A process and device for comprehensively utilizing by - product sulfur from methyl / ethyl chloride to prepare insoluble sulfur

Abstract

The present invention discloses a process and device for comprehensively utilizing by-product sulfur from methyl / ethyl chloride to prepare insoluble sulfur, including a distillation kettle. The distillation kettle is connected to a quench box through a pipeline. A turbulence component is fixed inside the quench box. A water channel fixedly connected to the quench box is provided at the lower end of the turbulence component. A cooling spray component is provided at the lower end of the water channel. A transmission rod is provided at the lower end of the water channel and is in transmission connection with the turbulence component and the cooling spray component. A grinding component is in transmission connection at the lower end of the transmission rod. The cooling spray component includes a cooling part and a spray part. The cooling part includes a cooling disc with a hollow interior. Multiple concentric cooling fins are provided at the upper end of the cooling disc. Air channels are formed on the cooling fins. A rotating ring is rotatably connected to the upper end of the cooling disc. By introducing cooled carbon disulfide into the cavity of the cooling disc and arranging cooling fins on the cooling disc to increase the contact area with the by-product sulfur vapor, it is convenient to quickly cool the by-product sulfur vapor.

Description

Technical Field

[0001] The invention relates to the technical field of sulfur preparation, in particular to a process and a device for preparing insoluble sulfur by comprehensively utilizing sulfur produced as a byproduct of methyl / ethyl chloride. Background Art

[0002] In the rubber industry, high thermal stability insoluble sulfur is increasingly used as a rubber vulcanizer. Its unique advantage is that it can effectively improve the performance of rubber products, such as reducing migration in rubber compounds, accelerating the vulcanization process and ensuring vulcanization uniformity, enhancing adhesion, and significantly improving the operating environment, thereby avoiding "frosting" on the surface of rubber products and semi-finished products, which is crucial to maintaining the appearance quality, vulcanization effect and aging resistance of rubber products. However, as a metastable substance, the stability of insoluble sulfur is easily affected by temperature fluctuations, resulting in a gradual decrease in content with increasing temperature or prolonged storage time. Therefore, improving the thermal stability and storage stability of insoluble sulfur has become a key technical problem that needs to be solved in the industry. At present, the production methods of insoluble sulfur mainly include two categories: high temperature method and low temperature method. Among them, the high temperature method is divided into gasification method and melting method. Although the gasification method has a high conversion rate, it involves the use of high-temperature sulfur vapor, which causes serious corrosion to the equipment, and the subsequent treatment process is complicated, involving flammable, explosive and highly toxic carbon disulfide, and the operating safety and investment cost are high. The melting method heats sulfur to a molten state and then rapidly cools it. The by-product sulfur produced in the production process of methyl / ethyl chloride is crystalline sulfur and sticky sulfur. Because it is wrapped and attached with methyl / ethyl chloride and other organic matter during the production process, it has a strong odor. During the packaging, transportation and storage processes, there are unorganized odor emissions, which have adverse environmental impacts. In addition, downstream companies are reluctant to use by-product sulfur with odor, resulting in low sales prices and frequent sales difficulties, causing inventory backlogs and affecting normal production.

[0003] Chinese Patent Application No. CN202220893755.9 discloses an insoluble sulfur gasification quenching device, belonging to the technical field of sulfur quenching. An insoluble sulfur gasification quenching device of the present utility model includes a quenching reaction tank. A quenching tank and a heating tank are arranged inside the quenching reaction tank. A cooling tank and an air pump are arranged at the top of the quenching reaction tank. A spraying mechanism, a stirring mechanism and a first temperature sensor are arranged inside the quenching tank. The present utility model solves the problem of uneven quenching in the prior art. The liquid sulfur and the coolant in the cooling tank are pumped into the spraying mechanism. The coolant flows into the liquid storage pipe and is sprayed out by the nozzle. There are no less than ten groups of nozzles, which can expand the spraying range of the coolant and improve the quenching speed of the liquid sulfur. The rotation of the stirring frame can improve the uniformity of the quenching of the liquid sulfur. The two stirring mechanisms are arranged relatively staggered, which can increase the contact area between the stirring frame and the liquid sulfur and accelerate the mixing speed of the two. The processing speed and efficiency of the liquid sulfur are improved, and the use performance of the sulfur gasification quenching device is enhanced.

[0004] Chinese Patent Application No. CN202220911919.6 discloses an insoluble sulfur highly adaptable rapid cooling and powder making device, belonging to the technical field of insoluble sulfur production. To solve the problems of poor powder making effect and low efficiency, a sandwich layer is provided inside the outer wall of the processing kettle. Cooling liquid for temperature reduction can be injected into the sandwich layer through the water inlet pipe, thereby reducing the temperature of the entire processing kettle and making the low-temperature environment inside the inner cavity more stable, improving the heat exchange effect, making the rapid cooling and powder making more efficient and stable. The cooling turntable is in a conical shape as a whole. Cooling blades are fixedly arranged on the side wall of the cooling turntable. The inside of the cooling turntable is hollow. Liquid nitrogen can be injected into the inside of the cooling turntable through the first conduit and the second conduit. Driven by the motor, the cooling turntable rotates to rapidly cool and make powder of the atomized insoluble sulfur sprayed into the inner cavity. The arrangement of the cooling blades expands the contact range between the cooling turntable and the insoluble sulfur spray, improving the effect of rapid cooling and powder making.

[0005] However, the following problems will occur during the use of the above solutions:

[0006] 1. When cooling the by-product sulfur vapor, it is cooled by directly contacting with cold air or indirectly through a heat exchange cavity, and multiple cycle cooling cannot be achieved, thus affecting the cooling effect of the by-product sulfur vapor and resulting in a low conversion rate of insoluble sulfur.

[0007] 2. When the by-product sulfur enters the cooling device through the pipeline, outward diffusion will occur, showing an umbrella-shaped diffusion movement trajectory. At the same time, the flow velocity in the central part is much greater than that at the edge, which will result in poor cooling effect of the by-product sulfur vapor in the central part and fail to achieve complete cooling.

