CN111377411B - Insoluble sulfur production method and production system - Google Patents
Insoluble sulfur production method and production system Download PDFInfo
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- CN111377411B CN111377411B CN201811643338.3A CN201811643338A CN111377411B CN 111377411 B CN111377411 B CN 111377411B CN 201811643338 A CN201811643338 A CN 201811643338A CN 111377411 B CN111377411 B CN 111377411B
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 198
- 239000011593 sulfur Substances 0.000 title claims abstract description 197
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 197
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 100
- 239000000463 material Substances 0.000 claims abstract description 119
- 238000010791 quenching Methods 0.000 claims abstract description 115
- 230000000171 quenching effect Effects 0.000 claims abstract description 111
- 238000000605 extraction Methods 0.000 claims abstract description 109
- 239000007788 liquid Substances 0.000 claims abstract description 55
- 238000001035 drying Methods 0.000 claims abstract description 46
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 28
- 238000007599 discharging Methods 0.000 claims abstract description 18
- 239000002245 particle Substances 0.000 claims description 49
- 239000007789 gas Substances 0.000 claims description 41
- 239000007791 liquid phase Substances 0.000 claims description 41
- 239000003795 chemical substances by application Substances 0.000 claims description 38
- 239000007787 solid Substances 0.000 claims description 37
- 239000000047 product Substances 0.000 claims description 33
- 239000007790 solid phase Substances 0.000 claims description 31
- 238000009826 distribution Methods 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 26
- 238000000926 separation method Methods 0.000 claims description 24
- 238000009833 condensation Methods 0.000 claims description 23
- 230000005494 condensation Effects 0.000 claims description 23
- 239000012071 phase Substances 0.000 claims description 18
- 239000012043 crude product Substances 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 238000005243 fluidization Methods 0.000 claims description 12
- 238000003860 storage Methods 0.000 claims description 12
- 239000003381 stabilizer Substances 0.000 claims description 10
- 239000003999 initiator Substances 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000007790 scraping Methods 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000004064 recycling Methods 0.000 claims description 4
- 239000008234 soft water Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000000084 colloidal system Substances 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 239000005864 Sulphur Substances 0.000 claims 1
- 238000005469 granulation Methods 0.000 abstract description 10
- 230000003179 granulation Effects 0.000 abstract description 10
- 238000010924 continuous production Methods 0.000 abstract description 4
- 125000004122 cyclic group Chemical group 0.000 abstract description 2
- 230000000694 effects Effects 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000001816 cooling Methods 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- -1 preferably 0.3-0.4% Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005491 wire drawing Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/02—Preparation of sulfur; Purification
- C01B17/12—Insoluble sulfur (mu-sulfur)
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
The invention discloses a production method and a production system of insoluble sulfur, wherein the production system comprises a polymerization kettle, a quenching device and a drying and curing unit; the discharge port of the polymerization kettle is communicated with the feed inlet of the quenching device through a pipeline, and the discharge port of the quenching device is communicated with the inlet of the drying unit through a pipeline; the quenching device comprises a shell, and the shell comprises a feeding quenching section, a material conveying section and a discharging section according to the material flowing direction; the feeding quenching section is internally provided with a feeding distributor and a quenching liquid distributor, the material conveying section comprises a plurality of layers of conveying belts, both ends of each layer of conveying belt are respectively provided with a fixed rotating shaft, and a discharger is arranged in the discharging section. Also provides a production method adopting the production system. The insoluble sulfur production method and the production system can realize continuous quenching and continuous extraction of the polymerized sulfur through continuous granulation, continuous conveying and continuous and cyclic extraction of the extractant, ensure the purity, the thermal stability and the yield of the product, and are suitable for large-scale continuous production.
Description
Technical Field
The invention belongs to the technical field of petrochemical industry, and relates to a production method and a production system of insoluble sulfur.
Background
Along with the rapid increase of petroleum consumption, global petroleum resources are increasingly in short supply, and the heavy and inferior of refinery raw materials are increasingly serious; meanwhile, environmental regulations of various countries are becoming strict, and the total sulfur content of petroleum products and natural gas is controlled more and more strictly. Therefore, the capacity of the sulfur recovery device of each large refinery and natural gas purification plant is rapidly increased. The common sulfur has saturated market at home and abroad, so the cost is low. How to provide high-added-value sulfur products with short market becomes the focus of the related enterprises.
The insoluble sulfur is a high-efficiency rubber vulcanizing agent, has the advantages of good distribution stability in rubber materials, uniform vulcanization crosslinking points of products and the like, can overcome surface blooming of the rubber materials, and improves the bonding property of rubber and steel wires or chemical fiber cords. From the international market, only a few countries and regions (e.g., usa, russia, japan, germany, france, india, and eastern europe, etc.) are currently producing insoluble sulfur.
Patent CN102070127A discloses a method for producing insoluble sulfur, which comprises the following steps: (1) melt polymerization; (2) atomizing and cold extracting; (3) curing; (4) carrying out centrifugal separation; (5) continuously drying; (6) crushing, screening and oil filling to obtain a finished product; the method is a continuous production method, but the method has high sulfur polymerization operation temperature and pressure, the operation temperature is 580-690 ℃, the operation pressure is 0.8-1.2 MPa, and the requirement on reaction equipment is high.
Patent CN107337184A discloses a heat-resistant stable insoluble sulfur and its production method, which comprises (1) premelting: putting raw material industrial sulfur into a sulfur melting pool at the temperature of 130-; (2) reaction: introducing liquid sulfur into a reaction kettle in N2Under the protection effect and the mechanical stirring condition, the temperature is adjusted to 240 ℃, 0.6 percent of KI is added, and the reaction is carried out for a period of time; (3) quenching: putting the product obtained in the step (2) into a reactor containing N2Gasifying the gas in the gasification chamber to form superheated steam, and spraying the superheated steam into quenching liquid for quenching; (4) and (3) extraction: extracting sulfur in the quenching liquid by using an organic solvent; (5) crushing: drying the extracted sulfur in a dryer at 45-50 ℃ until the water content is reduced to 2-4% of that before drying, then grinding in a tube mill, and crushing and sieving with a 400-mesh sieve of 300 meshes to obtain the heat-resistant stable insoluble sulfur.
At present, insoluble sulfur produced by the existing low-temperature melting method has poor thermal stability, low yield and complex systematic continuous operation process.
