CN102675242A - Refining method of vulkacit M - Google Patents
Refining method of vulkacit M Download PDFInfo
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- CN102675242A CN102675242A CN2012101397442A CN201210139744A CN102675242A CN 102675242 A CN102675242 A CN 102675242A CN 2012101397442 A CN2012101397442 A CN 2012101397442A CN 201210139744 A CN201210139744 A CN 201210139744A CN 102675242 A CN102675242 A CN 102675242A
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Abstract
The invention belongs to the technical field of fine chemical engineering, and relates to a refining method of vulkacit M. The method comprises the following steps of: adding recovered M and coarse M into an autoclave according to the mass ratio of 1:(8-12), adding organic solvent of which the weight is 1.3-2.22 times as heavy as the weight of M and heating, in the case that the pressure is 0.4-0.8MPa, and the temperature is 100-160DEG C, starting stirring in case of high temperature, cooling after 30-50min, discharging after the material is cooled to the room temperature, filtering, and drying, to be capable of obtaining the high-quality 2-mercaptobenzothiazole finished product and filter liquor; continuously taking organic solvent recovered by distilling the filter liquor as refined raw material; collecting the residual black solid tar after being repeatedly distilled, washing and extracting the tar by 10%-20% sodium hydroxide solution, wherein the PH value of the solution is 8-12, and transferring the organic matter in the solution into water phase; controlling the temperature at 45-75DEG C, charging air to oxidize for 2-4hours, and acidizing till the pH is 5-8 by 8-20% sulfuric acid; and filtering, and drying to obtain the recovered M to be continuously and cyclically refined. The invention is the method which is economical and environment-friendly, and can recycle the recovered M from the tar.
Description
Technical field
The invention belongs to the fine chemical technology field, relate to thiofide, is the process for purification of a kind of accelerator M (2-mercaptobenzothiazole).
Background technology
2-mercaptobenzothiazole (be called captax or accelerant MBT again, also can be called 2-mercaptobenzothiazole), it is good to vulcanize smooth performance, and sulfuration critical temperature low (125 ℃) can be widely used in various rubber, has broad cure range, can use separately.Therefore purposes is wider, and consumption is maximum.Main both at home and abroad at present employing aniline, dithiocarbonic anhydride and sulphur height are pressed into, and obtain the synthetic route of captax again through a series of separation, purification process.
Captax purified method mainly contains acid-base method and solvent method.Acid-base method be with bullion M through neutralization, pickling (have need secondary neutralization, pickling), washing, dry, pulverize and make refining M.Domestic rubber accelerator M crude product refining adopts acid-base method technology more, and products obtained therefrom purity is 97%, about 170～172 ℃ of fusing points, and complex process, condition control is harsh, and equipment corrosion produces a large amount of spent acid, salkali waste needs to handle.Solvent method is that thick M is made refining M with SX, drying, pulverizing.Solvent for use mainly contains CS
2, ethanol, tetracol phenixin and toluene etc.
Chinese patent CN101108834 discloses a kind of process for purification of 2 Mercaptobenzothiazole (MBT).After this method was dissolved in ethanol fully with thick M, cooling added the deionized water deposition, left standstill, filters, washed, drying.Obtain the purified accelerator M, prepared refining M purity reaches more than 99.5%.Since also have a certain amount of M in the refining filtrating that produces of bullion M, some by-product impurity and a large amount of solvents, though the retortable recovery of solvent, a large amount of solid tar of meeting accumulation behind the long-term solvent distillation, how handling this waste residue is a difficult problem.Chinese patent CN101402615 discloses the process for purification of a kind of thiofide 2-mercaptobenzothiazole (M); Its process characteristic is that extraction process and alkali-soluble acid analysis method are combined; The bullion 2 Mercaptobenzothiazole (MBT) is earlier with extracted in toluene three times; Resin impurity removed obtain the very high 2 Mercaptobenzothiazole (MBT) of purity, then the 2 Mercaptobenzothiazole (MBT) in the resin is purified with the alkali-soluble acid analysis method.Can obtain the purity height, fusing point is high, the 2 Mercaptobenzothiazole (MBT) that melting range is short.Above-mentioned technology 25 ~ 55 ℃ low temperature, normal pressure recover M, but extracted in toluene often, consumption is big, the depleted resin also can cause new pollution.In addition, the M of recovery does not explain use.
Summary of the invention
The objective of the invention is to propose a kind of process for purification of improved 2 Mercaptobenzothiazole (MBT).
