A method for desulfurization by reacting hydrogen sulfide with sulfur dioxide in brine

Abstract

This invention discloses a method for desulfurization by reacting hydrogen sulfide and sulfur dioxide in brine. Hydrogen sulfide and sulfur dioxide are introduced into a brine solution, and a liquid-phase Claus reaction is accelerated using a stirring paddle and steam to achieve rapid sulfur preparation and separation. Using the process method and apparatus of this invention, the sulfur dioxide and hydrogen sulfide gases are vigorously stirred in the brine solution by a bladed stirring paddle, which not only increases the contact area and reaction efficiency between the gas and liquid phases, but also solves the problem of difficult separation of sulfur suspension due to the salting-out effect. Furthermore, the process flow of this invention is simple and easy to operate, and the brine in the sulfur solution can be recycled after separation, reducing operating costs.

Description

Technical Field

[0001] This invention belongs to the field of industrial waste gas recycling technology, specifically, it relates to a method for desulfurization by reacting hydrogen sulfide and sulfur dioxide in brine. Background Technology

[0002] With the continuous acceleration of industrialization, the emission of large amounts of industrial waste gas has caused serious environmental pollution. Among these waste gases, hydrogen sulfide is a common harmful gas with a strong pungent odor and toxicity, posing a great threat to human health and the ecological environment. Therefore, the recovery of hydrogen sulfide gas is of great significance.

[0003] Currently, the main methods for treating hydrogen sulfide gas are divided into two categories: wet methods and dry methods. Wet methods include absorption methods and wet oxidation methods; dry methods include metal oxidation methods, activated carbon methods, molecular sieve methods, as well as biological methods and membrane separation methods.

[0004] Wet desulfurization uses solvents or solutions as desulfurizing agents. Through gas-liquid contact, H2S is absorbed by the liquid phase, achieving purification. The characteristics of wet desulfurization include the regeneration and recycling of the desulfurizing agent, a large sulfur capacity, continuous operation, and the ability to be scaled up for production. It is suitable for purifying feed gases with high sulfur content. Wet desulfurization is widely used due to its advantages such as high desulfurization efficiency, simple operation, and low operating costs. Wet desulfurization mainly includes ammonia desulfurization, amine desulfurization, and ionic liquid desulfurization. Different desulfurization methods can be selected based on the enterprise's conditions and the concentration differences of the smelting gas. For high-concentration hydrogen sulfide gas, it can be used for acid production or converted into elemental sulfur to recover sulfur resources, achieving efficient resource utilization.

[0005] Considering current market demand and transportation conditions, sulfur is easier to store and transport than sulfuric acid. Therefore, converting hydrogen sulfide into sulfur, a product with higher added value, is a better way to achieve this goal in terms of environmental friendliness and resource utilization. However, the existing process for converting hydrogen sulfide into sulfur still uses the traditional Claus process with fixed-bed catalytic oxidation. This process has excessively high operating costs and requires stringent reaction temperatures, severely limiting its application in actual production. Summary of the Invention

[0006] The purpose of this invention is to provide a process and apparatus for preparing sulfur by reacting hydrogen sulfide and sulfur dioxide in brine, in order to solve the problems of high production cost of traditional Claus process and energy consumption issues such as easy foaming and high-temperature regeneration and recycling when using organic solvents as absorbents. The process apparatus combined with the process method allows hydrogen sulfide and sulfur dioxide to undergo a Claus reaction in an aqueous solution, achieving solution recycling while obtaining high-purity sulfur products.

[0007] To solve the above-mentioned technical problems, the present invention provides a method for desulfurization by reacting hydrogen sulfide and sulfur dioxide in brine, comprising a process apparatus for the above method. The process apparatus includes a reactor body, a blade agitator installed inside the reactor body, a motor for controlling the blade agitator installed at the top of the reactor body, a tail gas outlet and a circulating liquid spray head at the upper part of the reactor body, a hydrogen sulfide inlet pipe and a sulfur dioxide inlet pipe respectively located in the middle of the reactor body, both extending below the surface of the reaction solution to allow for more thorough mixing of gas and liquid, an overflow trough located above the reaction solution inside the reactor body, a separation tank connected to the outlet of the overflow trough, and the other end of the separation tank connected to the circulating liquid spray head, a drain port at the lower part of the reactor body, and a discharge port at the bottom of the reactor body. The operating steps are as follows:

[0008] Close the outlet valve and the inlet valve, and open the inlet valve and the outlet valve to ensure the airtightness of the reaction apparatus. Flow a brine solution into the top of the reactor at a rate of 10-20 L / h, stirring continuously at a set stirring speed of 100-200 rpm. When the liquid in the reactor reaches the bottom of the overflow tank, stop the flow, open the inlet valve, and turn on the heating element to control the temperature of the reaction solution. First, introduce sulfur dioxide gas to bring the pH of the brine to 4-5, then introduce hydrogen sulfide gas. Following the gas reaction ratio will ensure more complete sulfur production.

[0009] Furthermore, the impeller is sealed to the reactor body by a sealing packing ring.

[0010] Furthermore, temperature and pH meters are installed on both sides of the reactor body.

[0011] Furthermore, the outlet of the overflow tank is a right-angle bend.

