CN107200309A - The method that sulphur monomer quenching polymerizate strand end-blocking prepares insoluble sulfur - Google Patents
The method that sulphur monomer quenching polymerizate strand end-blocking prepares insoluble sulfur Download PDFInfo
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- CN107200309A CN107200309A CN201710368856.8A CN201710368856A CN107200309A CN 107200309 A CN107200309 A CN 107200309A CN 201710368856 A CN201710368856 A CN 201710368856A CN 107200309 A CN107200309 A CN 107200309A
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- sulphur
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 184
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 92
- 239000011593 sulfur Substances 0.000 title claims abstract description 92
- 239000005864 Sulphur Substances 0.000 title claims abstract description 66
- 238000010791 quenching Methods 0.000 title claims abstract description 52
- 230000000171 quenching effect Effects 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 35
- 239000000178 monomer Substances 0.000 title claims abstract description 21
- 239000007788 liquid Substances 0.000 claims abstract description 47
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000010792 warming Methods 0.000 claims abstract description 14
- 238000000605 extraction Methods 0.000 claims abstract description 12
- 238000000889 atomisation Methods 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 9
- 238000011049 filling Methods 0.000 claims abstract description 8
- 238000007654 immersion Methods 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 239000000843 powder Substances 0.000 claims abstract description 6
- 238000007259 addition reaction Methods 0.000 claims abstract description 5
- 238000002309 gasification Methods 0.000 claims abstract description 5
- 238000002844 melting Methods 0.000 claims abstract description 4
- 230000008018 melting Effects 0.000 claims abstract description 4
- 239000007921 spray Substances 0.000 claims abstract description 4
- 239000003921 oil Substances 0.000 claims description 15
- 239000003153 chemical reaction reagent Substances 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 10
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 238000003860 storage Methods 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 238000005516 engineering process Methods 0.000 claims description 3
- 239000005543 nano-size silicon particle Substances 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910019213 POCl3 Inorganic materials 0.000 claims description 2
- 239000004480 active ingredient Substances 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- PXJJSXABGXMUSU-UHFFFAOYSA-N disulfur dichloride Chemical compound ClSSCl PXJJSXABGXMUSU-UHFFFAOYSA-N 0.000 claims description 2
- 239000000428 dust Substances 0.000 claims description 2
- 239000007800 oxidant agent Substances 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl chloride Substances ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 abstract description 4
- 239000000047 product Substances 0.000 description 25
- 238000009826 distribution Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 235000013339 cereals Nutrition 0.000 description 4
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229920001285 xanthan gum Polymers 0.000 description 3
- 238000001035 drying Methods 0.000 description 2
- 238000007337 electrophilic addition reaction Methods 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 description 1
- -1 heated up Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000007500 overflow downdraw method Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000010092 rubber production Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Classifications
-
- 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
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- 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
- C01P2006/12—Surface area
-
- 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
- C01P2006/32—Thermal properties
- C01P2006/37—Stability against thermal decomposition
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses the method that sulphur monomer quenching polymerizate strand end-blocking prepares insoluble sulfur, following steps are specifically included：(1) melting of raw material sulphur is warming up to flow regime, progressively gasification forms sulfur vapor for liquid sulfur heating；(2) sulfur vapor that step (1) gasifies, sprayed into through shower nozzle in tank, quenching liquid sprays misty liquid droplets by pressurization, and misty liquid droplets are atomized with sulfur vapor contacts the addition reaction for being rapidly completed strand two ends, and cooling obtains the intermediate containing insoluble sulfur；(3) continuous extraction and stably is carried out in the intermediate containing insoluble sulfur that will be produced in step (2), immersion carbon disulfide；(4) material is transferred in drier and dried；(5) rubber special filling oil is filled with, insoluble sulfur product is made.Sulfur vapor is fully contacted with the quenching liquid of high atomisation, and insoluble sulfur is once into powder, after extraction, dry, oil-filled, Quadratic Stability, forms insoluble sulfur product, and heat endurance is improved.
Description
Technical field
The invention belongs to technical field of fine, and in particular to sulphur monomer quenching polymerizate strand end-blocking is prepared not
The method of dissolubility sulphur.