Main technical schemes of the present invention: the process for purification of accelerator M, it is characterized in that recovery M and bullion M are added in the autoclave by mass ratio 1:8 ~ 1:12, adding quality again is the organic solvent of 1.3 ~ 2.22 times of M total masses, heats up; 0.4 ~ the 0.8Mpa that keep-ups pressure, 100 ~ 160 ℃ of temperature are opened under hot conditions and are stirred; Mixing speed is 330 ~ 550 r/min, lowers the temperature after keeping 30 ~ 50min, discharging during to room temperature to be cooled; Filter, oven dry obtains refining M and filtrating; The organic solvent that filtrating is reclaimed out through distillation continues to be used as the purified raw material; Collect the solid tar of remaining black after repeatedly distilling; Treatment step is following: 1. to use mass percentage concentration be the washing of 10 ~ 20% sodium hydroxide solution and extract this tar; The pH value of control solution is 8 ~ 12, and wherein organism is transferred to aqueous phase; 2. controlled temperature is 45 ~ 75 ℃, blasts atmospheric oxidation 2 ~ 4 hours, and it is that 8 ~ 20% sulfuric acid acidation is to pH=5 ~ 8 that mass percentage concentration is used in the back; 3. filter, dryly must reclaim M, it is refining that the M proportional mixing of recovery continues circulation in the bullion M.
Usually, the inventive method is energy-saving and emission-reduction, and bright employing organic solvent is made with extra care M, and solvent species is a kind of in Virahol, ethanol, tetracol phenixin and the toluene, preferred alcohol or toluene.
The present invention will reclaim M cover and be used among the thick M and make with extra care, and can solve the problem of utilizing that reclaims M.The mass ratio that reclaims M and bullion M is 1:8 ~ 1:12, can be optimized for 1:8 ~ 1:10.
It is that the organic solvent of 1.3 ~ 2.22 times of M total masses can reach refining effect preferably that the present invention adds quality, and the mass ratio that can optimize M and organic solvent is 1:1.5 ~ 1:2.
The present invention at high temperature opens stirring, refining M, and temperature of reaction is 100 ~ 160 ℃.Consider bullion M and the fusing point that reclaims M, can be optimized for 140 ~ 160 ℃.Purified pressure is 0.4 ~ 0.8Mpa, can be optimized for 0.6 ~ 0.8Mpa;
The selection of the present invention's lay special stress on NaOH concentration in the process of handling tar and the control of pH value of solution.Adopting mass percentage concentration generally speaking is washing of 10 ~ 20% sodium hydroxide solution and extraction tar, and the pH value of control solution is 8 ~ 12.If but selection use mass percentage concentration is 10 ~ 14% sodium hydroxide extraction tar, make the pH value that sodium hydroxide alkali is dissolved back solution be controlled at 10 ~ 11, then effect is better.The present invention blasts air under 45 ~ 75 ℃ temperature, the time is long more, and oxidation effectiveness is good more, but considers costs such as time and energy consumption, to keep 55 ~ 65 ℃ of temperature, is no more than 4 hours for best.
The present invention adopt mass percentage concentration be 15 ~ 20% sulfuric acid acidation to PH, 7 ~ 8.The sulfuric acid of the excessive concentrations hazardous that operates on the one hand on the other hand, is reacted wayward.
The process for purification of a kind of bullion M that the present invention proposes.With respect to prior art: (1) belongs to solvent method.(2) adopt high temperature, high-pressure process that bullion M is made with extra care, can reduce refining number of times, reach better effect.(3) in high temperature, high pressure purified process, wait to be heated to certain temperature and to open stirring again, protected stirring rake on the one hand, it is more abundant that M is dissolved in solvent.(4) adopt acid-base method to reclaim the M in the remaining solid tar in solvent distillation back.(5) M and the bullion M proportional mixing that reclaim get up to continue to be used as the purified raw material.
The inventive method is farthest utilized raw material on the one hand, saves cost, increases economic efficiency, and also reduces on the other hand and pollutes, the protection environment.The content of the captax made from extra care out and fusing point all meet the premium grads standard.Be a kind of more economic environmental protection, can recycle the method that reclaims M in the tar.
Description of drawings
Fig. 1 is an embodiment of the invention method block flowsheet synoptic diagram.
Embodiment
Below in conjunction with embodiment and accompanying drawing the present invention is described in detail, the embodiment method is shown in accompanying drawing 1.