[0012] Furthermore, a brine solution is introduced into the top of the reactor body at a rate of 15 L / h, and the stirring speed is set to 150 rpm.

[0013] Furthermore, the reaction ratio of hydrogen sulfide to sulfur dioxide is 0.5:1 to 4:1.

[0014] Furthermore, the reaction ratio of hydrogen sulfide to sulfur dioxide is 1.5:1.

[0015] Furthermore, the temperature of the reaction system is 25-80℃, and the concentration of the salt solution is 3 g / L-10 g / L.

[0016] Furthermore, the brine solution is selected from one or more of sodium chloride, magnesium chloride, sodium sulfate, magnesium sulfate, aluminum chloride, and aluminum sulfate.

[0017] Furthermore, the hydrogen sulfide gas is pure hydrogen sulfide gas, industrial regenerated flue gas, acid production tail gas, or smelting acid gas.

[0018] By adopting the above technical solution, the present invention has the following beneficial effects compared with the prior art.

[0019] (1) By optimizing the design of the reactor and separation device, the contact area and reaction efficiency between gas and liquid were increased, thereby improving the desulfurization efficiency;

[0020] (2) Salt water was used as the reaction solution for the liquid-phase Claus reaction, which reduced the reaction temperature and pressure, reduced energy consumption, and made separation easier. At the same time, the reaction solution can be recycled, avoiding the problems of foaming and increased energy consumption caused by the use of organic solvents.

[0021] (3) It achieves the simultaneous removal of hydrogen sulfide and sulfur dioxide to prepare sulfur, resulting in higher processing efficiency;

[0022] (4) The process is simple and easy to operate, which reduces operating costs;

[0023] (5) The generated sulfur products can be reused, are easy to store and transport, reduce the impact on the environment, and realize resource recycling and reuse. Attached Figure Description

[0024] Figure 1 This is a schematic diagram of the process apparatus of the present invention. Detailed Implementation

[0025] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments will be clearly and completely described below with reference to the accompanying drawings. The following embodiments are used to illustrate the present invention, but are not intended to limit the scope of the present invention.

[0026] Example 1, such as Figure 1As shown, this invention provides a method for desulfurization by reacting hydrogen sulfide and sulfur dioxide in brine, including a process apparatus for the above method. The process apparatus includes a reactor body, a bladed agitator 4 installed inside the reactor body, a motor 1 for controlling the bladed agitator 4 installed at the top of the reactor body, a tail gas outlet 3 and a circulating liquid spray head provided at the upper part of the reactor body, and a hydrogen sulfide inlet pipe 5 and a sulfur dioxide inlet pipe 6 respectively provided in the middle part of the reactor body. Both the hydrogen sulfide inlet pipe 5 and the sulfur dioxide inlet pipe 6 extend below the surface of the reaction solution, so that the gas and liquid can be more fully mixed. Inside the reactor body, the reaction solution... An overflow trough 9 is provided above the reactor body. A separation tank is connected to the outlet of the overflow trough, and the other end of the separation tank is connected to a circulating liquid spray head. The overflow trough is positioned slightly higher than the surface of the reaction solution and connected to the separation tank. The overflow outlet adopts a right-angle bend design to ensure a liquid seal with the overflow trough, preventing gas overflow. A drain port is provided at the bottom of the reactor body, and a discharge port 11 is provided at the bottom of the reactor body to facilitate the discharge of the bottom liquid when the reaction is shut down. The operating steps are as follows: close the discharge port valve and the air inlet valve, open the air inlet valve and the exhaust port valve to ensure the airtightness of the reaction device; spray water at a 10° angle from the top of the reactor body... A brine solution is introduced at a rate of -20 L / h, and stirring is performed simultaneously with the addition of liquid at a set stirring speed of 100-200 rpm. When the liquid level in the reactor reaches the bottom of the overflow tank, the liquid introduction is stopped, the air inlet valve is opened, and the heating element is activated to control the temperature of the reaction solution. Sulfur dioxide gas is first introduced to bring the pH of the brine to 4-5, followed by hydrogen sulfide gas. Following the gas-reaction ratio ensures more complete sulfur production. In the reaction apparatus, the angle between the spray head at the top of the reactor and the reactor wall is 2-90 degrees, preferably 45-90 degrees. The hydrogen sulfide inlet pipe 5 and the sulfur dioxide inlet pipe 6 are symmetrically arranged. In the reaction process, the pH of the brine is 4.0-5.0, the temperature is 25℃-80℃, the ratio of hydrogen sulfide to sulfur dioxide is 0.5:1-4:1, and the concentration of the brine solution is 3 g / L-10 g / L, preferably 5 g / L-8 g / L.

[0027] Example 2: In the desulfurization method of hydrogen sulfide and sulfur dioxide reacting in brine as described in Example 1, the impeller 4 and the reactor body are sealed by a sealing packing ring 2 to prevent gas leakage.

[0028] Example 3: In a method for desulfurization by reacting hydrogen sulfide and sulfur dioxide in brine as described in Example 1 or 2, a temperature detector 8 and a pH detector 7 are provided on both sides of the reactor body to facilitate monitoring of the reaction.

