orifice plate, efficient gas-liquid contact is achieved, and a synthesis reaction occurs to generate hydrogen sulfide. The gas after the initial reaction carries a trace amount of unreacted sulfur vapor into the second-effect zone, where it undergoes further deep reaction within the packing layer. The generated hydrogen sulfide gas, a small amount of residual hydrogen gas, and gaseous sulfur then enter the third-effect compensation synthesis zone for compensated synthesis. S3 Cooling and Product Collection The high-temperature hydrogen sulfide gas synthesized through the triple-effect process continues to rise to the condensation and sulfur replenishment zone, where it contacts the condensation coil for heat exchange, causing the gas temperature gradient to drop to 150~180℃. Gaseous sulfur condenses and precipitates out and flows back to the triple-effect zone. The high-purity hydrogen sulfide gas after condensation and separation enters the product gas tank through the hydrogen sulfide gas outlet and transmission pipeline.
[0027] Preferably, when the temperature of the second effect zone rises to 350°C, the supply of molten sulfur from the liquid sulfur supply pipe is stopped, and instead, molten sulfur preheated to 135°C is supplied to the second effect zone from the second liquid sulfur replenishment pipe. The liquid sulfur is heated by the reaction heat of the second effect zone itself to achieve temperature gradient control; the first liquid sulfur replenishment pipe serves as a backup for replenishing liquid sulfur.
[0028] Preferably, after transitioning to normal production, the process parameters are controlled as follows: The pressure in the first effect zone is 0.25~0.4MPa, the pressure in the second effect zone is 0.18~0.3MPa, and the pressure in the third effect zone is 0.15~0.25MPa. The temperature of the first effect zone is 300~500℃, the temperature of the second effect zone is 330±20℃, and the temperature of the third effect zone is 270~300℃.
[0029] Preferably, the catalyst packing material in the two-effect gas-liquid two-phase sulfur synthesis zone and the catalyst packing material in the three-effect compensation synthesis zone are both hydrogen sulfide synthesis catalysts. The catalyst packing material in the two-effect gas-liquid two-phase sulfur synthesis zone is a hydrogen sulfide synthesis catalyst with an optimal operating temperature of 330±20℃, and the catalyst packing material in the three-effect compensation synthesis zone is a hydrogen sulfide synthesis catalyst with an optimal operating temperature of 300±20℃. Attached Figure Description
[0030] Figure 1 This is a structural diagram of a multi-effect synthesis apparatus for hydrogen sulfide synthesis according to the present invention; Figure 2This is a schematic diagram of the structure of the liquid sulfur synthesis zone corresponding to a multi-effect synthesis device for hydrogen sulfide synthesis according to the present invention. Figure 3 This is a schematic diagram of the structure of the two-effect gas-liquid two-phase sulfur synthesis zone corresponding to a multi-effect synthesis device for hydrogen sulfide synthesis according to the present invention. Figure 4 This is a schematic diagram of the structure of the three-effect compensation synthesis zone and the condensation sulfur replenishment zone of a multi-effect synthesis device for hydrogen sulfide synthesis according to the present invention.
[0031] 1. Skirt support, 2. Sulfur exhaust pipe, 3. Liquid sulfur supply pipe, 4. Electric heating assembly, 5. Temperature sensor, 6. Hydrogen supply pipe, 7. Nitrogen inlet assembly, 8. Packing support assembly I, 9. Packing discharge port assembly I, 10. Shell, 11. Manhole, 12. Packing support assembly II, 13. Thermal insulation lining, 14. Side lifting lug, 15. Medium inlet, 16. Condensation coil, 17. Top lifting lug, 18. Hydrogen sulfide outlet assembly, 19. Medium outlet, 20. Second liquid sulfur replenishment pipe fitting, 21. Liquid sulfur level gauge, 22. First liquid sulfur replenishment pipe fitting, 23. Buckle plate, 24. Baffle plate, 25. Heating assembly support plate, 26. Steam jacket, 27. Catalyst packing, 28. Pressure sensor. Detailed Implementation
[0032] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.
