CN102275879B - Process for producing insoluble sulphur - Google Patents
Process for producing insoluble sulphur Download PDFInfo
- Publication number
- CN102275879B CN102275879B CN201110210853A CN201110210853A CN102275879B CN 102275879 B CN102275879 B CN 102275879B CN 201110210853 A CN201110210853 A CN 201110210853A CN 201110210853 A CN201110210853 A CN 201110210853A CN 102275879 B CN102275879 B CN 102275879B
- Authority
- CN
- China
- Prior art keywords
- sulphur
- insoluble
- sulfur
- liquid
- suspension
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention relates to a process for producing insoluble sulphur. In the process, industrial sulphur is used as a raw material. The process comprises the following steps of: a, heating; b, quenching; c, curing; d, extracting; e, filtering; f, drying; and g, sieving, wherein in the step b, sulphur powder and quenching liquid are added into quenching equipment in advance before quenching to form turbid liquid of the sulphur by stirring, and high-temperature sulphur is sprayed to the turbid liquid of the sulphur to be quenched or the quenching liquid or the turbid liquid of the sulphur is added to the bottom of the quenching equipment in advance, and the high-temperature sulphur is quenched by the turbid liquid of the sulphur in a spraying mode or the turbid liquid of the sulphur is added to the bottom of the quenching equipment in advance, and the high-temperature sulphur is sprayed and quenched by the quenching liquid. In the process, mutual adhesion among insoluble sulphur granules formed through quenching is prevented under the dispersing isolation action of the turbid liquid of the sulphur, and the curing effect and quality of the insoluble sulphur can be improved obviously.
Description
Technical field
The present invention relates to Manufacture of insoluble sulphur technology.
Background technology
Insoluble sulfur is common sulphur got, is insoluble to dithiocarbonic anhydride through thermopolymerization a polymerised sulphur; As a kind of senior promotor and vulcanization crosslinking agent of rubber industry, have no blooming, improve the bond strength of each interlayer of multilayer rubber goods, advantage such as incipient scorch phenomenon when effectively reducing sizing material and depositing.In tire production, particularly in the production of automobile all steel silk radial tyre, important source material is absolutely necessary.
Manufacture of insoluble sulphur mainly contains two kinds of methods at present: pyroprocess and cold method.Compare with cold method, pyroprocess is produced the intensification of route sulphur and is generally wanted more than 400 ℃.Because pyroprocess has per pass conversion height, advantage that product stability is good, is the operational path that present manufacturing enterprise mainly takes.
The technical process of producing insoluble sulfur is divided into basically: sulphur fusion intensification, chilling, curing, extraction, filtration, drying, screening; Wherein the most key process procedure is chilling and curing, and both influence the high thermal stability of the finished product to a great extent.The chilling purpose is to keep the trend of sulphur radical polymerization, suppresses the trend that polymerised sulphur is reverted simultaneously.Through apace the temperature of sulfur vapor being reduced to below 60 ℃, can achieve the above object.Solidifying purpose is the polymerised sulphur of chilling formation is hardened on the basis of further reactive polymeric.Insoluble sulfur is the rubber-like rubbery state before curing, has inter-adhesive trend.If do not deal carefully with, the particulate that forms in the quenching process can be inter-adhesive, makes sulfur granule become big, can influence the quality of product simultaneously.
Method such as disclosing a kind of continuous production high-thermostability insoluble sulfur at Chinese patent file CN 101343045A (CN200810139262.0) comprises step: a fusing, intensification, and b prepares solvent; The c reaction, d separates, solidifies, pulverizes, purifies, and e is dry; F screening, oil-filled, it is characterized in that: among the step b, solvent is a double solvents; It is made up of dithiocarbonic anhydride, methylene dichloride, SS auxiliary agent, and the SS auxiliary agent is the alkene that contains unsaturated link(age).In this evaporating method operational path, the solid behind the insoluble sulfur chilling separates with quench liquid, solidifies 1.5 hours at 47-53 ℃.Particle becomes big because the setting up period insoluble sulfur sticks together, and in follow-up extraction process, need carry out pulverization process.Even the insoluble sulfur of rubbery state is cured in dithiocarbonic anhydride, can't avoid the trend of adhesion equally, need carry out the pulverization process in later stage.It should be noted that insoluble sulfur when particle is big, fine solidifies very difficult the completion.Therefore, as the curing process of production important step, should receive enough attention.Improve curing process, as the important step that improves the product thermostability, the bottleneck that need break through beyond doubt.
