CN104401946B - A kind of gasification quenching technique of insoluble sulfur - Google Patents
A kind of gasification quenching technique of insoluble sulfur Download PDFInfo
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- CN104401946B CN104401946B CN201410623868.7A CN201410623868A CN104401946B CN 104401946 B CN104401946 B CN 104401946B CN 201410623868 A CN201410623868 A CN 201410623868A CN 104401946 B CN104401946 B CN 104401946B
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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)
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Abstract
The present invention relates to the gasification quenching technique of a kind of insoluble sulfur, Molten sulphur heat temperature raising is first at superheated liquid sulfur state by this process, the sulfur liquid of superheat state is injected in the cooling medium liquid curtain of circulated sprinkling, under huge differential pressure action, after overheated sulfur liquid is converted into the biphase the most cooled rear medium quenching absorption of scattered aerosol, enter into and retort bottom cooling medium liquid environment is carried out solidify, extract, obtain insoluble sulfur.Cooling medium is circulated spray and forms liquid curtain by this method, change tradition cooling medium and directly impact the way of Molten sulphur, the liquid curtain formed adds the contact area of sulfur biphase with aerosol, the quenching that can make cooling medium liquid curtain sulfur biphase to aerosol is the most careful, it is to avoid the rough way in traditional During Quenching.The insoluble sulfur product particle obtained by the method is thin, purity is high, finished product good dispersion, is suitable for industrialized production.
Description
Technical field
The present invention relates to the gasification quenching technique of a kind of insoluble sulfur, be specifically related to a kind of sulfur in Carbon bisulfide environment
Quenching is converted into the production technology of insoluble sulfur, belongs to technical field of fine.
Background technology
Insoluble sulfur is common sulfur through the polymerised sulphur obtained by thermal polymerization, insoluble in Carbon bisulfide, as a kind of rubber
Industry senior accelerator and vulcanization crosslinking agent, its have no blooming, improve each interlayer of multilayer rubber goods bonding strength,
Effectively reduce when sizing material is deposited the advantages such as incipient scorch phenomenon.In tire production, particularly at automobile full steel wire radial tyre
In production, it it is requisite important source material.
Generally, produce insoluble sulfur be melted Molten sulphur is heated to uniform temperature after, use cooling medium quenching, so
By solidifying, extract, be dried, pulverize, oil-filled insoluble sulfur finished product.Produce insoluble sulfur quenching at present, consolidate
Change, extraction process is typically to be passed directly in quenching media the high-temp liquid sulfur after the polymerization of 400 DEG C-450 DEG C, logical
Crossing quenching media impact makes high-temp liquid sulfur be broken up cooling by moment in quenching media, the polymerization then obtained cooling
Sulfur carries out solidifying, extraction with carbon disulfide.
Chinese patent literature CN101362837B discloses the production technology of a kind of rubber insoluble sulfur, and this technique uses
Existing conventional complex stabilizer replaced by new complex stabilizer, and the high heat stability performance of the insoluble sulfur of production is good, contains
Amount height, adds and is easily dispersed man-hour.But During Quenching is not improved or optimizes by this technique, still uses tradition
Process.
Chinese patent literature CN102398896B provides the production technology of a kind of rubber insoluble sulfur, though this technique is adopted
Carry out by the step of gasification quenching, but what the way of contact in the selection and During Quenching of quenching media do not has and change
Enter, still directly impact the mode of quenching with quenching liquid.
Knowable to prior art, owing to polymerised sulphur is impacted quenching with liquid condition, the insoluble sulfur product obtained exists
The technical barriers such as semi-finished product particle diameter distribution width, extraction process length, finished product heat stability and dispersibility difficulty control.Therefore, urgently
Need to seek to design the quenching technique of a kind of new insoluble sulfur.
Summary of the invention
For the deficiencies in the prior art, the present invention provides the gasification quenching technique of a kind of insoluble sulfur.
