Process and device for preparing insoluble sulfur by comprehensively utilizing methyl / ethyl byproduct sulfur

Abstract

The invention discloses a process and a device for preparing insoluble sulfur by comprehensively utilizing methyl / ethyl byproduct sulfur. The device comprises a distillation kettle, the distillation kettle is communicated with a quenching box through a pipeline, a turbulent flow assembly is fixed in the quenching box, a water channel fixedly connected with the quenching box is arranged at the lower end of the turbulent flow assembly, and a cooling spraying assembly is arranged at the lower end of the water channel. A transmission rod in transmission connection with the turbulent flow assembly and the cooling spraying assembly is arranged at the lower end of the water channel, the lower end of the transmission rod is in transmission connection with a grinding assembly, the cooling spraying assembly comprises a cooling part and a spraying part, the cooling part comprises a cooling disc, the interior of the cooling disc is hollow, and multiple circles of concentrically-arranged cooling pieces are arranged at the upper end of the cooling disc; the cooling plates are provided with air channels, the upper end of the cooling disc is rotationally connected with a rotating ring, cooled carbon disulfide is introduced into the cavity of the cooling disc, the cooling plates are arranged on the cooling disc, the contact area with byproduct sulfur steam is increased, and the byproduct sulfur steam can be rapidly cooled conveniently.

Description

Technical Field

[0001] The invention relates to the technical field of sulfur preparation, in particular to a process and a device for comprehensively utilizing methyl / ethyl by-product sulfur to prepare insoluble sulfur. 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 of methyl / ethyl chloride is crystalline sulfur and sticky sulfur. Because it is wrapped and attached to 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 number CN202220893755.9 discloses an insoluble sulfur gasification quenching device, which belongs to the field of sulfur quenching technology. The utility model discloses an insoluble sulfur gasification quenching device, including a quenching reaction box, a quenching box and a heating box are arranged in the quenching reaction box, a cooling box and an air pump are arranged on the top of the quenching reaction box, and a spray mechanism, a stirring mechanism and a first temperature sensor are arranged in the quenching box. The utility model solves the problem of uneven quenching in the existing process, and the liquid sulfur and the coolant in the cooling box are pumped into the spray mechanism, and the coolant flows into the liquid storage pipe and is sprayed by the nozzle. The nozzle is not less than ten groups, which can expand the range of the coolant spraying and improve the speed of liquid sulfur quenching; the uniformity of liquid sulfur quenching can be improved by rotating the stirring frame, and the two groups of stirring mechanisms are relatively staggered to increase the contact area between the stirring frame and the liquid sulfur, and accelerate the mixing speed of the two; the speed and efficiency of liquid sulfur processing are improved, and the performance of the sulfur gasification quenching device is improved.

[0004] Chinese patent application number CN202220911919.6 discloses a highly adaptable quenching milling device for insoluble sulfur, which belongs to the field of insoluble sulfur production technology. In order to solve the problems of poor milling effect and efficiency, a sandwich is provided inside the outer wall of the processing kettle, and the cooling liquid used for cooling can be injected into the inside of the sandwich through the water inlet pipe, thereby reducing the temperature of the entire processing kettle, making the low temperature environment inside the inner cavity more stable, improving the heat exchange effect, and making the quenching milling more efficient and stable. The cooling turntable is cone-shaped as a whole, and cooling blades are fixedly arranged on the side wall of the cooling turntable. The inside of the cooling turntable is hollow, and 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, and the insoluble sulfur sprayed into the inner cavity is quenched and milled. The setting of the cooling blades expands the contact range between the cooling turntable and the insoluble sulfur spray, and improves the effect of quenching and milling.

[0005] However, the above solution may cause the following problems during use: 1. When the by-product sulfur steam is cooled, the by-product sulfur steam is cooled by direct contact with cold air or indirect contact through a heat exchange chamber, and multiple cycles of cooling cannot be achieved, thereby affecting the cooling effect of the by-product sulfur steam and resulting in a low conversion rate of insoluble sulfur.