Background technology
Polymerised sulphur is to be formed by high temperature sulphur gas by drastically cooling, is the Main Ingredients and Appearance of insoluble sulfur.Polymerised sulphur is led to
Normal molecular weight is more than 20,000.Polymerised sulphur solubility in CS2 is extremely low, because polymerised sulphur would generally wrap up readily soluble in forming process
In CS2 raw material sulphur, therefore in the production process of insoluble sulfur, generally raw material sulphur is extracted as extractant from CS2
Go out.
Exist under raw material sulphur lower temperature in the form of S8, i.e., eight sulphur atoms form stable octatomic ring, by heating
112 DEG C -149 DEG C of molten condition is reached, now sulphur has preferable mobility；Again through further heating up to be formed 445 DEG C-
720 DEG C of sulfur vapors, the now octatomic ring of the sulphur open loop under high temperature action exists in forms such as S2, S4, S6, high temperature sulphur gas warp
The catenulate polymerised sulphur of the too urgent warm shape of sharp fall.
Drastically cooling make polymerised sulphur strand formed after, due to sulfur molecule electronic structure be 286, the sulphur atom at two ends
Outermost layer is still 6 electronics, in unstable active state.In tire and rubber production process, insoluble sulfur is made
For vulcanization accelerator, the internally mix of rubber is participated in the case where being not less than 100 DEG C, and is acted on simultaneously with a variety of rubber chemicals, gathering now
Sulphur is closed in high temperature or in the presence of having water, alkaline matter, reducing substances etc., strand easily occurs to be disintegrated and revert to elemental sulfur
Octatomic ring rock-steady structure.Therefore the polymerised sulphur without end capping reaction hardly possesses use value.
Whether the production method for the insoluble sulfur reported at present, the temperature heated up according to raw material sulphur reaches atmospheric boiling point temperature
Degree, can be divided into watery fusion method and the major class of high temperature gasification two；According to the species of sulphur quenching medium after heating, it can be divided into water-soluble
Liquid is the water law of quenching medium, using solvent as the solvent method of quenching medium, and the more commonly used solvent is carbon disulfide.Either water law is also
It is solvent method, most of techniques are that liquid or gaseous high temperature sulphur quenching first are turned into the intermediate product of strip or sheet or bulk
Or semi-finished product, then through extraction, dry, crushing, screening, oil-filled finished product, generally existing complex process, production operation environment
The problems such as difference, labor intensity height, product quality fluctuate big, heat endurance and are dispersed poor.For example, with the present invention the most
Close 580-635 DEG C of high temperature sulphur gas method quenching production insoluble sulfur of the use used by patent 104445087, using end
End is stable, and obtained middle product need to crush, complex process.Intermediate after crushing is unformed powder, substantially can shadow
Ring the dispersiveness of product；Insoluble sulfur product is made by later stage stable processing in intermediate, equally can not inherently ensure
Polymerised sulphur strand two ends efficiently accomplish addition reaction, reach the effect of end-blocking.
The content of the invention
For in prior art insoluble sulfur production process, the formation link of the polymerised sulphur existed is extensive, product heat is steady
Qualitative and dispersed dissatisfactory technical problem, it is an object of the invention to provide sulphur monomer quenching polymerizate strand envelope
The method that end prepares insoluble sulfur.
The technical scheme that the present invention takes is：
The method that sulphur monomer quenching polymerizate strand end-blocking prepares insoluble sulfur, specifically includes following steps：
(1) raw material sulphur is melted and is warming up to 112 DEG C -149 DEG C of flow regime, liquid sulfur be warming up to 445 DEG C -720 DEG C by
Step gasification forms sulfur vapor；
(2) sulfur vapor that step (1) gasifies, is sprayed into tank with 300Kg/hr-1200Kg/hr speed through shower nozzle, quenched
Cold hydraulic control temperature is 10 DEG C -40 DEG C and sprays misty liquid droplets by pressurization, and misty liquid droplets are rapidly completed with sulfur vapor atomization contact
The mass velocity ratio of the addition reaction at strand two ends, quenching liquid and sulphur steam is 5~50:1, misty liquid droplets connect with sulfur vapor
Control temperature is less than 110 DEG C during touching, and cooling obtains the intermediate containing insoluble sulfur；
(3) carried out in the intermediate containing insoluble sulfur that will be produced in step (2), immersion carbon disulfide continuous extraction and
It is stable, the insoluble sulfur content of intermediate is reached more than 96.5%；
(4) material is transferred in drier, not higher than 75 DEG C -85 DEG C are dried；
(5) the rubber special filling oil of the nano silicon containing percentage by weight 0.01% is filled with, is made insoluble
Sulfur product.