Technical scheme is as follows:
A kind of gasification quenching technique of insoluble sulfur, this technical process is as follows,
(1) primary industry sulfur is warming up to 550 DEG C-650 DEG C in heater, keeps the pressure in heater simultaneously
Power 0.5-1Mpa, makes industrial sulphur be in superheat state, obtains overheated sulfur liquid；
(2) the overheated sulfur liquid in step (1) is injected in retort in the cooling medium liquid curtain of circulated sprinkling,
The temperature of cooling medium is 20-60 DEG C, and overheated sulfur liquid is 1:10-100 with the mass-velocity ratio of cooling medium, reaction
Pressure in tank is maintained at 0.01-0.1Mpa, and under differential pressure action, overheated sulfur liquid is converted into the biphase sulfur of scattered aerosol
Sulphur, by cooling medium liquid curtain sulfur biphase to aerosol quenching；
(3), after the biphase sulfur of aerosol in step (2) is absorbed by the cooling medium quenching of circulated sprinkling, reaction is entered into
Pot bottom cooling medium liquid environment is formed solid-liquid two phase materials, solid-liquid two phase materials is solidified, extracts, obtains
Insoluble sulfur.
Preferably, described cooling medium is Carbon bisulfide or tetrachloroethylene or four hydrogen-based naphthalene, preferably Carbon bisulfide.
Preferably, in step (2), described overheated sulfur liquid is 1:30-50 with the mass-velocity ratio of cooling medium.
Preferably, in step (3), the temperature of solid-liquid two phase materials of formation is 40-70 DEG C.
It is further preferred that in step (3), in solid-liquid two phase materials of formation, solid phase mass concentration is 10-35%.
Preferably, described industrial sulphur is Molten sulphur.
Preferably, the retort in described step (1) is the vertical response tank with chuck.This design is advantageous in that,
Select the retort of jacketed, the temperature in retort can be controlled by recirculated water, effectively reaction in retort is produced
Heat pass.
The beneficial effects of the present invention is:
1. present invention process method is different from traditional liquid sulfur and is directly cooled the technique of media impingement quenching, by liquid sulfur
Sulphur is heated to superheat state, and under huge differential pressure action, it is biphase that overheated sulfur liquid is converted into scattered aerosol.?
Under the mixing that aerosol is biphase, the quenching adding the contact area with cooling medium, beneficially sulfur absorbs.
2. cooling medium is circulated spray and forms liquid curtain by present invention process method, changes tradition cooling medium and directly rushes
Hitting the way of Molten sulphur, on the one hand the liquid curtain after formation adds the contact area of sulfur biphase with aerosol, on the other hand
The quenching that can make cooling medium liquid curtain sulfur biphase to aerosol is the most careful, it is to avoid rough in traditional During Quenching
Way.
3. present invention process flow process is simple, production cost is low, efficiency is high, and the insoluble sulfur product particle made is thin, pure
Degree is high, finished product good dispersion, is suitable for industrialized production.
Accompanying drawing explanation
Fig. 1 is the FB(flow block) of present invention process method.
Detailed description of the invention
Below by embodiment and combine accompanying drawing the present invention will be further described, but it is not limited to this.
The equipment used in embodiment is existing procucts, and the operation being not particularly limited is all by prior art.
Embodiment 1:
By prepare 20 DEG C, 100L Carbon bisulfide quenching liquid join volume be 300L with chuck (heat-exchanger rig)
Vertical response tank in, use circulating pump to be transported in retort from vertical response pot bottom extraction Carbon bisulfide quenching liquid
The spray equipment in portion sprays, and forms the liquid curtain of circulated sprinkling in vertical response tank, and liquid curtain is that shape is sprayed in shower, control
The flow 1500L/h of circulating pump processed, the pressure in retort is maintained at 0.01Mpa.
It is heated to the Molten sulphur of 550 DEG C-580 DEG C by 1.05kg/min by heater that internal pressure is 0.6Mpa
Speed be passed in the liquid curtain of vertical response tank top, control the quantity of circulating water in vertical response tank chuck and keep material in tank
Temperature is at 55 DEG C-60 DEG C, and Molten sulphur is converted into the biphase sulfur of scattered aerosol under huge decompressing effect, and aerosol is biphase
After sulfur contacts quenching absorption with the cooling medium of circulated sprinkling, enter into vertical response pot bottom cooling medium liquid environment
Middle formation solid-liquid two phase materials, the temperature of solid-liquid two phase materials is 40 DEG C, and the mass concentration of solid phase is 10%, is continually fed into
I.e. stop after the Molten sulphur of 50kg adding, continue to keep Carbon bisulfide quenching liquid to circulate 120 minutes.