Summary of the invention
Deficiency to prior art; Be easy to the difficult problem of adhesion between the insoluble sulfur particle that the solution prior art exists in chilling solidifies; The present invention provides a kind of Manufacture of insoluble sulphur technology, avoids in the chilling solidification process inter-adhesive between the insoluble sulfur particle.
Method of the present invention is specially adapted to serialization and produces insoluble sulfur.
Technical scheme of the present invention is following:
A kind of production technique of high-thermostability insoluble sulfur is a raw material with the industrial sulphur, and step comprises that a heats up, the b chilling, and c solidifies, the d extraction, e filters, and f is dry, the g screening; Wherein,
Among the step b, in fast cooling device, add sulphur powder and quench liquid before the chilling in advance,, high temperature sulphur is ejected in the suspension liquid of said sulphur and carries out chilling through stirring the suspension liquid that forms sulphur; Perhaps,
The fast cooling device bottom adds the suspension liquid of quench liquid or said sulphur in advance, more said sulfur suspension is carried out chilling through the mode of spray to high temperature sulphur in the entering fast cooling device; Perhaps,
The fast cooling device bottom adds the suspension liquid of sulphur in advance, with quench liquid high temperature sulphur is sprayed chilling;
Through the dispersion buffer action of sulfur suspension, avoid inter-adhesive between the insoluble sulfur particle that chilling forms.
According to the present invention,
Among the step b, said sulphur powder is one of insoluble sulfur, common sulphur or combination.
Among the step b, said quench liquid is a dithiocarbonic anhydride, methylene dichloride, tetracol phenixin, ethylene dichloride, toluene, a kind of or any several kinds combination in the water, preferred dithiocarbonic anhydride.
Among the step b, the concentration of sulphur is 0.1～50wt% in the suspension liquid of said sulphur, preferred 5～15wt%.
Among the step b, the temperature of the suspension liquid of said sulphur is-10-60 ℃, and preferred 0-25 ℃.
Among the step b, the whisking appliance that the fast cooling device bottom is used to stir is that multilayer stirs, and keeps the suspended state of insoluble sulfur in liquid through full and uniform stirring.
Among the step b, described equipment is the conventional chilling conversion unit in this area, has the material mouth of whipping appts, pressure-controlling, temperature control and various needs.
Primary industry sulphur of the present invention is bulk, sheet, powder or liquid, preferred liquid sulphur; The solid industrial sulphur is 120-140 ℃ of fusion.
In the process step of the present invention, steps such as a intensification, c curing, d extraction, e filtration, f drying, g screening all can be by prior art.But the present invention also provides the more preferred step by step scheme in center following:
Step a heats up: the temperature 400-800 of high temperature sulphur ℃, and preferred 580-680 ℃.
The steps d extraction: extraction agent is a dithiocarbonic anhydride, methylene dichloride, tetracol phenixin, ethylene dichloride, a kind of or any several kinds combination in the toluene, wherein preferred dithiocarbonic anhydride.
The step g screening: the particle that sieves out is pulverized, and the powder after the pulverizing joins in insoluble sulfur finished product or the quench liquid; Preferably join the suspension liquid of preparation sulphur in the quench liquid, be used for step b chilling.
Compare with prior art; Technical characterstic of the present invention and beneficial effect are: the suspension liquid that forms through sulphur powder and quench liquid carries out chilling to high temperature sulphur; Through the dispersion buffer action of the sulphur powder in the sulfur suspension, the insoluble sulfur of avoiding chilling to form produces inter-adhesive in solidification process between the particle simultaneously.
The suspension liquid of the present invention through utilizing sulphur to the dispersion buffer action that insoluble sulfur rose, can obviously improve insoluble sulfur solidification effect and quality product in the chilling solidification process.
Description of drawings
Fig. 1 is a process flow diagram of the present invention.
Embodiment
Below through specific embodiment the present invention is further elaborated.But these specific embodiments are only in order to explaining the present invention, and are not used in qualification the present invention.