[0033] See the appendix of this invention. Figures 1 to 4 According to an embodiment of the present invention, a multi-effect synthesis device for hydrogen sulfide synthesis is provided. The device has a vertical columnar structure or a tower structure. The device is arranged from bottom to top as follows: a first-effect liquid sulfur synthesis zone, a second-effect gas-liquid two-phase sulfur synthesis zone, a third-effect compensation synthesis zone, and a condensation and sulfur replenishment zone, which are interconnected. The first-effect liquid sulfur synthesis zone is equipped with an electric heating component 4 and a baffle plate 24 for enhancing gas-liquid contact. There are multiple baffle plates, which are distributed in a staggered manner in the upper and lower levels to extend the gas flow path. The device is equipped with a hydrogen inlet (side wall) and a liquid sulfur inlet (bottom) corresponding to the first-effect liquid sulfur synthesis zone. The first-effect liquid sulfur synthesis zone is used for the main reaction of molten sulfur and hydrogen. Both the two-phase gas-liquid sulfur synthesis zone and the three-phase compensation synthesis zone are filled with catalyst packing 27. The two-phase gas-liquid sulfur synthesis zone is used for the deep reaction of residual sulfur vapor and hydrogen, and the three-phase compensation synthesis zone is used for the compensation catalytic synthesis of unconverted hydrogen, and the temperature drop is used to condense and reflux the gas phase sulfur. The condensation and sulfur replenishment zone is equipped with a condensation coil 16, which is used to gradually cool the rising gas, so that the gaseous sulfur condenses into liquid and falls down for reuse. The device is equipped with a hydrogen sulfide gas outlet at the top of the condensation and sulfur replenishment zone.
[0034] In other embodiments, the first-effect liquid sulfur synthesis zone is provided with: a heating component support plate 25, a hydrogen supply pipe 6, and a first liquid sulfur replenishment pipe 22. The heating component support plate 25 is fixed inside the device and is used to support the electric heating component 4. The side wall of the hydrogen supply pipe 6 and the area below the liquid sulfur immersion zone are provided with multiple vent holes. The first liquid sulfur replenishment pipe 22 is connected to and communicates with the side wall of the device and is used for first-effect sulfur replenishment. The bottom of the device corresponding to the first-effect liquid sulfur synthesis zone is connected to and communicates with a liquid sulfur supply pipe 3. The bottom of the device is provided with a sulfur discharge pipe 2, from which liquid sulfur can be discharged during maintenance.
[0035] In other embodiments, the device is provided with a steam jacket 26 corresponding to the first-effect liquid sulfur synthesis zone, which can preheat and maintain the temperature at a predetermined level.
[0036] In other specific embodiments, the device is provided with a packing support assembly and a packing discharge port assembly for both the two-effect gas-liquid two-phase sulfur synthesis zone and the three-effect compensation synthesis zone. The packing support assembly is used to support the catalyst packing 27, and the packing discharge port assembly is located on the side wall of the device in the corresponding zone. The device is provided with a heat insulation lining layer 13 for both the two-effect gas-liquid two-phase sulfur synthesis zone and the three-effect compensation synthesis zone, which can be a corundum casting layer.
[0037] In some other embodiments, the condenser coil 16 is provided with a medium inlet 15 (for condensate) and a medium outlet 19 (for steam) on both sides of the device; the top of the condensation and sulfur replenishment zone is provided with a hydrogen sulfide outlet pipe fitting 18, which is connected to the hydrogen sulfide gas outlet.
[0038] In some other specific embodiments, a nitrogen inlet assembly 7 is provided between the first-effect liquid sulfur synthesis zone and the second-effect gas-liquid two-phase sulfur synthesis zone of the device, which is used to purge the residual gas and liquid in the entire device during maintenance, so as to facilitate maintenance.
[0039] In other embodiments, a second liquid sulfur inlet pipe 20 and a manhole 11 are provided between the two-effect gas-liquid two-phase sulfur synthesis zone and the three-effect compensation synthesis zone corresponding to the device; the part of the second liquid sulfur inlet pipe 20 located inside the device is a liquid sulfur distributor, which is used to evenly distribute the liquid sulfur into the two-effect gas-liquid two-phase sulfur synthesis zone.