After in vertical retort, solid-liquid two phase materials of bottom carries out sucking filtration and washs with 100kg Carbon bisulfide, send into true
Empty drying baker is the driest, obtains 25.6kg insoluble sulfur powder, yield 51.2%.Detect its index as follows: 120
DEG C 15 minutes heat stability 55.3%, mean diameter 42 microns, purity 95.8%.
Process described in the present embodiment is simple to operation, changes the way of contact of Molten sulphur and Carbon bisulfide quenching liquid,
Instead of traditional Carbon bisulfide quenching liquid and directly impact the quenching mode of Molten sulphur, it is to avoid use tradition directly impact
Extensive style quenching mode, utilizes the cooling medium liquid curtain of circulated sprinkling and the way of contact of the sulfur under the biphase state of aerosol,
Adding the contact area of the two, quenching effect is more preferable.Use this process obtain insoluble sulfur powder particle thin,
Purity is high, finished product good dispersion.
Embodiment 2:
The gasification quenching technique of the insoluble sulfur described in the present embodiment, as described in Example 1, they are different for this technical process
Part is, internal pressure be 1Mpa heater in Molten sulphur is heated to 600 DEG C-610 DEG C and by
The speed of 1.05kg/min is passed into pressure and is maintained at 0.1Mpa vertical response tank upper temp is in 60 DEG C of liquid curtains；Finally
The temperature of solid-liquid two phase materials obtained is 70 DEG C, and the mass concentration of solid phase is 35%, and in vertical retort, bottom consolidates
After liquid two phase materials carries out sucking filtration and washs with 100kg Carbon bisulfide, send into vacuum drying oven the driest, obtain 25.8kg
Insoluble sulfur powder, yield 51.6%.Detect its index as follows: 120 DEG C of 15 minutes heat stability 56.1%, average particle
34 microns of footpath, purity 96.3%.
Embodiment 3:
The gasification quenching technique of the insoluble sulfur described in the present embodiment, as described in Example 1, they are different for this technical process
Part is, internal pressure be 1Mpa heater in Molten sulphur is heated to 620 DEG C-630 DEG C and by 0.9kg/min
Speed be passed in the liquid curtain of vertical response tank top；The temperature of solid-liquid two phase materials finally obtained is 40 DEG C, solid phase
Mass concentration is 35%, and in vertical retort, solid-liquid two phase materials of bottom carries out sucking filtration and washs with 100kg Carbon bisulfide
After, send into vacuum drying oven the driest, obtain 26.3kg insoluble sulfur powder, yield 52.6%.Detect its index
As follows: 120 DEG C of 15 minutes heat stability 57.3%, mean diameter 29 microns, purity 97.1%.
Embodiment 4:
The gasification quenching technique of the insoluble sulfur described in the present embodiment, as described in Example 1, they are different for this technical process
Part is, internal pressure be 0.5Mpa heater in Molten sulphur is heated to 640 DEG C-650 DEG C and by
The speed of 0.7kg/min is passed in the liquid curtain of vertical response tank top；The temperature of solid-liquid two phase materials finally obtained is 70
DEG C, the mass concentration of solid phase is 10%, and in vertical retort, solid-liquid two phase materials of bottom carries out sucking filtration and uses 100kg
After Carbon bisulfide washing, send into vacuum drying oven the driest, obtain 26.9kg insoluble sulfur powder, yield 53.8%.
Detect its index as follows: 120 DEG C of 15 minutes heat stability 59.1%, mean diameter 23 microns, purity 98.0%.