[0008] 3. Due to continuous accumulation in the cooling device, the cooled insoluble sulfur may become blocked or agglomerated. Summary of the Invention

[0009] In view of the above problems, the present invention provides a process and device for comprehensively utilizing by-product sulfur from methyl / ethyl chloride to prepare insoluble sulfur.

[0010] To achieve the above object, the present invention provides the following technical solution: A process and device for comprehensively utilizing by-product sulfur from methyl / ethyl chloride to prepare insoluble sulfur, including a distillation kettle, a quenching box, a reaction kettle, a condenser, a heating kettle, a mixing container, a fluidized bed and a dissolution kettle. The condenser is located at the gas phase outlet of the reaction kettle. Stirring devices are provided in the reaction kettle and the heating kettle. The distillation kettle is connected to the quenching box through a pipeline. A turbulence component is fixed inside the quenching box. A water channel fixedly connected to the quenching box is provided at the lower end of the turbulence component. A cooling spray component is provided at the lower end of the water channel. A transmission rod is provided at the lower end of the water channel and is in transmission connection with the turbulence component and the cooling spray component. A grinding component is in transmission connection at the lower end of the transmission rod.

[0011] The cooling spray component includes a cooling part and a spraying part. The cooling part includes a cooling disc with a hollow interior. Multiple concentric cooling fins are provided at the upper end of the cooling disc. Air channels are formed in the cooling fins. A rotating ring is rotatably connected to the upper end of the cooling disc. A water jacket is rotatably connected to the upper end of the rotating ring. The upper end of the water jacket is fixedly connected to the water channel. Multiple guide plates are fixed to the outer wall of the rotating ring. A scraping plate that fits the cooling fin is fixed to the lower end of the guide plate. A circulating fan blade is fixed to the upper end of the guide plate. The bending direction of the outermost part of the circulating fan blade is opposite to the body of the circulating fan blade. An outlet pipe is connected to the outer wall of the cooling disc and penetrates through the quenching box. The outer wall of the cooling disc is fixedly connected to the quenching box. The spraying part includes multiple concentric fixed support rings. Connecting rings are rotatably connected between every two adjacent fixed support rings. Multiple spray heads are rotatably connected to the connecting rings. A lower rotating ring is rotatably connected to the outermost fixed support ring. The outermost fixed support ring is fixedly connected to the quenching box through a support rod. An upper rotating ring is rotatably connected to the upper end of the lower rotating ring. The upper end of the upper rotating ring is rotatably connected to the cooling disc. A transmission part is fixed to the fixed support ring and is in transmission connection with the lower rotating ring and the upper rotating ring. The lower rotating ring and the upper rotating ring rotate in opposite directions through the transmission part. The innermost connecting ring is in transmission connection with the transmission rod.

[0012] Preferably, the water channel is cross-shaped, a transmission blade is fixed to the upper end of the transmission rod, the transmission blade is placed inside the cross intersection of the water channel, the transmission rod is rotatably connected to the water channel, each side of the water channel is tangent to the transmission blade, a Venturi tube is arranged near the transmission blade, the water channel is connected to the water jacket, and the water jacket is connected to the interior of the cooling plate.

[0013] Preferably, a cavity is formed between the fixed support ring, the connecting ring, the lower swivel ring, the upper swivel ring and the cooling plate, the cavity is connected to the cooling plate, the multiple circles of connecting rings are transmission connected to each other, the connecting rings are provided with transmission teeth, the transmission parts include a gear ring, a fixed rod and a gear set, the gear ring is fixed to the fixed support ring, the fixed rod is fixed on the gear ring, the outer end of the fixed rod is rotatably connected to the gear set, the gear set is transmission connected to the lower swivel ring and the upper swivel ring, the lower swivel ring rotates in opposite directions, and the upper end of the nozzle is provided with a gear meshing with the gear ring.

[0014] Preferably, the outer walls of the lower swivel and the upper swivel are provided with a plurality of flanges, and arc-shaped plates corresponding to the lower swivel and the upper swivel are provided between each of the flanges.

[0015] Preferably, the nozzle is a multi-head nozzle, the outermost circle of the multi-head nozzle is arranged to be inclined toward the outside of the nozzle, and the innermost circle of the multi-head nozzle is arranged directly below the nozzle.

[0016] Preferably, the spoiler assembly includes a spoiler fixing ring fixedly connected to the quench box, a plurality of upper U plates with openings facing downwards are fixed on the spoiler fixing ring, a fixing frame is slidably connected to the lower end of the spoiler fixing ring, a plurality of lower U plates with openings facing upwards are fixed on the fixing frame, and the fixing frame is provided with teeth.

[0017] Preferably, a transmission ring is fixed to the upper end of the transmission rod, and the transmission ring is respectively Intermittent A first reciprocating gear and a second reciprocating gear are meshed, the first reciprocating gear and the second reciprocating gear are meshed and connected, the second reciprocating gear is meshed and connected with the teeth on the fixed frame, and the outer wall of the transmission ring is provided with a plurality of groups of semi-toothed rings, and the distance between each group of semi-toothed rings is smaller than the distance between the two points where the first reciprocating gear, the second reciprocating gear and the transmission ring contact.

[0018] Preferably, the grinding assembly includes an upper plate and a lower plate, the upper end and the lower end of the upper plate are both provided with inverted conical grooves, the upper plate is transmission-connected to the transmission rod, the upper plate is rotationally connected to the quench box, the upper end of the lower plate is conical, one side of the conical shape of the lower plate corresponds to the lower end of the upper plate, two circles of filter holes are provided at the upper end of the lower plate, a plurality of grinding strips are fixed along the circumference of the lower end of the upper plate, a plurality of through holes are provided on the upper plate, a plurality of paddle plates are fixed along the circumference of the outer side of the upper plate, and a collection trough corresponding to the paddle plates is provided on the outer side of the quench box.