[0029] Example 4: In the desulfurization method of hydrogen sulfide and sulfur dioxide reacting in brine according to any one of Examples 1-3, the outlet of the overflow tank adopts a right-angle bend 10. In order to ensure that the height of the outlet is lower than the height of the liquid surface, the outlet adopts a right-angle bend design to ensure that it forms a liquid seal with the overflow tank and prevents gas from overflowing.

[0030] Example 5, in a method for desulfurization by reacting hydrogen sulfide and sulfur dioxide in brine according to any one of Examples 1-4, a brine solution is introduced into the top of the reactor at a rate of 15 L / h, and the stirring speed is set to 150 rpm.

[0031] Example 6, in a method for desulfurization by reacting hydrogen sulfide and sulfur dioxide in brine according to any one of Examples 1-5, the reaction ratio of hydrogen sulfide to sulfur dioxide is 0.5:1-4:1.

[0032] Example 7: In a method for desulfurization by reacting hydrogen sulfide and sulfur dioxide in brine according to any one of Examples 1-6, the reaction ratio of hydrogen sulfide to sulfur dioxide is 1.5:1.

[0033] Example 8, in a method for desulfurization by reacting hydrogen sulfide and sulfur dioxide in brine according to any one of Examples 1-7, the temperature of the reaction system is 25-80℃, and the concentration of the brine solution is 3 g / L-10 g / L.

[0034] Example 9, in a method for desulfurization by reacting hydrogen sulfide and sulfur dioxide in brine according to any one of Examples 1-8, the brine solution is selected from one or more of sodium chloride, magnesium chloride, sodium sulfate, magnesium sulfate, aluminum chloride, and aluminum sulfate.

[0035] Example 10, in a method for desulfurization by reacting hydrogen sulfide and sulfur dioxide in brine according to any one of Examples 1-9, the hydrogen sulfide gas is pure hydrogen sulfide gas, industrial regenerated flue gas, acid production tail gas, or smelting acid gas.

[0036] Example 11, a method for desulfurization of hydrogen sulfide and sulfur dioxide in brine according to any one of Examples 1-10, is completed by the following process apparatus and method: The reaction apparatus includes a reactor body, and a blade-type agitator is installed inside the reactor body, which is powered by a variable frequency motor installed at the top of the reactor; the top of the reactor is provided with a tail gas outlet and a circulating liquid spray head, and the middle of the reactor is provided with two symmetrical air inlets extending to below the surface of the reaction liquid; at the same time, an overflow trough is provided 5 cm above the liquid surface in the reactor, with an opening at the upper end and a liquid outlet at the lower end connected to a sedimentation separation tank, and the other end of the separation tank is connected to the spray area at the top of the reactor; the bottom of the reactor is provided with a drain port for draining the liquid in the reactor when the equipment is shut down. In addition, in order to facilitate the detection of the acidity of the reaction solution and the reaction temperature, detection ports such as pH detection ports, temperature detection ports, and redox potential detection ports are provided on both sides of the middle of the reactor. To ensure the outlet height is lower than the liquid level, a right-angle bend is used at the outlet to form a liquid seal with the overflow tank, preventing gas overflow. To ensure more complete reaction of the reacting gases in the liquid phase, the top spray head needs to be angled, with the angle between the spray head and the reactor wall being 20-90 degrees, preferably 45-90 degrees. To ensure the reactor's airtightness, a sealing packing ring is installed between the agitator and the reactor body to prevent gas leakage.The reaction process includes the following steps: (1) Close the liquid outlet valve and the gas inlet valve, and open the liquid inlet valve and the exhaust valve to ensure the airtightness of the reaction device; (2) Pass a brine solution into the top of the reactor at a rate of 10 L / h-20 L / h, and stir at a set speed of 100 rpm-200 rpm. (3) When the liquid in the reactor reaches the position below the overflow tank, stop the liquid feeding, open the air inlet valve, and turn on the heating to control the temperature of the reaction solution. First, introduce sulfur dioxide gas to make the pH value of the brine around 4-5, and then introduce hydrogen sulfide gas. According to the gas reaction ratio, sulfur can be generated more fully; (4) In the above process method, the reaction pH value of the brine solution is <7, and the most preferred value is 4-5; (5) In the above process method, the reaction ratio of hydrogen sulfide to sulfur dioxide is 0.5:1-4:1, and more preferably 1:1-2:1; (6) In the above process method, the temperature of the reaction system is 25-80℃, and the most preferred value is 40-60℃. The concentration of the brine solution is 3 g / L-10 g / L, and the most preferred value is 5 g / L-8 g / L. g / L; (7) In the above process, the reaction solution is water or at least one inorganic salt that is miscible with water, which can settle the sulfur suspension. At the same time, the separated solution can be recycled and does not react with hydrogen sulfide or sulfur dioxide, thus ensuring the purity of the sulfur product; (8) In the above process, it is further preferred that the reaction solution is selected from one or more of sodium chloride, magnesium chloride, sodium sulfate, magnesium sulfate, aluminum chloride, and aluminum sulfate; (9) In the above process, the hydrogen sulfide gas can be pure hydrogen sulfide gas, industrial regenerated flue gas, acid production tail gas, smelting acid gas, etc.

