CN111377414A - Insoluble sulfur extraction method and system - Google Patents
Insoluble sulfur extraction method and system Download PDFInfo
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- CN111377414A CN111377414A CN201811643431.4A CN201811643431A CN111377414A CN 111377414 A CN111377414 A CN 111377414A CN 201811643431 A CN201811643431 A CN 201811643431A CN 111377414 A CN111377414 A CN 111377414A
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- 238000000605 extraction Methods 0.000 title claims abstract description 138
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 129
- 239000011593 sulfur Substances 0.000 title claims abstract description 127
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 127
- 239000007791 liquid phase Substances 0.000 claims abstract description 45
- 239000007787 solid Substances 0.000 claims abstract description 41
- 238000009833 condensation Methods 0.000 claims abstract description 23
- 230000005494 condensation Effects 0.000 claims abstract description 23
- 238000003860 storage Methods 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims description 88
- 239000002245 particle Substances 0.000 claims description 51
- 239000007789 gas Substances 0.000 claims description 43
- 239000000047 product Substances 0.000 claims description 37
- 239000003795 chemical substances by application Substances 0.000 claims description 29
- 238000001035 drying Methods 0.000 claims description 29
- 239000007790 solid phase Substances 0.000 claims description 29
- 238000000926 separation method Methods 0.000 claims description 25
- 239000012071 phase Substances 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical group O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 8
- 239000012043 crude product Substances 0.000 claims description 7
- 238000004064 recycling Methods 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 4
- 239000001569 carbon dioxide Substances 0.000 claims description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 4
- 239000000084 colloidal system Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 230000008929 regeneration Effects 0.000 claims description 4
- 238000011069 regeneration method Methods 0.000 claims description 4
- 230000000694 effects Effects 0.000 abstract description 14
- 238000010924 continuous production Methods 0.000 abstract description 2
- 238000005243 fluidization Methods 0.000 description 10
- 239000007788 liquid Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 6
- 238000010791 quenching Methods 0.000 description 6
- 230000000171 quenching effect Effects 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 2
- 238000004378 air conditioning Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 241000135164 Timea Species 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution 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
- 238000001914 filtration Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 229910002011 hydrophilic fumed silica Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 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
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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Classifications
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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)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D11/00—Solvent extraction
- B01D11/02—Solvent extraction of solids
- B01D11/0215—Solid material in other stationary receptacles
- B01D11/0253—Fluidised bed of solid materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D11/00—Solvent extraction
- B01D11/02—Solvent extraction of solids
- B01D11/028—Flow sheets
- B01D11/0284—Multistage extraction
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D11/00—Solvent extraction
- B01D11/02—Solvent extraction of solids
- B01D11/0288—Applications, solvents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D11/00—Solvent extraction
- B01D11/02—Solvent extraction of solids
- B01D11/0292—Treatment of the solvent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D11/00—Solvent extraction
- B01D11/02—Solvent extraction of solids
- B01D11/0292—Treatment of the solvent
- B01D11/0296—Condensation of solvent vapours
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Extraction Or Liquid Replacement (AREA)
Abstract
The invention discloses an insoluble sulfur extraction method and an extraction system, wherein the extraction system 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. The insoluble sulfur extraction system and the extraction method can improve the purity of the product, have high thermal stability and product yield, are suitable for large-scale continuous production, and have the advantages of safety, reliability, low operation cost, remarkable energy-saving effect and the like.
Description
Technical Field
The invention relates to the technical field of chemical equipment, in particular to an insoluble sulfur continuous extraction system.
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 CN107324290A discloses a high grade insoluble sulfur extraction process, which comprises the following steps: adding hydrophilic fumed silica and trimethylolpropane into a sodium citrate solution, and uniformly stirring to obtain a mixture; placing the insoluble sulfur crude product and 2-hydroxy-4-n-octoxy benzophenone in a ball mill for grinding and crushing, drying and sieving, then adding the mixture, stirring uniformly and drying for 1-1.5h under the vacuum condition at 60-65 ℃ to obtain powder; mixing the powder material and the composite extracting agent according to the solid-to-liquid ratio of 1:5-6, adjusting the temperature to 75 +/-1 ℃, and carrying out heat preservation reaction for 40-60 min; filtering, separating, reserving filter residue, washing the filter residue with deionized water, 2% sodium sulfite solution and polyethylene glycol respectively, then vacuum drying at 50 ℃, and crushing to obtain the high-grade insoluble sulfur.
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 of (2) and mechanical stirring, the temperature is adjusted to 240 ℃, 0.6% of KI is added, and the reaction is carried out for a period of timeA (c) is added; (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.
