CN104843651A - Production process for preparing insoluble sulphur through low temperature method - Google Patents
Production process for preparing insoluble sulphur through low temperature method Download PDFInfo
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- CN104843651A CN104843651A CN201410054106.XA CN201410054106A CN104843651A CN 104843651 A CN104843651 A CN 104843651A CN 201410054106 A CN201410054106 A CN 201410054106A CN 104843651 A CN104843651 A CN 104843651A
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- insoluble sulfur
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Abstract
The present invention relates to a production process for preparing insoluble sulphur through a low temperature method, wherein ordinary industrial sulphur is adopted as a raw material, heating liquefaction, polymerization reaction, quenching, drying, crushing, extraction and oil filling are sequentially performed, the polymerization reaction is performed at a temperature of 220-300 DEG C, and stabilizers are respectively added during the polymerization reaction stage, the quenching stage, and the oil filling stage, such that the prepared insoluble sulphur has high thermal stability and high content. The process for producing the insoluble sulphur has advantages of low production equipment investment, simple process, low energy consumption, and the like.
Description
Technical field
The invention belongs to technical field of fine, be specifically related to the production technique that a kind of low temperature process prepares insoluble sulfur.
Background technology
Insoluble sulfur is widely used in the manufacturing of tire and other rubber composite product mainly as a kind of senior promotor of rubber industry and vulcanizing agent, in the sizing material that the carcass sizing material of such as tire, buffering sizing material, the white rubber such as sidewall rubber and tyre retreading, sebific duct, adhesive tape and framework material bond, also can be used in the sizing material of the rubber items such as cable, rubber roll, oil sealing, rubber overshoes, be also applied in the large light-colour rubber goods of sulfur consumption simultaneously.Because insoluble sulfur can make meridian, steel wire and rubber paste more firmly, effectively prevent sizing material crocking, improve heat-resisting, the wear resisting property of tire, therefore, insoluble sulfur is requisite important source material in tire production.
At present, the method producing insoluble sulfur both at home and abroad mainly contains scorification, gasification, contact process three kinds.Gasification technical maturity, per pass conversion is high, but have that energy consumption is high simultaneously, equipment and corrosion of piping serious, operate dangerous, technological process is more complicated, invest the shortcomings such as large.Contact process raw material is easy to get; production cost is low; there is certain economy and competitive power; but due to the toxicity of unstripped gas, especially the harm of hydrogen sulfide to human body is larger; this processing requirement production equipment strict seal; this is difficult to realize in the industrial production, and in actually operating, labour protection, environmental requirement etc. are difficult to reach related standards.Meanwhile, the raw material availability of contact process is high not as the production method with sulphur being directly raw material.Scorification temperature of reaction is low, equipment atmospheric operation, produces, have the advantage of less investment, instant effect, operational safety without " three wastes ".But scorification is produced insoluble sulfur technical study and is mostly still rested on laboratory stage or Industrial Simulation experimental stage.
Studies in China person has also carried out large quantifier elimination to the hot insoluble sulfur of height, and achieve good effect, such as: Chinese patent CN201110210853.4 discloses a kind of production technique of insoluble sulfur, Chinese patent CN201110297138.9 discloses the new production technique of a kind of rubber insoluble sulfur, provides a kind of method that pyroprocess prepares high hot insoluble sulfur.
Along with the development of the development of rubber item, particularly radial, new requirement is constantly proposed, i.e. high-content, high-temperature stability, polymolecularity to the performance of insoluble sulfur and quality index; The radial-ply tyre production line that domestic each giant tyre company introduces, also proposes the requirement of the insoluble sulfur using " three is high " performance.It can be said that the high-content of bright insoluble sulfur, high-temperature stability and polymolecularity will be its developing direction.This is the requirement of modern rubber high temperature process technology, be also insoluble sulfur open up a market application fundamental way.But existing pyroprocess produces insoluble sulfur energy consumption and equipment requirements is high, and security is low; Therefore develop the high hot insoluble sulfur of low temperature process production to have broad application prospects.
Summary of the invention
The object of the invention is to prepare for existing evaporating method the present situation that insoluble sulfur technological investment is high, energy consumption is high, there is provided a kind of watery fusion legal system for the new process of production of insoluble sulfur, the insoluble sulfur prepared possesses the feature of high thermal stability, high-content.