[0037] Example 12, in a method for desulfurization of hydrogen sulfide and sulfur dioxide in brine according to any one of Examples 1-11, the reaction apparatus includes a reaction vessel and a separation tank. A paddle-type stirrer 4 with a motor is provided at the upper end of the reaction vessel, and the stirrer 4 is sealed to the reaction vessel by a sealing packing ring 2. Simultaneously, a tail gas outlet 3 is provided at the top of the reaction vessel, and a hydrogen sulfide inlet 5 and a sulfur dioxide inlet 6 are respectively provided in the middle part of the reaction vessel. The inlets extend below the surface of the reaction solution, allowing for more thorough mixing of gas and liquid. Furthermore, temperature detectors 8 and... are provided on both sides of the reaction vessel. The pH meter 7 allows for easier detection of the pH value and temperature of the reaction solution. Two symmetrical overflow tanks 9 are located a few centimeters away from the reaction solution in the reactor. The outlet of the overflow tank adopts a right-angle bend 10, which ensures a liquid seal with the overflow tank while facilitating the outflow of sulfur liquid. The outlet of the overflow tank is connected to a separation tank. After solid-liquid separation, the reaction solution is returned to the reaction system for recycling through a spray head at the top of the reactor. Finally, a discharge port 11 is provided at the bottom of the reactor to facilitate the discharge of the remaining solution in the reactor when the reaction is shut down.

[0038] The specific reaction process is as follows:

[0039] The specific operational procedure for preparing sulfur using the above-mentioned apparatus via the liquid-phase Claus reaction of sulfur dioxide and hydrogen sulfide is as follows:

[0040] (1) Close the liquid outlet valve and the gas inlet valve, and open the liquid inlet valve and the gas outlet valve to ensure the airtightness of the reaction device;

[0041] (2) Add 1L of salt solution to the reactor and heat it while stirring;

[0042] (3) When the temperature of the reaction liquid in the reactor reaches 60°C, sulfur dioxide gas is introduced. When the pH value of the pH meter is 4.5, hydrogen sulfide gas is introduced. The color of the reaction liquid quickly turns into a light yellow sulfur solution. The generated sulfur solution is gradually introduced into the separation tank through the overflow outlet under the action of the stirring paddle after vigorous stirring. After the sulfur in the separation tank is separated from the solution, the solution enters the spray head at the top of the reactor through the circulation pump and re-enters the reaction system.

[0043] (4) The flow rate ratio of hydrogen sulfide to sulfur dioxide gas in the above process reactor is set to 1:1;

[0044] (5) In the above process, the reaction solution is a 5 g / L magnesium chloride solution;

[0045] (6) After hydrogen sulfide and sulfur dioxide have reacted stably in the reaction apparatus for 1 hour, the washed sulfur is collected, dried and weighed, and the conversion rate of hydrogen sulfide is calculated to be 90.2%.

[0046] Example 13, in a desulfurization method according to any one of Examples 1-12, involving the reaction of hydrogen sulfide and sulfur dioxide in brine, the reaction apparatus includes a reaction vessel and a separation tank. A motor-driven impeller 4 is installed at the upper end of the reaction vessel, and the impeller 4 is sealed to the reaction vessel by a sealing packing ring 2. Simultaneously, a tail gas outlet 3 is provided at the top of the reaction vessel, and a hydrogen sulfide inlet 5 and a sulfur dioxide inlet 6 are respectively provided in the middle part of the reaction vessel. The inlets extend below the surface of the reaction solution, allowing for more thorough mixing of gas and liquid. Furthermore, temperature detectors 8 and... are provided on both sides of the reaction vessel. The pH meter 7 allows for easier detection of the pH value and temperature of the reaction solution. Two symmetrical overflow tanks 9 are located a few centimeters away from the reaction solution in the reactor. The outlet of the overflow tank adopts a right-angle bend 10, which ensures a liquid seal with the overflow tank while facilitating the outflow of sulfur liquid. The outlet of the overflow tank is connected to a separation tank. After solid-liquid separation, the reaction solution is returned to the reaction system for recycling through a spray head at the top of the reactor. Finally, a discharge port 11 is provided at the bottom of the reactor to facilitate the discharge of the remaining solution in the reactor when the reaction is shut down.

[0047] The specific reaction process is as follows:

[0048] The specific operational procedure for preparing sulfur using the above-mentioned apparatus via the liquid-phase Claus reaction of sulfur dioxide and hydrogen sulfide is as follows:

[0049] (1) Close the liquid outlet valve and the gas inlet valve, and open the liquid inlet valve and the gas outlet valve to ensure the airtightness of the reaction device;

[0050] (2) Add 1L of salt solution to the reactor and heat it while stirring;

[0051] (3) When the temperature of the reaction liquid in the reactor reaches 60°C, sulfur dioxide gas is introduced. When the pH value of the pH meter is 4-5, hydrogen sulfide gas is introduced. The color of the reaction liquid quickly turns into a light yellow sulfur solution. The generated sulfur solution is gradually introduced into the separation tank through the overflow outlet under the action of the stirring paddle after vigorous stirring. After the sulfur in the separation tank is separated from the solution, the solution enters the spray head at the top of the reactor through the circulation pump and re-enters the reaction system.

[0052] (4) The flow rate ratio of hydrogen sulfide to sulfur dioxide gas in the above process reactor is set to 1.5:1;

[0053] (5) In the above process, the reaction solution is a 5 g / L magnesium chloride solution;

[0054] (6) After hydrogen sulfide and sulfur dioxide have reacted stably in the reaction apparatus for 1 hour, the washed sulfur is collected, dried and weighed, and the conversion rate of hydrogen sulfide is calculated to be 94.3%.