[0019] A process for comprehensively utilizing by - product sulfur from methyl / ethyl chloride to prepare insoluble sulfur, which is characterized by including the following steps:

[0020] S1: Put a quantitative amount of by - product sulfur into the reaction kettle. A condenser is set at the gas phase outlet of the reaction kettle. Slowly drip carbon disulfide into the reaction kettle. After dissolving the by - product sulfur, start the stirring device in the reaction kettle to stir. Through stratification, separate the carbon disulfide system dissolved with sulfur and organic matter from water and insoluble organic matter; conduct tower - type negative - pressure rectification by heating to respectively recover carbon disulfide and methyl / ethyl chloride chloride products, and separate other low - boiling organic impurities; sulfur recrystallizes and precipitates, remaining in the reaction kettle;

[0021] S2: Pass steam into the jacket of the reaction kettle to gradually heat the sulfur to 140 °C to melt the sulfur into a liquid. The carbon disulfide vapor is condensed and recovered through the condenser at the gas phase outlet; after reaching the temperature, add catalyst A, keep warm and stir for 45 minutes, pump the melted liquid sulfur into the heating kettle, add catalyst B, raise the temperature program - matically to 250 °C, keep warm and stir for 30 minutes; add catalyst C, slowly raise the temperature to 320 °C, keep warm and stir for 30 minutes, put the sulfur in the heating kettle into the distillation kettle, raise the temperature to 420 - 440 °C to generate sulfur vapor;

[0022] S3: Mix sulfur vapor and high - purity nitrogen in a volume ratio of 1:2 and enter the quench box. Immediately spray with a large - flux cold water to rapidly reduce the gas temperature to below 90 °C to generate sulfur, which is stored in water. Perform solid - liquid separation to obtain an insoluble sulfur and a small amount of soluble sulfur system. When the sulfur vapor comes to the quench box, the sulfur vapor first passes through the flow - disturbing component for flow - disturbing, so that the sulfur vapor can flow evenly in the quench box to improve the cooling effect of the sulfur vapor. The flow - disturbed sulfur vapor comes to the cooling spray component for cooling. The sulfur vapor first contacts and cools with the cooling part, and at the same time, the circulating fan blade makes the sulfur vapor circulate and cool here. The cooled sulfur vapor comes to the spray part for spray cooling. The obtained solution enters the mixing container and carbon disulfide is introduced;

[0023] S4: Perform solid - liquid separation of insoluble sulfur and soluble sulfur; after the insoluble sulfur is separated, it is dried by a fluidized bed and then packaged; the sulfur dissolved in carbon disulfide is recycled to the dissolution kettle and used in the next batch.

[0024] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0025] 1. Cooled carbon disulfide is introduced into the cavity of the cooling plate, and cooling fins are arranged on the cooling plate to increase the contact area with the by-product sulfur vapor, so as to facilitate rapid cooling of the by-product sulfur vapor. At the same time, the rotating ring is driven to rotate by the rotation of the transmission rod, and the rotating ring drives the guide plate, the scraper and the circulating fan blades to rotate. The circulating fan blades form a fan effect, so that the by-product sulfur vapor passing through the spoiler assembly quickly contacts the cooling fins to form heat exchange. In order to calculate that the cooled by-product sulfur vapor will flow out through the airway, the edge of the circulating fan blade Reverse bending treatment will generate upward wind force, which will discharge the by-product sulfur vapor that is not completely cooled upward. Then the downward and upward wind force generated by the circulating fan blades will form a cycle, blowing the by-product sulfur vapor to the cooling plate for cooling multiple times. The cooled gas will pass through the gaps of the lower rotating ring and the upper rotating ring and fall to the spray part. The cooled carbon disulfide will be sprayed out through the nozzle, and the gas will be cooled and mixed again, so as to further cool the by-product sulfur vapor in the gas and improve the conversion rate of the by-product sulfur vapor into insoluble sulfur.

[0026] 2. The transmission ring is driven to rotate by the transmission rod. Since the teeth of the transmission ring are multiple sets of non-adjacent teeth, the transmission will be transmitted with the second reciprocating gear when the transmission ring rotates. The second reciprocating gear drives the teeth to swing. When the transmission ring leaves the second reciprocating gear and meshes with the first reciprocating gear, the first reciprocating gear and the second reciprocating gear are driven. The meshing of the second reciprocating gear and the teeth drives the fixed frame to rotate in the opposite direction, thereby achieving the effect of the reciprocating swing of the fixed frame. When the by-product sulfur vapor enters the quench box, it will first impact the upper U plate to disperse the by-product sulfur vapor. In addition, the reciprocating movement of the fixed frame drives the lower U plate to move, thereby playing a turbulent role on the by-product sulfur vapor, so that the by-product sulfur vapor falls evenly and is evenly cooled.

[0027] 3. Carbon disulfide is sprayed out through the nozzle to impact the insoluble sulfur formed by cooling, and impacts it to the upper and lower plates. The upper plate is driven to rotate through the transmission rod, and then the upper plate grinds and crushes the insoluble sulfur. In addition, the flow of carbon disulfide causes the powdered insoluble sulfur to be discharged into the aggregate trough, and it is discharged from the aggregate trough by the movement of the paddle. In the process of grinding the insoluble sulfur by the upper and lower plates, carbon disulfide will be separated from the powdered insoluble sulfur through the filter holes. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 The overall process diagram of the present invention is

[0029] Figure 2 It is a schematic diagram of the overall structure of the present invention;

[0030] Figure 3 It is a cross-sectional schematic diagram of the quench box of the present invention;

[0031] Figure 4 Overall schematic diagram of the cooling spray assembly of the present invention;

[0032] Figure 5 Cross-sectional schematic diagram of the cooling spray assembly of the present invention;

[0033] Figure 6 Schematic diagram of the cooling part of the present invention;

[0034] Figure 7 Schematic diagram of the circulating fan blade of the present invention;

[0035] Figure 8 Cross-sectional schematic diagram of the water channel of the present invention;

[0036] Figure 9 Schematic diagram of the spray part of the present invention;

[0037] Figure 10 Exploded schematic diagram of the spray part of the present invention;

[0038] Figure 11 Exploded schematic diagram of the spray part of the present invention;

[0039] Figure 12 Schematic diagram of the flow disturbance assembly of the present invention;

[0040] Figure 13 Cross-sectional schematic diagram of the flow disturbance assembly of the present invention;

[0041] Figure 14 Cross-sectional schematic diagram of the grinding assembly of the present invention.