Further, raw material sulphur uses powder or bulk in the step (1), and melting is warming up to 112 DEG C -125 DEG C of stream
Dynamic state, liquid sulfur is warming up to 460 DEG C of -650 DEG C of formation sulfur vapors further across coil pipe stove or gasification tank.
Further, quenching liquid is the aqueous solution containing end-capping reagent in the step (2), end-capping reagent be containing dust technology and
FeCl3、AlCl3, KCl, KI, KBr inorganic salts one kind, or contain Cl2、Br2Halogen simple substance, or above-mentioned inorganic salts and halogen
One or more of mixtures.
Further, quenching liquid is the solvent containing end-capping reagent in the step (2), and solvent is carbon disulfide or four chlorinations
Carbon, preferably carbon disulfide；End-capping reagent is to contain oxidant or halogen or salt, such as FeCl3、KCl、KI、KBr、I2、Cl2、Br2、
S2Cl2、HClO、NaClO、Ca(ClO)2、SOCl、POCl3One or more of mixtures of active ingredient.
Further, the percentage by weight of end-capping reagent and the aqueous solution is 0.02-0.25 in the quenching liquid：1；Quenching liquid
The percentage by weight of middle end-capping reagent and solvent is 0.02-0.25：1.
Further, quenching hydraulic control temperature is 15 DEG C -30 DEG C in the step (2).
Further, quenching liquid is pressed to form misty liquid droplets, the chi of misty liquid droplets by pump or storage tank in the step (2)
It is very little to be less than 500 microns.
Further, the mass velocity ratio of quenching medium and sulphur is 10~35 in the step (2):1.
Further, temperature is controlled to be 20 in the misty liquid droplets of quenching liquid and sulfur vapor contact process in the step (2)
DEG C~100 DEG C.
Further, the insoluble sulfur product in the step (5) continues 15 points under conditions of temperature is 120 DEG C
Clock, undecomposed insoluble sulfur product content accounts for more than the 50% of total content.
Beneficial effects of the present invention are：
Temperature and pressure and appropriate rate of release of the invention by controlling high temperature sulphur steam, with quenching for high atomisation
Cold liquid is fully contacted, and moment completes the electrophilic addition reaction of grain forming and strand end-blocking, insoluble in the production process
Sulphur is once into powder, it is not necessary to which subsequent step is crushed to block insoluble sulfur, is alleviated labor intensity, is improved labor
Rotating ring border；The heat endurance and dispersiveness of insoluble sulfur, stabilized product quality are improved simultaneously.
Quenching liquid pressurizes the misty liquid droplets particle diameter sprayed by pump or storage tank should be uniform tiny, and it is micro- that droplet sizes are less than 500
Rice, is conducive to fully contacting with sulfur vapor, effectively separates sulfur vapor, and misty liquid droplets use appropriate velocity ratio with sulfur vapor,
Be conducive to quickly sulphur gas cooling to form particle, the yield of insoluble sulfur obtains a certain degree of raising.
Promote to be rapidly completed using the energy of high temperature sulphur steam when quenching liquid misty liquid droplets are fully contacted with high temperature sulphur steam
The addition reaction at strand two ends, and particle is directly formed, the extraction of quenching liquid process, drying containing particle or suspension,
After oil-filled, Quadratic Stability, insoluble sulfur product is formed, the heat endurance of insoluble sulfur is improved, can reached in temperature
To continue 15 minutes under conditions of 120 DEG C：The target that more than 50% insoluble sulfur will not decompose.