[0055] Example 14, in a method for desulfurization of hydrogen sulfide and sulfur dioxide in brine according to any one of Examples 1-13, the reaction apparatus includes a reaction vessel and a separation tank. A paddle-type agitator 4 with a motor is provided at the upper end of the reaction vessel, and the agitator 4 is sealed to the reaction vessel by a sealing packing ring 2. Simultaneously, a tail gas outlet 3 is provided at the top of the reaction vessel, and a hydrogen sulfide inlet 5 and a sulfur dioxide inlet 6 are respectively provided in the middle part of the reaction vessel. The inlets extend below the surface of the reaction solution, allowing for more thorough mixing of gas and liquid. Furthermore, temperature detectors 8 and... are provided on both sides of the reaction vessel. The pH meter 7 allows for easier detection of the pH value and temperature of the reaction solution. Two symmetrical overflow tanks 9 are located a few centimeters away from the reaction solution in the reactor. The outlet of the overflow tank adopts a right-angle bend 10, which ensures a liquid seal with the overflow tank while facilitating the outflow of sulfur liquid. The outlet of the overflow tank is connected to a separation tank. After solid-liquid separation, the reaction solution is returned to the reaction system for recycling through a spray head at the top of the reactor. Finally, a discharge port 11 is provided at the bottom of the reactor to facilitate the discharge of the remaining solution in the reactor when the reaction is shut down.

[0056] The specific reaction process is as follows:

[0057] The specific operational procedure for preparing sulfur using the above-mentioned apparatus via the liquid-phase Claus reaction of sulfur dioxide and hydrogen sulfide is as follows:

[0058] (1) Close the liquid outlet valve and the gas inlet valve, and open the liquid inlet valve and the gas outlet valve to ensure the airtightness of the reaction device;

[0059] (2) Add 1L of salt solution to the reactor and heat it while stirring;

[0060] (3) When the temperature of the reaction liquid in the reactor reaches 60°C, sulfur dioxide gas is introduced. When the pH value of the pH meter is 4-5, hydrogen sulfide gas is introduced. The color of the reaction liquid quickly turns into a light yellow sulfur solution. The generated sulfur solution is gradually introduced into the separation tank through the overflow outlet under the action of the stirring paddle after vigorous stirring. After the sulfur in the separation tank is separated from the solution, the solution enters the spray head at the top of the reactor through the circulation pump and re-enters the reaction system.

[0061] (4) The flow rate ratio of hydrogen sulfide to sulfur dioxide gas in the above process reactor is set to 2:1;

[0062] (5) In the above process, the reaction solution is a 5 g / L magnesium chloride solution;

[0063] (6) After hydrogen sulfide and sulfur dioxide have reacted stably in the reaction apparatus for 1 hour, the washed sulfur is collected, dried and weighed, and the conversion rate of hydrogen sulfide is calculated to be 98.9%.

[0064] Example 15, in a desulfurization method according to any one of Examples 1-14, involving the reaction of hydrogen sulfide and sulfur dioxide in brine, the reaction apparatus includes a reaction vessel and a separation tank. A motor-driven impeller 4 is installed at the upper end of the reaction vessel, and the impeller 4 is sealed to the reaction vessel by a sealing packing ring 2. Simultaneously, a tail gas outlet 3 is provided at the top of the reaction vessel, and a hydrogen sulfide inlet 5 and a sulfur dioxide inlet 6 are respectively provided in the middle part of the reaction vessel. The inlets extend below the surface of the reaction solution, allowing for more thorough mixing of gas and liquid. Furthermore, temperature detectors 8 and... are provided on both sides of the reaction vessel. The pH meter 7 allows for easier detection of the pH value and temperature of the reaction solution. Two symmetrical overflow tanks 9 are located a few centimeters away from the reaction solution in the reactor. The outlet of the overflow tank adopts a right-angle bend 10, which ensures a liquid seal with the overflow tank while facilitating the outflow of sulfur liquid. The outlet of the overflow tank is connected to a separation tank. After solid-liquid separation, the reaction solution is returned to the reaction system for recycling through a spray head at the top of the reactor. Finally, a discharge port 11 is provided at the bottom of the reactor to facilitate the discharge of the remaining solution in the reactor when the reaction is shut down.

[0065] The specific reaction process is as follows:

[0066] The specific operational procedure for preparing sulfur using the above-mentioned apparatus via the liquid-phase Claus reaction of sulfur dioxide and hydrogen sulfide is as follows:

[0067] (1) Close the liquid outlet valve and the gas inlet valve, and open the liquid inlet valve and the gas outlet valve to ensure the airtightness of the reaction device;

[0068] (2) Add 1L of salt solution to the reactor and heat it while stirring;

[0069] (3) When the temperature of the reaction liquid in the reactor reaches 60°C, sulfur dioxide gas is introduced. When the pH value of the pH meter is 4-5, hydrogen sulfide gas is introduced. The color of the reaction liquid quickly turns into a light yellow sulfur solution. The generated sulfur solution is gradually introduced into the separation tank through the overflow outlet under the action of the stirring paddle after vigorous stirring. After the sulfur in the separation tank is separated from the solution, the solution enters the spray head at the top of the reactor through the circulation pump and re-enters the reaction system.