[0006] 2. When the by-product sulfur enters the cooling device through the pipeline, it will diffuse outward, presenting an umbrella-shaped diffusion trajectory. At the same time, the flow velocity in the central part is much greater than the flow velocity at the edge, which will result in poor cooling effect of the by-product sulfur steam in the central part and fail to achieve a complete cooling effect.

[0007] 3. After cooling, the insoluble sulfur will continue to accumulate in the cooling device, causing blockage or agglomeration. Summary of the invention

[0008] In view of the above problems, the present invention provides a process and device for preparing insoluble sulfur by comprehensively utilizing methyl / ethyl by-product sulfur.

[0009] To achieve the above-mentioned purpose, the present invention provides the following technical scheme: a process and device for preparing insoluble sulfur by comprehensively utilizing methyl / ethyl by-product sulfur, comprising a distillation kettle, a quench box, a reactor, a condenser, a heating kettle, a mixing container, a fluidized bed and a dissolving kettle, wherein the condenser is located at the gas phase outlet of the reactor, the reactor and the heating kettle are provided with a stirring device, the distillation kettle is connected with the quench box through a pipeline, a spoiler assembly is fixed inside the quench box, a water channel fixedly connected to the quench box is provided at the lower end of the spoiler assembly, a cooling spray assembly is provided at the lower end of the water channel, a transmission rod transmission-connected to the spoiler assembly and the cooling spray assembly is provided at the lower end of the water channel, and a grinding assembly is transmission-connected to the lower end of the transmission rod; The cooling spray assembly comprises a cooling part and a spray part, the cooling part comprises a cooling plate, the interior of the cooling plate is hollow, the upper end of the cooling plate is provided with a plurality of concentrically arranged cooling fins, the cooling fins are provided with air channels, the upper end of the cooling plate is rotatably connected with a rotating ring, the upper end of the rotating ring is rotatably connected with a water jacket, the upper end of the water jacket is fixedly connected with the water channel, a plurality of guide plates are fixed to the outer wall of the rotating ring, a scraper fitted with the cooling fins 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 outermost bending direction of the circulating fan blade is opposite to that of the circulating fan blade body, the outer wall of the cooling plate is connected with a water outlet pipe, and the water outlet pipe penetrates A quench box, the outer wall of the cooling plate is fixedly connected to the quench box, the spray part includes a plurality of concentrically arranged fixed support rings, each of the fixed support rings is rotatably connected with a connecting ring, each of the connecting rings is rotatably connected with a plurality of nozzles, the outermost fixed support ring is rotatably connected with a lower swivel, the outermost fixed support ring is fixedly connected to the quench box through a support rod, the upper end of the lower swivel is rotatably connected with an upper swivel, the upper end of the upper swivel is rotatably connected to the cooling plate, a transmission member is fixed on the fixed support ring, the transmission member is transmission-connected to the lower swivel and the upper swivel, the lower swivel and the upper swivel rotate in opposite directions through the transmission member, and the innermost connecting ring is transmission-connected to the transmission rod.

[0010] 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.

[0011] 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.

[0012] 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.

[0013] 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.

[0014] 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.

[0015] 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.

[0016] 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.