The equipment that uses among the embodiment is existing procucts, and the not special operation that limits is all by prior art.Wherein, fast cooling device is a STJ type graphite quench tower, and the Nantong safe graphite equipment of perseverance System Co., Ltd is on sale.Extraction kettle is selected the Continuous Countercurrent Extraction jar for use, and Hua Chang light equipment factory in Gaoyou, Jiangsu is on sale.
Embodiment 1:
In quench tower bottom, be 25 ℃, mixed uniformly methylene dichloride and dithiocarbonic anhydride, be used as the quench liquid of high temperature sulphur by 1: 10 mass ratio adding temperature.In above-mentioned quench liquid, adding insoluble sulfur content then is the sulphur powder of 60wt%, is the sulfur suspension of 10wt% through stirring formation concentration.
In 640-660 ℃ of gasification, 650 ℃ of temperature controls with the screw-blade of 135 kilograms/hour speed through shower nozzle, disperse to be ejected in the sulfur suspension of quench tower bottom with Molten sulphur, and sulfur vapor temperature moment is reduced to below 50 ℃.Through the suspended state of the insoluble sulfur behind the stirring maintenance chilling, the sulfur suspension dispersion isolation that is added in advance simultaneously is cured.System temperature remains on 55 ± 5 ℃ and solidified 2.5 hours.
Insoluble sulfur after in the suspension liquid of fast cooling device bottom, solidifying completion pumps into the extraction kettle top and carries out counter-current extraction with dithiocarbonic anhydride; The extraction kettle bottom is not contained the suspension liquid of the insoluble sulfur of solubility sulphur; The liquid overwhelming majority is a dithiocarbonic anhydride in the suspension liquid, only contains the methylene dichloride of minute quantity.
The dithiocarbonic anhydride suspension liquid of the insoluble sulfur that does not contain solubility sulphur that extraction is obtained carries out drying, and the gaseous state dithiocarbonic anhydride that obtains in the drying process carries out recycling through condensation.
The exsiccant insoluble sulfur is sieved, and a small amount of larger particles that sieves out carries out ball mill pulverizing, and the material after the pulverizing joins in the quench liquid preparation sulfur suspension again and is used for the chilling of high temperature sulphur is solidified.
Embodiment 2:
In the dithiocarbonic anhydride quench liquid, add insoluble sulfur, the sulfur suspension of compound concentration 10wt%.This suspension liquid sprays through the spray equipment at quench tower top, forms the dispersive drop, and control sulfur suspension spray rate is 520 kilograms/hour.
The Molten sulphur gasification that heats up, 660 ℃ of temperature controls are ejected in the quench tower with 130 kilograms/hour speed, through above-mentioned sulfur suspension dispersant liquid drop from top to bottom sulfur vapor are carried out chilling, and sulfur vapor temperature moment is reduced to below 50 ℃; Insoluble sulfur behind the chilling falls into jar pond, quench tower bottom with suspension liquid, stirs through the bottom to keep the suspended state of insoluble sulfur in dithiocarbonic anhydride, and the isolation of the insoluble sulfur particles dispersed in the sulfur suspension that is added into, be cured.Keep system temperature to solidify 2.5 hours for 55 ± 5 ℃.
Insoluble sulfur after in the sulfur suspension of fast cooling device bottom, solidifying completion utilizes the dithiocarbonic anhydride counter-current extraction with being pumped to the extraction kettle top.
Insoluble sulfur after extraction is accomplished carries out filtration drying.The dithiocarbonic anhydride that evaporates in the drying process is sent into the chilling program and is utilized after condensation.
Dry back is through the further empty screening that divides, and a small amount of larger particles that filters out carries out ball mill pulverizing, and the material after the pulverizing is packed as finished product.
Embodiment 3:
Of embodiment 2, different is in the toluene quench liquid, to add common sulphur powder, is mixed with the suspension liquid of concentration 10wt%.
Embodiment 4:
Adding insoluble sulfur content to the dithiocarbonic anhydride quench liquid is the sulphur powder of 60wt%, is mixed with the 15wt% suspension liquid.Fast cooling device adds entry in advance before chilling.Sulfur suspension cools off high temperature sulphur through the mode of spray, and the insoluble sulfur behind the chilling is below suspension liquid falls into the quench tower bottom water surface.Other concrete operations are with embodiment 2.
