CN103539079B - Method for one-step preparation of insoluble sulfur - Google Patents
Method for one-step preparation of insoluble sulfur Download PDFInfo
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- CN103539079B CN103539079B CN201310511388.7A CN201310511388A CN103539079B CN 103539079 B CN103539079 B CN 103539079B CN 201310511388 A CN201310511388 A CN 201310511388A CN 103539079 B CN103539079 B CN 103539079B
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Abstract
The invention relates to a method for one-step preparation of insoluble sulfur. In a production process of insoluble sulfur, rapid cooling is one of very key process steps, realizes an effect of instantly stopping a reversible reaction and further directly affects the content of insoluble sulfur in a product. The method provided by the invention comprises the following steps of directly heating raw material sulfur to 120-150 DEG C, forming a large number of sulfur liquid droplets by centrifugal atomization through an atomizer, and increasing the specific surface area of sulfur; then heating to 180-240 DEG C by circulating hot nitrogen for ring-opening polymerization, and keeping for 2-25 seconds; further cooling by circulating cold nitrogen, and cooling to below 60 DEG C at 2-20 seconds; performing cyclone separation, collecting and packaging to obtain the insoluble sulfur product, wherein the average particle size of the product is 10 mu m-50 mu m; recycling the separated nitrogen. The method provided by the invention has the advantages of simple process, safety, environmental friendliness and low cost.
Description
Technical field
The present invention relates to a kind of method that single stage method prepares insoluble sulfur, particularly utilize spray art and cold nitrogen to insoluble sulfur chilling, effectively contained the carrying out of reversed reaction, obtained the method for insoluble sulfur.This invented technology is simple, safety and environmental protection, cost are low.
Background technology
Insoluble sulfur (IS) is also known as polymerised sulphur, also known as μ type sulphur, referring to the sulphur being insoluble to dithiocarbonic anhydride, is the long chain polymer of sulphur, there is chemistry and physical inertness, in sizing material, distributional stability is good, and goods vulcanization crosslinking point is even, has best no blooming with the rubber of its sulfuration, and effectively can prevent sizing material from the course of processing, occurring early stage incipient scorch and promote the bonding of rubber and steel wire or chemical fibre cord thread, be the dedicated vulcanization agent of radial tyre production.Along with the raising of tire meridian rate, the demand of high quality insoluble sulphur is also increased rapidly.Also a few countries such as the U.S., Germany, Russia, Japan etc. are only had to produce abroad.China will lean on a large amount of import just can satisfy the demands every year.Therefore, the market outlook of domestic insoluble sulfur are very good.
The method of the domestic and international IS of preparation mainly contains high temp. gasification and watery fusion method from temperature point, from quenching medium, can be divided into immersion method and solvent method again.The advantage that high temp. gasification prepares IS is that the content of IS in product is relatively high, and shortcoming is that under whole reaction process is in high-temperature and high-pressure conditions, harsher to the requirement of conversion unit, in production process, potential safety hazard is large.What the difference of watery fusion method and evaporating method was to quench is sulphur melt instead of overheated sulfur vapor, so it is low to have temperature of reaction, equipment corrosion is little, atmospheric operation, less investment, and instant effect operates the advantages such as comparatively safe, but in product, the content of IS is lower.
No matter be evaporating method or scorification, its key problem in technology mainly the choosing of stablizer, the determination of quench liquid and cooling mode.But most domestic manufacturer and part Chinese patent adopt is take water as the method for hardening liquid, what also have part Chinese patent to adopt is the method that dithiocarbonic anhydride and one package stabilizer coordinate in varing proportions.The dispersity of insoluble sulfur taking water as the method production of quench liquid is poor, high high-temp stability can not meet the requirement of radial, in production process, wastewater flow rate is large, environmental issue is given prominence to, and Chinese patent 01101968.9 proposes one " production method of scorification insoluble absolute sulfur " to this specially.Be that the insoluble sulfur that quench liquid is produced can meet the demand of radial substantially with dithiocarbonic anhydride, but only have 42.7 DEG C, flash-point-30 DEG C because of its boiling point, production process is extremely inflammable and explosive.
In addition, the chilling of liquid stream adopts Dumpage type or dropping type substantially, and quenching effect is poor, causes low conversion rate, and this is also that scorification produces the reason of insoluble sulfur content lower than evaporating method.Meanwhile, the thick product of insoluble sulfur of generation is block or particulate state, not easily pulverizes after solidification.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, high, the simple to operate safety of a kind of transformation efficiency, the insoluble sulfur production method that toxicity is little, production cost is low are provided.
The present invention also aims to, at sulphur melt low temperature, be atomized under low viscosity, improve production security, also effectively saved the energy.