[0017] A process for preparing insoluble sulfur by comprehensively utilizing methyl / ethyl by-product sulfur, characterized in that it comprises the following steps: S1: a quantitative amount of by-product sulfur is put into a reactor, a condenser is arranged at the gas phase outlet of the reactor, carbon disulfide is slowly dripped into the reactor, and after the by-product sulfur is dissolved, a stirring device in the reactor is started to stir, and the carbon disulfide system containing sulfur and organic matter is separated from water and insoluble organic matter by stratification; tower negative pressure distillation is performed by heating to recover carbon disulfide and methyl / ethyl chloride products respectively, and other low-boiling point organic impurities are separated; sulfur is recrystallized and precipitated and retained in the reactor; S2: Steam is introduced into the jacket of the reactor to gradually heat the sulfur to 140°C, melt the sulfur into liquid, and condense and recover the carbon disulfide vapor through the condenser at the gas phase outlet; after the temperature is reached, catalyst A is added, and the mixture is stirred at the temperature for 45 minutes. The melted liquid sulfur is pumped into the heating kettle, and catalyst B is added. The temperature is programmed to 250°C, and the mixture is stirred at the temperature for 30 minutes; catalyst C is added, and the temperature is slowly raised to 320°C, and the mixture is stirred at the temperature for 30 minutes. The sulfur in the heating kettle is put into the distillation kettle, 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. A large amount of cold water is immediately sprayed to sharply reduce the gas temperature to below 90°C to generate 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, the sulfur vapor first passes through a turbulent assembly for turbulence, so that the sulfur vapor can flow evenly in the quench box, 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 and cools with the cooling part, and at the same time, the circulating fan blades cause the sulfur vapor to circulate and cool here. The cooled sulfur vapor enters the spray part for spray cooling, and the obtained solution enters the mixing container and is introduced into carbon disulfide. S4: The insoluble sulfur is separated from the soluble sulfur by solid-liquid separation; after the insoluble sulfur is separated, it is dried in a fluidized bed and then packaged; the sulfur dissolved in the carbon disulfide is returned to the dissolving kettle and used in the next batch.

[0018] Compared with the prior art, the present invention has the following beneficial effects: 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.

[0019] 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.

[0020] 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

[0021] Figure 1 The overall process diagram of the present invention is Figure 2 It is a schematic diagram of the overall structure of the present invention; Figure 3 It is a cross-sectional schematic diagram of the quench box of the present invention; Figure 4 It is an overall schematic diagram of the cooling spray assembly of the present invention; Figure 5 It is a cross-sectional schematic diagram of a cooling spray assembly of the present invention; Figure 6 It is a schematic diagram of the cooling part of the present invention; Figure 7 It is a schematic diagram of the circulating fan blade of the present invention; Figure 8 It is a schematic cross-sectional view of a waterway of the present invention; Fig. 9 It is a schematic diagram of the spraying part of the present invention; Fig.10 It is a schematic diagram of the explosion of the spray part of the present invention; Fig.11 It is a schematic diagram of the explosion of the spray part of the present invention; Fig.12 is a schematic diagram of a spoiler assembly of the present invention; Fig.13 is a cross-sectional schematic diagram of a spoiler assembly of the present invention; Fig.14 It is a schematic cross-sectional view of the grinding assembly of the present invention.

[0022] Explanation of the markings in the figure: 1. distillation kettle; 2. quench box; 3. turbulent fixed ring; 4. water channel; 5. cooling plate; 6. fixed support ring; 7. transmission rod; 21. collecting trough; 31. upper U plate; 32. lower U plate; 33. fixed frame; 34. transmission ring; 35. first reciprocating gear; 36. second reciprocating gear; 37. teeth; 51. cooling fin; 52. air channel; 53. rotating ring; 54. guide plate; 55. water outlet pipe; 61. connecting ring; 62. nozzle; 63. lower reciprocating gear ring; 64, upper rotating ring; 65, transmission part; 66, flange; 67, arc plate; 71, transmission blade; 72, water jacket; 81, upper plate; 82, lower plate; 541, scraper; 542, circulating fan blade; 611, transmission tooth; 651, gear ring; 652, fixing rod; 653, gear set; 811, through hole; 812, grinding strip; 813, paddle plate; 821, filter hole; 30, reaction kettle; 40, condenser; 50, heating kettle; 60, fluidized bed; 70, dissolving kettle. DETAILED DESCRIPTION

[0023] 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.

[0024] See also Figure 1 , Figure 2 and Figure 3A process and device for preparing insoluble sulfur by comprehensively utilizing methyl / ethyl by-product sulfur, 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 to heat the by-product sulfur and carbon disulfide to 300-400 degrees to form by-product sulfur vapor, and the still 1 is connected to the quench box 2 through a pipeline, and a A spoiler assembly is provided, wherein the spoiler assembly spoils the by-product sulfur steam entering the quench box 2, so that the by-product sulfur steam falls evenly and prevents the by-product sulfur steam from being locally concentrated. A water channel 4 fixedly connected to the quench box 2 is provided at the lower end of the spoiler assembly, and a cooling spray assembly is provided at the lower end of the water channel 4. The cooling spray assembly circulates and cools the by-product sulfur steam to ensure that the by-product sulfur steam is quickly cooled, thereby converting the by-product sulfur steam into insoluble sulfur. A transmission rod 7 transmission-connected to the spoiler assembly and the cooling spray assembly is provided at the lower end of the water channel 4. A grinding assembly is transmission-connected to the lower end of the transmission rod 7. The grinding assembly grinds the insoluble sulfur into powder to facilitate subsequent processing and transportation.