Sulfur vapor cooling is from during simple substance is changed into polymer, and the insoluble sulfur of generation is very unstable, because it
Strand two ends are exposed, and insoluble sulfur generation that the effect of the end-capping reagent in the present invention is exactly and this is unstable is electrophilic
Addition reaction this it is closed at both ends make insoluble sulfur more stablize, solve the exposed unstability in insoluble sulfur two ends
Technical problem, while it also avoid directly raw material is passed through below quenching liquid liquid level causing product stability poor in the prior art
Technical problem, end-capping reagent serve strengthen insoluble sulfur stability effect.
Brief description of the drawings
Fig. 1 is method flow schematic diagram of the invention.
Embodiment
Illustrate technical scheme according to following instance, the present invention includes but are not limited to following several examples：
As shown in figure 1, the present invention is refined by former sulphur, heated up, material spray, extraction, drying, obtained product powder, stably filled
Oil, inspection, packaging, storage.
Embodiment 1
The method that sulphur monomer quenching polymerizate strand end-blocking prepares insoluble sulfur, specifically includes following steps：
The first step, after solid sulfur is melted, is warming up to 130 DEG C, progressively gasifies to 550 DEG C.
Second step, the sulfur vapor that the first step is gasified is sprayed into tank through shower nozzle with 300Kg/hr speed, is 25 with temperature
DEG C, sulphur quality multiple be 45:1st, the aqueous solution atomization contact containing 0.02 parts by weight ferric trichloride, 0.03 parts by weight nitric acid,
And cool down；The pseudoplastic behavior formed be powdery, size distribution be less than 100 mesh contents be 98%, intermediate contain 55% it is insoluble
Property sulphur.
Continuous extraction and stably is carried out in 3rd step, the insoluble sulfur that second step is produced, immersion carbon disulfide, in making
Mesosome insoluble sulfur content reaches more than 96.5%.
4th step, material is transferred in drier, and not higher than 85 DEG C are dried；
Finally, the rubber special filling oil containing 0.01 parts by weight nano silicon is filled with, OT6033 types are made insoluble
Property product.
Embodiment 2
The method that sulphur monomer quenching polymerizate strand end-blocking prepares insoluble sulfur, specifically includes following steps：
The first step, after solid sulfur is melted, is warming up to 120 DEG C, progressively gasifies to 580 DEG C.
Second step, the sulfur vapor gasified through the first step is sprayed into tank with shower nozzle with 400Kg/hr speed, is 15 with temperature
DEG C, sulphur quality multiple be 15:1st, the carbon disulfide solution atomization containing 0.02 parts by weight iodine, 0.03 parts by weight of potassium nitrate
Contact, and cool down；The pseudoplastic behavior formed is powdery, and it is 97% that size distribution, which is less than 80 mesh contents, and intermediate contains 58%
Insoluble sulfur.
Continuous extraction and stably is carried out in 3rd step, the insoluble sulfur that second step is produced, immersion carbon disulfide, in making
Mesosome insoluble sulfur content reaches more than 97.5%.
4th step, material is transferred in drier, and not higher than 85 DEG C are dried；
Finally, the rubber special filling oil containing 0.01 parts by weight altax is filled with, the insoluble production of OT7020 types is made
Product.
Embodiment 3
The method that sulphur monomer quenching polymerizate strand end-blocking prepares insoluble sulfur, specifically includes following steps：
The first step, after solid sulfur is melted, is warming up to 140 DEG C, progressively gasifies to 635 DEG C,
Second step, the sulfur vapor that the first step is gasified is sprayed into tank with 1200Kg/hr speed through shower nozzle, is with temperature
25 DEG C, sulphur quality multiple be 25:1st, the carbon tetrachloride solution atomization containing 0.02 parts by weight iodine, 0.03 parts by weight HClO
Contact, and cool down；The pseudoplastic behavior formed is powdery, and it is 93% that size distribution, which is less than 80 mesh contents, and intermediate contains 58%
Insoluble sulfur.
Continuous extraction and stably is carried out in 3rd step, the insoluble sulfur that second step is produced, immersion carbon disulfide, in making
Mesosome insoluble sulfur content reaches more than 98.5%.
4th step, material is transferred in drier, and not higher than 75 DEG C are dried；
Finally, the rubber special filling oil containing 0.01 parts by weight accelerator methyl styrene, xanthans is filled with, is made
The insoluble product of OT8010 types.