[0040] The upper edge of the manhole is flush with the lower edge of the second liquid sulfur inlet component 20, which facilitates the entry and exit of maintenance personnel and the installation and maintenance of the liquid sulfur distributor. The main body of this device is made of stainless steel. Each effect zone of the device is equipped with a temperature sensor 5 and a pressure sensor 28 for real-time monitoring of the reaction conditions in each effect zone. Both the temperature sensor 5 and the pressure sensor 28 are electrically connected to an external DCS system.
[0041] This invention also discloses a method for preparing high-purity hydrogen sulfide using the above-mentioned multi-effect synthesis apparatus, which includes the following steps: S1 Preheating and Feeding Saturated steam at 0.2~0.3MPa is introduced into the steam jacket of the first-effect liquid sulfur synthesis zone of the device to preheat to 135°C, and the electric heating components are turned on simultaneously to raise the temperature of the first-effect zone to 145°C; after injecting molten sulfur into the first-effect zone to 3 / 4 of its volume through the liquid sulfur supply pipe at the bottom of the device, the electric heating power is increased to raise the temperature of the liquid sulfur in the first-effect zone to 300~500°C. S2 main reaction and deep reaction Hydrogen gas at 300~500℃ is introduced through the hydrogen inlet. Under the disturbance of the baffle plate, efficient gas-liquid contact is achieved, and a synthesis reaction occurs to generate hydrogen sulfide. The gas after the initial reaction carries a trace amount of unreacted sulfur vapor into the second-effect zone, where it undergoes further deep reaction in the packing layer. The generated hydrogen sulfide gas, a small amount of residual hydrogen gas, and gaseous sulfur then enter the third-effect compensation synthesis zone for compensation synthesis. S3 Cooling and Product Collection The high-temperature hydrogen sulfide gas synthesized through the triple-effect process continues to rise to the condensation and sulfur replenishment zone, where it contacts the condensation coil for heat exchange, causing the gas temperature gradient to drop to 150~180℃. Gaseous sulfur condenses and precipitates out and flows back to the triple-effect zone. The high-purity hydrogen sulfide gas after condensation and separation enters the product gas tank through the hydrogen sulfide gas outlet and transmission pipeline.
[0042] When the temperature of the second effect zone rises to 350℃, the supply of molten sulfur from the liquid sulfur supply pipe is stopped. Instead, the second liquid sulfur supply pipe is used to supply molten sulfur preheated to 135℃ to the second effect zone. The liquid sulfur is heated by the reaction heat of the second effect zone itself to achieve temperature gradient control. The first liquid sulfur supply pipe is used as a backup liquid sulfur supply.
[0043] After resuming normal production, the process parameters are controlled as follows: The pressure in the first effect zone is 0.25~0.4MPa, the pressure in the second effect zone is 0.18~0.3MPa, and the pressure in the third effect zone is 0.15~0.25MPa. The temperature in the first effect zone is 300~500℃, the temperature in the second effect zone is 330±20℃, and the temperature in the third effect zone is 270~300℃. The temperature in the first effect zone is controlled and maintained at 300~500℃, the temperature in the second effect zone is stabilized at 330±20℃, and the temperature in the third effect zone is maintained at 270~300℃. The pressure and temperature gradients of each effect are matched in a coordinated manner to ensure continuous gas-liquid phase change, optimize the reaction driving force step by step, and suppress the formation of side reactions.
[0044] Both the catalyst packing material in the two-phase gas-liquid sulfur synthesis zone and the catalyst packing material in the three-phase compensation synthesis zone are hydrogen sulfide synthesis catalysts. The catalyst packing material in the two-phase gas-liquid sulfur synthesis zone is a hydrogen sulfide synthesis catalyst with an optimal operating temperature of 330±20℃, which can be Clariant HyProGen™ 101 catalyst.
[0045] The catalyst packing material in the three-effect compensation synthesis zone is a hydrogen sulfide synthesis catalyst with an optimal operating temperature of 300±20℃, and can be a Co-Mo based catalyst.
[0046] This device achieves segmented, directional reactions of elemental sulfur and hydrogen through gradient temperature and pressure coupling control in each effect zone. The first effect zone completes the main reaction, achieving a hydrogen conversion rate of over 85%. The second effect zone enhances mass transfer efficiency, increasing the hydrogen conversion rate to over 98%. The third effect zone compensates for incompletely converted hydrogen through catalytic synthesis, while simultaneously cooling the gaseous sulfur to condense it into a liquid state for recovery and reuse. The purity of the hydrogen sulfide gas exiting the tower reaches over 99%. This invention offers advantages such as low energy consumption, high raw material conversion rate, and high utilization rates of sulfur and hydrogen. The produced hydrogen sulfide can be used in downstream applications such as rubber vulcanization, pesticide synthesis, metal smelting, and the preparation of electronic-grade chemicals.
