CN100581993C - Process for extracting insoluble sulfur - Google Patents
Process for extracting insoluble sulfur Download PDFInfo
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- CN100581993C CN100581993C CN200710118271A CN200710118271A CN100581993C CN 100581993 C CN100581993 C CN 100581993C CN 200710118271 A CN200710118271 A CN 200710118271A CN 200710118271 A CN200710118271 A CN 200710118271A CN 100581993 C CN100581993 C CN 100581993C
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Abstract
The invention relates to method for extracting insoluble sulfur from a product of IS-90 obtained from a polymerization insoluble sulfur crude product by utilizing tetranap. The method is characterized in that a product of high purity with the content of insoluble sulfur larger than 90m percent is obtained and extracted from a product with the content of insoluble sulfur being 40-80m percent after ordinary sulfur polymerization by using tetranap as an extracting solvent at the temperature of 70-90 DEG C for 10-45 minutes; the mass ratio of the solvent is between 2.3 and 9; the solvent has the characteristics of good effect, low toxicity, no easy volatilization, and good safety, can be used as a novel safe, environmental-friendly and high efficient insoluble sulfur extracting solvent instead of CS2 and tetracarp, and is suitable for the extraction separation of obtaining the insoluble sulfur product of high purity from the product obtained after ordinary sulfur polymerization. The adoption of the technology can greatly reduce investment expense of devices and improve the safety of operation process.
Description
Technical field
The present invention relates to a kind of insoluble sulfur extracting process that utilizes naphthane extraction polymerization insoluble sulfur crude product to obtain the product of IS-90.
Background technology
Insoluble sulfur, chemical name are polymerised sulphur (being called for short IS), and it is that raw material makes with common sulphur, and by the linear polymeric that a large amount of sulphur atoms is polymerized, its molecular weight is 30000～40000.Because of common sulphur at CS
2In solubleness very big, and polymerised sulphur is insoluble to CS
2So, be called insoluble sulfur usually.According to polymerised sulphur content difference, product is divided into IS-60 (IS content 〉=60%), IS-90 (IS content 〉=90%) two classes.Some physical properties of insoluble sulfur and rubber are approaching, are vulcanizing agents good in the Rubber processing, are widely used in natural rubber and synthetic rubber, wherein consumption maximum in the doughnut production.
Insoluble sulfur preparation technology is mainly successively through three operations: polymerization, extraction, oil-filled.Common sulphur is through polyreaction, obtain the crude product that IS content reaches a certain numerical value,, adopt solvent-extracted mode to make common sulphur be dissolved in the solvent in order to realize separating of common sulphur and polymerised sulphur, thereby obtain the insoluble sulfur product of higher degree, carry out the oil-filled product of making at last again.
The thirties in last century, U.S. Stauffer company at first obtains the patent of the insoluble sulphur of grade in the preparation (IS content 40～50%), has realized suitability for industrialized production the forties.Britain, Germany, USSR (Union of Soviet Socialist Republics), Japan and other countries are are all researched and developed insoluble sulfur afterwards.Occur high-quality (IS content is more than 90%) insoluble sulfur after the seventies, and further formed oil-filled type insoluble sulfur series product.China began one's study from the seventies, the suitability for industrialized production that just realized insoluble sulfur in 1976, and the insoluble sulfur IS-60 of low-quality (60%) can not satisfy the requirement of radial rubber vulcanization during major part can only be produced at present.Because the promotion of domestic market demand, the high quality insoluble sulphur production technology is just conducted a research recent years.Generally adopt gasification or scorification polymerization, extracting and purifying technology to produce IS-90 at present both at home and abroad.Evaporating method polymerization temperature height, seriously corroded, explosive, dangerous big, but transformation efficiency is higher, and IS can reach 60-70%.The melt phase polycondensation temperature is low, safe, but transformation efficiency only is about 40%.Adopt the in the majority of evaporating method explained hereafter insoluble sulfur as a whole.Because CS
2Solvent cost is low, extraction efficiency is high and easily recovery, and therefore, the insoluble sulfur extracting and purifying technology adopts CS basically
2Solvent, but CS
2Inflammable, explosive, toxicity is big, volatile race damage, production operation are dangerous big, has seriously restricted the expansion of ordinary production and unit scale, the problem that the exploitation of novel extraction solvent becomes domestic and international concern and needs to be resolved hurrily.