[0070] (4) The flow rate ratio of hydrogen sulfide to sulfur dioxide gas in the above process reactor is set to 2:1;

[0071] (5) In the above process, the reaction solution is a 5 g / L magnesium sulfate solution;

[0072] (6) After hydrogen sulfide and sulfur dioxide have reacted stably in the reaction apparatus for 1 hour, the washed sulfur is collected, dried and weighed, and the conversion rate of hydrogen sulfide is calculated to be 96.5%.

[0073] Example 16, in a method for desulfurization of hydrogen sulfide and sulfur dioxide in brine according to any one of Examples 1-15, the reaction apparatus includes a reaction vessel and a separation tank. A motor-driven impeller 4 is installed at the upper end of the reaction vessel, and the impeller 4 is sealed to the reaction vessel by a sealing packing ring 2. Simultaneously, a tail gas outlet 3 is provided at the top of the reaction vessel, and a hydrogen sulfide inlet 5 and a sulfur dioxide inlet 6 are respectively provided in the middle part of the reaction vessel. The inlets extend below the surface of the reaction solution, allowing for more thorough mixing of gas and liquid. Furthermore, temperature detectors 8 and... are provided on both sides of the reaction vessel. The pH meter 7 allows for easier detection of the pH value and temperature of the reaction solution. Two symmetrical overflow tanks 9 are located a few centimeters away from the reaction solution in the reactor. The outlet of the overflow tank adopts a right-angle bend 10, which ensures a liquid seal with the overflow tank while facilitating the outflow of sulfur liquid. The outlet of the overflow tank is connected to a separation tank. After solid-liquid separation, the reaction solution is returned to the reaction system for recycling through a spray head at the top of the reactor. Finally, a discharge port 11 is provided at the bottom of the reactor to facilitate the discharge of the remaining solution in the reactor when the reaction is shut down.

[0074] The specific reaction process is as follows:

[0075] The specific operational procedure for preparing sulfur using the above-mentioned apparatus via the liquid-phase Claus reaction of sulfur dioxide and hydrogen sulfide is as follows:

[0076] (1) Close the liquid outlet valve and the gas inlet valve, and open the liquid inlet valve and the gas outlet valve to ensure the airtightness of the reaction device;

[0077] (2) Add 1L of salt solution to the reactor and heat it while stirring;

[0078] (3) When the temperature of the reaction liquid in the reactor reaches 60°C, sulfur dioxide gas is introduced. When the pH value of the pH meter is 4-5, hydrogen sulfide gas is introduced. The color of the reaction liquid quickly turns into a light yellow sulfur solution. The generated sulfur solution is gradually introduced into the separation tank through the overflow outlet under the action of the stirring paddle after vigorous stirring. After the sulfur in the separation tank is separated from the solution, the solution enters the spray head at the top of the reactor through the circulation pump and re-enters the reaction system.

[0079] (4) The flow rate ratio of hydrogen sulfide to sulfur dioxide gas in the above process reactor is set to 2:1;

[0080] (5) In the above process, the reaction solution is a 6 g / L magnesium sulfate solution;

[0081] (6) After hydrogen sulfide and sulfur dioxide have reacted stably in the reaction apparatus for 1 hour, the washed sulfur is collected, dried and weighed, and the conversion rate of hydrogen sulfide is calculated to be 99.5%.

[0082] Example 17, in a method for desulfurization of hydrogen sulfide and sulfur dioxide in brine according to any one of Examples 1-16, the reaction apparatus includes a reaction vessel and a separation tank. A paddle-type agitator 4 with a motor is provided at the upper end of the reaction vessel, and the agitator 4 is sealed to the reaction vessel by a sealing packing ring 2. Simultaneously, a tail gas outlet 3 is provided at the top of the reaction vessel, and a hydrogen sulfide inlet 5 and a sulfur dioxide inlet 6 are respectively provided in the middle part of the reaction vessel. The inlets extend below the surface of the reaction solution, allowing for more thorough mixing of gas and liquid. Furthermore, temperature detectors 8 and... are provided on both sides of the reaction vessel. The pH meter 7 allows for easier detection of the pH value and temperature of the reaction solution. Two symmetrical overflow tanks 9 are located a few centimeters away from the reaction solution in the reactor. The outlet of the overflow tank adopts a right-angle bend 10, which ensures a liquid seal with the overflow tank while facilitating the outflow of sulfur liquid. The outlet of the overflow tank is connected to a separation tank. After solid-liquid separation, the reaction solution is returned to the reaction system for recycling through a spray head at the top of the reactor. Finally, a discharge port 11 is provided at the bottom of the reactor to facilitate the discharge of the remaining solution in the reactor when the reaction is shut down.