Technical scheme of the present invention is:
(1) melting: by raw material sulphur direct heating to 120 ~ 150 DEG C, make its melting;
(2) be atomized: sulphur liquid becomes the sulphur droplet of particle diameter 10 μm ~ 50 μm through spraying gun centrifugal atomizing;
(3) be polymerized: the N2 that heater via is heated to 200 ~ 300 DEG C mixes with sulphur droplet after gas distributor distributes; Sulphur drop stops 2 ~ 25 seconds on tower body top, and nitrogen outlet temperature controls at 180 ~ 240 DEG C;
(4) chilling: the sulphur after polymerization is cooled to-40 ~ 0 DEG C with through refrigerating unit again and nitrogen after gas distributor distributes mixes, and enters tower body bottom, be cooled to less than 60 DEG C at 2 ~ 20 seconds;
(5) be separated packaging: cyclonic separation, collect, packaging, obtains insoluble sulfur product;
Object of the present invention realizes further by following scheme:
In prepared insoluble sulfur product, insoluble sulfur massfraction is higher than 60%.
Selected raw material Sulfur from Sulphur sulphur massfraction >98%.
The nitrogen of discharging from tower body by with residual sulphur separation of particles, recycle.
Common crystallization sulphur is octatomic ring structure, and when reaching certain temperature, ring-opening polymerization forms polymerised sulphur, and the molecular weight of polymerised sulphur can be embodied by viscosity size; The viscosity of sulphur liquid first increases with the rising of temperature, after reduce with the rising of temperature, when about 196 DEG C, viscosity is maximum.The principle that the present invention is based on first is heated to 120 ~ 150 DEG C to sulphur, makes its melting, and now viscosity is very little is convenient to Cemented filling.Then polymerization temperature is heated to it, makes its ring-opening polymerization, form polymerised sulphur, because polymerised sulphur at high temperature belongs to unstable structure, extremely easily to transform to common sulphur, therefore need, to its chilling, at utmost polymerised sulphur structure to be maintained.
Beneficial effect of the present invention
(1) the present invention is at sulphur melt low temperature, is atomized, improves production security under viscosity, has also effectively saved the energy.
(2) the present invention with to insoluble sulfur drop chilling, makes insoluble sulfur content significantly improve by centrifugal atomizing technique and cold nitrogen.The insoluble sulfur particle diameter simultaneously obtained is little, is uniformly dispersed, the series of steps such as the extraction avoided in conventional production process is washed, drying, pulverizing.
(3) technique involved in the present invention is simple, energy consumption is little, security is good, production efficiency is high, is easy to industrialization.
Accompanying drawing explanation
Fig. 1 is liquid stream viscosity with temperature change curve
Fig. 2 is this experiment production technological process
In Fig. 3, embodiment and comparative example, insoluble sulfur DSC schemes
Embodiment
Embodiment 1:
By raw material sulphur direct heating is made its melting to 120 DEG C; Sulphur liquid after melting becomes the sulphur droplet of median size 10 μm under pressure through spraying gun centrifugal atomizing; Heater via is heated to the N of 200 DEG C simultaneously
2mix with sulphur droplet after gas distributor distributes; Sulphur droplet stops 25 seconds on tower body top, and nitrogen outlet temperature controls at 180 DEG C; Sulphur after polymerization is cooled to 0 DEG C with through refrigerating unit again and mixes through the nitrogen that gas distributor distributes, and enters tower body bottom, is cooled to less than 60 DEG C at 2 seconds; Cyclonic separation, collects, and packaging, obtains insoluble sulfur product; The nitrogen of discharging from tower body by with residual sulphur separation of particles, recycle.
Embodiment 2:
Its melting is made by raw material sulphur is heated to 130 DEG C; Sulphur liquid after melting becomes the sulphur droplet of median size 20 μm through spraying gun centrifugal atomizing; Heater via is heated to the N of 230 DEG C simultaneously
2mix with sulphur droplet after gas distributor distributes; Sulphur droplet stops 25 seconds on tower body top, and nitrogen outlet temperature controls at 200 DEG C; Sulphur after polymerization is cooled to-10 DEG C with through refrigerating unit again and mixes through the nitrogen that gas distributor distributes, and enters tower body bottom, is cooled to less than 60 DEG C at 5 seconds; Cyclonic separation, collects, and packaging, obtains insoluble sulfur product; The nitrogen of discharging from tower body by with residual sulphur separation of particles, recycle.