The research of novel extraction solvent report is few at present, and research work all rests in the discussion of solvent extraction effect basically, dissolution process mechanism and the rule of sulphur in different solvents almost do not reported, the point of penetration that lacks effective research means and research, thereby all do not obtain can real gratifying result.The novel extraction agent of existing report mainly contains: zellon, tetracol phenixin, trichloroethane, zellon and trichloroethane mixed solution and CO
2Supercritical extraction etc., but these extraction agents all can't truly replace CS
2, except production cost can't and CS
2Outside comparing, effect of extracting also and CS
2Bigger gap is arranged.
The solvent of the mixed solvent method of Institutes Of Technology Of Taiyuan research has boiling point height, flash-point height, temperature of combustion height, advantage that flammable range is little, and toxicity also is lower than CS
2Adopt mixed solvent and traditional CS
2The solvent phase ratio, operational danger is little, toxicity is low, solvent is easy to reclaim, and the same during as extraction agent with the use zellon, and technological process can be saved the sfgd. and the relevant device of various complexity, thereby has reduced investment and running cost.All right in addition by-product high purity sulphur has improved economic benefit, is a research direction that merits attention therefore.But relevant report does not relate to a series of detailed problems that comprise effect of extracting, agent sulphur ratio, solvent loss etc., and after reporting certainly, does not see this skilled industry application always.
Non-CS
2The solvent extraction effect is generally lower, but security is better than CS
2Extraction, but also there is certain toxicity in this kind solvent.
Summary of the invention
It is low to the objective of the invention is to develop a kind of toxicity of utilizing, and boiling point is higher, and not volatile, poor solubility is bigger, and effect of extracting naphthane is preferably made extraction agent, the extracting process of extraction insoluble sulfur.
Extraction solvent of the present invention is the naphthalene series compound naphthane; Extract be after the common sulphur polymerization insoluble sulfur content at the product of 40-80m%, extraction temperature is that 70～90 ℃, solvent quality ratio are 2.3～9,10～45 minutes time, can obtain the high purity product (m% is a mass percent) of insoluble sulfur content＞90m%.
By the research of solvent, and, selected naphthalene series substance matter naphthane as novel replace solvents on multiple solvent experimental study and the correlated basis to the inherent dissolution mechanism of sulphur dissolving power.Relatively see Table 1 with the effect of extracting of different types of extraction agent.
Table 1: the molar solubility of different solvents (mol/mol)
Through analysis of experiments and contrast, under identical extraction conditions, naphthane effect of extracting the best, its extraction numerical value is 0.529mol/mol (molar solubility) under 80 ℃.
The solvent of invention has following advantage:
1, effect of extracting: suitable with dithiocarbonic anhydride significantly better than zellon;
2, volatility: well below zellon and dithiocarbonic anhydride, solvent loss is few;
3, toxicity: be significantly less than dithiocarbonic anhydride, also be lower than zellon;
4, flammable, security: though flammable, flash-point is higher than dithiocarbonic anhydride far away, and is difficult for spontaneous combustion;
5, chemical stability: be higher than zellon and dithiocarbonic anhydride, be easy to store.
Solvent of the present invention has that effect of extracting is good, toxicity is low, not volatile, characteristics that security is good, can substitute CS
2, zellon becomes safety, environmental protection, novel insoluble sulphur extraction solvent efficiently, is applicable to the extraction and separation technology that obtains high purity insoluble sulfur product from the product after the common sulphur polymerization.Adopt this technology, will reduce the facility investment expense greatly, and improve the security of operating process, fundamentally solve in the insoluble sulfur production process, help to solve the production-scale bottleneck problem of restriction the paying property of poison and the security of human body.
Embodiment
Embodiment 1-2
With the IS mass content is that 48.6% industrial insoluble sulfur crude product is as raw material, adopting solvent of the present invention is extraction agent, 80 ℃ of extraction temperature, and 15 minutes extraction time, carry out extraction experiments, the content of IS such as following table 2 in the product that obtains by regulating solvent ratio.
It is the extraction agent experimental result that table 2 adopts solvent of the present invention
| Solvent ratio (m: m) | 4.35 | 4.85 |
| IS content in the product, m% | 92.23 | 95.00 |
Embodiment 3-4
With the different insoluble sulfur crude product of IS content as raw material, adopting industrialized dithiocarbonic anhydride, zellon and solvent of the present invention respectively is extraction agent, 80 ℃ of extraction temperature (then is 25 ℃ to dithiocarbonic anhydride), carry out extraction experiments during 15 minutes extraction time, the content of IS such as following table 3 in the product that obtains.