Claims (7)
1. a gasification quenching technique for insoluble sulfur, this technical process is as follows,
(1) primary industry sulfur is warming up to 550 DEG C-650 DEG C in heater, keeps the pressure 0.5-1Mpa in heater simultaneously, make industrial sulphur be in superheat state, obtain overheated sulfur liquid；
(2) the overheated sulfur liquid in step (1) is injected in retort in the cooling medium liquid curtain of circulated sprinkling, the temperature of cooling medium is 20-60 DEG C, overheated sulfur liquid is 1:10-100 with the mass-velocity ratio of cooling medium, pressure in retort is maintained at 0.01-0.1Mpa, under differential pressure action, overheated sulfur liquid is converted into the biphase sulfur of scattered aerosol, by cooling medium liquid curtain sulfur biphase to aerosol quenching；
(3), after the biphase sulfur of aerosol in step (2) is absorbed by the cooling medium quenching of circulated sprinkling, enter into formation solid-liquid two phase materials in retort bottom coohng media fluid environment, solid-liquid two phase materials is solidified, extracts, obtains insoluble sulfur.
2. the gasification quenching technique of insoluble sulfur as claimed in claim 1, it is characterised in that described cooling medium is Carbon bisulfide or tetrachloroethylene or four hydrogen-based naphthalenes.
3. the gasification quenching technique of insoluble sulfur as claimed in claim 1 or 2, it is characterised in that in step (2), described overheated sulfur liquid is 1:30-50 with the mass-velocity ratio of cooling medium.
4. the gasification quenching technique of insoluble sulfur as claimed in claim 1, it is characterised in that in step (3), the temperature of solid-liquid two phase materials of formation is 40-70 DEG C.
5. the gasification quenching technique of insoluble sulfur as claimed in claim 4, it is characterised in that in step (3), in solid-liquid two phase materials of formation, solid phase mass concentration is 10-35%.
6. the gasification quenching technique of insoluble sulfur as claimed in claim 1, it is characterised in that described industrial sulphur is Molten sulphur.
7. the gasification quenching technique of insoluble sulfur as claimed in claim 1, it is characterised in that the retort in described step (1) is the vertical response tank with chuck.
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| CN107986242A (en) * | 2017-12-15 | 2018-05-04 | 谭建中 | The method that continuous one-step " mist mist slurry " method prepares " four is high " insoluble sulfur |
| CN114011558B (en) * | 2021-11-05 | 2022-08-09 | 山东阳谷华泰化工股份有限公司 | Particle size control method of insoluble sulfur |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1110025A (en) * | 1977-02-05 | 1981-10-06 | John T. Higgins | Granulation of sulfur |
| RU2107657C1 (en) * | 1997-04-11 | 1998-03-27 | Вячеслав Александрович Чиндяскин | Method of production of insoluble sulfur and device for its embodiment |
| ES2171105B1 (en) * | 2000-02-08 | 2003-11-01 | Repsol Petroleo Sa | PROCEDURE FOR THE PRODUCTION OF POLYMER 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 |
| CN2897989Y (en) * | 2005-08-10 | 2007-05-09 | 中国石油化工集团公司 | Insoluble sulfur spray cooling tower |
| CN101362837B (en) * | 2008-08-31 | 2010-09-08 | 河南省开仑化工有限责任公司 | Preparation technology of insoluble sulfur for rubber |
| CN101367506A (en) * | 2008-09-16 | 2009-02-18 | 无锡市华盛化工助剂厂 | Method for preparing insoluble sulfur |
| CN202226660U (en) * | 2011-07-26 | 2012-05-23 | 山东阳谷华泰化工股份有限公司 | Multifunctional insoluble sulfur production device |
| CN102275879B (en) * | 2011-07-26 | 2012-09-19 | 山东阳谷华泰化工股份有限公司 | Process for producing insoluble sulphur |
| CN102398896B (en) * | 2011-09-30 | 2014-06-04 | 河南省开仑化工有限责任公司 | New production technology of insoluble sulfur for rubber use |
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Denomination of invention: Gasification quenching process for insoluble sulfur Effective date of registration: 20211216 Granted publication date: 20161130 Pledgee: Industrial Bank Limited Liaocheng Branch Pledgor: SHANDONG YANGGU HUATAI CHEMICAL Co.,Ltd. Registration number: Y2021980015266 |
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