Claims (11)
1. the production technique of a high-thermostability insoluble sulfur is a raw material with the industrial sulphur, and step comprises that a heats up, the b chilling, and c solidifies, the d extraction, e filters, and f is dry, the g screening; It is characterized in that,
Among the step b, in fast cooling device, add sulphur powder and quench liquid before the chilling in advance,, high temperature sulphur is ejected in the suspension liquid of sulphur and carries out chilling through stirring the suspension liquid that forms sulphur; Perhaps, the fast cooling device bottom adds the suspension liquid of quench liquid or sulphur in advance, and sulfur suspension carries out chilling through the mode of spray to high temperature sulphur; Perhaps, the fast cooling device bottom adds the suspension liquid of sulphur in advance, with quench liquid high temperature sulphur is sprayed chilling; Through the dispersion buffer action of sulfur suspension, avoid inter-adhesive between the insoluble sulfur particle that chilling forms;
Among the step b, the sulphur powder of adding is the combination of insoluble sulfur or insoluble sulfur and common sulphur;
Among the step b, quench liquid is a dithiocarbonic anhydride, methylene dichloride, tetracol phenixin, ethylene dichloride, toluene, a kind of or any several kinds combination in the water.
2. Manufacture of insoluble sulphur technology according to claim 1 is characterized in that: among the step b, the mass concentration of sulphur is 0.1～50wt% in the said sulfur suspension.
3. Manufacture of insoluble sulphur technology according to claim 1 is characterized in that: among the step b, the mass concentration of sulphur is 5～15wt% in the said sulfur suspension.
4. Manufacture of insoluble sulphur technology according to claim 1 is characterized in that: among the step b, the temperature of described sulfur suspension is-and 10-60 ℃.
5. Manufacture of insoluble sulphur technology according to claim 1 is characterized in that: among the step b, the temperature of described sulfur suspension is 0-25 ℃.
6. Manufacture of insoluble sulphur technology according to claim 1 is characterized in that: said primary industry sulphur is bulk, sheet, powder or liquid.
7. Manufacture of insoluble sulphur technology according to claim 1 is characterized in that: said primary industry sulphur is Molten sulphur.
8. Manufacture of insoluble sulphur technology according to claim 1 is characterized in that: step a heats up, the temperature 400-800 of high temperature sulphur ℃.
9. Manufacture of insoluble sulphur technology according to claim 1 is characterized in that: step a heats up, the temperature 580-680 of high temperature sulphur ℃.
10. Manufacture of insoluble sulphur technology according to claim 1 is characterized in that: the steps d extraction, extraction agent is a dithiocarbonic anhydride, methylene dichloride, tetracol phenixin, ethylene dichloride, a kind of or any several kinds combination in the toluene.
11. Manufacture of insoluble sulphur technology according to claim 1 is characterized in that: step g screening, the particle that sieves out is pulverized, and the powder after the pulverizing joins in the insoluble sulfur finished product or in the quench liquid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110210853A CN102275879B (en) | 2011-07-26 | 2011-07-26 | Process for producing insoluble sulphur |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110210853A CN102275879B (en) | 2011-07-26 | 2011-07-26 | Process for producing insoluble sulphur |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102275879A CN102275879A (en) | 2011-12-14 |
| CN102275879B true CN102275879B (en) | 2012-09-19 |
Family
ID=45101683
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110210853A Active CN102275879B (en) | 2011-07-26 | 2011-07-26 | Process for producing insoluble sulphur |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102275879B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101491969B1 (en) * | 2013-09-16 | 2015-02-11 | 에이치설퍼 주식회사 | Process for production of high quality insoluble sulfur |
| CN104401946B (en) * | 2014-11-07 | 2016-11-30 | 山东阳谷华泰化工股份有限公司 | A kind of gasification quenching technique of insoluble sulfur |
| CN104359293B (en) * | 2014-11-07 | 2016-04-13 | 山东阳谷华泰化工股份有限公司 | A kind of drying process of insoluble sulfur and process equipment thereof |
| CN109368599B (en) * | 2018-11-02 | 2022-03-15 | 山东阳谷华泰化工股份有限公司 | Preparation method of insoluble sulfur and anti-reversion stabilizer used by same |
