CN102603668B - Method for treating 2-mercaptobenzothiazole production waste - Google Patents
Method for treating 2-mercaptobenzothiazole production waste Download PDFInfo
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Abstract
The invention discloses a method for treating 2-mercaptobenzothiazole production waste. The method comprises the steps of: heating the 2-mercaptobenzothiazole production waste to 90-95 DEG C, carrying out solid-liquid separation to obtain solid matter and liquid A, returning the solid matter to an accelerator M workshop, refining and purifying the solid matter to obtain a product accelerator M, distilling and separating the liquid A to obtain a fraction B and a fraction C, cooling residues in a distillation kettle to obtain asphalt-shaped matter D, absorbing hydrogen sulfide gas generated in the distillation separation process by using a sodium hydroxide solution to obtain a sodium hydrosulfide solution, concentrating the sodium hydrosulfide solution to obtain sodium hydrosulfide solids, rectifying and separating the fraction C to obtain aniline and benzothiazole. The method disclosed by the invention is capable of realizing the resourceful treatment of the 2-mercaptobenzothiazole production waste and has the advantages of various by-products, good product quality, simpleness in process flow, easiness in operation, mildness in reaction condition, low production cost and is environment-friendly.
Description
Technical field
The present invention relates to Chemical Manufacture waste disposal technical field, be specifically related to a kind for the treatment of process of 2-mercaptobenzothiazole processing waste.
Background technology
2-mercaptobenzothiazole is captax, is the important vulcanization accelerator of rubber industry, is again fertile material and the intermediate of other most of promotor, can the multiple promotor of output after further synthesizing processing.2-mercaptobenzothiazole output accounts for first place in various rubber ingredients, there is the output of hundreds of thousands of ton every year in the whole world, and domestic Conservative estimation also will have the output of 200,000 tons in 2012.
The production method commonly used of captax is high-pressure process, take dithiocarbonic anhydride, sulphur, aniline is raw material, first dithiocarbonic anhydride and sulphur are mixed and made into to molten sulphur liquid in the ratio of 3: 1, molten sulphur liquid drops in autoclave and heats in the ratio of 1: 1 with aniline more afterwards, while reaching 3.0-9.5Mpa, keeps making half an hour captax when temperature reaches 280-290 ℃, pressure.The high-pressure process reaction product is complicated mixture, wherein take captax as main, and the content of captax is 77-85%, also has in addition unreacted raw material, intermediate product and by product etc., the general designation spent resin, and its content is 15-23%.The reaction product that high-pressure process makes also must be about to captax and separate with spent resin through further refining purification, makes the satisfactory captax of purity.At present the process for purification of captax mainly contains two kinds of acid-base method and Toluene Extractions.After refining, except the product captax obtained, remaining waste material is the 2-mercaptobenzothiazole processing waste of indication of the present invention.Wherein the main component of the refining residue waste material obtained of acid-base method and approximately content be: M content >=5%, aniline content approximately 2.4%, benzothiazole >=22%, a small amount of hydrogen sulfide, all the other are the complicated impurity that is difficult to characterize.The main component of the refining residue waste material obtained of Toluene Extraction and about content thereof: M content≤25%, aniline content approximately 1.8%, benzothiazole >=18%, toluene level 2.2-2.8%, a small amount of hydrogen sulfide, all the other are the complicated impurity that is difficult to characterize.The captax that to produce 200,000 tons in 2012 by domestic conservative estimation calculates, and will produce the 2-mercaptobenzothiazole processing waste of 4.6 ten thousand tons.
Main component M in the 2-mercaptobenzothiazole processing waste, toluene, aniline, benzothiazole etc., these residues mostly can not natural degradations, and dangerous, in the environmental protection register, be listed in danger useless, a large amount of M waste residues are both dangerous, and contaminate environment, become the difficult problem of environmental protection again.Process at present the 2-mercaptobenzothiazole processing waste following methods is arranged: one, directly as end shelves waterproof roll or concrete mold separant, its shortcoming is that objectionable constituent are not processed, the user uses the rear objectionable impurities can long-term diffusion, contaminate environment, is detrimental to health; Two, as burning in boiler kerosene or blast furnace sealing material, this treatment process is directly to burn in fact, and atmosphere has been caused again to pollution.The most important thing is that above two kinds for the treatment of processs are all the utilizations to the simple and low value of 2-mercaptobenzothiazole processing waste, thus cause the price of current 2-mercaptobenzothiazole processing waste always not high, 1200 yuan/tons only of historic highs.Therefore, developing a kind of recycling processing method of 2-mercaptobenzothiazole processing waste, to increase value-added content of product, increase economic efficiency, effectively reduce environmental pollution, is to be badly in need of at present the difficult problem solved.
Summary of the invention
The object of the present invention is to provide a kind for the treatment of process of 2-mercaptobenzothiazole processing waste.
In order to realize above purpose, the technical solution adopted in the present invention is: a kind for the treatment of process of 2-mercaptobenzothiazole processing waste comprises the following steps:
(1) solid-liquid separation: the 2-mercaptobenzothiazole processing waste is heated to 90～95 ℃, puts into afterwards whizzer and carry out solid-liquid separation, obtain solid substance and liquid A, described solid substance returns to the captax workshop and makes with extra care purification, obtains the product captax;
(2) liquid distillation: described liquid A is added in the still kettle of distillation tower and carry out fractionation by distillation, controlling vacuum tightness in distillation tower is more than 0.07Mpa; The tower top temperature of distillation tower is 60～115 ℃, the gained fraction collection, for fraction B, the tower top temperature of distillation tower is 115～190 ℃, collects the gained cut, obtains cut C, tower top temperature starts to reduce and stops distilling while without cut, flowing out, open drain hole and emit residue in still kettle, described residue, through cooling, obtains bituminous substances D; The hydrogen sulfide produced in the fractionation by distillation process absorbs with sodium hydroxide solution, makes sodium hydrosulfide, then through the concentrated Sodium sulfhydrate solid that obtains;
(3) rectification process: described cut C is the miscellany of aniline and benzothiazole, described cut C is added in the rectifying still of rectifying tower and carries out rectifying separation, and controlling vacuum tightness in rectifying tower is more than 0.07Mpa; The tower top temperature of rectifying tower is 175～180 ℃, and the gained fraction collection, obtain aniline, and the tower top temperature of rectifying tower is 180～190 ℃, and the gained fraction collection, obtain benzothiazole, and tower top temperature starts to reduce and stop while without cut, flowing out rectifying.