[0047] The apparatus and methods disclosed in the embodiments are described simply because they correspond to the methods disclosed in the embodiments. For relevant details, please refer to the method section.
[0048] The above description of the disclosed embodiments enables those skilled in the art to make or use the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the invention is not to be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims
1. A multi-effect synthesis apparatus for hydrogen sulfide synthesis, characterized in that, The device has a vertical columnar structure, and its interior is arranged from bottom to top as follows: a first-effect liquid sulfur synthesis zone, a second-effect gas-liquid two-phase sulfur synthesis zone, a third-effect compensation synthesis zone, and a condensation and sulfur replenishment zone. The first-effect liquid sulfur synthesis zone is equipped with an electric heating component (4) and a baffle plate (24) for enhancing gas-liquid contact. The device is equipped with a hydrogen inlet and a liquid sulfur inlet corresponding to the first-effect liquid sulfur synthesis zone. The first-effect liquid sulfur synthesis zone is used for the main reaction of molten sulfur and hydrogen. Both the two-phase gas-liquid sulfur synthesis zone and the three-phase compensation synthesis zone are filled with catalyst packing (27). The two-phase gas-liquid sulfur synthesis zone is used for the deep reaction of residual sulfur vapor and hydrogen. The three-phase compensation synthesis zone is used for the compensation catalytic synthesis of unconverted hydrogen and uses the temperature drop to condense and reflux the gas phase sulfur. The condensation and sulfur replenishment zone is equipped with a condensation coil (16) for gradient cooling of the rising gas, so that the gaseous sulfur condenses into liquid and falls for reuse. The device is equipped with a hydrogen sulfide gas outlet at the top of the condensation and sulfur replenishment zone.
2. The multi-effect synthesis apparatus for hydrogen sulfide synthesis according to claim 1, characterized in that, The first-effect liquid sulfur synthesis zone is provided with: a heating component support plate (25), a hydrogen supply pipe (6) and a first liquid sulfur replenishment pipe (22). The heating component support plate (25) is fixed inside the device and is used to support the electric heating component (4). The side wall of the hydrogen supply pipe (6) and below the liquid sulfur immersion zone are provided with multiple gas outlet holes. The first liquid sulfur replenishment pipe (22) is connected to and communicates with the side wall of the device and is used for first-effect sulfur replenishment. The bottom of the device corresponding to the first-effect liquid sulfur synthesis zone is connected to and communicates with a liquid sulfur supply pipe (3). The bottom of the device is provided with a sulfur discharge pipe (2).
3. A multi-effect synthesis apparatus for hydrogen sulfide synthesis according to claim 2, characterized in that, The device is equipped with a steam jacket (26) corresponding to the first-effect liquid sulfur synthesis zone.
4. The multi-effect synthesis apparatus for hydrogen sulfide synthesis according to claim 1, characterized in that, The device is equipped with a packing support assembly and a packing discharge port assembly for both the two-effect gas-liquid two-phase sulfur synthesis zone and the three-effect compensation synthesis zone. The packing support assembly is used to support the catalyst packing (27). The packing discharge port assembly is located on the side wall of the device in the corresponding zone. The device is equipped with a heat-insulating inner lining layer (13) for both the two-effect gas-liquid two-phase sulfur synthesis zone and the three-effect compensation synthesis zone.
5. A multi-effect synthesis apparatus for hydrogen sulfide synthesis according to claim 1, characterized in that, The condenser coil (16) is provided with a medium inlet (15) and a medium outlet (19) on both sides of the corresponding device; the top of the condenser sulfur replenishment zone is provided with a hydrogen sulfide outlet pipe fitting (18), which is connected to the hydrogen sulfide gas outlet.
6. A multi-effect synthesis apparatus for hydrogen sulfide synthesis according to claim 1, characterized in that, A nitrogen inlet assembly (7) is provided between the first-effect liquid sulfur synthesis zone and the second-effect gas-liquid two-phase sulfur synthesis zone of the device, which is used to purge the residual gas and liquid in the entire device during maintenance.