Table 3 adopts solvent of the present invention, zellon, the dithiocarbonic anhydride extraction results to different material
| Solvent | IS content in the raw material, m% | Solvent ratio | IS content in the product, m% |
| Solvent of the present invention | 40.6 | 6 | 91.91 |
| Solvent of the present invention | 43.5 | 6 | 92.43 |
| Zellon | 43.5 | 17 | 91.62 |
| Dithiocarbonic anhydride | 43.5 | 7.5 | 92.14 |
From the result of table 3, effect of extracting and the dithiocarbonic anhydride solvent phase of obvious extraction solvent of the present invention when purification insoluble sulfur product worked as, but will be significantly better than tetrachloroethylene solvent.
Embodiment 5-9
With the IS mass content be 48.6% industrial insoluble sulfur crude product as raw material, 15 minutes extraction time, the effect of extracting of solvent of the present invention under differing temps and solvent ratio, result such as following table 4.
The extraction results of table 4 solvent of the present invention under differing temps and solvent ratio
| Solvent ratio, m: m | Extraction temperature, ℃ | IS content in the product, m% |
| 4.85 | 80℃ | 95.00 |
| 4.85 | 75℃ | 89.02 |
| 4.85 | 70℃ | 86.92 |
| 5.62 | 80℃ | 97.86 |
| 5.62 | 70℃ | 91.14 |
By table 4 result as seen, reduce extraction temperature, the effect of extracting of solvent will descend.
Embodiment 10-11
With the IS mass content is that 48.6% industrial insoluble sulfur crude product is as raw material, adopting solvent of the present invention is extraction agent, 80 ℃ of extraction temperature, and 10 minutes extraction time, carry out extraction experiments, the content of IS such as following table 5 in the product that obtains by regulating solvent ratio.
Table 5 adopts the extraction experiments result of solvent of the present invention
| Solvent ratio (m: m) | 8.11 | 9 |
| IS content in the product, m % | 87.68 | 91.87 |
Embodiment 12-13
With the IS mass content be 48.6% industrial insoluble sulfur crude product as raw material, adopt extraction solvent of the present invention, 80 ℃ of extraction temperature, 45 minutes extraction time, carry out extraction experiments, the content of IS such as following table 6 in the product that obtains by regulating solvent ratio
Table 6 adopts extraction agent experimental result of the present invention
| Solvent ratio (m: m) | 6.3 | 6.72 |
| IS content in the product, m% | 92.80 | 95.06 |
Claims (1)
1. the extracting process of an insoluble sulfur, it is characterized in that: to insoluble sulfur content after the common sulphur polymerization at the product of 40-80m%, make extraction solvent with naphthane, be 4.35～9 at 70～90 ℃, solvent quality ratio, the time is to extract under the condition in 10～45 minutes, obtain the high purity product of insoluble sulfur content＞90m%, wherein m% is a mass percent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710118271A CN100581993C (en) | 2007-07-04 | 2007-07-04 | Process for extracting insoluble sulfur |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710118271A CN100581993C (en) | 2007-07-04 | 2007-07-04 | Process for extracting insoluble sulfur |
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|---|---|
| CN101337659A CN101337659A (en) | 2009-01-07 |
| CN100581993C true CN100581993C (en) | 2010-01-20 |
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|---|---|---|---|
| CN200710118271A Active CN100581993C (en) | 2007-07-04 | 2007-07-04 | Process for extracting insoluble sulfur |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102502521A (en) * | 2011-11-02 | 2012-06-20 | 陕西科技大学 | Preparation method for sulfur micro-emulsion |
| CN106986311B (en) * | 2017-04-11 | 2019-01-25 | 上海京海（安徽）化工有限公司 | A kind of high content insoluble sulfur extraction process |
-
2007
- 2007-07-04 CN CN200710118271A patent/CN100581993C/en active Active
Non-Patent Citations (2)
| Title |
|---|
| 橡胶添加剂不溶性硫的研究进展. 王勇等.弹性体，第16卷第(6)期. 2006 |
| 橡胶添加剂不溶性硫的研究进展. 王勇等.弹性体，第16卷第(6)期. 2006 * |
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