[0025] See also Figure 3 , Figure 4 , Figure 5 , Figure 6 and Figure 7Considering that when the by-product sulfur steam is cooled, it is impossible to achieve multiple cycles of cooling by directly contacting with cold air or indirectly contacting with the heat exchange chamber to cool the by-product sulfur steam, thereby affecting the cooling effect of the by-product sulfur steam and resulting 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 plate 5, the cooling plate 5 is hollow inside, and the upper end of the cooling plate 5 is provided with a plurality of concentrically arranged cooling fins 51, and the cooling fins 51 are all provided with air channels 52, and the cooled carbon disulfide entering the water jacket 72 through the water channel 4 will flow into the interior of the cooling plate 5, and at the same time, a part of the carbon disulfide continues to flow down and flows into 962 for spraying, and the carbon disulfide flowing into the cooling plate 5 The carbon will reduce the temperature of the cooling plate 5 and the cooling fins 51. When the by-product sulfur vapor contacts the cooling plate 5 and the cooling fins 51, rapid heat exchange cooling is performed to convert 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 to the outside of the cooling plate 5 through the airway 52. ​​The upper end of the cooling plate 5 is rotatably connected to a rotating ring 53. The upper end of the rotating ring 53 is rotatably connected to a water jacket 72. The upper end of the water jacket 72 is fixedly connected to the waterway 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, and the transmission rod 7 drives the guide plate 54 to rotate, and the scraper 541 rotates accordingly. The scraper 541 shovels the insoluble sulfur accumulated in the cooling plate 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, it generates centrifugal force by itself, and the insoluble sulfur at the guide plate 54 also generates centrifugal force. The insoluble sulfur slides in the guide plate 54 to the outside of the guide plate 54, thereby cleaning out the insoluble sulfur accumulated on the cooling plate 51. 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 runs through the quench box 2 The carbon disulfide after heat exchange inside the cooling disk 5 is discharged through the outlet pipe 55. The outer wall of the cooling disk 5 is fixed with a pillar. The cooling disk 5 is fixedly connected to the quench box 2 through the pillar. By introducing cooled carbon disulfide into the cavity of the cooling disk 5, a cooling plate 51 is arranged on the cooling disk 5 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 53 is driven to rotate by the rotation of the transmission rod 7. The rotating ring 53 drives the guide plate 54, the scraper 541 and the circulating blade 542 to rotate. The circulating blade 542 forms a fan effect, so that the by-product sulfur vapor passing through the spoiler assembly quickly contacts the cooling plate 51 to form heat exchange. In order to calculate the cooled by-product sulfur vapor, it will flow out through the airway 52.The reverse bending of the edge of the circulating blade 542 will generate upward wind force, thereby discharging the by-product sulfur vapor that has not been completely cooled upward. Then, the downward and upward wind force generated by the circulating blade 542 forms a cycle, blowing the by-product sulfur vapor to the cooling plate 51 for cooling multiple times, thereby improving the conversion rate of the by-product sulfur vapor into insoluble sulfur.

[0026] See also Figure 2 and Figure 8 Considering that when the carbon disulfide liquid is introduced into the interior 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 cross-shaped, and a transmission blade 71 is fixed to the upper end of the transmission rod 7. The transmission blade 71 is placed inside the cross 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 near the transmission blade 71 of the water channel 4. The water channel 4 is connected to the water jacket 7. 2 is connected, the water jacket 72 is connected with the interior of the cooling disk 5, and the external cooling carbon disulfide is transported to the water channel 4 through the 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, and the high-flow rate carbon disulfide directly impacts the transmission blade 71, and then the transmission blade 71 drives the transmission rod 7 to rotate, and there is no need to add a power source to drive the transmission rod 7, which indirectly saves the use of energy.