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. The utility model discloses a set up refrigerator and fan, reach the effect of discharging into cooler bin and insulation can with air conditioning, through first shower nozzle, reach the effect of blowing in the cooler bin with air conditioning, through the agitator tank, reach the effect of mixing water and insoluble sulphur stirring, through water pump and inlet tube, reach the effect with its suction, through the second shower nozzle, reach atomizing effect, can effectually cool off and atomize insoluble sulphur, make things convenient for people's use. At present, the problems of low extraction efficiency, long time and difficult control of the purity of the product generally exist in the extraction of crude insoluble sulfur.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide an insoluble sulfur extraction method and an insoluble sulfur extraction system, the insoluble sulfur extraction system and the insoluble sulfur extraction method can improve the product purity and the product yield, the obtained product has good thermal stability, is suitable for large-scale continuous production, and has the advantages of safety, reliability, low operation cost, obvious energy-saving effect and the like.
The invention provides an insoluble sulfur extraction system in a first aspect, which 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 first-stage fluidized bed extraction tower is connected with the first-stage cyclone separator; 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.
In the insoluble sulfur extraction system, the liquid phase pulverizer can 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, sulfur particles are pulverized to 100-300 meshes, preferably 100-200 meshes.
In the insoluble sulfur extraction system, a first-stage fluidized bed extraction tower and a 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 fluidizing 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 fluidizing section, and the diameter of the separating section is 1.2-2 times, preferably 1.3-1.5 times that of the fluidizing 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 insoluble sulfur extraction system, the dryer is a fluidized bed dryer, drying gas is introduced from a gas 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 insoluble sulfur extraction system, 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 insoluble sulfur extraction system, the cooling mode of the condensation separator can adopt water cooling, and 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, preferably a tube-plate condensation separator.
In the insoluble sulfur extraction system, the heater can adopt low-pressure steam heating and high-temperature water heating, preferably high-temperature water heating, and the structural form of the heater can adopt one or more of a shell-and-tube heater, a plate heater and the like, preferably a plate heater.
In the insoluble sulfur extraction system, the dry gas is nitrogen or inert gas, the dry gas is recycled, and a fresh dry gas feeding pipeline is arranged on the heater.
In the insoluble sulfur extraction system, the bottom of the extractant storage tank is provided with a fresh extractant feeding pipeline.
In a second aspect, the present invention provides a method for extracting insoluble sulfur, comprising the following steps:
the first-stage fluidized bed extraction tower is used for receiving the sulfur coarse product particles 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, treating the 1 st liquid-solid mixed material flow to obtain a liquid-phase 2 nd material flow and a solid-phase 3 rd material flow, and recycling the liquid-phase 2 nd material flow to an extractant regeneration device;
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.
In the insoluble sulfur extraction 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 extraction 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 insoluble sulfur extraction method, 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 extraction 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 an extractant in a 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 insoluble sulfur extraction method, the particle size of the sulfur coarse 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 extraction method of the present invention, the extractant may be carbon dioxide and/or paraxylene, preferably carbon dioxide.
In the insoluble sulfur extraction 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 method for extracting insoluble sulfur, the dryer is a fluidized bed dryer, the drying gas is introduced from a gas 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 ℃.
Compared with the prior art, the insoluble sulfur extraction system and the extraction method have the following advantages:
1. in the insoluble sulfur extraction method, 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 fluidization, dissolution and separation of sulfur particles in an extractant, thereby enhancing the dissolution and extraction effects 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.
2. In the insoluble sulfur extraction method, 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 processing 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.
3. In the insoluble sulfur extraction method, 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 a continuous extraction system for insoluble sulfur according to the present invention.