CN207435026U discloses an insoluble sulfur quenching device with rapid quenching and atomizing effects, which comprises a box body, wherein the bottom of the surface of an inner cavity of the box body is fixedly connected with a first supporting plate, the right side of the top of the first supporting plate is fixedly connected with a second supporting plate, one end of the second supporting plate, which is far away from the first supporting plate, is fixedly connected with the top of the inner cavity of the box body, and the second supporting plate divides the box body into a cooling box and a heat preservation box; the right side of the bottom of the inner cavity of the box body is fixedly connected with a refrigerator. According to the invention, the effect of discharging cold air into the cooling box and the heat preservation box is achieved by arranging the refrigerating machine and the fan, the effect of blowing the cold air into the cooling box is achieved by the first spray head, the effect of stirring and mixing water and insoluble sulfur is achieved by the stirring box, the effect of sucking the water and the insoluble sulfur is achieved by the water pump and the water inlet pipe, the atomization effect is achieved by the second spray head, the insoluble sulfur can be effectively cooled and atomized, and the use of people is facilitated.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide an insoluble sulfur production method and an insoluble sulfur production system, wherein the insoluble sulfur production method and the insoluble sulfur production system can realize continuous quenching and continuous extraction of polymerized sulfur through continuous granulation, continuous conveying and continuous and cyclic extraction of an extracting agent, ensure the purity, the thermal stability and the yield of a product, are suitable for large-scale continuous production, and have the characteristics of safety, reliability, simple equipment and operation, low operation cost, obvious energy-saving effect and the like in the production process.
The invention provides an insoluble sulfur production system, which comprises a polymerization kettle, a quenching device and a drying and curing unit; the discharge port of the polymerization kettle is communicated with the feed inlet of the quenching device through a pipeline, and the discharge port of the quenching device is communicated with the inlet of the drying unit through a pipeline.
In the insoluble sulfur production system, the quenching device comprises a shell, and the shell internally comprises a feeding quenching section, a material conveying section and a discharging section according to the material flowing direction; the feeding quenching section is internally provided with a feeding distributor and a quenching liquid distributor, the material conveying section comprises a plurality of layers of conveying belts, both ends of each layer of conveying belt are respectively provided with a fixed rotating shaft, and a discharger is arranged in the discharging section.
In the quenching device, the shells of the feeding quenching section and the material conveying section are of square structures, and the shell of the discharging section is of an inverted cone structure.
In the quenching device, the feeding distributor comprises a feeding pipe and a rake type distribution pipe, and the material enters the rake type distribution pipe through the feeding pipe; the rake type distribution pipe comprises a fixed pipe and a rotating pipe, the fixed pipe is positioned inside the rotating pipe, and the outer diameter of the fixed pipe is consistent with the inner diameter of the rotating pipe; a material outlet channel is formed in the axial direction of the fixed pipe; a plurality of rows of perforated strip seams are uniformly distributed in the axial direction of the rotating pipe, 2-12 rows of the perforated strip seams are arranged in the belt empty strip seams, 4-10 rows are preferred, the size of a hole in each row of the perforated strip seams is 0.5-3 mm, 1-2 mm is preferred, the distance between two adjacent holes is 3-15 mm, 5-12 mm is preferred, and the shape of the hole is one or more of a circle, a polygon and an ellipse.
In the quenching device, the material outlet channel can be a strip seam with a plurality of holes or a strip seam with a through hole, and the width of the strip seam is 2-10 mm, preferably 3-6 mm. When the material outlet channel is a slit with a plurality of holes, the size of the holes is 0.5-3 mm, preferably 1-2 mm, and the distance between every two adjacent holes is 3-15 mm, preferably 5-12 mm. The shape of the hole can be any one of circular, polygonal and elliptical shapes according to requirements.
In the quenching device, the rotary pipe in the feeding distributor and the rotary pipe of the quenching liquid distributor are respectively connected with a driving device through gears or belts and used for driving the rotary pipes to rotate, and the driving device can be a motor and the like.
In the quenching device, the quenching liquid distributor comprises a feed pipe and a rake type distribution pipe, and the quenching liquid enters the rake type distribution pipe through the feed pipe; the rake type distribution pipe comprises a fixed pipe and a rotating pipe, the fixed pipe is arranged in the rotating pipe, and the outer diameter of the fixed pipe is consistent with the inner diameter of the rotating pipe; a quenching liquid outlet channel is formed in the axial direction of the fixed pipe, and the direction of the quenching liquid outlet channel is positioned at the bottom of the fixed pipe; a plurality of seams are uniformly distributed in the axial direction of the rotating pipe, a scraping blade is arranged on one side of each seam of the rotating pipe, the number of the seams is 2-12, 4-10 is preferred, and the width of each seam is 5-20 mm, 8-16 mm is preferred.
In the quenching device, the quenching liquid outlet channel is a strip seam with a through hole, and the width of the strip seam is 10-40 mm, preferably 20-35 mm.
In the quenching device, the direction of the material outlet channel of the feeding distributor is positioned in the direction of the radial 45-degree angle tangency of the rake type distribution pipe of the feeding distributor and the rake type distribution pipe of the quenching liquid distributor.
In the quenching device, the distance between two adjacent layers of conveying belts is 15-50 mm, preferably 20-40 mm, the number of layers of the conveying belts is related to the residence time of materials in the quenching device, and the movement speed of the conveying belts is 1-50 mm/s, preferably 3-10 mm/s. The length of each conveying belt is 1-6 m, and preferably 2-4 m.
In the quenching device, the conveyer belt is connected with the driving device, and the driving device drives the conveyer belt to operate for conveying materials. The driving device comprises a driving motor and a driving gear, the driving motor drives the driving gear to rotate, and the driving gear drives the fixed rotating shaft of the conveying belt to rotate. The drive motor may be arranged inside or outside the quenching device, preferably outside the quenching device.
In the quenching device, the discharger is a rake type stirring discharger.
In the insoluble sulfur production system, the production system also comprises an extraction unit, and a discharge hole of the dryer is communicated with a feed inlet of the extraction unit through a pipeline.
The extraction unit comprises a first-stage fluidized bed extraction tower, a first-stage cyclone separator, a liquid phase crusher, a second-stage fluidized bed extraction tower, a second-stage cyclone separator, a dryer, a gas-solid cyclone separator, a condensation separator and an extractant storage tank; wherein: the material outlet of the first-stage fluidized bed extraction tower is communicated with the feed inlet of the first-stage cyclone separator through a pipeline, the solid phase material outlet at the bottom of the first-stage cyclone separator is communicated with the feed inlet of the second-stage fluidized bed extraction tower through a liquid phase pulverizer, the material outlet of the second-stage fluidized bed extraction tower is communicated with the feed inlet of the second-stage cyclone separator through a pipeline, the liquid phase material outlet at the top of the second-stage cyclone separator is communicated with the extracting agent feed inlet of the first-stage fluidized bed extraction tower through a pipeline, the solid phase material outlet at the bottom of the second-stage cyclone separator is communicated with the feed inlet of a dryer through a pipeline, the discharge outlet of the dryer is communicated with the inlet of the gas-solid cyclone separator through a pipeline, the gas phase outlet at the top of the gas-solid cyclone separator is communicated with the inlet of a condensation separator through a pipeline, the gas phase material outlet of the condensation separator is communicated with the dry gas inlet of the dryer through a pipeline.
