CN104211657A - Refining method of rubber vulcanizing accelerant M - Google Patents
Refining method of rubber vulcanizing accelerant M Download PDFInfo
- Publication number
- CN104211657A CN104211657A CN201410439853.5A CN201410439853A CN104211657A CN 104211657 A CN104211657 A CN 104211657A CN 201410439853 A CN201410439853 A CN 201410439853A CN 104211657 A CN104211657 A CN 104211657A
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- China
- Prior art keywords
- mercaptobenzothiazole
- mbt
- purification
- sodium salt
- product
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
- C07D277/62—Benzothiazoles
- C07D277/68—Benzothiazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
- C07D277/70—Sulfur atoms
- C07D277/72—2-Mercaptobenzothiazole
Abstract
The invention relates to a refining method of a rubber vulcanizing accelerant M, belonging to the technical field of rubber vulcanizing accelerant M purification. The refining method of the rubber vulcanizing accelerant M comprises the following steps of (1) adding a crude M sodium salt solution into a reaction kettle, adding water, controlling the mass concentration of sodium salt at 55-65%, dropwise adding dilute sulphuric acid, and neutralizing the pH value of the solution to 7-10; (2) adding an extracting agent into the solution obtained in the step (1), and then, introducing pure oxygen; and (3) adding dilute sulphuric acid into the solution obtained in the step (2), regulating the pH value to 5-9, and then, carrying out aftertreatment to obtain the refined rubber vulcanizing accelerant M. The refining method is capable of sufficiently utilizing raw materials, low in cost, simple in process, energy-saving and environment-friendly.
Description
Technical field
The present invention relates to a kind of process for purification of 2 Mercaptobenzothiazole (MBT), belong to the purification techniques field of 2 Mercaptobenzothiazole (MBT).
Background technology
2 Mercaptobenzothiazole (MBT) (2-mercaptobenzothiazole) is the universal promotor of widely used one in Rubber processing industry, be the kind that thiofide volume of production and marketing is maximum both at home and abroad at present, be also the main raw material producing sulfenamide type accelerators simultaneously.
There are Flexsys Inc. of the U.S., German Lanxess Corporation, Chemtura Corporation of the U.S. etc. in the main manufacturing enterprise of external 2 Mercaptobenzothiazole (MBT), these companies respectively from U.S. Meng Shan all, Bayer Bitterfeld GmbH, Uniroyal,Inc. of the U.S. peel off or buy.The operational path of comprehensive above several rubber accelerator M, the synthesis of external main production company rubber accelerator M has following common feature, and 1, all employing aniline process produce; 2, reaction conditions: temperature 200-300 DEG C, pressure is 50-150kg/cm
3; 3, the treating process of thick M generally adopts solvent extration; 4, the Returning reacting system such as by product benzothiazole circulates; 5, to unreacted CS
2with by product H
2s etc. are reclaimed.
It is the aniline process that raw material and dithiocarbonic anhydride, sulphur carry out reacting that current domestic production corporate boss will adopt with aniline, is divided into high-pressure process and non-pressure process.Because high-pressure process can realize continuous prodution, and cost is lower and industrially favored, and the large more options high-pressure process of recent year is produced.High pressure aniline process is aniline, CS
2synthesize at high temperature under high pressure with sulphur three kinds of raw materials, then obtain rubber accelerator M through a series of aftertreatment separation, purification.Its classical technical process is as follows: first aniline and CS
2be obtained by reacting crude product M under being dissolved in 220 ~ 280C, 8.0 ~ 10.0MPa, a series of separation circuit such as then, oxidation molten through alkali, filtration, acidifying, dehydration, drying obtains fine work M.According to the difference of aftertreatment, acid-base method and solvent method can be divided into again.
High pressure aniline process manufacturing condition is stablized, cost is lower, quality product is high, but still it is high to there is raw materials consumption, batch production cost is high, in whole reaction process, the composition of nearly 10-15% can not be converted into captax completely, in crude product M, the content of captax is about 85%-90%, also has unreacted material (aniline in addition, sulphur, dithiocarbonic anhydride, account for 5-7%), intermediate product (thiambutosine, benzothiazole and anilino benzothiazole, account for 4%-7%), tarry matters (spent resin) the about 1%-2% that other by products and structure are failed to understand, meanwhile, discharge of wastewater is many, and power load is high, the waste gas H of high-pressure synthesis
2the CS of S and surplus
2do not reclaim, the hydrogen sulfide contamination of discharge is serious.Therefore, improve the yield of product further, reduce costs, energy-saving and emission-reduction etc. becomes urgent need to solve the problem.
Summary of the invention
The object of this invention is to provide a kind of process for purification of 2 Mercaptobenzothiazole (MBT), it makes full use of raw material, and cost is low, and technique is simple, energy-conserving and environment-protective.