Embodiment 1
200g bullion M, 20g recovery M and 335g toluene are added in the GS-0.5 type autoclave, under the situation of leak test sealing, heat up, 0.8Mpa keep-ups pressure.When temperature is increased to 160 ℃, open stirring, rotating speed is 450 r/min.Lower the temperature after keeping 30min, to be cooled to the room temperature discharging, oven dry obtains the refining M of 178.7g, 240.3g filtrating.The content of refining back M is 98.4%, and fusing point is 170.8 ℃.To filtrate and reclaim out solvent, continue to be used as the purified raw material through distillation.Collect the solid tar of remaining black after repeatedly distilling, the sodium hydroxide solution with 10% washs and extracts this tar, and the pH value of control solution is 11, and wherein organism is transferred to aqueous phase.The temperature of control water blasted atmospheric oxidation 4 hours at 55 ~ 60 ℃, the back with 20% sulfuric acid acidation to PH=7.Filter, dryly must reclaim M.The content that reclaims M is 89.2%, and fusing point is 154 ℃.
Embodiment 2
Operational condition is with embodiment 1, and organic solvent changes ethanol into, and all the other conditions are constant.The content that obtains refining M at last is 68.1%, and fusing point is 168.2 ℃.The content that reclaims M is 79.3%, and fusing point is 143 ℃.
Embodiment 3
Operational condition is opened stirring with embodiment 1 when temperature is increased to 140 ℃, all the other conditions are constant.The content that obtains refining M at last is 98.1%, and fusing point is 170.2 ℃.The content that reclaims M is 89.3%, and fusing point is 153 ℃.
Embodiment 4
Operational condition changes the time that blasts air into 2 hours with embodiment 1.All the other conditions are constant, and the content that obtains refining M at last is 99.0%, and fusing point is 170.6 ℃.The content that reclaims M is 88.6%, and fusing point is 153 ℃.
Embodiment 5
Operational condition reclaims 200g bullion M, 16g in M and the 335g solvent adding autoclave with embodiment 1, and all the other conditions are constant, and the content that obtains refining M at last is 99.2%, and fusing point is 171.2 ℃.The content that reclaims M is 88.3%, and fusing point is 153 ℃.
Claims (10)
1. the process for purification of an accelerator M is characterized in that recovery M and bullion M are added in the autoclave by mass ratio 1:8 ~ 1:12, and adding quality again is the organic solvent of 1.3 ~ 2.22 times of M total masses, heats up; 0.4 ~ the 0.8Mpa that keep-ups pressure, 100 ~ 160 ℃ of temperature are opened under hot conditions and are stirred; Mixing speed is 330 ~ 550 r/min, lowers the temperature after keeping 30 ~ 50min, discharging during to room temperature to be cooled; Filter, oven dry obtains refining M and filtrating; The organic solvent that filtrating is reclaimed out through distillation continues to be used as the purified raw material; Collect the solid tar of remaining black after repeatedly distilling; Treatment step is following: 1. to use mass percentage concentration be the washing of 10 ~ 20% sodium hydroxide solution and extract this tar; The pH value of control solution is 8 ~ 12, and wherein organism is transferred to aqueous phase; 2. controlled temperature is 45 ~ 75 ℃, blasts atmospheric oxidation 2 ~ 4 hours, and it is that 8 ~ 20% sulfuric acid acidation is to pH=5 ~ 8 that mass percentage concentration is used in the back; 3. filter, dryly must reclaim M, it is refining that the M proportional mixing of recovery continues circulation in the bullion M.
2. according to the said method of claim 1, it is characterized in that organic solvent is a kind of in Virahol, ethanol, tetracol phenixin and the toluene.
3. method according to claim 1, the mass ratio that it is characterized in that reclaiming M and bullion M is 1:8 ~ 1:10.
4. method according to claim 1, the mass ratio that it is characterized in that M and organic solvent is 1:1.5 ~ 1:2.
5. method according to claim 1 is characterized in that opening under the hot conditions and stirs.
6. method according to claim 1 is characterized in that the purified temperature is 140 ~ 160 ℃; Purified pressure is 0.6 ~ 0.8Mpa.
7. method according to claim 1, it is characterized in that using mass percentage concentration is 10 ~ 14% sodium hydroxide washing and extraction tar.
8. method according to claim 1 is characterized in that step 1., and the pH value of control solution is controlled at 10 ~ 11.
9. method according to claim 1 is characterized in that step 2., under the temperature that controlled temperature is 55 ~ 65 ℃.
10. method according to claim 1 is characterized in that step is 2., to use mass percentage concentration be 15 ~ 20% sulfuric acid acidation to pH be 7 ~ 8.