Technical scheme of the present invention:
A production technique for high-thermostability insoluble sulfur, with general industry sulphur for raw material, processing step comprises:
A () is heated up and is liquefied, general industry sulphur (content >=99.9%) liquefies under temperature is 150 ± 10 DEG C of conditions;
B () polyreaction, by sulphur and the 0.01% ~ 0.3%(massfraction of liquefying) one package stabilizer add in the reactor that band stirs, 220 ~ 300 DEG C of polyreactions 10 ~ 90 minutes;
C () is quenched, quenching liquid is water, and temperature controls at 5 ~ 20 DEG C, adds the one package stabilizer of 0.001% ~ 0.1% in quenching liquid, and in quenching process, liquid-state sulfur sprays and cools in quenching liquid after pressurization;
D () is dry, drying 10 ~ 15 hours under 60 ~ 80 DEG C of conditions;
E () pulverizes, smashing fineness requires more than 200 orders;
F () extracts, adopt dithiocarbonic anhydride to extract under 10 ~ 40 DEG C of conditions;
G () is dry, the insoluble sulfur after extraction under 40 ~ 80 DEG C of conditions dry 2 ~ 12 hours;
H () is oil-filled, in dried sulphur, add naphthenic oil, obtains oil-filled type insoluble sulfur after stirring.
Polyreaction of the present invention can be that separate unit reactor batch production or multiple stage reactor hocket, and reactor discharge opening is connected with tundish, realizes continuous seepage during multiple stage reactor alternating polymerization.
Stable composition agent content of the present invention is 0.01% ~ 0.3% of sulphur quality, and one package stabilizer is by I
2, KI, CH
2one or more compositions in=CHCl, DM, DZ.
Oil feeding process of the present invention be extraction dry after add 0.05% ~ 0.1% one package stabilizer fully stir, then oil-filled high-thermostability insoluble sulfur.
Compared with the prior art, technical characterstic of the present invention and beneficial effect are: add one package stabilizer in polymerization, quenching and oil-filled stage respectively, the insoluble sulfur prepared is made to possess high thermal stability and high-content, 120 DEG C ╳ 15min >=50%, content >=98% of insoluble sulfur.This technique has production unit for the production of insoluble sulfur and technique is simple, low power consumption and other advantages.
Accompanying drawing explanation
Fig. 1 is the process flow diagram of the embodiment of the present invention.
Embodiment
Below by way of specific embodiment, the present invention is further elaborated.
The technological process of embodiment as shown in Figure 1.
Embodiment 1:
By content be 99.9% general industry sulphur 1kg pour in high-order sulfur melting groove and be warming up to 150 DEG C of liquefaction, utilize high potential difference by molten sulfur and one package stabilizer (composition: 0.5gI
2+ 2.5gDZ) add in the reactor of band stirring, polyreaction 35min under 250 DEG C of conditions, flows into tundish by the sulphur of melting by discharge valve, sprays in quenching liquid through nozzle, quenching liquid temp controls at 10 DEG C, adds the one package stabilizer of 0.01% in quenching liquid.Under 60 DEG C of conditions, drying 10 hours, is crushed to more than 200 orders, adopts dithiocarbonic anhydride to extract at 20 DEG C; Insoluble sulfur after extraction under 60 DEG C of conditions dry 5 hours, adds the one package stabilizer of 0.05%, oil-filled high-thermostability insoluble sulfur.Be 50.4% when analyzing its thermostability 120 DEG C ╳ 15min, the content of insoluble sulfur is 98.3%.
Embodiment 2:
By content be 99.9% general industry sulphur 1kg pour in high-order sulfur melting groove and be warming up to 150 DEG C of liquefaction, utilize high potential difference by molten sulfur and one package stabilizer (composition: 0.3gKI+1.5gDM) add in the reactor of band stirring, polyreaction 30min under 260 DEG C of conditions, the sulphur of melting is flowed into tundish by discharge valve, spray in quenching liquid through nozzle, quenching liquid temp controls at 12 DEG C, adds the one package stabilizer of 0.02% in quenching liquid.Under 65 DEG C of conditions, drying 12 hours, is crushed to more than 200 orders, adopts dithiocarbonic anhydride to extract at 40 DEG C; Insoluble sulfur after extraction under 70 DEG C of conditions dry 3 hours, adds the one package stabilizer of 0.08%, oil-filled high-thermostability insoluble sulfur.Be 51.5% when analyzing its thermostability 120 DEG C ╳ 15min, the content of insoluble sulfur is 98.7%.