[0042] Explanation of the labels in the figure: 1, distillation kettle; 2, quench box; 3, flow disturbance fixing ring; 4, water channel; 5, cooling plate; 6, fixing support ring; 7, transmission rod; 21, aggregate trough; 31, upper U-shaped plate; 32, lower U-shaped plate; 33, fixing frame; 34, transmission ring; 35, first reciprocating gear; 36, second reciprocating gear; 37, tooth; 51, cooling fin; 52, air duct; 53, rotating ring; 54, guide plate; 55, water outlet pipe; 61, connecting ring; 62, nozzle; 63, lower rotating ring; 64, upper rotating ring; 65, transmission part; 66, flange; 67, arc-shaped plate; 71, transmission blade; 72, water jacket; 81, upper plate; 82, lower plate; 541, scraper; 542, circulating fan blade; 611, transmission tooth; 651, toothed ring; 652, fixing rod; 653, gear set; 811, through hole; 812, grinding bar; 813, deflector; 821, filter hole; 30, reaction kettle; 40, condenser; 50, heating kettle; 60, fluidized bed; 70, dissolution kettle. Detailed implementation manners

[0043] The following embodiments of the present invention are described in further detail in conjunction with the accompanying drawings and examples. The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention.

[0044] See also Figure 1 , Figure 2 and Figure 3 A process and device for preparing insoluble sulfur by comprehensively utilizing sulfur produced as a byproduct of methyl / ethyl chloride, comprising a still 1, a quench box 2, a reactor 30, a condenser 40, a heating kettle 50, a fluidized bed 60 and a dissolving kettle 70, wherein the condenser 40 is located at the gas phase outlet of the reactor 30, and a stirring device is provided in the reactor 30 and the heating kettle 50. The still 1, the quench box 2, the reactor 30, the condenser 40, the heating kettle 50, the fluidized bed 60, the dissolving kettle 70 and the stirring device are existing equipment and will not be described in detail herein. The still 1 is used for heating byproduct sulfur and carbon disulfide to 300-400 degrees to form byproduct sulfur vapor, and the still 1 is connected to the quench box 2 through a pipeline, and the interior of the quench box 2 is solid. A spoiler component is provided, which disturbs the by-product sulfur vapor entering the quench box 2, so that the by-product sulfur vapor falls evenly and prevents the by-product sulfur vapor from being locally concentrated. A water channel 4 fixedly connected to the quench box 2 is provided at the lower end of the spoiler component, and a cooling spray component is provided at the lower end of the water channel 4. The cooling spray component circulates and cools the by-product sulfur vapor to ensure rapid cooling of the by-product sulfur vapor, thereby converting the by-product sulfur vapor into insoluble sulfur. A transmission rod 7 transmission-connected to the spoiler component and the cooling spray component is provided at the lower end of the water channel 4. A grinding component is transmission-connected to the lower end of the transmission rod 7. The grinding component grinds the insoluble sulfur into powder to facilitate subsequent processing and transportation.

[0045] See also Figure 3 , Figure 4 , Figure 5 , Figure 6 and Figure 7, considering that when cooling the by - product sulfur vapor, direct contact with cold air or indirect contact through a heat exchange chamber cannot achieve multiple - cycle cooling, which affects the cooling effect of the by - product sulfur vapor and results in a low conversion rate of insoluble sulfur. The cooling spray assembly includes a cooling part and a spray part. The cooling part includes a cooling disk 5 with a hollow interior. At the upper end of the cooling disk 5, there are multiple concentric cooling fins 51. Air channels 52 are opened on the cooling fins 51. The cooled carbon disulfide that enters the water jacket 72 through the water channel 4 will flow into the interior of the cooling disk 5. At the same time, a part of the carbon disulfide continues to flow downward and is ejected at 962. The carbon disulfide flowing into the interior of the cooling disk 5 will lower the temperature of the cooling disk 5 and the cooling fins 51. When the by - product sulfur vapor contacts the cooling disk 5 and the cooling fins 51, rapid heat exchange cooling occurs, converting the by - product sulfur vapor into insoluble sulfur. The insoluble sulfur will accumulate between the cooling fins 51. At the same time, part of the gas flows outward from the cooling disk 5 through the air channels 52. A rotating ring 53 is rotatably connected to the upper end of the cooling disk 5. The upper end of the rotating ring 53 is rotatably connected to the water jacket 72. The upper end of the water jacket 72 is fixedly connected to the water channel 4. A plurality of guide plates 54 are fixed to the outer wall of the rotating ring 53. A scraper 541 that fits the cooling fins 51 is fixed to the lower end of the guide plate 54. A circulating fan blade 542 is fixed to the upper end of the guide plate 54. The guide plate 54 is in an inverted - U shape. The rotating ring 53 is fixedly connected to the transmission rod 7. The transmission rod 7 drives the guide plate 54 to rotate, and at the same time, the scraper 541 rotates accordingly. The scraper 541 shovels the insoluble sulfur accumulated in the cooling fins 51 to the guide plate 54. The guide plate 54 is tangent to the rotating ring 53 and is set at a certain angle. When the guide plate 54 rotates, its own centrifugal force is generated, and at the same time, the centrifugal force of the insoluble sulfur at the guide plate 54 is also generated. The insoluble sulfur slides outward in the guide plate 54, thus clearing the insoluble sulfur accumulated in the cooling fins 51. The bending direction of the outermost part of the circulating fan blade 542 is opposite to the body of the circulating fan blade 542. A water outlet pipe 55 is communicated with the outer wall of the cooling disk 5. The water outlet pipe 55 penetrates the quenching box 2. The carbon disulfide after heat exchange inside the cooling disk 5 is discharged through the water outlet pipe 55. A support column is fixed to the outer wall of the cooling disk 5. The cooling disk 5 is fixedly connected to the quenching box 2 through the support column. By introducing cooled carbon disulfide into the cavity of the cooling disk 5 and setting cooling fins 51 on the cooling disk 5 to increase the contact area with the by - product sulfur vapor, it is convenient to quickly cool the by - product sulfur vapor. At the same time, the transmission rod 7 rotates to drive the rotating ring 53 to rotate. The rotating ring 53 drives the guide plate 54, the scraper 541, and the circulating fan blade 542 to rotate. The circulating fan blade 542 forms the effect of a fan, enabling the by - product sulfur vapor passing through the flow - disturbance component to quickly contact the cooling fins 51 to form heat exchange. The cooled by - product sulfur vapor to be calculated will flow out through the air channels 52.When the edge of the circulating fan blade 542 is bent reversely, an upward wind force will be generated, which will cause the uncompletely cooled by-product sulfur vapor to be discharged upward. Then, the downward and upward wind forces generated by the circulating fan blade 542 form a cycle, and the by-product sulfur vapor is blown onto the cooling fins 51 for cooling multiple times, improving the conversion rate of the by-product sulfur vapor into insoluble sulfur.