Embodiment 4
The method that sulphur monomer quenching polymerizate strand end-blocking prepares insoluble sulfur, specifically includes following steps：
The first step, after solid sulfur is melted, is warming up to 112 DEG C, progressively gasifies to 445 DEG C,
Second step, the sulfur vapor that the first step is gasified is sprayed into tank through shower nozzle with 300Kg/hr speed, is 10 with temperature
DEG C, sulphur quality multiple be 5:1st, the carbon tetrachloride solution atomization containing 0.02 parts by weight iodine, 0.03 parts by weight HClO connects
Touch, it is 80 DEG C that temperature is controlled in atomization contact process, and is cooled down；The pseudoplastic behavior formed is powdery, and size distribution is less than 80 mesh
Content is 95%, and intermediate contains 50% insoluble sulfur.
Continuous extraction and stably is carried out in 3rd step, the insoluble sulfur that second step is produced, immersion carbon disulfide, in making
Mesosome insoluble sulfur content reaches more than 96.5%.
4th step, material is transferred in drier, and not higher than 75 DEG C are dried；
Finally, the rubber special filling oil containing 0.01 parts by weight accelerator methyl styrene, xanthans is filled with, is made not
Insoluble products A.
Embodiment 5
The method that sulphur monomer quenching polymerizate strand end-blocking prepares insoluble sulfur, specifically includes following steps：
The first step, after solid sulfur is melted, is warming up to 149 DEG C, progressively gasifies to 720 DEG C,
Second step, the sulfur vapor that the first step is gasified is sprayed into tank with 1200Kg/hr speed through shower nozzle, is with temperature
40 DEG C, sulphur quality multiple be 50:1st, the carbon tetrachloride solution atomization containing 0.02 parts by weight iodine, 0.03 parts by weight HClO
Control temperature to be 100 DEG C in contact, atomization contact process, and cool down；The pseudoplastic behavior formed is powdery, and size distribution is less than 80
Mesh content is 96%, and intermediate contains 54% insoluble sulfur.
Continuous extraction and stably is carried out in 3rd step, the insoluble sulfur that second step is produced, immersion carbon disulfide, in making
Mesosome insoluble sulfur content reaches more than 97%.
4th step, material is transferred in drier, and not higher than 85 DEG C are dried；
Finally, the rubber special filling oil containing 0.01 parts by weight accelerator methyl styrene, xanthans is filled with, type is made
Insoluble product B.
Specific index is as follows：
For OT6033 type insoluble sulfur products, its index reaches：
Insoluble sulfur content：64-67%；Oil content：32-33%；Heat endurance (120 DEG C/15min)：50.5%.Grain
Footpath distribution is as follows：
For OT7020 type insoluble sulfur products, its index reaches：
Insoluble sulfur content：68-70%；Oil content：19-21%；Heat endurance (120 DEG C/15min)：50.8%.Grain
Footpath distribution is as follows：
For OT8010 type insoluble sulfur products, its index reaches：
Insoluble sulfur content：88-90%；Oil content：9-11%；Heat endurance (120 DEG C/15min)：51.8%.Grain
Footpath distribution is as follows：
For the insoluble sulfur product A in embodiment 4, the index of product is insoluble sulfur content 88-89%；Oil content
The heat endurance of 10-11% conversion per pass 46% (120 DEG C/15min)：48.5%.
For the insoluble sulfur product B in embodiment 5, the index of product is insoluble sulfur content 89-91%；Oil content
9-10%；Conversion per pass 65%；Heat endurance (120 DEG C/15min)：52.5%.
Described above is not limitation of the present invention, it should be pointed out that：Come for those skilled in the art
Say, on the premise of essential scope of the present invention is not departed from, some variations, modifications, additions or substitutions can also be made, these improvement
Protection scope of the present invention is also should be regarded as with retouching.