In the extraction unit, the liquid-phase pulverizer may be one or more of a colloid mill, a wet ball mill and the like, preferably a colloid mill, and after treatment by the liquid-phase pulverizer, the sulfur particles are pulverized to 100-300 meshes, preferably 100-200 meshes.
In the extraction unit, the first-stage fluidized bed extraction tower and the second-stage fluidized bed extraction tower are of a reducing hole tower structure, the extraction tower comprises a shell, the shell comprises an expanding section, a vulcanizing section and a separating section from bottom to top, the diameter of the upper part of the expanding section is the same as that of the vulcanizing section, and the diameter of the separating section is 1.2-2 times, preferably 1.3-1.5 times that of the vulcanizing section; the top of the separation section is provided with a feed inlet, the side wall of the shell of the separation section is provided with a material outlet, and the bottom of the expanding section is provided with an extractant feed inlet.
In the extraction unit, the dryer is a fluidized bed dryer, drying gas is introduced from an air inlet at the bottom of the dryer, the drying gas is nitrogen or inert gas, and the temperature of the drying gas is 60-80 ℃, preferably 65-75 ℃.
In the extraction unit, the first-stage cyclone separator, the second-stage cyclone separator and the gas-solid cyclone separator are all devices known to those skilled in the art, and can be commercially available.
In the extraction unit, the cooling mode of the condensation separator adopts water cooling, the structural form of the condensation separator can adopt one or more of a shell-and-tube condensation separator and a tube-plate condensation separator, and the tube-plate condensation separator is preferably adopted.
In the extraction unit, the heater can be heated by low-pressure steam or high-temperature water, preferably high-temperature hot water, and the heater can be one or more of a shell-and-tube heater, a plate heater and the like, preferably a plate heater.
In the extraction unit, a fresh dry gas feed line is provided on the heater.
In the extraction unit, the bottom of the extractant storage tank is provided with a fresh extractant feeding pipeline.
The invention provides a production method of insoluble sulfur, which adopts the insoluble sulfur production system, and the production method comprises the following steps:
(1) preheating liquid sulfur to 110-120 ℃, feeding the liquid sulfur into a polymerization kettle, adding an initiator into the polymerization kettle, and heating to perform polymerization reaction under the protection of nitrogen;
(2) the polymerization reaction effluent obtained in the step (1) enters a quenching unit for treatment;
(3) and (3) drying and curing the product obtained in the step (2) to obtain an insoluble sulfur crude product.
In the production method of insoluble sulfur, the polymerization temperature in the step (1) is 200-270 ℃, and preferably 250-260 ℃; the polymerization time is 30 to 60 minutes, preferably 30 to 45 minutes.
In the insoluble sulfur production method, the initiator in the step (1) adopts one or more of potassium persulfate, dimethyl sulfoxide and the like. The addition amount of the initiator is 0.05wt% -0.3 wt% of the addition amount of the liquid sulfur, and preferably 0.1wt% -0.2 wt%.
In the production method of insoluble sulfur, the quenching temperature in the step (2) is 50-70 ℃, preferably 55-65 ℃, and the quenching time is 30-90 minutes, preferably 45-60 minutes.
In the insoluble sulfur production method, the quenching medium used in the quenching unit in the step (2) is soft water, preferably, a stabilizer is added at the same time, and the stabilizer adopts FeCl3And HNO3And (4) mixing the solution. Stabilizer FeCl3The adding amount is 0.1-0.5% (mass fraction) of the sulfur, preferably 0.3-0.4%, and HNO3The adding amount is 1-5 percent (mass fraction) of the mass of the sulfur, and preferably 2-4 percent.
In the production method of insoluble sulfur, the drying and curing treatment temperature in the step (3) is 55-75 ℃, preferably 60-65 ℃, and the treatment time is 40-55 hours, preferably 45-50 hours.
In the insoluble sulfur production method, the production method further comprises a step (4), wherein the step (4) is to introduce the insoluble sulfur crude product obtained in the step (3) into an extraction unit, contact the insoluble sulfur crude product with an extractant for reaction, and obtain a refined insoluble sulfur product after treatment, and the method specifically comprises the following steps:
the first-stage fluidized bed extraction tower is used for receiving the sulfur crude product and the extractant, and obtaining a 1 st liquid-solid mixed material flow after treatment;
the first-stage cyclone separator is used for receiving the 1 st liquid-solid mixed material flow from the first-stage fluidized bed extraction tower and obtaining a liquid-phase 2 nd material flow and a solid-phase 3 rd material flow after treatment;
the liquid phase pulverizer is used for receiving and processing the solid phase 3 rd material flow from the primary cyclone separator to obtain a pulverized solid phase 3 rd material flow after processing;
the second-stage fluidized bed extraction tower is used for receiving the crushed solid phase 3 rd material flow and the extracting agent from the liquid phase crusher and obtaining a 4 th liquid-solid mixed material flow after treatment;
the liquid phase pulverizer is used for receiving and processing the solid phase 3 rd material flow from the primary cyclone separator to obtain a pulverized solid phase 3 rd material flow after processing;
the second-stage fluidized bed extraction tower is used for receiving the solid-phase 3 rd material flow and the extracting agent from the first-stage cyclone separator and obtaining a 4 th liquid-solid mixed material flow after treatment;
the second-stage cyclone separator is used for receiving the 4 th liquid-solid mixed material flow from the second-stage fluidized bed extraction tower, processing the 4 th liquid-solid mixed material flow to obtain a liquid-phase 5 th material flow and a solid-phase 6 th material flow, and recycling the liquid-phase 5 th material flow serving as an extracting agent to the first-stage fluidized bed extraction tower for use;
the dryer is used for receiving the solid phase 6 th material flow and the drying gas from the secondary cyclone separator, and obtaining a 7 th material flow after drying treatment;
the gas-solid cyclone separator is used for receiving the 7 th material flow from the dryer and obtaining a gas-phase 8 th material flow and an insoluble sulfur product after separation;
a condensation separator for receiving the gas phase 8 th material flow from the gas-solid cyclone separator, and obtaining a gas phase 9 th material flow and a liquid phase 10 th material flow after condensation separation;
an extractant storage tank for receiving a liquid phase 10 th stream from the condensate separator and fresh extractant from the extractant feed line.
In the insoluble sulfur production method, the solid phase 3 rd material flow is treated by a liquid phase pulverizer to obtain a pulverized solid phase 3 rd material flow, and the particle size of the pulverized solid phase 3 rd material flow is 100-300 meshes, preferably 100-200 meshes.
In the insoluble sulfur production method, the liquid-solid volume ratio of the extractant to the sulfur crude product in the first-stage fluidized bed extraction tower is 4-10: 1, preferably 6-8: 1, and the liquid-solid volume ratio of the second-stage fluidized bed extraction tower is 2-6: 1, preferably 2-4: 1.