[0046] Please refer to Figure 2 and Figure 8 Considering that when the carbon disulfide liquid is introduced into the inside of the quench box 2, the impact of the carbon disulfide will generate power. The force generated by the impact of the carbon disulfide is utilized to reduce the use of energy. The water channel 4 is in a cross shape. The upper end of the transmission rod 7 is fixed with a transmission blade 71. The transmission blade 71 is placed inside the cross intersection of the water channel 4. The transmission rod 7 is rotatably connected to the water channel 4. Each side of the water channel 4 is tangent to the transmission blade 71. A Venturi tube is arranged at the water channel 4 near the transmission blade 71. The water channel 4 is communicated with the water jacket 72. The water jacket 72 is communicated with the inside of the cooling disc 5. The external cooling carbon disulfide is transported into the water channel 4 by a high-pressure pump. Since each side of the water channel 4 is tangent to the transmission blade 71 and a Venturi tube is arranged at the water channel 4 near the transmission blade 71, the high-pressure carbon disulfide will increase the flow rate of the carbon disulfide after passing through the Venturi tube. The high-flow carbon disulfide directly impacts the transmission blade 71, and then the transmission blade 71 drives the transmission rod 7 to rotate, without the need to add a power source to drive the transmission rod 7, indirectly saving the use of energy.

[0047] Please refer to Figure 3 、 Figure 4 、 Figure 8 、 Figure 9 and Figure 10, considering that some by - product sulfur vapor is not completely cooled, the by - product sulfur vapor is cooled again by spraying to improve the conversion rate of the by - product sulfur vapor into insoluble sulfur. The spraying part includes a plurality of concentrically arranged fixed support rings 6. A connecting ring 61 is rotatably connected between every two of the fixed support rings 6. Transmission teeth 611 are provided on each of the connecting rings 61. A plurality of nozzles 62 are rotatably connected to each of the connecting rings 61. A lower rotating ring 63 is rotatably connected to the outermost fixed support ring 6. An upper rotating ring 64 is rotatably connected to the upper end of the lower rotating ring 63. The upper end of the upper rotating ring 64 is rotatably connected to the cooling plate 5. A transmission member 65 is fixed on the fixed support ring 6. The transmission member 65 is in transmission connection with the lower rotating ring 63 and the upper rotating ring 64. The lower rotating ring 63 and the upper rotating ring 64 rotate in opposite directions through the transmission member 65. A plurality of flanges 66 are provided on the outer walls of the lower rotating ring 63 and the upper rotating ring 64. An arc - shaped plate 67 corresponding to the lower rotating ring 63 and the upper rotating ring 64 is provided between every two of the flanges 66. The transmission rod 7 is in transmission connection with the connecting ring 61. The innermost connecting ring 61 is in transmission connection with the transmission rod 7. When the transmission rod 7 rotates, it drives the innermost connecting ring 61 to rotate. Also, since transmission teeth 611 are fixed on multiple layers of the connecting rings 61, the connecting rings 61 are driven by the transmission teeth 611 and gears, so that the transmission rod 7 rotates to drive the connecting rings 61 to rotate. A toothed ring 651 is fixed on the fixed support ring 6 and is fixedly connected to the toothed ring 651 through a fixed rod 652. At the same time, the nozzle 62 meshes with the toothed ring 651. Thus, while the connecting ring 61 drives the nozzle 62 to rotate, the nozzle 62 rotates itself, making the carbon disulfide sprayed by the nozzle 62 more uniform and dense, and improving the conversion rate of the by - product sulfur vapor into insoluble sulfur. A cavity is formed between the fixed support ring 6, the connecting ring 61, the lower rotating ring 63, the upper rotating ring 64 and the cooling plate 5. The cavity is communicated with the cooling plate 5. Multiple circles of the connecting rings 61 are in transmission connection with each other. The transmission member 65 includes a toothed ring 651, a fixed rod 652 and a gear set 653. The toothed ring 651 is fixed on the fixed support ring 6. The fixed rod 652 is fixed on the toothed ring 651. The outer end of the fixed rod 652 is rotatably connected to the gear set 653. The gear set 653 is in transmission connection with the lower rotating ring 63 and the upper rotating ring 64. The lower rotating ring 63 and the upper rotating ring 64 rotate in opposite directions. The upper end of the nozzle 62 is provided with a gear that meshes with the toothed ring 651. The joints of the fixed support ring 6, the lower rotating ring 63, the upper rotating ring 64 and the cooling plate 5 are all sealed. The gear set 653 meshes with the lower rotating ring 63 and the outermost transmission teeth 611, indirectly enabling the transmission rod 7 to drive the lower rotating ring 63 to rotate. At the same time, the upper end of the gear set 653 meshes with the upper rotating ring 64 for transmission, prompting the lower rotating ring 63 and the upper rotating ring 64 to rotate in opposite directions. Coupled with the cooperation of the flanges 66 and the arc - shaped plates 67 on the outer walls of the lower rotating ring 63 and the upper rotating ring 64, when the arc - shaped plates 67 do not overlap with each other, the upper end of the cooling plate 5 is in a sealed state, thereby enabling the by - product sulfur vapor to be cooled in a cycle.When the arc-shaped plates 67 overlap each other, the cooled and transformed gas will move downward through the gap for spray cooling. When the arc-shaped plates 67 approach each other, they will mutually extrude and crush the insoluble sulfur carried out by the material guiding plate 54 to prevent it from caking. When the arc-shaped plates 67 on the lower rotating ring 63 and the upper rotating ring 64 overlap, the insoluble sulfur will fall from the gap between them to the grinding assembly for grinding. The spray head 62 is a multi-nozzle. The outermost circle of the multi-nozzle is inclined outward of the spray head 62, and the innermost circle of the multi-nozzle is arranged directly below the spray head 62. The cooled gas will fall to the spraying part through the notches of the lower rotating ring 63 and the upper rotating ring 64, and the cooled carbon disulfide will be sprayed out through the spray head 62 to cool and mix the gas again, further cooling the by-product sulfur vapor in the gas and improving the conversion rate of the by-product sulfur vapor to insoluble sulfur.