Embodiment 3:
By by raw material sulphur direct heating to 130 DEG C, make its melting; Sulphur liquid becomes the sulphur droplet of median size 20 μm through spraying gun centrifugal atomizing; Heater via is heated to the N of 250 DEG C simultaneously
2mix with sulphur droplet after gas distributor distributes; Sulphur drop stops 20 seconds on tower body top, and nitrogen outlet temperature controls at 210 DEG C; Sulphur after polymerization is cooled to-20 DEG C with through refrigerating unit again and nitrogen after gas distributor distributes mixes, and enters tower body bottom, be cooled to less than 60 DEG C at 5 seconds; Cyclonic separation, collects, and packaging, obtains insoluble sulfur product; The nitrogen of discharging from tower body by with residual sulphur separation of particles, recycle.
Embodiment 4:
By raw material sulphur direct heating is made its melting to 140 DEG C; Sulphur liquid after melting becomes the sulphur droplet of median size 30 μm through spraying gun centrifugal atomizing; Heater via is heated to the N of 250 DEG C simultaneously
2mix with sulphur droplet after gas distributor distributes; Sulphur droplet stops 15 seconds on tower body top, and nitrogen outlet temperature controls at 210 DEG C; Sulphur after polymerization is cooled to-20 DEG C with through refrigerating unit again and nitrogen after gas distributor distributes mixes, and enters tower body bottom, be cooled to less than 60 DEG C at 10 seconds; Cyclonic separation, collects, and packaging, obtains insoluble sulfur product; The nitrogen of discharging from tower body by with residual sulphur separation of particles, recycle.
Embodiment 5:
By by raw material sulphur direct heating to 140 DEG C, make its melting; Sulphur liquid after melting becomes the sulphur droplet of median size 30 μm through spraying gun centrifugal atomizing; Heater via is heated to the N of 260 DEG C simultaneously
2mix with sulphur droplet after gas distributor distributes; Sulphur drop stops 15 seconds on tower body top, and nitrogen outlet temperature controls at 220 DEG C; Sulphur after polymerization is cooled to-30 DEG C with through refrigerating unit again and nitrogen after gas distributor distributes mixes, and enters tower body bottom, be cooled to less than 60 DEG C at 10 seconds; Cyclonic separation, collects, and packaging, obtains insoluble sulfur product; The nitrogen of discharging from tower body by with residual sulphur separation of particles, recycle.
Embodiment 6:
By raw material sulphur direct heating is made its melting to 140 DEG C; Sulphur liquid after melting becomes the sulphur droplet of median size 40 μm through spraying gun centrifugal atomizing; Heater via is heated to the N of 280 DEG C simultaneously
2mix with sulphur droplet after gas distributor distributes; Sulphur droplet stops 10 seconds on tower body top, and nitrogen outlet temperature controls at 230 DEG C; Sulphur after polymerization is cooled to-30 DEG C with through refrigerating unit again and mixes through the nitrogen that gas distributor distributes, and enters tower body bottom, is cooled to less than 60 DEG C at 10 seconds; Cyclonic separation, collects, and packaging, obtains insoluble sulfur product; The nitrogen of discharging from tower body by with residual sulphur separation of particles, recycle.
Embodiment 7:
Its melting is made by raw material sulphur is heated to 150 DEG C; Sulphur liquid after melting becomes the sulphur droplet of median size 40 μm through spraying gun centrifugal atomizing; Heater via is heated to the N of 280 DEG C simultaneously
2mix with sulphur droplet after gas distributor distributes; Sulphur droplet stops 5 seconds on tower body top, and nitrogen outlet temperature controls at 230 DEG C; Sulphur after polymerization is cooled to-40 DEG C with through refrigerating unit again and mixes through the nitrogen that gas distributor distributes, and enters tower body bottom, is cooled to less than 60 DEG C at 15 seconds; Cyclonic separation, collects, and packaging, obtains insoluble sulfur product; The nitrogen of discharging from tower body by with residual sulphur separation of particles, recycle.
Embodiment 8:
By by raw material sulphur direct heating to 150 DEG C, make its melting; Sulphur liquid becomes the sulphur droplet of median size 50 μm through spraying gun centrifugal atomizing; Heater via is heated to the N of 300 DEG C simultaneously
2mix with sulphur droplet after gas distributor distributes; Sulphur drop stops 2 seconds on tower body top, and nitrogen outlet temperature controls at 240 DEG C; Sulphur after polymerization is cooled to-40 DEG C with through refrigerating unit again and nitrogen after gas distributor distributes mixes, and enters tower body bottom, be cooled to less than 60 DEG C at 20 seconds; Cyclonic separation, collects, and packaging, obtains insoluble sulfur product; The nitrogen of discharging from tower body by with residual sulphur separation of particles, recycle.
Comparative example 1:
By raw material sulphur is heated to 180 DEG C, then the mixture in still is poured in the water-bath under room temperature and cool, water is separated, and constant weight is dried at 60 DEG C, finally pulverize in ball mill, and sieve with 325 object standard sieves, obtain the thick product of insoluble sulfur.