Embodiment 3:
By content be 99.9% general industry sulphur 1kg pour in high-order sulfur melting groove and be warming up to 150 DEG C of liquefaction, utilize high potential difference by molten sulfur and one package stabilizer (composition: 1.0gI
2+ 1.5gDZ) add in the reactor of band stirring, polyreaction 35min under 250 DEG C of conditions, flows into tundish by the sulphur of melting by discharge valve, sprays in quenching liquid through nozzle, quenching liquid temp controls at 8 DEG C, adds the one package stabilizer of 0.05% in quenching liquid.Under 70 DEG C of conditions, drying 13 hours, is crushed to more than 200 orders, adopts dithiocarbonic anhydride to extract at 30 DEG C; Insoluble sulfur after extraction under 40 DEG C of conditions dry 12 hours, adds the one package stabilizer of 0.03%, oil-filled high-thermostability insoluble sulfur.Be 48.1% when analyzing its thermostability 120 DEG C ╳ 15min, the content of insoluble sulfur is 99.0%.
Embodiment 4:
By content be 99.9% general industry sulphur 1kg pour in high-order sulfur melting groove and be warming up to 150 DEG C of liquefaction, utilize high potential difference by molten sulfur and one package stabilizer (composition: 0.2gI
2+ 1.5g CH
2=CHCl) add in the reactor of band stirring, polyreaction 50min under 250 DEG C of conditions, flows into tundish by the sulphur of melting by discharge valve, sprays in quenching liquid through nozzle, and quenching liquid temp controls at 13 DEG C, adds the one package stabilizer of 0.08% in quenching liquid.Under 64 DEG C of conditions, drying 10 hours, is crushed to more than 200 orders, adopts dithiocarbonic anhydride to extract at 30 DEG C; Insoluble sulfur after extraction under 60 DEG C of conditions dry 4 hours, adds the one package stabilizer of 0.04%, oil-filled high-thermostability insoluble sulfur.Be 50.3% when analyzing its thermostability 120 DEG C ╳ 15min, the content of insoluble sulfur is 98.5%.
Claims (6)
1. low temperature process prepares a production technique for insoluble sulfur, it is characterized in that comprising the following steps:
A () is heated up and is liquefied, sulphur liquefies under temperature is 140 ~ 160 DEG C of conditions;
(b) polyreaction, liquefaction sulphur and mass content are 0.01% ~ 0.3% one package stabilizer polyreaction 10 ~ 90 minutes at 220 ~ 300 DEG C;
C () is quenched, in quenching process, liquid-state sulfur sprays and cools in quenching liquid after pressurization;
D () is dry, drying 10 ~ 15 hours under 60 ~ 80 DEG C of conditions;
E () pulverizes, smashing fineness is more than 200 orders;
F () extracts, adopt dithiocarbonic anhydride to extract under 10 ~ 40 DEG C of conditions;
G () is dry, the insoluble sulfur after extraction under 40 ~ 80 DEG C of conditions dry 2 ~ 12 hours;
H () is oil-filled, in dried sulphur, add naphthenic oil, obtains oil-filled type insoluble sulfur after stirring.
2. a kind of low temperature process prepares the production technique of insoluble sulfur according to claim 1, it is characterized in that described polyreaction is that separate unit reactor batch production or multiple stage reactor hocket, reactor discharge opening is connected with tundish, realizes carrying out continuously of polyreaction and quenching process during the polymerization of multiple stage reactor.
3. a kind of low temperature process prepares the production technique of insoluble sulfur according to claim 1, it is characterized in that described sulphur is general industry sulphur, content >=99.9%.
4. a kind of low temperature process prepares the production technique of insoluble sulfur according to claim 1, it is characterized in that described one package stabilizer is by I
2, KI, CH
2one or more compositions in=CHCl, DM, DZ.