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| CN2012101397442A CN102675242A (en) | 2012-05-08 | 2012-05-08 | Refining method of vulkacit M |
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| CN2012101397442A CN102675242A (en) | 2012-05-08 | 2012-05-08 | Refining method of vulkacit M |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103739569A (en) * | 2014-01-09 | 2014-04-23 | 山东尚舜化工有限公司 | Method for purifying rubber vulcanization accelerator MBT (2-mercaptobenzothiazole) |
| CN104211657A (en) * | 2014-09-01 | 2014-12-17 | 淄博高汇化工有限公司 | Refining method of rubber vulcanizing accelerant M |
| CN105524014A (en) * | 2015-12-31 | 2016-04-27 | 濮阳蔚林化工股份有限公司 | Purification method of rubber vulcanization accelerator 2-mercaptobenzothiazole |
| CN109535099A (en) * | 2018-10-24 | 2019-03-29 | 科迈化工股份有限公司 | Method by recycling MBT in resin |
| CN111620836A (en) * | 2020-06-23 | 2020-09-04 | 河南省化工研究所有限责任公司 | Method for refining 2-mercaptobenzothiazole |
| CN113461638A (en) * | 2020-03-30 | 2021-10-01 | 中石化南京化工研究院有限公司 | Recycling method of accelerator M tar |
Citations (5)
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| US4343946A (en) * | 1980-06-23 | 1982-08-10 | Pennwalt Corporation | Purification of 2-mercaptobenzothiazole |
| US4371698A (en) * | 1979-03-06 | 1983-02-01 | P C U K Produits Chimiques Ugine Kuhlmann | Process for the purification of mercaptobenzothiazole |
| CN1898220A (en) * | 2003-12-23 | 2007-01-17 | 杜斯乐联合股份公司 | Method of obtaining 2-mercaptobenzothiazole |
| CN101108834A (en) * | 2007-06-25 | 2008-01-23 | 天津市科迈化工有限公司 | Method of refining rubber vulcanization accelerant MBT |
| CN101402615A (en) * | 2008-11-12 | 2009-04-08 | 山东阳谷华泰化工有限公司 | Fine purification method for rubber vulcanization accelerant 2-mercaptobenzothiazole (M) |
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2012
- 2012-05-08 CN CN2012101397442A patent/CN102675242A/en active Pending
Patent Citations (5)
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| US4371698A (en) * | 1979-03-06 | 1983-02-01 | P C U K Produits Chimiques Ugine Kuhlmann | Process for the purification of mercaptobenzothiazole |
| US4343946A (en) * | 1980-06-23 | 1982-08-10 | Pennwalt Corporation | Purification of 2-mercaptobenzothiazole |
| CN1898220A (en) * | 2003-12-23 | 2007-01-17 | 杜斯乐联合股份公司 | Method of obtaining 2-mercaptobenzothiazole |
| CN101108834A (en) * | 2007-06-25 | 2008-01-23 | 天津市科迈化工有限公司 | Method of refining rubber vulcanization accelerant MBT |
| CN101402615A (en) * | 2008-11-12 | 2009-04-08 | 山东阳谷华泰化工有限公司 | Fine purification method for rubber vulcanization accelerant 2-mercaptobenzothiazole (M) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103739569A (en) * | 2014-01-09 | 2014-04-23 | 山东尚舜化工有限公司 | Method for purifying rubber vulcanization accelerator MBT (2-mercaptobenzothiazole) |
| CN103739569B (en) * | 2014-01-09 | 2016-03-23 | 山东尚舜化工有限公司 | A kind of method of purification of rubber vulcanization accelerant MBT |
| CN104211657A (en) * | 2014-09-01 | 2014-12-17 | 淄博高汇化工有限公司 | Refining method of rubber vulcanizing accelerant M |
| CN105524014A (en) * | 2015-12-31 | 2016-04-27 | 濮阳蔚林化工股份有限公司 | Purification method of rubber vulcanization accelerator 2-mercaptobenzothiazole |
| CN105524014B (en) * | 2015-12-31 | 2017-05-24 | 蔚林新材料科技股份有限公司 | Purification method of rubber vulcanization accelerator 2-mercaptobenzothiazole |
| CN109535099A (en) * | 2018-10-24 | 2019-03-29 | 科迈化工股份有限公司 | Method by recycling MBT in resin |
| CN113461638A (en) * | 2020-03-30 | 2021-10-01 | 中石化南京化工研究院有限公司 | Recycling method of accelerator M tar |
| CN113461638B (en) * | 2020-03-30 | 2023-10-13 | 中石化南京化工研究院有限公司 | Recycling method of accelerator M tar |
| CN111620836A (en) * | 2020-06-23 | 2020-09-04 | 河南省化工研究所有限责任公司 | Method for refining 2-mercaptobenzothiazole |
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Application publication date: 20120919 |