The process for purification of 2 Mercaptobenzothiazole (MBT) of the present invention, comprises the following steps:
(1) thick M sodium salt solution is added in reactor, adds water, make sodium salt mass concentration control at 55-65%, drip dilute sulphuric acid, neutralization solution pH to 7-10;
(2) in step (1) gained solution, add extraction agent, then pass into pure oxygen;
(3) in step (2) gained solution, add dilute sulphuric acid, adjust ph, to 5-9, then obtains fine work 2 Mercaptobenzothiazole (MBT) through last handling process.
Described extraction agent is the mixing solutions of water, 27.5wt% hydrogen peroxide and 93wt% sulfuric acid, and the volume ratio of water, 27.5wt% hydrogen peroxide and 93wt% sulfuric acid is 4200:430:160.
The agitator motor rotating speed of described reactor is 50-60r/min.
The intake of described pure oxygen is 2.0-4.0m
3/ h; The time passing into pure oxygen is 0.5-1.0h.
Thick M sodium salt, for synthesizing with high pressure aniline process, then uses the sodium salt of sodium hydroxide solubilizing reaction gained.
Add water in step (1) and the mass concentration of sodium salt controlled at 55-65%, because concentration affects the yield of product, excessive concentration or too lowly all can reduce yield.
Adding dilute sulphuric acid in step (1) regulates pH at 7-10, because pH affects yield and the fusing point of product, and too high or too low yield and the fusing point that all can reduce product of pH.
In step (2), temperature of reaction controls at 40-50 DEG C.
In step (3), last handling process for first to carry out sedimentation, separation, then carries out filtering, wash, dry.
Add a certain amount of hydrogen peroxide in extraction agent, decrease the process of follow-up waste water, therefore hydrogen peroxide serves water-saving effect; Hydrogen peroxide can also play energy-conservation effect in addition, because need temperature of reaction to control at 40-50 DEG C in the process for purification of 2 Mercaptobenzothiazole (MBT), and in extraction process, the impurity in hydrogen peroxide and crude product M sodium salt reacts, release heat in reaction process, thus save steam consumption.
In crude product M sodium salt, pass into pure oxygen, pure oxygen can intermediate product benzothiazole in catalysis crude product M sodium salt and anilino benzothiazole continue to generate M with sulfur reaction, thus makes M content increase in crude product M, and the method takes full advantage of raw material, has saved cost.
The present invention has following beneficial effect:
(1) process for purification of 2 Mercaptobenzothiazole (MBT) of the present invention, it makes full use of raw material, and cost is low, and energy-conserving and environment-protective are simple for process, are convenient to large-scale commercial production.
(2) the fine work rubber accelerator M that obtains of the present invention, color is vivid, and purity improves 0.5-1.5% compared to existing technology, and yield improves 2-4%, and oxidization time shortens 1-1.5h, and cost reduces 200-400 yuan/ton.
Embodiment
Below in conjunction with embodiment, the present invention is further illustrated, but it does not limit enforcement of the present invention.
Raw materials usedly be commercially available prod.
The process for purification of described 2 Mercaptobenzothiazole (MBT), comprises the following steps:
(1) thick M sodium salt solution is put into reactor, add water, make sodium salt mass concentration control at 55-65%, drip dilute sulphuric acid, neutralization solution pH to 7-10;
(2) in step (1) gained solution, add extraction agent, then pass into pure oxygen, temperature of reaction controls at 40-50 DEG C;
(3) in step (2) gained solution, add dilute sulphuric acid, adjust ph, to 5-9, then obtains fine work 2 Mercaptobenzothiazole (MBT) through last handling process.Last handling process for first to carry out sedimentation, separation, then carries out filtering, wash, dry.
Extraction agent is the mixing solutions of water, 27.5wt% hydrogen peroxide and 93wt% sulfuric acid, and the volume ratio of water, 27.5wt% hydrogen peroxide and 93wt% sulfuric acid is 4200:430:160.
The agitator motor rotating speed of reactor is 50-60r/min.
Embodiment 1
Still interior reaction temperature 40 DEG C, under 58r/min agitation condition, pH value 9, reaction 0.5h, investigate the impact on M yield and product performance of oxygen add-on, it the results are shown in Table 1.
Table 1 oxygen add-on is on the impact of M yield and product performance
| Oxygen add-on m 3/h | Yield % | Product colour | Product is fusing point DEG C just |
| 0.5 | 81.2 | Light brown | Defective |
| 1.0 | 85.5 | Yellow | 170.2 |
| 2.0 | 90.4 | Faint yellow | 170.3 |
| 3.0 | 90.8 | Faint yellow | 170.1 |
| 4.0 | 90.9 | Faint yellow | 170.2 |
As can be seen from Table 1, along with the increase of oxygen add-on, yield also increases, and product colour and first fusing point also defectively to change to high-quality product from original.When oxygen add-on is 2.0-4.0m
3during/h, the yield of product tends towards stability, and therefore, oxygen add-on is 2.0m
3/ h is better.
Embodiment 2
Oxygen add-on 2.0m in still
3under/h, 58r/min agitation condition, pH value 9, reaction 0.5h, investigate the impact of temperature of reaction on M yield and product performance, it the results are shown in Table 2.