[0048] Please refer to Figure 3 、 Figure 12 and Figure 13, considering that when the by - product sulfur enters the quench box 2 through the pipeline, there will be a phenomenon of outward diffusion, presenting an umbrella - shaped diffusion movement trajectory. At the same time, the flow velocity in the central part is much greater than that at the edge, which will result in poor cooling effect of the by - product sulfur vapor in the central part and fail to achieve the complete cooling effect. The turbulence component includes a turbulence fixing ring 3 fixedly connected to the quench box 2. A plurality of upper U - shaped plates 31 with openings facing downwards are fixed on the turbulence fixing ring 3. There are gaps between every two of the plurality of upper U - shaped plates 31. The lower end of the turbulence fixing ring 3 is slidably connected with a fixing frame 33. A plurality of lower U - shaped plates 32 with openings facing upwards are fixed on the fixing frame 33. There are teeth 37 on the fixing frame 33. The upper end of the transmission rod 7 is fixedly connected with a transmission ring 34. The transmission ring 34 is intermittently meshed with a first reciprocating gear 35 and a second reciprocating gear 36 respectively. The first reciprocating gear 35 and the second reciprocating gear 36 are meshed with each other. The second reciprocating gear 36 is meshed with the teeth 37 on the fixing frame 33. The outer wall of the transmission ring 34 is provided with several groups of semi - tooth rings and there are no teeth in other positions. The distance between each group of semi - tooth rings is less than the distance between the two points where the first reciprocating gear 35, the second reciprocating gear 36 are in contact with the transmission ring 34. By driving the transmission ring 34 to rotate through the transmission rod 7, and since the semi - tooth rings of the transmission ring 34 are multiple groups of non - adjacent semi - tooth rings, when the transmission ring 34 rotates, it will drive the second reciprocating gear 36. The second reciprocating gear 36 drives the teeth 37 to swing. When the transmission ring 34 leaves the second reciprocating gear 36 and meshes with the first reciprocating gear 35, the first reciprocating gear 35 and the second reciprocating gear 36 are in transmission, and the second reciprocating gear 36 meshes with the teeth 37 to drive the fixing frame 33 to rotate in the reverse direction, thus achieving the effect of the reciprocating swing of the fixing frame 33. When the by - product sulfur vapor enters the quench box 2, it will first impact the upper U - shaped plates 31 to disperse the by - product sulfur vapor. Coupled with the reciprocating movement of the fixing frame 33 driving the lower U - shaped plates 32 to move, it plays a role in disturbing the flow of the by - product sulfur vapor, making the by - product sulfur vapor fall evenly and cooling the by - product sulfur vapor evenly.

[0049] Please refer to Figure 3 and Figure 14Considering that the insoluble sulfur after cooling may be blocked or agglomerated in the cooling device due to continuous accumulation, the grinding assembly includes an upper plate 81 and a lower plate 82, the upper and lower ends of the upper plate 81 are both provided with inverted conical grooves, the upper plate 81 is transmission-connected with the transmission rod 7, the upper plate 81 is rotationally connected with the quench box 2, the upper end of the lower plate 82 is conical and corresponds to the lower end of the upper plate 81, the upper end of the lower plate 82 is provided with two circles of filter holes 821, the lower end of the upper plate 81 is fixed with a plurality of grinding strips 812 along its circumference, the upper plate 81 is provided with a plurality of through holes 811, and the through holes 811 are communicated with the gap between the upper plate 81 and the lower plate 82, A plurality of paddles 813 are fixed along the circumference of the outer side of the upper plate 81, and a collection trough 21 corresponding to the paddles 813 is provided on the outer side of the quench box 2. Carbon disulfide is sprayed out through the nozzle 62 to impact the insoluble sulfur formed by cooling, and impacts it to the upper plate 81 and the lower plate 82. The upper plate 81 is driven to rotate by the transmission rod 7, and then the upper plate 81 grinds and crushes the insoluble sulfur. With the flow of carbon disulfide, the powdered insoluble sulfur is discharged into the collection trough 21, and is discharged from the collection trough 21 by the paddle 813. In the process of grinding the insoluble sulfur by the upper plate 81 and the lower plate 82, the carbon disulfide is separated from the powdered insoluble sulfur through the filter hole 821.

[0050] When the present invention is used:

[0051] A fixed amount of by-product sulfur is fed into a special reactor 30 through a closed feeding device, carbon disulfide is slowly dripped into the reactor, and stirring is started after the by-product sulfur is dissolved; the carbon disulfide system containing sulfur and organic matter is separated from water and insoluble organic matter through stratification, and tower negative pressure distillation is performed through heating to recover carbon disulfide and methyl / ethyl chloride chloride products, and other low-boiling point organic impurities are separated; sulfur is recrystallized and precipitated and retained in the reactor;

[0052] Then, steam was introduced into the jacket of the reactor to gradually heat the sulfur to 140°C and melt the sulfur into liquid. A condenser was set at the gas phase outlet of the reactor, and carbon disulfide vapor was condensed and recovered through the condenser at the gas phase outlet. After the temperature reached, catalyst A was added and the mixture was kept warm and stirred for 45 minutes.