Claims (10)
1. the method that sulphur monomer quenching polymerizate strand end-blocking prepares insoluble sulfur, it is characterised in that specifically include as
Lower step：
(1) melting of raw material sulphur is warming up to 112 DEG C -149 DEG C of flow regime, liquid sulfur is warming up to 445 DEG C -720 DEG C progressively gas
Change forms sulfur vapor；
(2) sulfur vapor that step (1) gasifies, is sprayed into tank, quenching liquid through shower nozzle with 300Kg/hr-1200Kg/hr speed
Temperature is controlled to spray misty liquid droplets by pressurization for 10 DEG C -40 DEG C, misty liquid droplets are rapidly completed molecule with sulfur vapor atomization contact
The mass velocity ratio of the addition reaction at chain two ends, quenching liquid and sulphur steam is 5~50:1, misty liquid droplets were contacted with sulfur vapor
Temperature is controlled to be less than 110 DEG C in journey, cooling obtains the intermediate containing insoluble sulfur；
(3) continuous extraction is carried out in the intermediate containing insoluble sulfur that will be produced in step (2), immersion carbon disulfide and steady
It is fixed, the insoluble sulfur content of intermediate is reached more than 96.5%；
(4) material is transferred in drier, not higher than 75 DEG C -85 DEG C are dried；
(5) the rubber special filling oil of the nano silicon containing percentage by weight 0.01% is filled with, insoluble sulfur is made
Product.
2. the method that sulphur monomer quenching polymerizate strand end-blocking prepares insoluble sulfur according to claim 1, it is special
Levy and be, raw material sulphur uses powder or bulk in the step (1), melting is warming up to 112 DEG C -125 DEG C of flow regime, liquid
Sulphur is warming up to 460 DEG C of -650 DEG C of formation sulfur vapors further across coil pipe stove or gasification tank.
3. the method that sulphur monomer quenching polymerizate strand end-blocking prepares insoluble sulfur according to claim 1, it is special
Levy and be, quenching liquid is the aqueous solution containing end-capping reagent in the step (2), end-capping reagent is to contain dust technology and FeCl3、AlCl3、
One kind of KCl, KI, KBr inorganic salts, or contain Cl2、Br2Halogen simple substance, or above-mentioned inorganic salts and halogen are one or more of
Mixture.
4. the method that sulphur monomer quenching polymerizate strand end-blocking prepares insoluble sulfur according to claim 1, it is special
Levy and be, quenching liquid is the solvent containing end-capping reagent in the step (2), solvent is carbon disulfide or carbon tetrachloride, preferably two sulphur
Change carbon；End-capping reagent is to contain oxidant or halogen or salt, such as FeCl3、KCl、KI、KBr、I2、Cl2、Br2、S2Cl2、HClO、
NaClO、Ca(ClO)2、SOCl、POCl3One or more of mixtures of active ingredient.
5. the method that the sulphur monomer quenching polymerizate strand end-blocking according to claim 3 or 4 prepares insoluble sulfur, its
It is characterised by, the percentage by weight of end-capping reagent and the aqueous solution is 0.02-0.25 in the quenching liquid：1；In quenching liquid end-capping reagent and
The percentage by weight of solvent is 0.02-0.25：1.
6. the method that sulphur monomer quenching polymerizate strand end-blocking prepares insoluble sulfur according to claim 1, it is special
Levy and be, quenching hydraulic control temperature is 15 DEG C -30 DEG C in the step (2).
7. the method that sulphur monomer quenching polymerizate strand end-blocking prepares insoluble sulfur according to claim 1, it is special
Levy and be, quenching liquid is pressed to form misty liquid droplets by pump or storage tank in the step (2), the size of misty liquid droplets is less than 500
Micron.
8. the method that sulphur monomer quenching polymerizate strand end-blocking prepares insoluble sulfur according to claim 1, it is special
Levy and be, the mass velocity ratio of quenching medium and sulphur is 10~35 in the step (2):1.
9. the method that sulphur monomer quenching polymerizate strand end-blocking prepares insoluble sulfur according to claim 1, it is special
Levy and be, the misty liquid droplets of quenching liquid are with controlling temperature to be 20 DEG C~100 DEG C in the step (2) in sulfur vapor contact process.