In the production method of insoluble sulfur, the fluidizing speed of the extractant in the first-stage fluidized bed extraction tower is 3-8 m/s, preferably 4-6 m/s; the fluidizing speed of the extractant in the secondary fluidized bed extraction tower is 0.5-3 m/s, preferably 1-2 m/s.
In the insoluble sulfur production method, the particle size of the sulfur coarse product particles entering the first-stage fluidized bed extraction tower is 1-3 mm, the sulfur coarse product acts with the extractant in the diameter expanding section of the fluidized bed extraction tower, and soluble sulfur in the sulfur coarse product is dissolved in the extractant, so that the particle size and the particle size weight of the sulfur coarse product particles are continuously reduced; the coarse sulfur product with the reduced particle size flows into a fluidization section of the first-stage fluidized bed extraction tower along with the extractant, and the particle size of particles entering the fluidization section is 0.5-3 mm; soluble sulfur is further dissolved in the extracting agent in the fluidization section, under the action of flowing of the extracting agent, particles finally enter the separation section to realize particle size separation of the particles smaller than 1mm, the particles smaller than 1mm obtained by separation enter the first-stage cyclone separator, and the particles larger than 1mm are returned and treated by gravity.
In the production method of insoluble sulfur, the particle size of the coarse sulfur product entering the secondary fluidized bed extraction tower is 100-300 meshes. The coarse sulfur products with the grain sizes of 100-300 meshes react with the extracting agent in the diameter expanding section and the fluidizing section of the fluidized bed, and soluble sulfur in the coarse sulfur products is further dissolved in the extracting agent; the extraction agent is used for cleaning the soluble sulfur on the surfaces of the insoluble sulfur particles in the separation section, so that the purity of the insoluble sulfur product is improved.
In the insoluble sulfur production method, the gas phase 9 th material flow obtained after condensation and separation is heated to 60-80 ℃ by a heater, preferably 65-75 ℃ and then enters a dryer as a drying gas for use.
In the insoluble sulfur production method, the dryer is a fluidized bed dryer, the drying gas is introduced from the air inlet at the bottom of the dryer, the drying gas is nitrogen or inert gas, and the temperature of the drying gas is 60-80 ℃, preferably 65-75 ℃.
In the production method of insoluble sulfur, the extraction temperature in the step (4) is 50-100 ℃, and preferably 60-80 ℃.
In the insoluble sulfur production method of the invention, the extractant can be one or more of cyclohexane, benzene, p-xylene and the like, and preferably p-xylene.
Compared with the prior art, the insoluble sulfur production method and the insoluble sulfur production system have the following advantages:
1. in the insoluble sulfur production method and the production system, continuous granulation, belt conveying quenching, continuous drying curing and extraction are adopted, so that the continuous production process of high-performance insoluble sulfur is realized, the production efficiency is improved, and the yield and the thermal stability of the product are ensured.
2. In the insoluble sulfur production method and the production system, the feeding distributor and the quenching liquid distributor are adopted to carry out rotary distribution granulation and quenching liquid flushing, thereby realizing polymerized sulfur granulation, being beneficial to polymerized sulfur quenching, improving the yield of insoluble sulfur, and solving the problems of high viscosity of polymerized sulfur, difficult granulation, wire drawing and the like during granulation.
3. In the insoluble sulfur production method and the production system, the extraction process adopts a two-stage fluidized bed extraction tower for extraction, and the fluidization effect of a liquid-solid fluidized bed is utilized to realize the continuous extraction process of fluidizing, dissolving and separating sulfur particles in an extractant, thereby enhancing the dissolving and extracting effect of the extractant on soluble sulfur; along with the sequential flow of the extracting agent in the diameter expanding section, the fluidizing section and the separating section in the fluidized bed, the particle size and the weight of the sulfur particles are continuously reduced, and the effect of separating soluble sulfur from insoluble sulfur is achieved.
4. In the insoluble sulfur production method and the production system, the crude sulfur product is extracted by the first-stage fluidized bed and then subjected to liquid-phase crushing, and finally, in the process of further extracting by the second-stage fluidized bed, the first-stage fluidized bed reduces the treatment scale of the liquid-phase crusher after extracting soluble sulfur, and the liquid-phase crusher reduces the particle size of sulfur particles after crushing, thereby enhancing the extraction effect of the second-stage fluidized bed. The whole process realizes the processes of continuous extraction, crushing, re-extraction and cleaning, and achieves the effect of continuous operation of an extraction system; meanwhile, a liquid phase crushing mode is adopted, the problem that the thermal stability and yield of the product are influenced by temperature rise when sulfur particles are crushed due to the existing two-stage dry type crushing is avoided, the performance of the product is ensured, and the problems that the extraction efficiency is low and the product purity does not reach the standard in the existing extraction system are solved.
5. In the insoluble sulfur production method and the production system, fresh extractant firstly enters a second-stage fluidized bed extraction tower, crushed sulfur particles are further extracted and cleaned, and then second-stage cyclone separation liquid is used as extraction liquid of a first-stage fluidized bed extraction tower; compared with an intermittent extraction mode, the utilization effect of the extracting agent is improved, the using amount of the extracting agent is reduced, and the subsequent energy consumption for regenerating the extracting agent and the operation cost of a system are saved.
Drawings
FIG. 1 is a schematic view of an insoluble sulfur production system according to the present invention.
FIG. 2 is a front view of a quenching apparatus in an insoluble sulfur production system according to the present invention.
FIG. 3 is a side view of a quenching apparatus in an insoluble sulfur production system according to the present invention.
FIG. 4 is a top view of a quench device feed distributor and a quench liquid distributor in an insoluble sulfur production system according to the present invention.
FIG. 5 is a front view of a quench device feed distributor and a quench liquid distributor in an insoluble sulfur production system according to the present invention.
FIG. 6 is a schematic diagram of an extraction unit in the insoluble sulfur production system of the present invention.
Detailed Description
The following examples further illustrate specific aspects of the present invention, but are not limited to the following examples.
In the description of the present invention, it should be noted that the terms "upper", "lower", "inner", "outer", "top", "bottom", and the like indicate orientations or positional relationships based on those shown in the drawings, and are only for convenience of description and simplicity of description, but do not indicate or imply that the referred device or element must have a specific orientation, be constructed in a specific orientation, and be operated, and thus, should not be construed as limiting the present invention. Furthermore, the terms "first" and "second" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
In the description of the present invention, it should be noted that, unless otherwise explicitly specified or limited, the terms "provided", "disposed", "connected", "mounted", and the like are to be construed broadly, and may be, for example, fixedly connected, detachably connected, or integrally connected; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.