[0027] See also Figure 3 , Figure 4 , Figure 8 , Fig. 9 and Fig.10Considering that part of the by-product sulfur steam has not been completely cooled, the by-product sulfur steam is cooled again by spraying to improve the conversion rate of the by-product sulfur steam into insoluble sulfur. The spraying part includes a plurality of concentrically arranged fixed support rings 6, and each of the fixed support rings 6 is rotatably connected with a connecting ring 61, and each of the connecting rings 61 is provided with a transmission tooth 611, and each of the connecting rings 61 is rotatably connected with a plurality of nozzles 62. The outermost fixed support ring 6 is rotatably connected with a lower rotating ring 63, and the upper end of the lower rotating ring 63 is rotatably connected with an upper rotating ring 64, and 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, and 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 through the transmission member 65. The outer walls of the lower rotating ring 63 and the upper rotating ring 64 are provided with a plurality of flanges 66. The flanges 66 are provided with arc plates 67 corresponding to the lower rotating ring 63 and the upper rotating ring 64 between each other. The transmission rod 7 is transmission-connected with the connecting ring 61. The innermost connecting ring 61 is transmission-connected with the transmission rod 7. When the transmission rod 7 rotates, it drives the innermost connecting ring 61 to rotate. Because the connecting rings 61 of the multiple layers are all fixed with transmission teeth 611, the connecting ring 61 is transmitted through the transmission teeth 611 and the gears, and then the rotation of the transmission rod 7 drives the connecting ring 61 to rotate. The gear ring 651 is fixed on the fixed support ring 6 and is fixedly connected with the gear ring 651 through the fixed rod 652. The nozzle 62 is meshed with the gear ring 651, and then the connecting ring 61 drives the nozzle 62 to rotate while the nozzle 62 rotates, so that the carbon disulfide sprayed by the nozzle 62 is more uniform and dense, and the conversion rate of the by-product sulfur vapor into insoluble sulfur is improved. 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, and the cavity is connected to the cooling plate 5. Multiple circles of the connecting ring 61 are mutually connected in transmission. The transmission member 65 includes a gear ring 651, a fixed rod 652 and a gear set 653. The gear ring 651 is fixed on the fixed support ring 6, and the fixed rod 652 is fixed on the gear ring 651. The outer end of the fixed rod 652 is rotatably connected with the gear set 653. The gear set 653 is connected to the lower rotating ring 63 and the upper The rotating ring 64 is connected by transmission, the lower rotating ring 63 rotates in the opposite direction with the upper rotating ring 64, the upper end of the nozzle 62 is provided with a gear meshing with the gear ring 651, the connection between the fixed support ring 6, the lower rotating ring 63, the upper rotating ring 64 and the cooling plate 5 is sealed, the gear set 653 meshes with the lower rotating ring 63 and the outermost transmission tooth 611, indirectly causing the transmission rod 7 to drive the lower rotating ring 63 to rotate, and at the same time the upper end of the gear set 653 meshes with the upper rotating ring 64 for transmission, causing the lower rotating ring 63 and the upper rotating ring 64 to rotate in the opposite direction, and the flange 66 and the arc plate 67 of the outer wall of the lower rotating ring 63 and the upper rotating ring 64 cooperate, when the arc plates 67 do not overlap each other, the upper end of the cooling plate 5 is in a sealed state, and then the by-product sulfur steam is circulated and cooled,When the arc plates 67 overlap each other, the gas after cooling and conversion will move downward through the gap for spray cooling. When the arc plates 67 are close to each other, the insoluble sulfur brought out by the guide plate 54 will be squeezed and crushed to prevent it from agglomerating. When the arc plates 67 on the lower rotating ring 63 and the upper rotating ring 64 overlap, the insoluble sulfur falls from the gap to the grinding assembly for grinding. The nozzle 62 is a multi-head nozzle, the outermost circle of the multi-head nozzle is inclined to the outside of the nozzle 62, and the innermost circle of the multi-head nozzle is set directly below the nozzle 62. The cooled gas will pass through the gap between the lower rotating ring 63 and the upper rotating ring 64 and fall to the spray part. The cooled carbon disulfide will be sprayed out through the nozzle 62, and the gas will be cooled and mixed again, and the by-product sulfur vapor in the gas will be further cooled, so as to improve the conversion rate of the by-product sulfur vapor into insoluble sulfur.