[0083] The specific reaction process is as follows:

[0084] The specific operational procedure for preparing sulfur using the above-mentioned apparatus via the liquid-phase Claus reaction of sulfur dioxide and hydrogen sulfide is as follows:

[0085] (1) Close the liquid outlet valve and the gas inlet valve, and open the liquid inlet valve and the gas outlet valve to ensure the airtightness of the reaction device;

[0086] (2) Add 1L of salt solution to the reactor and heat it while stirring;

[0087] (3) When the temperature of the reaction liquid in the reactor reaches 60°C, sulfur dioxide gas is introduced. When the pH value of the pH meter is 4-5, hydrogen sulfide gas is introduced. The color of the reaction liquid quickly turns into a light yellow sulfur solution. The generated sulfur solution is gradually introduced into the separation tank through the overflow outlet under the action of the stirring paddle after vigorous stirring. After the sulfur in the separation tank is separated from the solution, the solution enters the spray head at the top of the reactor through the circulation pump and re-enters the reaction system.

[0088] (4) The flow rate ratio of hydrogen sulfide to sulfur dioxide gas in the above process reactor is set to 2:1;

[0089] (5) In the above process, the reaction solution is an 8 g / L magnesium sulfate solution;

[0090] (6) After hydrogen sulfide and sulfur dioxide have reacted stably in the reaction apparatus for 1 hour, the washed sulfur is collected, dried and weighed, and the conversion rate of hydrogen sulfide is calculated to be 93.6%.

[0091] Example 18, in a method for desulfurization of hydrogen sulfide and sulfur dioxide in brine according to any one of Examples 1-17, the reaction apparatus includes a reaction vessel and a separation tank. A paddle-type agitator 4 with a motor is provided at the upper end of the reaction vessel, and the agitator 4 is sealed to the reaction vessel by a sealing packing ring 2. Simultaneously, a tail gas outlet 3 is provided at the top of the reaction vessel, and a hydrogen sulfide inlet 5 and a sulfur dioxide inlet 6 are respectively provided in the middle part of the reaction vessel. The inlets extend below the surface of the reaction solution, allowing for more thorough mixing of gas and liquid. Furthermore, temperature detectors 8 and... are provided on both sides of the reaction vessel. The pH meter 7 allows for easier detection of the pH value and temperature of the reaction solution. Two symmetrical overflow tanks 9 are located a few centimeters away from the reaction solution in the reactor. The outlet of the overflow tank adopts a right-angle bend 10, which ensures a liquid seal with the overflow tank while facilitating the outflow of sulfur liquid. The outlet of the overflow tank is connected to a separation tank. After solid-liquid separation, the reaction solution is returned to the reaction system for recycling through a spray head at the top of the reactor. Finally, a discharge port 11 is provided at the bottom of the reactor to facilitate the discharge of the remaining solution in the reactor when the reaction is shut down.

[0092] The specific reaction process is as follows:

[0093] The specific operational procedure for preparing sulfur using the above-mentioned apparatus via the liquid-phase Claus reaction of sulfur dioxide and hydrogen sulfide is as follows:

[0094] (1) Close the liquid outlet valve and the gas inlet valve, and open the liquid inlet valve and the gas outlet valve to ensure the airtightness of the reaction device;

[0095] (2) Add 1L of salt solution to the reactor and heat it while stirring;

[0096] (3) When the temperature of the reaction liquid in the reactor reaches 25°C, sulfur dioxide gas is introduced. When the pH value of the pH meter is 4-5, hydrogen sulfide gas is introduced. The color of the reaction liquid quickly turns into a light yellow sulfur solution. The generated sulfur solution is gradually introduced into the separation tank through the overflow outlet under the action of the stirring paddle after vigorous stirring. After the sulfur in the separation tank is separated from the solution, the solution enters the spray head at the top of the reactor through the circulation pump and re-enters the reaction system.

[0097] (4) The flow rate ratio of hydrogen sulfide to sulfur dioxide gas in the above process reactor is set to 2:1;

[0098] (5) In the above process, the reaction solution is a 6 g / L magnesium sulfate solution;

[0099] (6) After hydrogen sulfide and sulfur dioxide have reacted stably in the reaction apparatus for 1 hour, the washed sulfur is collected, dried and weighed, and the conversion rate of hydrogen sulfide is calculated to be 92.8%.

[0100] Example 19, in a method for desulfurization of hydrogen sulfide and sulfur dioxide in brine according to any one of Examples 1-18, the reaction apparatus includes a reaction vessel and a separation tank. A motor-driven impeller 4 is provided at the upper end of the reaction vessel, and the impeller 4 is sealed to the reaction vessel by a sealing packing ring 2. Simultaneously, a tail gas outlet 3 is provided at the top of the reaction vessel, and a hydrogen sulfide inlet 5 and a sulfur dioxide inlet 6 are respectively provided in the middle part of the reaction vessel. The inlets extend below the surface of the reaction solution, allowing for more thorough mixing of gas and liquid. Furthermore, temperature detectors 8 and... are provided on both sides of the reaction vessel. The pH meter 7 allows for easier detection of the pH value and temperature of the reaction solution. Two symmetrical overflow tanks 9 are located a few centimeters away from the reaction solution in the reactor. The outlet of the overflow tank adopts a right-angle bend 10, which ensures a liquid seal with the overflow tank while facilitating the outflow of sulfur liquid. The outlet of the overflow tank is connected to a separation tank. After solid-liquid separation, the reaction solution is returned to the reaction system for recycling through a spray head at the top of the reactor. Finally, a discharge port 11 is provided at the bottom of the reactor to facilitate the discharge of the remaining solution in the reactor when the reaction is shut down.