10. the method that sulphur monomer quenching polymerizate strand end-blocking prepares insoluble sulfur according to claim 1, it is special
Levy and be, the insoluble sulfur product in the step (5) continues 15 minutes under conditions of temperature is 120 DEG C, undecomposed
Insoluble sulfur product content accounts for more than the 50% of total content.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108203081A (en) * | 2018-03-19 | 2018-06-26 | 无锡华盛橡胶新材料科技股份有限公司 | A kind of production method and production equipment of oil-filled insoluble sulfur |
| CN109888196A (en) * | 2017-12-06 | 2019-06-14 | 中国科学院大连化学物理研究所 | A kind of porous sulphur/carbon composite and preparation method thereof and lithium-sulfur cell application |
| CN111377414A (en) * | 2018-12-29 | 2020-07-07 | 中国石油化工股份有限公司 | Insoluble sulfur extraction method and system |
| CN111377412A (en) * | 2018-12-29 | 2020-07-07 | 中国石油化工股份有限公司 | Insoluble sulfur continuous quenching device |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101798066A (en) * | 2010-04-15 | 2010-08-11 | 江西恒兴源化工有限公司 | Method for preparing nano insoluble sulphur |
| CN102398896A (en) * | 2011-09-30 | 2012-04-04 | 河南省开仑化工有限责任公司 | New production technology of insoluble sulfur for rubber use |
| CN103303873A (en) * | 2013-05-23 | 2013-09-18 | 上海京海（安徽）化工有限公司 | Preparation method of modified high-dispersion high-thermal-stability insoluble sulfur |
| CN104555943A (en) * | 2013-10-12 | 2015-04-29 | 江苏宏泰橡胶助剂有限公司 | Method for preparing high-quality insoluble sulphur from continuous pipelined overheated sulphur steam |
| CN105752941A (en) * | 2016-01-22 | 2016-07-13 | 上海京海（安徽）化工有限公司 | Method for preparing high-purity and high-dispersibility insoluble sulfur |
-
2017
- 2017-05-23 CN CN201710368856.8A patent/CN107200309A/en not_active Withdrawn
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101798066A (en) * | 2010-04-15 | 2010-08-11 | 江西恒兴源化工有限公司 | Method for preparing nano insoluble sulphur |
| CN102398896A (en) * | 2011-09-30 | 2012-04-04 | 河南省开仑化工有限责任公司 | New production technology of insoluble sulfur for rubber use |
| CN103303873A (en) * | 2013-05-23 | 2013-09-18 | 上海京海（安徽）化工有限公司 | Preparation method of modified high-dispersion high-thermal-stability insoluble sulfur |
| CN104555943A (en) * | 2013-10-12 | 2015-04-29 | 江苏宏泰橡胶助剂有限公司 | Method for preparing high-quality insoluble sulphur from continuous pipelined overheated sulphur steam |
| CN105752941A (en) * | 2016-01-22 | 2016-07-13 | 上海京海（安徽）化工有限公司 | Method for preparing high-purity and high-dispersibility insoluble sulfur |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109888196A (en) * | 2017-12-06 | 2019-06-14 | 中国科学院大连化学物理研究所 | A kind of porous sulphur/carbon composite and preparation method thereof and lithium-sulfur cell application |
| CN109888196B (en) * | 2017-12-06 | 2021-06-22 | 中国科学院大连化学物理研究所 | Porous sulfur/carbon composite material, preparation method thereof and application of porous sulfur/carbon composite material in lithium-sulfur battery |
| CN108203081A (en) * | 2018-03-19 | 2018-06-26 | 无锡华盛橡胶新材料科技股份有限公司 | A kind of production method and production equipment of oil-filled insoluble sulfur |
| CN108203081B (en) * | 2018-03-19 | 2023-09-01 | 无锡华盛橡胶新材料科技股份有限公司 | Production method and production equipment of oil-filled insoluble sulfur |
| CN111377414A (en) * | 2018-12-29 | 2020-07-07 | 中国石油化工股份有限公司 | Insoluble sulfur extraction method and system |
| CN111377412A (en) * | 2018-12-29 | 2020-07-07 | 中国石油化工股份有限公司 | Insoluble sulfur continuous quenching device |
| CN111377414B (en) * | 2018-12-29 | 2021-08-06 | 中国石油化工股份有限公司 | Insoluble sulfur extraction method and system |
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