As shown in fig. 1, the present invention provides an insoluble sulfur production system, which comprises a polymerizer 101, a quenching apparatus 102, a drying and curing unit 103; the discharge port of the polymerization kettle 101 is communicated with the feed port of the quenching device 102 through a pipeline, and the discharge port of the quenching device 102 is communicated with the inlet of the drying unit 103 through a pipeline. Further preferably, the insoluble sulfur production system further comprises an extraction unit 104, and the discharge port of the drying unit 103 is communicated with the feed port of the extraction unit 104 through a pipeline.
The specific working process of the insoluble sulfur production system is as follows: preheating the liquid sulfur 100 to 110-120 ℃, feeding the liquid sulfur into a polymerization kettle 101, and simultaneously adding an initiator into the polymerization kettle 101, wherein the addition amount of the initiator is 0.05-0.3 wt% of the addition amount of the liquid sulfur. Heating to 200-270 ℃ under the protection of nitrogen for polymerization reaction, and keeping the temperature for 30-60 minutes; extruding the polymerized liquid sulfur into a quenching device 102 for granulation and quenching, wherein the quenching temperature is 50-70 ℃, and the quenching time is 30-90 minutes; soft water is used as quenching medium, stabilizer is added at the same time, and FeCl is used as stabilizer3And HNO3Mixing the solution; stabilizer FeCl3The addition amount is 0.1-0.5% (mass fraction) of the sulfur, HNO3The adding amount is 1-5 percent (mass fraction) of the mass of the sulfur. The quenched crude product is lifted to a drying and curing unit 103, the drying and curing temperature is 55-75 ℃, and the processing time is 40-55 hours. The dried and cured crude product is then extracted in the extraction unit 104 to obtain an insoluble sulfur product.
As shown in fig. 2, fig. 3, fig. 4 and fig. 5, the quenching apparatus 102 in the insoluble sulfur production system of the present invention is constructed as follows: the quenching device comprises a shell, and the shell comprises a feeding quenching section, a material conveying section and a discharging section according to the material flowing direction; the shell of the feeding quenching section and the shell of the material conveying section are of square structures, and the shell of the discharging section is of an inverted cone structure. A feed distributor 2 and a quenching liquid distributor 3 are arranged in the feed quenching section, the feed distributor 2 comprises a feed pipe 1 and a rake type distribution pipe, and materials enter the rake type distribution pipe through the feed pipe 1; the rake type distribution pipe comprises a fixed pipe 8 and a rotating pipe 9, the fixed pipe 8 is positioned inside the rotating pipe 9, and the outer diameter of the fixed pipe 8 is consistent with the inner diameter of the rotating pipe 9; a material outlet channel is arranged in the axial direction of the fixed pipe 8; the material outlet channel can be a strip seam with a plurality of holes or a strip seam with a through hole, and the width of the strip seam is 2-10 mm, preferably 3-6 mm. When the material outlet channel is a slit with a plurality of holes, the size of the holes is 0.5-3 mm, preferably 1-2 mm, and the distance between every two adjacent holes is 3-15 mm, preferably 5-12 mm. The shape of the hole can be any one of circular, polygonal and elliptical shapes according to requirements. A plurality of rows of perforated strip seams are uniformly distributed in the axial direction of the rotating pipe 8, 2-12 rows, preferably 4-10 rows, of the perforated strip seams are arranged in the belt, the size of a hole in each row of the perforated strip seams is 0.5-3 mm, preferably 1-2 mm, the distance between two adjacent holes is 3-15 mm, preferably 5-12 mm, and the shape of the hole is one or more of a circle, a polygon and an ellipse. The quenching liquid distributor 3 comprises a feeding pipe 15 and a rake type distribution pipe, and the quenching liquid enters the rake type distribution pipe through the feeding pipe 15; the rake type distribution pipe comprises a fixed pipe 10 and a rotating pipe 12, the fixed pipe 10 is arranged in the rotating pipe 12, and the outer diameter of the fixed pipe 10 is consistent with the inner diameter of the rotating pipe 12; a quenching liquid outlet channel 13 is formed in the axial direction of the fixed pipe 10, the quenching liquid outlet channel 13 is a strip seam with a through hole, the width of the strip seam is 10-40 mm, the preferred width is 20-35 mm, and the direction of the quenching liquid outlet channel 13 is positioned at the bottom of the fixed pipe 10; a plurality of seams are uniformly distributed in the axial direction of the rotating pipe 12, a scraping blade 11 is arranged on one side of each seam of the rotating pipe, 2-12 seams are arranged, 4-10 seams are preferably arranged, and the width of each seam is 5-20 mm, preferably 8-16 mm. The direction of the material outlet channel of the feeding distributor 2 is positioned in the direction that the rake type distribution pipe of the feeding distributor 2 is tangential to the radial 45-degree angle of the rake type distribution pipe of the quenching liquid distributor 3. The rotary pipe 9 in the feeding distributor 2 and the rotary pipe 12 of the quenching liquid distributor 3 are both connected with a driving device for driving the rotary pipes to rotate, and the driving device can be a motor and the like. The material conveying section comprises a plurality of layers of conveying belts 4, two ends of each layer of conveying belt 4 are respectively provided with a fixed rotating shaft 17, the distance between every two adjacent layers of conveying belts is 15-50 mm, preferably 20-40 mm, the number of layers of the conveying belts 4 is related to the residence time of materials in the quenching device, and the movement speed of the conveying belts is 1-50 mm/s, preferably 3-10 mm/s. The length of each conveying belt 4 is 1-6 m, preferably 2-4 m, and a discharging device 5 is arranged in the discharging section. The conveyer belt 4 is connected with a driving device, and the driving device drives the conveyer belt to operate for conveying materials. The driving device comprises a driving motor 16 and a driving gear 18, the driving motor 16 drives the driving gear 18 to rotate, and the driving gear 18 drives the fixed rotating shaft 17 of the conveying belt to rotate. The drive motor 16 can be arranged inside or outside the quenching device, preferably outside the quenching device.
The quenching device works as follows: the polymerization sulfur enters a feeding distributor 2 through a feeding pipe 1, is extruded out of the feeding distributor 2 through a strip seam of a fixed pipe 8, and is granulated into sulfur particles with the particle size of 0.5-3 mm along with the anticlockwise rotation of an outer rotating pipe 9; meanwhile, quenching liquid enters the quenching liquid distributor 3 through the feeding pipe 15, the quenching liquid distributor 3 rotates anticlockwise, sulfur particles are scraped from the granulating holes of the rotating pipe 9 of the feeding distributor 2 under the action of the scraping piece 11, and when the rotating pipe 12 of the quenching liquid distributor 3 rotates continuously until the quenching liquid can be discharged from the strip seam 13 on the fixed pipe 10 of the quenching liquid distributor to wash the scraping piece 11, the high-viscosity sulfur particles are washed into the conveying belt 4; the sulfur particles naturally fall into the lower layer of conveying belt on the conveying belt 4 by the upper layer of conveying belt until entering the discharging device 5, and the quenched sulfur particles are discharged out of the quenching device through the discharging pipe 6 by the discharging device 5.