Detailed Description
The following description will further illustrate specific aspects of the present invention by way of the drawings in conjunction with the detailed description, but is 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 figure 1, the invention provides a continuous extraction system for insoluble sulfur, which comprises a first-stage fluidized bed extraction tower 12, a first-stage cyclone separator 14, a liquid phase pulverizer 15, a second-stage fluidized bed extraction tower 16, a second-stage cyclone separator 17, a dryer 19, a gas-solid cyclone separator 20, a condensation separator 22 and an extractant storage tank 27; the primary fluidized bed extraction tower 12 and the secondary fluidized bed extraction tower 16 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 12 is communicated with the feed inlet of the first-stage cyclone separator 14 through a pipeline, the solid-phase material outlet at the bottom of the first-stage cyclone separator 14 is communicated with the feed inlet of the second-stage fluidized bed extraction tower 16 after passing through a liquid phase crusher 15, and the liquid phase at the top of the first-stage cyclone separator 14 is conveyed to an extractant regeneration device through a pipeline for recycling. The material outlet of the second-stage fluidized bed extraction tower 16 is communicated with the feed inlet of the second-stage cyclone separator 17 through a pipeline, the liquid phase material outlet at the top of the second-stage cyclone separator 17 is communicated with the extracting agent feed inlet of the first-stage fluidized bed extraction tower 12 after passing through the vulcanizing pump 13, the solid phase material outlet at the bottom of the second-stage cyclone separator 17 is communicated with the feed inlet of the dryer 19 through a pipeline, the discharge outlet of the dryer 19 is communicated with the inlet of the gas-solid cyclone separator 20 through a pipeline, the solid phase at the bottom of the gas-solid cyclone separator 20 is an insoluble sulfur solid product 21, the gas phase outlet at the top of the gas-solid cyclone separator 20 is communicated with the inlet of the condensation separator 22 through a pipeline, the gas phase outlet of the condensation separator 22 is communicated with the dry gas inlet of the. The outlet of the liquid phase material of the condensation separator 22 is communicated with an extractant storage tank 27 through a pipeline, the bottom of the extractant storage tank 27 is provided with a fresh extractant feeding pipeline 26, and the discharge port of the extractant storage tank 27 is respectively communicated with the extractant inlet of the second-stage fluidized bed extraction tower 16 and the inlet of the vulcanizing pump 13 after passing through the extractant pump 18.
The specific working process of the extraction system is as follows: the method comprises the following steps that (1) a sulfur crude product (with the particle size of 1-3 mm) 11 enters a first-stage fluidized bed extraction tower 12 and reacts with an extracting agent in an expanding section A of the fluidized bed extraction tower 12, and soluble sulfur in the sulfur crude product 11 is dissolved in the extracting agent, so that the particle size and the particle size weight of the sulfur crude product 11 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 12 along with the extractant, and the particle size of sulfur particles entering the fluidization section B is 0.5-3 mm; soluble sulfur is further dissolved in an extracting agent in a 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 virtue of gravity for further extraction, the sulfur particles with the particle size smaller than 1mm obtained by separation enter a primary cyclone separator 14, the sulfur particles with the particle size smaller than 1mm and the extracting agent realize solid-liquid separation in the primary cyclone separator 14, a liquid phase 2-th material flow 2 is obtained at the top of the primary cyclone separator 14, and a solid phase 3-th material flow 3 is obtained at the bottom of the primary cyclone separator 14, wherein the liquid phase 2-th material flow 2 is recycled to an extracting agent regeneration device, the solid phase 3-th material flow 3 enters a liquid phase pulverizer 15 to pulverize the sulfur particles into 100-300 meshes, the pulverized sulfur particles enter a secondary fluidized bed extraction tower 16, and the sulfur particles are further extracted by, Cleaning, feeding the extracted 4 th liquid-solid mixed material flow 4 into a second-stage cyclone separator 17, separating in the second-stage cyclone separator 17 to obtain a liquid-phase 5 th material flow 5 and a solid-phase 6 th material flow 6, and conveying the liquid-phase 5 th material flow 5 to the first-stage fluidized bed extraction tower 12 through a fluidization pump 13 to be used as an extracting agent. The solid phase 6 th material flow 6 enters a dryer 19 and contacts with a drying gas for drying, the 7 th material flow 7 obtained after drying treatment enters a gas-solid cyclone separator 20, an insoluble sulfur solid product 21 and a gas phase 8 th material flow 8 are obtained through separation, the gas phase 8 th material flow 8 is condensed and separated from the top of the gas-solid cyclone separator 20 to a condensation separator 22, a gas phase 9 th material flow 9 and a liquid phase 10 th material flow 10 are obtained after separation, the liquid phase 10 th material flow 10 is used as an extracting agent and returned to an extracting agent storage tank 27 for recycling, and the separated gas phase 9 th material flow 9 is heated by a heater 23 and then enters the dryer as a drying gas through a circulating fan 25 for use. A fresh extractant feeding pipeline 26 is arranged at the bottom of the extractant storage tank 27, a discharge port of the extractant storage tank 27 is respectively communicated with an extractant inlet of the second-stage fluidized bed extraction tower 16 and an inlet of the vulcanizing pump 13 after passing through the extractant pump 18, and the extractant is used for adjusting the liquid-solid volume ratio of the extractant in the first-stage fluidized bed extraction tower 12 and the second-stage fluidized bed extraction tower 16 to the crude sulfur product.