[0053] Next, the melted liquid sulfur is pumped into the heating kettle 50, and the catalyst B is added. The temperature is programmed to 250°C, and the mixture is kept warm and stirred for 30 minutes. The catalyst C is added, and the temperature is slowly raised to 320°C, and the mixture is kept warm and stirred for 30 minutes. The sulfur in the heating kettle 50 is put into the distillation kettle 1, and the temperature is raised to 420-440°C to generate sulfur vapor. The sulfur vapor and high-purity nitrogen are mixed in a volume ratio of 1:2 and enter the quench box 2. A large-flux cold water spray is immediately used to sharply reduce the gas temperature to below 90°C, and sulfur is generated and stored in water for solid-liquid separation.

[0054] Finally, the obtained solid enters the mixing container and carbon disulfide is introduced to separate insoluble sulfur from soluble sulfur by solid-liquid separation. After the insoluble sulfur is separated, it is dried by the fluidized bed 60 and then packaged. The carbon disulfide vapor generated by the fluidized bed 60 is condensed and recycled back to the reaction kettle 30. The sulfur dissolved in carbon disulfide is recycled to the dissolution kettle 70 for the next batch, or can be directly recycled to the reaction kettle 30.

[0055] Although the embodiments of the present invention have been shown and described, those of ordinary skill in the art can understand that various changes, modifications, substitutions, and variations can be made to these embodiments without departing from the principles and spirit of the present invention. The scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A device for preparing insoluble sulfur by comprehensively utilizing sulfur produced as a byproduct of methyl / ethyl chloride, comprising a distillation kettle (1), a quench box (2), a reaction kettle (30), a condenser (40), a heating kettle (50), a mixing container, a fluidized bed (60) and a dissolving kettle (70), wherein the condenser (40) is located at the gas phase outlet of the reaction kettle (30), and a stirring device is provided in the reaction kettle (30) and the heating kettle (50), and characterized in that: The distillation kettle (1) is connected to a quench box (2) via a pipeline; a spoiler assembly is fixed inside the quench box (2); a water channel (4) fixedly connected to the quench box (2) is provided at the lower end of the spoiler assembly; a cooling spray assembly is provided at the lower end of the water channel (4); a transmission rod (7) drivingly connected to the spoiler assembly and the cooling spray assembly is provided at the lower end of the water channel (4); and a grinding assembly is drivingly connected to the lower end of the transmission rod (7); The cooling spray assembly comprises a cooling portion and a spray portion, the cooling portion comprising a cooling plate (5), the interior of the cooling plate (5) being hollow, the upper end of the cooling plate (5) being provided with a plurality of concentrically arranged cooling fins (51), each of the cooling fins (51) being provided with an air channel (52), the upper end of the cooling plate (5) being rotatably connected to a rotating ring (53), the upper end of the rotating ring (53) being rotatably connected to a water jacket (72), the upper end of the water jacket (72) being connected to the water channel ( 4) fixedly connected, the outer wall of the rotating ring (53) is fixed with a plurality of guide plates (54), the lower end of the guide plate (54) is fixed with a scraper (541) that fits the cooling fin (51), the upper end of the guide plate (54) is fixed with a circulating blade (542), the outermost bending direction of the circulating blade (542) is opposite to the main body of the circulating blade (542), the outer wall of the cooling plate (5) is connected with a water outlet pipe (55), and the water outlet pipe (55) penetrates A quench box (2), the outer wall of the cooling plate (5) is fixedly connected to the quench box (2), the spraying part comprises a plurality of concentrically arranged fixed support rings (6), each of the fixed support rings (6) is rotatably connected to a connecting ring (61), each of the connecting rings (61) is rotatably connected to a plurality of spray heads (62), the outermost fixed support ring (6) is rotatably connected to a lower rotating ring (63), and the outermost fixed support ring (6) is fixed to the quench box (2) via a support rod. The upper end of the lower rotating ring (63) is rotatably connected to the upper rotating ring (64), the upper end of the upper rotating ring (64) is rotatably connected to the cooling plate (5), a transmission member (65) is fixed on the fixed support ring (6), the transmission member (65) is transmission-connected to the lower rotating ring (63) and the upper rotating ring (64), the lower rotating ring (63) and the upper rotating ring (64) rotate in opposite directions via the transmission member (65), and the innermost connecting ring (61) is transmission-connected to the transmission rod (7).

2. The device for preparing insoluble sulfur by comprehensively utilizing sulfur produced as a byproduct of methyl / ethyl chloride according to claim 1, characterized in that: The water channel (4) is cross-shaped, a transmission blade (71) is fixed to the upper end of the transmission rod (7), the transmission blade (71) is placed inside the cross intersection of the water channel (4), the transmission rod (7) is rotatably connected to the water channel (4), each side of the water channel (4) is tangentially arranged to the transmission blade (71), a Venturi tube is arranged near the transmission blade (71) of the water channel (4), the water channel (4) is connected to a water jacket (72), and the water jacket (72) is connected to the inside of the cooling plate (5).

3. A device for preparing insoluble sulfur by comprehensively utilizing sulfur produced as a byproduct of methyl / ethyl chloride according to claim 2, characterized in that: A cavity is formed between the fixed support ring (6), the connecting ring (61), the lower rotating ring (63), the upper rotating ring (64) and the cooling plate (5); the cavity is in communication with the cooling plate (5); a plurality of circles of the connecting ring (61) are connected to each other in a transmission manner; each of the connecting rings (61) is provided with a transmission tooth (611); the transmission member (65) comprises a gear ring (651), a fixed rod (652) and a gear set (653); the gear ring (651) is fixed to the fixed support ring (6); a fixed rod (652) is fixed to the gear ring (651); an outer end of the fixed rod (652) is rotatably connected to the gear set (653); the gear set (653) is connected to the lower rotating ring (63) and the upper rotating ring (64); the lower rotating ring (63) rotates in opposite directions to the upper rotating ring (64); and a gear meshing with the gear ring (651) is provided at the upper end of the nozzle (62).