As shown in FIG. 6, the structure of the extraction unit in the insoluble sulfur production system of the present invention is as follows: the extraction unit comprises a first-stage fluidized bed extraction tower 612, a first-stage cyclone separator 614, a liquid phase pulverizer 615, a second-stage fluidized bed extraction tower 616, a second-stage cyclone separator 617, a dryer 619, a gas-solid cyclone separator 620, a condensation separator 622 and an extractant storage tank 627; the primary fluidized bed extraction tower 612 and the secondary fluidized bed extraction tower 616 are of a reducing tower structure, the extraction tower comprises a shell, the shell comprises an expanding section A, a fluidizing section B and a separating section C from bottom to top, the diameter of the upper part of the expanding section A is the same as that of the fluidizing section B, and the diameter of the separating section C is 1.2-2 times, preferably 1.3-1.5 times that of the fluidizing section B; the top of the separation section C is provided with a feed inlet, the side wall of the shell of the separation section C is provided with a material outlet, and the bottom of the diameter expanding section A is provided with an extractant feed inlet. Wherein: the material outlet of the first-stage fluidized bed extraction tower 612 is communicated with the feed inlet of the first-stage cyclone separator 614 through a pipeline, the solid-phase material outlet at the bottom of the first-stage cyclone separator 614 is communicated with the feed inlet of the second-stage fluidized bed extraction tower 616 after passing through a liquid phase crusher 615, and the liquid phase at the top of the first-stage cyclone separator 614 is sent to an extractant regeneration device through a pipeline for recycling. The material outlet of the second-stage fluidized bed extraction tower 616 is communicated with the material inlet of the second-stage cyclone separator 617 through a pipeline, the liquid phase material outlet at the top of the second-stage cyclone separator 617 is communicated with the extractant material inlet of the first-stage fluidized bed extraction tower 612 after passing through a vulcanizing pump 613, the solid phase material outlet at the bottom of the second-stage cyclone separator 617 is communicated with the material inlet of the dryer 619 through a pipeline, the material outlet of the dryer 619 is communicated with the inlet of the gas-solid cyclone separator 620 through a pipeline, the solid phase at the bottom of the gas-solid cyclone separator 620 is an insoluble sulfur solid product 621, the gas phase outlet at the top of the gas-solid cyclone separator 20 is communicated with the inlet of the condensation separator 622 through a pipeline, the gas phase outlet of the condensation separator 622 is communicated with the dry gas inlet of the dryer 619 through a circulating fan 625 after passing through a heater 623, and a fresh dry gas feeding pipeline 624 is arranged on the heater 23. The liquid material outlet of the condensation separator 622 is communicated with an extractant storage tank 627 through a pipeline, the bottom of the extractant storage tank 627 is provided with a fresh extractant feeding pipeline 626, and the discharge port of the extractant storage tank 627 is respectively communicated with the extractant inlet of the second-stage fluidized bed extraction tower 616 and the inlet of the vulcanizing pump 613 through an extractant pump 618.
The specific working process of the extraction unit of the invention is as follows: the sulfur crude product (with the particle size of 1-3 mm) 611 enters a first-stage fluidized bed extraction tower 612, and reacts with an extracting agent in an expanding section A of the fluidized bed extraction tower 612, so that the soluble sulfur in the sulfur crude product 611 is dissolved in the extracting agent, and the particle size weight of the sulfur crude product 611 are continuously reduced; the coarse sulfur product with the reduced particle size flows into a fluidization section B of the first-stage fluidized bed extraction tower 612 along with the extractant, and the particle size of sulfur particles entering the fluidization section B is 0.5-3 mm; the soluble sulfur is further dissolved in the extracting agent in the fluidization section B, under the action of flowing of the extracting agent, sulfur particles finally enter a separation section C for separation, the sulfur particles with the particle size larger than 1mm return to the fluidization section B by gravity for further extraction, the sulfur particles with the particle size smaller than 1mm obtained by separation enter a first-stage cyclone separator 614, the sulfur particles with the particle size smaller than 1mm and the extracting agent realize solid-liquid separation in the first-stage cyclone separator 614, a liquid-phase 2-stream 602 is obtained at the top of the first-stage cyclone separator 614, and a solid-phase 3-stream 603 is obtained at the bottom of the first-stage cyclone separator 614, wherein the liquid-phase 2-stream 602 is recycled to an extracting agent regeneration device, the solid-phase 3-stream 603 enters a liquid-phase pulverizer 615 to pulverize the sulfur particles into 100-300 meshes, the pulverized sulfur particles enter a second-stage fluidized bed extraction tower 16, and the sulfur particles are further extracted by the extracting agent in the second-stage fluidized bed extraction tower 616, Washing, the extracted 4 th liquid-solid mixed stream 604 enters the second-stage cyclone separator 17, separation is realized in the second-stage cyclone separator 617, a liquid-phase 5 th stream 605 and a solid-phase 6 th stream 606 are obtained, and the liquid-phase 5 th stream 5 is conveyed to the first-stage fluidized bed extraction tower 612 through the fluidization pump 613 to be used as an extracting agent. The solid phase 6 th material flow 606 enters a dryer 619 to be contacted with drying gas for drying, the 7 th material flow 607 obtained after drying treatment enters a gas-solid cyclone separator 620 to be separated to obtain an insoluble sulfur solid product 621 and a gas phase 8 th material flow 608, the gas phase 8 th material flow 608 is condensed and separated from the top of the gas-solid cyclone separator 620 to a condensation separator 622 to obtain a gas phase 9 th material flow 609 and a liquid phase 10 th material flow 610 after separation, the liquid phase 10 th material flow 610 is taken as an extracting agent to return to an extracting agent storage tank 627 for recycling, and the separated gas phase 9 th material flow 609 is heated by a heater 23 to be taken as drying gas to enter the dryer through a circulating fan 625 for use. A fresh extracting agent feeding pipeline 626 is arranged at the bottom of the extracting agent storage tank 27, a discharge hole of the extracting agent storage tank 627 is respectively communicated with an extracting agent inlet of the second-stage fluidized bed extracting tower 616 and an inlet of the vulcanizing pump 613 after passing through the extracting agent pump 618, and the extracting agent is used for adjusting the liquid-solid volume ratio of the extracting agent in the first-stage fluidized bed extracting tower 612 and the second-stage fluidized bed extracting tower 616 to the crude sulfur product.