Comparative example 2:
By raw material sulphur is heated to 210 DEG C, then the mixture in still is poured in the water-bath under room temperature and cool, water is separated, and constant weight is dried at 60 DEG C, finally pulverize in ball mill, and sieve with 325 object standard sieves, obtain the thick product of insoluble sulfur.
Comparative example 3:
By raw material sulphur is heated to 220 DEG C, then the mixture in still is poured in the water-bath under room temperature and cool, water is separated, and constant weight is dried at 60 DEG C, finally pulverize in ball mill, and sieve with 325 object standard sieves, obtain the thick product of insoluble sulfur.
Comparative example 4:
By raw material sulphur is heated to 240 DEG C, then the mixture in still is poured in the water-bath under room temperature and cool, water is separated, and constant weight is dried at 60 DEG C, finally pulverize in ball mill, and sieve with 325 object standard sieves, obtain the thick product of insoluble sulfur.
Insoluble sulfur performance test results in table 1, embodiment and comparative example
Claims (4)
1. single stage method prepares a method for insoluble sulfur, it is characterized in that:
(1) melting: by raw material sulphur direct heating to 120 ~ 150 DEG C, make its melting;
(2) be atomized: the sulphur liquid after melting becomes the sulphur droplet of 10 μm ~ 50 μm through spraying gun centrifugal atomizing;
(3) be polymerized: heater via is heated to the N of 200 ~ 300 DEG C
2mix with sulphur droplet after gas distributor distributes; Sulphur drop stops 2 ~ 25 seconds on tower body top, and nitrogen outlet temperature controls at 180 ~ 240 DEG C;
(4) chilling: the sulphur after polymerization is cooled to-40 ~ 0 DEG C with through refrigerating unit again and nitrogen after gas distributor distributes mixes, and enters tower body bottom, be cooled to less than 60 DEG C at 2 ~ 20 seconds;
(5) be separated packaging: cyclonic separation, collect, packaging, obtains insoluble sulfur product.
2. insoluble sulfur preparation method according to claim 1, is characterized in that: in prepared insoluble sulfur product, insoluble sulfur massfraction is higher than 60%.
3. insoluble sulfur preparation method according to claim 1, is characterized in that: selected raw material Sulfur from Sulphur sulphur massfraction >98%.
4. insoluble sulfur preparation method according to claim 1, is characterized in that: nitrogen warp and the residual sulphur separation of particles of discharging from tower body, recycle.
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| CN201310511388.7A CN103539079B (en) | 2013-10-25 | 2013-10-25 | Method for one-step preparation of insoluble sulfur |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106829877B (en) * | 2017-03-06 | 2018-10-23 | 杨松 | It is a kind of to prepare insoluble sulfur mist projection granulating tower |
| CN108854930A (en) * | 2018-08-22 | 2018-11-23 | 江苏先导干燥科技有限公司 | A kind of novel intelligent spray reaction device and its reaction method |
| CN111056536A (en) * | 2020-01-15 | 2020-04-24 | 常州领裕干燥工程有限公司 | Rotary kiln type spray reaction device for preparing insoluble sulfur through closed cycle |
| CN111135784A (en) * | 2020-01-15 | 2020-05-12 | 常州领裕干燥工程有限公司 | Spray reaction device for preparing insoluble sulfur by vertical tower type closed cycle |
| CN111039263A (en) * | 2020-01-15 | 2020-04-21 | 常州领裕干燥工程有限公司 | Spray reaction device for preparing insoluble sulfur in closed cycle manner |
| CN111056537A (en) * | 2020-01-15 | 2020-04-24 | 常州领裕干燥工程有限公司 | Spray reaction device for preparing insoluble sulfur by box-type closed cycle |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| GB652421A (en) * | 1947-07-24 | 1951-04-25 | Monsanto Chemicals | Improvements in or relating to the manufacture of insoluble sulphur |
| GB727206A (en) * | 1952-04-28 | 1955-03-30 | Bayer Ag | Production of carbon disulphide-insoluble sulphur |
| ES2171105B1 (en) * | 2000-02-08 | 2003-11-01 | Repsol Petroleo Sa | PROCEDURE FOR THE PRODUCTION OF POLYMER SULFUR. |
| CN1270966C (en) * | 2003-04-24 | 2006-08-23 | 刘强 | One-step method for preparing insolubility sulfur |
| CN1241830C (en) * | 2003-06-04 | 2006-02-15 | 中国科学院大连化学物理研究所 | Method for preparing insoluble sulphur |
| CN101066753B (en) * | 2007-05-29 | 2010-06-02 | 江西恒兴源化工有限公司 | Continuous one-step process for producing insoluble sulphur |
| CN102730648B (en) * | 2012-07-03 | 2013-11-13 | 山东尚舜化工有限公司 | Production method of high-quality insoluble sulfur |
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