[0028] See also Figure 3 , Fig.12 and Fig.13, considering that the by-product sulfur will diffuse outward when entering the quench box 2 through the pipeline, presenting an umbrella-shaped diffusion motion trajectory, and the flow velocity of the central part is much greater than the flow velocity of the edge, which will make the cooling effect of the by-product sulfur steam in the central part poor, and fail to achieve a complete cooling effect, the spoiler assembly includes a spoiler fixing ring 3 fixedly connected to the quench box 2, and the spoiler fixing ring 3 is fixed with a plurality of upper U plates 31 with openings facing downward, and a gap is provided between the plurality of upper U plates 31, and the lower end of the spoiler fixing ring 3 is slidably connected with a fixing frame 33, and the fixing frame 33 is fixed with a plurality of lower U plates 32 with openings facing upward, and the fixing frame 33 is provided with teeth 37, and the upper end of the transmission rod 7 is fixed with a transmission ring 34, and 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 and connected, and the second reciprocating gear 36 is meshed and connected with the teeth 37 on the fixing frame 33, and the outer wall of the transmission ring 34 is provided with If there is a group of semi-toothed rings and no teeth at other positions, the distance between each group of semi-toothed rings is smaller than the distance between the two points where the first reciprocating gear 35, the second reciprocating gear 36 and the transmission ring 34 contact, and the transmission ring 34 is driven to rotate by the transmission rod 7. Since the semi-toothed rings of the transmission ring 34 are multiple groups of non-adjacent semi-toothed rings, when the transmission ring 34 rotates, it will transmit with the second reciprocating gear 36, and 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 transmission ring 34 will rotate. When the first reciprocating gear 35 and the second reciprocating gear 36 are closed, the second reciprocating gear 36 is engaged with the teeth 37 to drive the fixed frame 33 to rotate in the opposite direction, thereby realizing the reciprocating swing effect of the fixed frame 33. When the by-product sulfur vapor enters the quench box 2, it will first impact the upper U plate 31 to disperse the by-product sulfur vapor. In addition, the reciprocating movement of the fixed frame 33 drives the lower U plate 32 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.

[0029] See also Figure 3 and Fig.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.

[0030] When the present invention is used: 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 by heating to recover carbon disulfide and methyl / ethyl chloride products, and other low-boiling point organic impurities are separated; sulfur is recrystallized and precipitated and retained in the reactor; 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. 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. Finally, the obtained solid enters into a mixing container and is introduced into carbon disulfide to separate the insoluble sulfur from the soluble sulfur; after the insoluble sulfur is separated, it is dried in a fluidized bed 60 and then packaged, and the carbon disulfide vapor generated in the fluidized bed 60 is condensed and reflowed into the reactor 30; the sulfur dissolved in the carbon disulfide is recycled to the dissolution reactor 70 for use in the next batch, or it can be directly reflowed into the reactor 30.

[0031] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that 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 methyl / ethyl by-product sulfur, 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 methyl / ethyl by-product sulfur 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. The device for preparing insoluble sulfur by comprehensively utilizing methyl / ethyl by-product sulfur 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 methyl / ethyl by-product sulfur 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. The device for preparing insoluble sulfur by comprehensively utilizing methyl / ethyl by-product sulfur 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 methyl / ethyl by-product sulfur 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 methyl / ethyl by-product sulfur 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 methyl / ethyl by-product sulfur 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 methyl / ethyl by-product sulfur, characterized in that: The device for preparing insoluble sulfur by comprehensively utilizing methyl / ethyl by-product sulfur 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 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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