7. A multi-effect synthesis apparatus for hydrogen sulfide synthesis according to claim 1, characterized in that, A second liquid sulfur inlet pipe (20) and a manhole (11) are provided between the two-effect gas-liquid two-phase sulfur synthesis zone and the three-effect compensation synthesis zone corresponding to the device; the part of the second liquid sulfur inlet pipe (20) located inside the device is a liquid sulfur distributor, which is used to evenly distribute liquid sulfur into the two-effect gas-liquid two-phase sulfur synthesis zone.
8. A multi-effect synthesis apparatus for hydrogen sulfide synthesis according to claim 1, characterized in that, The main body of the device is made of stainless steel. Each effect zone of the device is equipped with a temperature sensor (5) and a pressure sensor (28) for real-time monitoring of the reaction conditions in each effect zone. The temperature sensor (5) and the pressure sensor (28) are both electrically connected to an external DCS system.
9. A method for preparing high-purity hydrogen sulfide using the multi-effect synthesis apparatus according to any one of claims 1 to 8, characterized in that, Includes the following steps: S1 Preheating and Feeding Saturated steam at 0.2~0.3MPa is introduced into the steam jacket of the first-effect liquid sulfur synthesis zone of the device to preheat to 135°C, and the electric heating components are turned on simultaneously to raise the temperature of the first-effect zone to 145°C; after injecting molten sulfur into the first-effect zone to 3 / 4 of its volume through the liquid sulfur supply pipe at the bottom of the device, the electric heating power is increased to raise the temperature of the liquid sulfur in the first-effect zone to 300~500°C. S2 main reaction and deep reaction Hydrogen gas at 300~500℃ is introduced through the hydrogen inlet. Under the disturbance of the baffle plate, efficient gas-liquid contact is achieved, and a synthesis reaction occurs to generate hydrogen sulfide. The gas after the initial reaction carries a trace amount of unreacted sulfur vapor into the second-effect zone, where it undergoes further deep reaction in the packing layer. The generated hydrogen sulfide gas, a small amount of residual hydrogen gas, and gaseous sulfur then enter the third-effect compensation synthesis zone for compensation synthesis. S3 Cooling and Product Collection The high-temperature hydrogen sulfide gas synthesized through the triple-effect process continues to rise to the condensation and sulfur replenishment zone, where it contacts the condensation coil for heat exchange, causing the gas temperature gradient to drop to 150~180℃. Gaseous sulfur condenses and precipitates out and flows back to the triple-effect zone. The high-purity hydrogen sulfide gas after condensation and separation enters the product gas tank through the hydrogen sulfide gas outlet and transmission pipeline.
10. The method according to claim 9, characterized in that, When the temperature of the second effect zone rises to 350℃, the supply of molten sulfur from the liquid sulfur supply pipe is stopped. Instead, the second liquid sulfur supply pipe is used to supply molten sulfur preheated to 135℃ to the second effect zone. The liquid sulfur is heated by the reaction heat of the second effect zone itself to achieve temperature gradient control. The first liquid sulfur supply pipe is used as a backup liquid sulfur supply.
11. The method according to claim 9, characterized in that, After resuming normal production, the process parameters are controlled as follows: The pressure in the first effect zone is 0.25~0.4MPa, the pressure in the second effect zone is 0.18~0.3MPa, and the pressure in the third effect zone is 0.15~0.25MPa. The temperature of the first effect zone is 300~500℃, the temperature of the second effect zone is 330±20℃, and the temperature of the third effect zone is 270~300℃.
12. The method according to claim 9, characterized in that, The catalyst packing in the two-effect gas-liquid two-phase sulfur synthesis zone and the catalyst packing in the three-effect compensation synthesis zone are both hydrogen sulfide synthesis catalysts. The catalyst packing in the two-effect gas-liquid two-phase sulfur synthesis zone is a hydrogen sulfide synthesis catalyst with an optimal operating temperature of 330±20℃, and the catalyst packing in the three-effect compensation synthesis zone is a hydrogen sulfide synthesis catalyst with an optimal operating temperature of 300±20℃.