4. The device for preparing insoluble sulfur by comprehensively utilizing sulfur produced as a byproduct of methyl / ethyl chloride according to claim 3, characterized in that: The outer walls of the lower rotating ring (63) and the upper rotating ring (64) are both provided with a plurality of flanges (66), and arc-shaped plates (67) corresponding to the lower rotating ring (63) and the upper rotating ring (64) are provided between each of the flanges (66).

5. A device for preparing insoluble sulfur by comprehensively utilizing sulfur produced as a byproduct of methyl / ethyl chloride according to claim 4, characterized in that: The nozzle (62) is a multi-head nozzle, the outermost circle of the multi-head nozzle is arranged obliquely toward the outside of the nozzle (62), and the innermost circle of the multi-head nozzle is arranged directly below the nozzle (62).

6. The device for preparing insoluble sulfur by comprehensively utilizing sulfur produced as a byproduct of methyl / ethyl chloride according to claim 5, characterized in that: The spoiler assembly comprises a spoiler fixing ring (3) fixedly connected to the quench box (2), a plurality of upper U-plates (31) with openings facing downwards being fixed on the spoiler fixing ring (3), a fixing frame (33) being slidably connected at the lower end of the spoiler fixing ring (3), a plurality of lower U-plates (32) with openings facing upwards being fixed on the fixing frame (33), and teeth (37) being provided on the fixing frame (33).

7. The device for preparing insoluble sulfur by comprehensively utilizing sulfur produced as a byproduct of methyl / ethyl chloride according to claim 6, characterized in that: A transmission ring (34) is fixed to the upper end of the transmission rod (7), and the transmission ring (34) is respectively Intermittent A first reciprocating gear (35) and a second reciprocating gear (36) are meshed and connected, the first reciprocating gear (35) and the second reciprocating gear (36) are meshed and connected, the second reciprocating gear (36) is meshed and connected with teeth (37) on the fixed frame (33), and the outer wall of the transmission ring (34) is provided with a plurality of groups of semi-toothed rings, and the distance between each group of semi-toothed rings is smaller than the distance between two contact points between the first reciprocating gear (35), the second reciprocating gear (36) and the transmission ring (34).

8. The device for preparing insoluble sulfur by comprehensively utilizing sulfur produced as a byproduct of methyl / ethyl chloride according to claim 7, characterized in that: The grinding assembly comprises an upper plate (81) and a lower plate (82), the upper end and the lower end of the upper plate (81) are both provided with an inverted conical groove, the upper plate (81) is transmission-connected to a transmission rod (7), the upper plate (81) is rotationally connected to a quench box (2), the upper end of the lower plate (82) is conical, one conical side of the lower plate (82) corresponds to the lower end of the upper plate (81), the upper end of the lower plate (82) is provided with two circles of filter holes (821), the lower end of the upper plate (81) is fixed with a plurality of grinding strips (812) along its circumference, the upper plate (81) is provided with a plurality of through holes (811), the outer side of the upper plate (81) is fixed with a plurality of paddles (813) along its circumference, and the outer side of the quench box (2) is provided with a collection trough (21) corresponding to the paddles (813).

9. A process for preparing insoluble sulfur by comprehensively utilizing sulfur produced as a byproduct of methyl / ethyl chloride, characterized in that: The device for preparing insoluble sulfur by comprehensively utilizing sulfur produced as a by-product of methyl / ethyl chloride as described in claim 8 comprises the following steps: S1: adding a certain amount of by-product sulfur into a reactor (30), setting a condenser (40) at the gas phase outlet of the reactor (30), slowly dripping carbon disulfide into the reactor, dissolving the by-product sulfur, starting the stirring device in the reactor (30) to stir, and separating the carbon disulfide system containing sulfur and organic matter from water and insoluble organic matter through stratification; performing tower negative pressure distillation by heating, respectively recovering carbon disulfide and methyl / ethyl chloride chloride products, and separating other low-boiling point organic impurities; and re-crystallizing the sulfur and leaving it in the reactor (30); S2: Steam is introduced into the jacket of the reaction kettle (30) to gradually heat the sulfur to 140°C, so that the sulfur is melted into liquid, and the carbon disulfide vapor is condensed and recovered through the condenser (40) at the gas phase outlet; after the temperature is reached, catalyst A is added, and the mixture is kept warm and stirred for 45 minutes. The melted liquid sulfur is pumped into the heating kettle (50), and catalyst B is added. The temperature is programmed to 250°C and kept warm and stirred for 30 minutes; catalyst C is added, and the temperature is slowly raised to 320°C and kept warm and stirred for 30 minutes. The sulfur in the heating kettle (50) is put into the distillation kettle (1), and the temperature is raised to 420-440°C to generate sulfur vapor; S3: sulfur vapor and high-purity nitrogen are mixed in a volume ratio of 1:2 and enter a quench box (2). A large amount of cold water is immediately sprayed to rapidly reduce the gas temperature to below 90°C, thereby generating sulfur, which is stored in water and separated into solid and liquid to obtain an insoluble sulfur and a small amount of soluble sulfur system. When the sulfur vapor enters the quench box (2), the sulfur vapor first passes through a turbulent assembly for turbulence, so that the sulfur vapor can flow evenly in the quench box (2), thereby improving the cooling effect of the sulfur vapor. The turbulent sulfur vapor enters the cooling spray assembly for cooling. The sulfur vapor first contacts with the cooling part for cooling. At the same time, the circulating fan blades (542) cause the sulfur vapor to circulate and cool here. The cooled sulfur vapor enters the spraying part for spray cooling. The obtained solution enters the mixing container and is introduced into carbon disulfide. S4: Insoluble sulfur and soluble sulfur are separated into solid and liquid forms; after the insoluble sulfur is separated, it is dried in a fluidized bed (60) and then packaged; the sulfur dissolved in carbon disulfide is returned to the dissolving kettle (70) and used in the next batch.

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