Example 1:
3 tons/hour of liquid sulfur is preheated to 118 ℃ and enters a polymerization kettle, and the amount of the initiator added into the polymerization kettle is 0.1wt% of the amount of the liquid sulfur. Heating to 250 ℃ under the protection of nitrogen for polymerization reaction, and keeping the temperature for 45 minutes; extruding the polymerized liquid sulfur into a quenching device for granulation and quenching, wherein the granulation is strip-shaped particles with the diameter of 2mm, the quenching temperature is 60 ℃, and the quenching time is 60 minutes; soft water is used as quenching medium, and stabilizer FeCl is added3The adding amount is 0.3 percent (mass fraction) of the sulfur mass, HNO3The adding amount is 2 percent of the mass of the sulfur (mass fraction). The quenched crude product is lifted to a drying and curing unitThe drying and curing temperature is 65 ℃, the processing time is 48 hours, and the yield of the insoluble sulfur crude product obtained after drying is 38%. And (4) extracting the dried and cured crude product in an extraction unit. Carbon disulfide is used as an extracting agent, and the extraction temperature of a first-stage fluidized bed extraction tower and a second-stage fluidized bed extraction tower is 80 ℃; 2mm sulfur coarse product particles enter a primary fluidized bed extraction tower, the flow rate of a fluidization section is 5m/s, solid phases of the extracted particles after being separated by a primary cyclone separator enter a liquid phase crusher to be crushed to 150 meshes, the crushed sulfur coarse product is further extracted and cleaned in a secondary fluidized bed extraction tower, the flow rate of the fluidization section of the secondary fluidized bed extraction tower is 1.5m/s, liquid and solid are separated in the secondary cyclone separator, and then the crushed sulfur coarse product is treated by a dryer and a gas-solid cyclone separator to obtain an insoluble sulfur product, the drying temperature is 75 ℃, the condensation temperature of drying gas is 35 ℃, the yield of the obtained insoluble sulfur product is 37.4%, and the mass fraction of the insoluble sulfur is 92.3%.
Claims (33)
1. An insoluble sulfur production system, characterized in that: the production system comprises a polymerization kettle, a quenching device and a drying and curing unit; the discharge port of the polymerization kettle is communicated with the feed inlet of the quenching device through a pipeline, and the discharge port of the quenching device is communicated with the inlet of the drying unit through a pipeline;
the quenching device comprises a shell, and the shell comprises a feeding quenching section, a material conveying section and a discharging section according to the material flowing direction; a feeding distributor and a quenching liquid distributor are arranged in the feeding quenching section, a plurality of layers of conveying belts are arranged in the material conveying section, two ends of each layer of conveying belt are provided with fixed rotating shafts, and a discharger is arranged in the discharging section;
the feed distributor comprises a feed pipe and a rake type distribution pipe, and the material enters the rake type distribution pipe through the feed pipe; the rake type distribution pipe comprises a fixed pipe and a rotating pipe, the fixed pipe is positioned inside the rotating pipe, and the outer diameter of the fixed pipe is consistent with the inner diameter of the rotating pipe; a material outlet channel is formed in the axial direction of the fixed pipe; a plurality of rows of perforated strip seams are uniformly distributed in the axial direction of the rotating pipe;
the quenching liquid distributor comprises a feeding pipe and a rake type distribution pipe, and the quenching liquid enters the rake type distribution pipe through the feeding pipe; the rake type distribution pipe comprises a fixed pipe and a rotating pipe, the fixed pipe is arranged in the rotating pipe, and the outer diameter of the fixed pipe is consistent with the inner diameter of the rotating pipe; a quenching liquid outlet channel is formed in the axial direction of the fixed pipe, a plurality of slits are uniformly distributed in the axial direction of the rotating pipe, and a scraping blade is arranged on one side of each slit of the rotating pipe.
2. The insoluble sulfur production system according to claim 1, wherein: the shell of the feeding quenching section and the shell of the material conveying section are of square structures, and the shell of the discharging section is of an inverted cone structure.
3. The insoluble sulfur production system according to claim 1, wherein: the perforated strip seams are arranged in 2-12 rows, the size of holes in each row of perforated strip seams is 0.5-3 mm, and the distance between every two adjacent holes is 3-15 mm.
4. The insoluble sulfur production system according to claim 1, wherein: the material outlet channel is a strip seam with a plurality of holes or a strip seam with a through hole.
5. The insoluble sulfur production system according to claim 4, wherein: the width of the strip seam is 2-10 mm.
6. The insoluble sulfur production system according to claim 4, wherein: when the material outlet channel is a strip seam with a plurality of holes, the size of the holes is 0.5-3 mm, and the distance between every two adjacent holes is 3-15 mm.
7. The insoluble sulfur production system according to claim 1, wherein: the rotary pipe in the feeding distributor and the rotary pipe of the quenching liquid distributor are respectively connected with a driving device through gears or belts, and the driving device is a motor.
8. The insoluble sulfur production system according to claim 1, wherein: the direction of the quenching liquid outlet channel is positioned at the bottom of the fixed pipe; the strip seam on the rotating pipe is provided with 2-12 strips, and the width of the strip seam is 5-20 mm.
9. The insoluble sulfur production system according to claim 8, wherein: the quenching liquid outlet channel is a strip seam with a through hole, and the width of the strip seam is 10-40 mm.
10. The insoluble sulfur production system according to claim 1, wherein: the direction of the material outlet channel of the feeding distributor is positioned in the direction of the radial 45-degree angle tangency of the rake type distribution pipe of the feeding distributor and the rake type distribution pipe of the quenching liquid distributor.
11. The insoluble sulfur production system according to claim 1, wherein: the distance between two adjacent layers of conveying belts is 15-50 mm, and the length of each conveying belt is 1-6 m.
12. The insoluble sulfur production system according to claim 1, wherein: the conveying belt is connected with the driving device, and the driving device drives the conveying belt to operate and is used for conveying materials.
13. The insoluble sulfur production system of claim 12, wherein: the driving device comprises a driving motor and a driving gear, the driving motor drives the driving gear to rotate, and the driving gear drives the fixed rotating shaft of the conveying belt to rotate.
14. The insoluble sulfur production system according to claim 1, wherein: the discharging device is a rake type stirring discharging device.
15. Insoluble sulphur production system according to any one of claims 1 to 14, wherein: the production system comprises an extraction unit, wherein a discharge hole of the drying unit is communicated with a feed inlet of the extraction unit through a pipeline; the extraction unit comprises a first-stage fluidized bed extraction tower, a first-stage cyclone separator, a liquid phase crusher, a second-stage fluidized bed extraction tower, a second-stage cyclone separator, a dryer, a gas-solid cyclone separator, a condensation separator and an extractant storage tank; wherein: the material outlet of the first-stage fluidized bed extraction tower is communicated with the feed inlet of the first-stage cyclone separator through a pipeline, the solid phase material outlet at the bottom of the first-stage cyclone separator is communicated with the feed inlet of the second-stage fluidized bed extraction tower through a liquid phase pulverizer, the material outlet of the second-stage fluidized bed extraction tower is communicated with the feed inlet of the second-stage cyclone separator through a pipeline, the liquid phase material outlet at the top of the second-stage cyclone separator is communicated with the extracting agent feed inlet of the first-stage fluidized bed extraction tower through a pipeline, the solid phase material outlet at the bottom of the second-stage cyclone separator is communicated with the feed inlet of a dryer through a pipeline, the discharge outlet of the dryer is communicated with the inlet of the gas-solid cyclone separator through a pipeline, the gas phase outlet at the top of the gas-solid cyclone separator is communicated with the inlet of a condensation separator through a pipeline, the gas phase material outlet of the condensation separator is communicated with the dry gas inlet of the dryer through a pipeline.