5. a kind of low temperature process prepares the production technique of insoluble sulfur according to claim 1, it is characterized in that described quenching liquid is the aqueous solution containing 0.001% ~ 0.1% one package stabilizer, controls quenching liquid temp at 5 ~ 20 DEG C.
6. a kind of low temperature process prepares the production technique of insoluble sulfur according to claim 1, it is characterized in that oil-filled before add 0.05% ~ 0.1% one package stabilizer fully stir, then oil-filled high-thermostability insoluble sulfur.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105502303A (en) * | 2016-01-22 | 2016-04-20 | 上海京海（安徽）化工有限公司 | Production process for preparing insoluble sulfur high in thermal stability and content |
| CN106829877A (en) * | 2017-03-06 | 2017-06-13 | 杨松 | One kind prepares insoluble sulfur mist projection granulating tower |
| CN106987025A (en) * | 2017-04-11 | 2017-07-28 | 上海京海（安徽）化工有限公司 | A kind of oil-filled type insoluble sulfur of high thermal stability and its preparation |
| CN107324289A (en) * | 2017-09-01 | 2017-11-07 | 上海京海（安徽）化工有限公司 | The production technology of grade insoluble sulphur in prepared by watery fusion method |
| CN107337184A (en) * | 2017-09-01 | 2017-11-10 | 上海京海（安徽）化工有限公司 | A kind of Heat-resistant stable insoluble sulfur and its production method |
| CN108129693A (en) * | 2017-12-22 | 2018-06-08 | 蔚林新材料科技股份有限公司 | Oil-filled type insoluble sulfur and its preparation method and application |
| CN114426263A (en) * | 2020-10-13 | 2022-05-03 | 中国石油化工股份有限公司 | Method for preparing insoluble sulfur by low-temperature melting process |
| EP4071109A4 (en) * | 2019-12-31 | 2023-05-24 | China Petroleum & Chemical Corporation | Production system and method for insoluble sulfur |
-
2014
- 2014-02-18 CN CN201410054106.XA patent/CN104843651A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105502303A (en) * | 2016-01-22 | 2016-04-20 | 上海京海（安徽）化工有限公司 | Production process for preparing insoluble sulfur high in thermal stability and content |
| CN106829877A (en) * | 2017-03-06 | 2017-06-13 | 杨松 | One kind prepares insoluble sulfur mist projection granulating tower |
| CN106829877B (en) * | 2017-03-06 | 2018-10-23 | 杨松 | It is a kind of to prepare insoluble sulfur mist projection granulating tower |
| CN106987025A (en) * | 2017-04-11 | 2017-07-28 | 上海京海（安徽）化工有限公司 | A kind of oil-filled type insoluble sulfur of high thermal stability and its preparation |
| CN106987025B (en) * | 2017-04-11 | 2019-05-24 | 上海京海（安徽）化工有限公司 | A kind of oil-filled type insoluble sulfur of high thermal stability and its preparation |
| CN107324289A (en) * | 2017-09-01 | 2017-11-07 | 上海京海（安徽）化工有限公司 | The production technology of grade insoluble sulphur in prepared by watery fusion method |
| CN107337184A (en) * | 2017-09-01 | 2017-11-10 | 上海京海（安徽）化工有限公司 | A kind of Heat-resistant stable insoluble sulfur and its production method |
| CN108129693A (en) * | 2017-12-22 | 2018-06-08 | 蔚林新材料科技股份有限公司 | Oil-filled type insoluble sulfur and its preparation method and application |
| CN108129693B (en) * | 2017-12-22 | 2020-10-30 | 蔚林新材料科技股份有限公司 | Oil-extended insoluble sulfur and preparation method and application thereof |
| EP4071109A4 (en) * | 2019-12-31 | 2023-05-24 | China Petroleum & Chemical Corporation | Production system and method for insoluble sulfur |
| CN114426263A (en) * | 2020-10-13 | 2022-05-03 | 中国石油化工股份有限公司 | Method for preparing insoluble sulfur by low-temperature melting process |
| CN114426263B (en) * | 2020-10-13 | 2023-07-04 | 中国石油化工股份有限公司 | Method for preparing insoluble sulfur by low-temperature melting process |
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