[0101] The specific reaction process is as follows:

[0102] The specific operational procedure for preparing sulfur using the above-mentioned apparatus via the liquid-phase Claus reaction of sulfur dioxide and hydrogen sulfide is as follows:

[0103] (1) Close the liquid outlet valve and the gas inlet valve, and open the liquid inlet valve and the gas outlet valve to ensure the airtightness of the reaction device;

[0104] (2) Add 1L of salt solution to the reactor and heat it while stirring;

[0105] (3) When the temperature of the reaction liquid in the reactor reaches 80°C, sulfur dioxide gas is introduced. When the pH value of the pH meter is 4-5, hydrogen sulfide gas is introduced. The color of the reaction liquid quickly turns into a light yellow sulfur solution. The generated sulfur solution is gradually introduced into the separation tank through the overflow outlet under the action of the stirring paddle after vigorous stirring. After the sulfur in the separation tank is separated from the solution, the solution enters the spray head at the top of the reactor through the circulation pump and re-enters the reaction system.

[0106] (4) The flow rate ratio of hydrogen sulfide to sulfur dioxide gas in the above process reactor is set to 2:1;

[0107] (5) In the above process, the reaction solution is a 6 g / L magnesium sulfate solution;

[0108] (6) After hydrogen sulfide and sulfur dioxide have reacted stably in the reaction apparatus for 1 hour, the washed sulfur is collected, dried and weighed, and the conversion rate of hydrogen sulfide is calculated to be 98.9%.

[0109] The above description is merely a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope disclosed in the present invention, based on the technical solution and inventive concept of the present invention, shall fall within the scope of protection of the present invention.

Claims

1. A method for desulfurization by reacting hydrogen sulfide with sulfur dioxide in brine, comprising: The process apparatus used in the above method includes a reactor body, a blade agitator (4) installed inside the reactor body, a motor (1) for controlling the blade agitator (4) installed at the top of the reactor body, a tail gas outlet (3) and a circulating liquid spray head provided at the upper part of the reactor body, a hydrogen sulfide inlet pipe (5) and a sulfur dioxide inlet pipe (6) respectively provided in the middle part of the reactor body, both the hydrogen sulfide inlet pipe (5) and the sulfur dioxide inlet pipe (6) extending below the surface of the reaction solution to allow for more thorough mixing of gas and liquid, an overflow trough (9) provided above the reaction solution inside the reactor body, a separation tank connected to the outlet of the overflow trough, and the other end of the separation tank connected to the circulating liquid spray head, a drain port provided at the lower part of the reactor body, and a discharge port (11) provided at the bottom of the reactor body. The operation steps are as follows: Close the outlet valve and the inlet valve, and open the inlet valve and the outlet valve to ensure the airtightness of the reaction apparatus. Flow a brine solution into the top of the reactor at a rate of 10-20 L / h, stirring continuously at a set stirring speed of 100-200 rpm. When the liquid in the reactor reaches the bottom of the overflow tank, stop the flow, open the inlet valve, and turn on the heating element to control the temperature of the reaction solution. First, introduce sulfur dioxide gas to bring the pH of the brine to 4-5, then introduce hydrogen sulfide gas. Following the gas reaction ratio will ensure more complete sulfur production.

2. The method for desulfurization by reacting hydrogen sulfide and sulfur dioxide in brine according to claim 1, characterized in that, The impeller (4) is sealed to the reactor body by a sealing packing ring (2).

3. The method for desulfurization by reacting hydrogen sulfide and sulfur dioxide in brine according to claim 1, characterized in that, Temperature detector (8) and pH detector (7) are installed on both sides of the reactor body.

4. The method for desulfurization by reacting hydrogen sulfide and sulfur dioxide in brine according to claim 1, characterized in that, The outlet of the overflow tank is a right-angle bend (10).

5. The method for desulfurization by reacting hydrogen sulfide and sulfur dioxide in brine according to claim 1, characterized in that, A brine solution is introduced into the top of the reactor at a rate of 15 L / h, and the stirring speed is set to 150 rpm.

6. The method of claim 1, wherein the hydrogen sulfide and sulfur dioxide are reacted in the brine to remove sulfur compounds. The reaction ratio of hydrogen sulfide to sulfur dioxide is 0.5:1 to 4:

1.

7. The method of claim 6, wherein the hydrogen sulfide and sulfur dioxide are reacted in the brine to remove sulfur compounds. The reaction ratio of hydrogen sulfide to sulfur dioxide is 1.5:

1.

8. The method of claim 1, wherein the hydrogen sulfide and sulfur dioxide are reacted in the brine to remove sulfur compounds. The temperature of the reaction system is 25-80℃, and the concentration of the salt solution is 3 g / L-10 g / L.

9. The method for desulfurization by reacting hydrogen sulfide and sulfur dioxide in brine according to claim 1, characterized in that, The brine solution is selected from one or more of sodium chloride, magnesium chloride, sodium sulfate, magnesium sulfate, aluminum chloride, and aluminum sulfate.

10. The method of claim 1, wherein the hydrogen sulfide and sulfur dioxide are reacted in the brine to remove sulfur compounds. The hydrogen sulfide gas is pure hydrogen sulfide gas, industrial regenerated flue gas, acid production tail gas, or smelting acid gas.

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