16. The insoluble sulfur production system of claim 15, wherein: the liquid phase pulverizer selects one or more of a colloid mill and a wet ball mill.
17. The insoluble sulfur production system of claim 15, wherein: the extraction tower comprises a shell, the shell comprises an expanding section, a vulcanizing section and a separating section from bottom to top, the diameter of the upper part of the expanding section is the same as that of the vulcanizing section, and the diameter of the separating section is 1.2-2 times that of the vulcanizing section; the top of the separation section is provided with a feed inlet, the side wall of the shell of the separation section is provided with a material outlet, and the bottom of the expanding section is provided with an extractant feed inlet.
18. The insoluble sulfur production system of claim 15, wherein: the dryer is a fluidized bed dryer, drying gas is introduced from an air inlet at the bottom of the dryer, the drying gas is nitrogen or inert gas, and the temperature of the drying gas is 60-80 ℃.
19. A production method of insoluble sulfur is characterized in that: the production method adopts the insoluble sulfur production system of any one of claims 1 to 14, and comprises the following steps:
(1) preheating liquid sulfur to 110-120 ℃, feeding the liquid sulfur into a polymerization kettle, adding an initiator into the polymerization kettle, and heating to perform polymerization reaction under the protection of nitrogen;
(2) the polymerization reaction effluent obtained in the step (1) enters a quenching device for treatment;
(3) and (3) drying and curing the product obtained in the step (2) to obtain an insoluble sulfur crude product.
20. The process for producing insoluble sulfur according to claim 19, wherein: the polymerization temperature in the step (1) is 200-270 ℃; the polymerization time is 30 to 60 minutes.
21. The process for producing insoluble sulfur according to claim 19, wherein: in the step (1), the initiator is one or more of potassium persulfate and dimethyl sulfoxide; the addition amount of the initiator is 0.05wt% -0.3 wt% of the addition amount of the liquid sulfur.
22. The process for producing insoluble sulfur according to claim 19, wherein: in the step (2), the quenching temperature is 50-70 ℃, and the quenching time is 30-90 minutes.
23. The process for the production of insoluble sulfur according to claim 22, wherein: the quenching medium used in the quenching device in the step (2) is soft water, and meanwhile, a stabilizing agent is added, wherein the stabilizing agent adopts FeCl3And HNO3And (4) mixing the solution.
24. The process for producing insoluble sulfur according to claim 23, wherein: stabilizer FeCl3The adding amount is 0.1-0.5 percent of the mass of the sulfur, and HNO3The adding amount is 1-5% of the mass of the sulfur.
25. The process for producing insoluble sulfur according to claim 19, wherein: in the step (3), the drying and curing treatment temperature is 55-75 ℃, and the treatment time is 40-55 hours.
26. The process for producing insoluble sulfur according to claim 19, wherein: the production method also comprises a step (4), wherein the step (4) is to enable the insoluble sulfur crude product obtained in the step (3) to enter an extraction unit, contact with an extracting agent for reaction, and obtain a refined insoluble sulfur product after treatment, and the production method specifically comprises the following steps:
the first-stage fluidized bed extraction tower is used for receiving the sulfur crude product and the extractant, and obtaining a 1 st liquid-solid mixed material flow after treatment;
the first-stage cyclone separator is used for receiving the 1 st liquid-solid mixed material flow from the first-stage fluidized bed extraction tower and obtaining a liquid-phase 2 nd material flow and a solid-phase 3 rd material flow after treatment;
the liquid phase pulverizer is used for receiving and processing the solid phase 3 rd material flow from the primary cyclone separator to obtain a pulverized solid phase 3 rd material flow after processing;
the second-stage fluidized bed extraction tower is used for receiving the crushed solid phase 3 rd material flow and the extracting agent from the liquid phase crusher and obtaining a 4 th liquid-solid mixed material flow after treatment;
the second-stage cyclone separator is used for receiving the 4 th liquid-solid mixed material flow from the second-stage fluidized bed extraction tower, processing the 4 th liquid-solid mixed material flow to obtain a liquid-phase 5 th material flow and a solid-phase 6 th material flow, and recycling the liquid-phase 5 th material flow serving as an extracting agent to the first-stage fluidized bed extraction tower for use;
the dryer is used for receiving the solid phase 6 th material flow and the drying gas from the secondary cyclone separator, and obtaining a 7 th material flow after drying treatment;
the gas-solid cyclone separator is used for receiving the 7 th material flow from the dryer and obtaining a gas-phase 8 th material flow and an insoluble sulfur product after separation;
a condensation separator for receiving the gas phase 8 th material flow from the gas-solid cyclone separator, and obtaining a gas phase 9 th material flow and a liquid phase 10 th material flow after condensation separation;
an extractant storage tank for receiving a liquid phase 10 th stream from the condensate separator and fresh extractant from the extractant feed line.
27. The process for the production of insoluble sulfur according to claim 26, wherein: the particle size of the crushed solid phase 3 rd material flow is 100-300 meshes.
28. The process for the production of insoluble sulfur according to claim 26, wherein: the liquid-solid ratio of the extractant to the sulfur crude product in the first-stage fluidized bed extraction tower is 4-10: 1, and the liquid-solid ratio of the second-stage fluidized bed extraction tower is 2-6: 1.
29. The process for the production of insoluble sulfur according to claim 26, wherein: the fluidizing speed of the extractant in the first-stage fluidized bed extraction tower is 3-8 m/s; the fluidization speed of the extractant in the secondary fluidized bed extraction tower is 0.5-3 m/s.
30. The process for the production of insoluble sulfur according to claim 26, wherein: and heating the gas-phase 9 th material flow obtained after condensation and separation to 60-80 ℃ by a heater, and then taking the gas as dry gas to enter a dryer for use.
31. The process for the production of insoluble sulfur according to claim 26, wherein: the dryer is a fluidized bed dryer, drying gas is introduced from an air inlet at the bottom of the dryer, the drying gas is nitrogen or inert gas, and the temperature of the drying gas is 60-80 ℃.
32. The process for the production of insoluble sulfur according to claim 26, wherein: in the step (4), the extraction temperature is 50-100 ℃.
33. The process for the production of insoluble sulfur according to claim 26, wherein: the extracting agent is one or more of cyclohexane, benzene and p-xylene.
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| WO2004018356A1 (en) * | 2002-08-22 | 2004-03-04 | Franco Cataldo | Process for the production of polymeric sulphur |
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