Table 2 temperature of reaction is on the impact of M yield and product performance
| Temperature of reaction DEG C | Yield % | Product colour | Product is fusing point DEG C just |
| 50 | 85.0 | Light brown | 170.1 |
| 45 | 88.7 | Faint yellow | 170.3 |
| 40 | 90.4 | Faint yellow | 170.3 |
| 35 | 89.1 | Faint yellow | 170.4 |
| 30 | 77.9 | Brown | Defective |
As can be seen from Table 2, below 40 DEG C, along with the rising product yield of temperature increases thereupon, product colour by brown to faint yellow transformation, first fusing point by defective to qualified transformation.After 50 DEG C, because the increase of by product makes colour-darkening, first fusing point also declines.It can thus be appreciated that 40 DEG C of reactions better.
Embodiment 3
Oxygen add-on 2.0m in still
3under/h, temperature of reaction 40 DEG C, 58r/min agitation condition, pH value 9.Investigate the impact of reaction time on yield and product performance, the results are shown in Table 3.
Table 3 reaction times is on the impact of product yield and product performance
| Reaction times h | Product yield % | Product colour | Product is fusing point DEG C just |
| 0.2 | 88.5 | Grey | 170.1 |
| 0.35 | 90.3 | Faint yellow | 170.4 |
| 0.5 | 90.4 | Faint yellow | 170.3 |
| 0.75 | 90.7 | Faint yellow | 170.6 |
| 1.0 | 90.8 | Light brown | 170.1 |
As can be seen from Table 3, product yield increases in time and increases, and product colour is constantly deepened, and is because the increase of over oxidation and by product causes.Therefore, the reaction times is that 0.5h is better.
Claims (7)
1. a process for purification for 2 Mercaptobenzothiazole (MBT), is characterized in that comprising the following steps:
(1) thick M sodium salt solution is added in reactor, adds water, make sodium salt mass concentration control at 55-65%, drip dilute sulphuric acid, neutralization solution pH to 7-10;
(2) in step (1) gained solution, add extraction agent, then pass into pure oxygen;
(3) in step (2) gained solution, add dilute sulphuric acid, adjust ph, to 5-9, then obtains fine work 2 Mercaptobenzothiazole (MBT) through last handling process.
2. the process for purification of 2 Mercaptobenzothiazole (MBT) according to claim 1, is characterized in that: extraction agent is the mixing solutions of water, 27.5wt% hydrogen peroxide and 93wt% sulfuric acid.
3. the process for purification of 2 Mercaptobenzothiazole (MBT) according to claim 2, is characterized in that: the volume ratio of water, 27.5wt% hydrogen peroxide and 93wt% sulfuric acid is 4200:430:160.
4. the process for purification of 2 Mercaptobenzothiazole (MBT) according to claim 1, is characterized in that: the agitator motor rotating speed of reactor is 50-60r/min.
5. the process for purification of 2 Mercaptobenzothiazole (MBT) according to claim 1, is characterized in that: the intake of pure oxygen is 2.0-4.0m
3/ h; The time passing into pure oxygen is 0.5-1.0h.
6. the process for purification of 2 Mercaptobenzothiazole (MBT) according to claim 1, is characterized in that: in step (2), temperature of reaction controls at 40-50 DEG C.
7. the process for purification of 2 Mercaptobenzothiazole (MBT) according to claim 1, is characterized in that: in step (3), and last handling process for first to carry out sedimentation, separation, then carries out filtering, wash, dry.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105175353A (en) * | 2015-10-15 | 2015-12-23 | 内蒙古科迈化工有限公司 | Method for performing ammonolysis on oxygen to obtain rubber accelerator MBT by oxidization-synthesis |
| CN105883808A (en) * | 2014-11-07 | 2016-08-24 | 王兴路 | Method for preparing carbon disulfide |
| CN108144462A (en) * | 2017-11-22 | 2018-06-12 | 孝感市锐思新材科技有限公司 | A kind of preparation method of 2-mercaptobenzothiazole purification material |
| CN112919469A (en) * | 2021-01-28 | 2021-06-08 | 河南乾瑞化工科技有限公司 | Recycling method of waste resin of accelerator M |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105883808A (en) * | 2014-11-07 | 2016-08-24 | 王兴路 | Method for preparing carbon disulfide |
| CN105175353A (en) * | 2015-10-15 | 2015-12-23 | 内蒙古科迈化工有限公司 | Method for performing ammonolysis on oxygen to obtain rubber accelerator MBT by oxidization-synthesis |
| CN108144462A (en) * | 2017-11-22 | 2018-06-12 | 孝感市锐思新材科技有限公司 | A kind of preparation method of 2-mercaptobenzothiazole purification material |
| CN112919469A (en) * | 2021-01-28 | 2021-06-08 | 河南乾瑞化工科技有限公司 | Recycling method of waste resin of accelerator M |
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Application publication date: 20141217 |