| CN109264673B (en) * | 2018-11-15 | 2022-04-01 | 东营市海科瑞林化工有限公司 | Production device and production system for reducing formation of large-particle elastomer in insoluble sulfur production process |
| CN109133013B (en) * | 2018-11-15 | 2021-12-31 | 东营市海科瑞林化工有限公司 | Production device and production system for adjusting density of quenching liquid in insoluble sulfur production process |
| CN112661120B (en) * | 2020-12-17 | 2023-05-23 | 临涣焦化股份有限公司 | Method for preparing insoluble sulfur from coking desulfurization waste residues |
| CN113247866B (en) * | 2021-05-18 | 2022-08-26 | 山东阳谷华泰化工股份有限公司 | Method and equipment for extracting insoluble sulfur |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101343045A (en) * | 2008-08-26 | 2009-01-14 | 山东省单县化工有限公司 | Method for continuous preparation of sulfur with high heat-stability and insolubility |
| CN102070127A (en) * | 2011-02-17 | 2011-05-25 | 四川晨辉化工有限公司 | Method for producing insoluble sulfur |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2171105B1 (en) * | 2000-02-08 | 2003-11-01 | Repsol Petroleo Sa | PROCEDURE FOR THE PRODUCTION OF POLYMER SULFUR. |
| ITRM20020434A1 (en) * | 2002-08-22 | 2004-02-23 | Franco Cataldo | PROCEDURE FOR THE SYNTHESIS OF POLYMERIC SULFUR. |
-
2011
- 2011-07-26 CN CN201110210853A patent/CN102275879B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101343045A (en) * | 2008-08-26 | 2009-01-14 | 山东省单县化工有限公司 | Method for continuous preparation of sulfur with high heat-stability and insolubility |
| CN102070127A (en) * | 2011-02-17 | 2011-05-25 | 四川晨辉化工有限公司 | Method for producing insoluble sulfur |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102275879A (en) | 2011-12-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102275879B (en) | Process for producing insoluble sulphur | |
| CN102070127B (en) | Method for producing insoluble sulfur | |
| CN101186029B (en) | Resin reinforced high-speed grinding wheel | |
| CN103890042A (en) | Thermoplastic polyimides | |
| EP3174916B1 (en) | Process for preparing a polyamide, a nylon salt to be used therein and a process for making the salt | |
| CN103539079B (en) | Method for one-step preparation of insoluble sulfur | |
| CN103204479A (en) | Production method for high-content insoluble sulfur | |
| CN103303873A (en) | Preparation method of modified high-dispersion high-thermal-stability insoluble sulfur | |
| CN103204478A (en) | Production method for high-stability insoluble sulfur | |
| CN102268167B (en) | Preparation method of low styrene volatile unsaturated polyester resin composite material | |
| CN103539078B (en) | Method for preparation of insoluble sulfur | |
| CN106946230B (en) | Continuous production method of insoluble sulfur | |
| CN105645361A (en) | Liquid phase method for producing insoluble sulfur | |
| US3058159A (en) | Method for producing a pearl-formed solid-state condensation-type resin | |
| US9234074B2 (en) | Flakes of ester mixtures and methods for their production | |
| CN104449787A (en) | Method for producing solid particle asphalt | |
| CN101899190A (en) | Production method of polytetrafluoroethylene granular powder | |
| CN111004515A (en) | Asphalt regenerant | |
| CN103122151A (en) | Preparation method of pitch applied to high-strength and high-modulus pitch-based fiber | |
| NO319746B1 (en) | Process for the preparation of porous granules of ammonium nitrate | |
| CN101973818A (en) | Process for pelleting urea formaldehyde controlled-release compound fertilizer in high tower | |
| JP5063843B2 (en) | Method for dripping granulation of slurry melt and method for producing urea-based composite fertilizer granule using the same | |
| CN103318848A (en) | Production method of high-dispersion high-thermal-stability insoluble sulfur | |
| JP2019163510A (en) | Granule, method for producing granule and method for producing sintered ore | |
| CN102140254A (en) | Method for preparing high-efficiency modified asphalt |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Production process of insoluble sulfur Effective date of registration: 20211216 Granted publication date: 20120919 Pledgee: Industrial Bank Limited Liaocheng Branch Pledgor: SHANDONG YANGGU HUATAI CHEMICAL Co.,Ltd. Registration number: Y2021980015266 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20220824 Granted publication date: 20120919 Pledgee: Industrial Bank Limited Liaocheng Branch Pledgor: SHANDONG YANGGU HUATAI CHEMICAL Co.,Ltd. Registration number: Y2021980015266 |