Example 1:
carbon disulfide is used as an extracting agent, sulfur coarse product particles (3 mm) enter a primary fluidized bed extraction tower, the flow rate of a fluidizing section is 6m/s, the solid phase of the extracted particles after being separated by a primary cyclone separator enters a liquid phase crusher to be crushed to 100 meshes, the crushed sulfur coarse product is further extracted and cleaned in a secondary fluidized bed extraction tower, the flow rate of the fluidizing section of the secondary fluidized bed extraction tower is 2m/s, the sulfur coarse product is subjected to liquid-solid separation in the secondary cyclone separator, and then is treated by a dryer and a gas-solid cyclone separator to obtain an insoluble sulfur product, the drying temperature is 65 ℃, the condensation temperature of dried gas is 35 ℃, the yield of the obtained insoluble sulfur product is 38%, and the mass fraction of the insoluble sulfur is 91.5%.
Example 2:
carbon disulfide is used as an extracting agent, sulfur coarse product particles (2 mm) enter a primary fluidized bed extraction tower, the flow rate of a fluidizing section is 5m/s, a solid phase of the extracted particles after being separated by a primary cyclone separator enters a liquid phase crusher to be crushed to 200 meshes, the crushed sulfur coarse product is further extracted and cleaned in a secondary fluidized bed extraction tower, the flow rate of the fluidizing section of the secondary fluidized bed extraction tower is 1.5m/s, liquid and solid are separated in the secondary cyclone separator, and then an insoluble sulfur product is obtained after being processed by a drier and a gas-solid cyclone separator, the drying temperature is 63 ℃, the condensation temperature of drying gas is 40 ℃, the yield of the obtained insoluble sulfur product is 37%, and the mass fraction of the insoluble sulfur is 92.1%.
Claims (14)
1. An insoluble sulfur extraction system 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.
2. The insoluble sulfur extraction system of claim 1, wherein: the liquid phase pulverizer selects one or more of a colloid mill and a wet ball mill, and preferably selects the colloid mill.
3. The insoluble sulfur extraction system of claim 1, wherein: the extraction tower comprises a shell, wherein the shell comprises an expanding section, a fluidizing 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 fluidizing section, and the diameter of the separating section is 1.2-2 times, preferably 1.3-1.5 times that of the fluidizing 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.
4. The insoluble sulfur extraction system of claim 1, wherein: the dryer is a fluidized bed dryer, drying gas is introduced from a gas 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 ℃.
5. The insoluble sulfur extraction system of claim 1, wherein: the bottom of the extractant storage tank is provided with a fresh extractant feeding pipeline.
6. An insoluble sulfur extraction process, comprising:
the first-stage fluidized bed extraction tower is used for receiving the sulfur coarse product particles 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, treating the 1 st liquid-solid mixed material flow to obtain a liquid-phase 2 nd material flow and a solid-phase 3 rd material flow, and recycling the liquid-phase 2 nd material flow to an extractant regeneration device;
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.
7. The insoluble sulfur extraction process of claim 6, wherein: the particle size of the crushed solid phase 3 rd material flow is 100-300 meshes, and preferably 100-200 meshes.
8. The insoluble sulfur extraction process of claim 6, 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, preferably 6-8: 1, and the liquid-solid ratio of the extractant to the sulfur crude product in the second-stage fluidized bed extraction tower is 2-6: 1, preferably 2-4: 1.
9. The insoluble sulfur extraction process of claim 6, wherein: the fluidizing speed of the extractant in the first-stage fluidized bed extraction tower is 3-8 m/s, and 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.
10. The insoluble sulfur extraction process of claim 6, wherein: the particle size of the sulfur coarse product particles entering the first-stage fluidized bed extraction tower is 1-3 mm.
11. The insoluble sulfur extraction process of claim 6, wherein: the particle size of the sulfur coarse product particles entering the secondary fluidized bed extraction tower is 100-300 meshes.
12. The insoluble sulfur extraction process of claim 6, wherein: the extractant is carbon dioxide and/or paraxylene, preferably carbon dioxide.
13. The insoluble sulfur extraction process of claim 6, wherein: and heating the gas-phase 9 th material flow obtained after condensation and separation to 60-80 ℃ by a heater, preferably 65-75 ℃, and then taking the gas as a drying gas to enter a dryer for use.
14. The insoluble sulfur extraction process of claim 6, wherein: the dryer is a fluidized bed dryer, drying gas is introduced from a gas 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 ℃.
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