The fraction B that the treatment process of 2-mercaptobenzothiazole processing waste provided by the invention obtains is mixture or the water of toluene and water, when the 2-mercaptobenzothiazole processing waste is the refining residue waste material obtained of acid-base method, fraction B is water, when the 2-mercaptobenzothiazole processing waste was the refining residue waste material obtained of Toluene Extraction, fraction B was the mixture of toluene and water.When fraction B was the mixture of toluene and water, fraction B was through standing, and natural layering separablely goes out toluene.The bituminous substances D softening temperature obtained is more than 220 ℃, objectionable constituent wherein and residual M are carbonized, its stable chemical nature, for black have no irritating odor and to environment without harm general waste material, can by production of resins enterprise, be used as a kind of modified resin, can also extract oil fuel and also can produce good economic benefit.The purity of the aniline obtained is greater than 99.5%, and the purity of benzothiazole is greater than 98%, but direct marketing.
The treatment process of 2-mercaptobenzothiazole processing waste provided by the invention has the following advantages: one, the environmental protection contribution is large, by the various poisonous and harmfuls by the 2-mercaptobenzothiazole processing waste, volatile material, extract, make the 2-mercaptobenzothiazole processing waste no longer to environment, produce harm, fundamentally solved the environmental pollution difficult problem of 2-mercaptobenzothiazole processing waste; And in whole treating processes, do not have waste water, waste gas to produce, avoided secondary environmental pollution; Two, economize on resources, the material of approximately 45% left and right in the 2-mercaptobenzothiazole processing waste has all become useful product, has greatly saved the resources of production; Three, good in economic efficiency, added value of product is high, after adopting the disposal methods of 2-mercaptobenzothiazole processing waste provided by the invention, the output value of 2-mercaptobenzothiazole processing waste is extended to original more than six times, the product captax, toluene, aniline, benzothiazole, the Sodium sulfhydrate that obtain, be all important industrial chemicals, economic worth is high.
The present invention has realized the recycling treatment of 2-mercaptobenzothiazole processing waste, and it is many to have the byproduct kind, good product quality, technical process is simple, facility investment is few, easy handling, reaction conditions gentle, production cost is low and meet the advantage such as environmental requirement.The present invention has good economic benefit, environmental benefit and social benefit, is applicable to industrial production and promotes, and has broad application prospects.
Embodiment
Embodiment 1
The treatment process of the 2-mercaptobenzothiazole processing waste that the present embodiment provides, 2-mercaptobenzothiazole processing waste wherein are the refining residue waste material obtained of acid-base method, comprise the following steps:
(1) solid-liquid separation: the 2-mercaptobenzothiazole processing waste of getting 200kg, with being steam heated to 90 ℃, put into afterwards whizzer and carry out solid-liquid separation, obtain the liquid A of solid substance 64kg and 126kg, solid substance returns to the captax workshop and makes with extra care purification, obtains the product captax of 40kg;
(2) liquid distillation: liquid A is added in the still kettle of distillation tower and carry out fractionation by distillation, controlling vacuum tightness in distillation tower is 0.07Mpa; The tower top temperature of distillation tower is 60～115 ℃, the gained cut is water, the tower top temperature of distillation tower is 115～190 ℃, collects the gained cut, obtains cut C, be total to 49.6kg, for the miscellany of aniline and benzothiazole, tower top temperature starts to reduce and stops distilling while without cut, flowing out, opens drain hole and emits residue in still kettle, residue, through cooling, obtains bituminous substances D; The hydrogen sulfide produced in the fractionation by distillation process absorbs with sodium hydroxide solution, makes sodium hydrosulfide, then through the concentrated Sodium sulfhydrate solid 10.8kg that obtains;
(3) rectification process: cut C is added in the rectifying still of rectifying tower and carry out rectifying separation, controlling vacuum tightness in rectifying tower is 0.07Mpa; The tower top temperature of rectifying tower is 175～180 ℃, and the gained fraction collection, obtain aniline, and the tower top temperature of rectifying tower is 180～190 ℃, and the gained fraction collection, obtain benzothiazole, and tower top temperature starts to reduce and stop while without cut, flowing out rectifying.The heavy 4.8kg of the aniline obtained, purity is 99.5%.The heavy 44kg of the benzothiazole obtained, purity is 99%.
Embodiment 2
The treatment process of the 2-mercaptobenzothiazole processing waste that the present embodiment provides, 2-mercaptobenzothiazole processing waste wherein are the refining residue waste material obtained of Toluene Extraction, comprise the following steps:
(1) solid-liquid separation: the 2-mercaptobenzothiazole processing waste of getting 200kg, with being steam heated to 95 ℃, put into afterwards whizzer and carry out solid-liquid separation, obtain the liquid A of solid substance 65kg and 125kg, solid substance returns to the captax workshop and makes with extra care purification, obtains the product captax of 42kg;
(2) liquid distillation: liquid A is added in the still kettle of distillation tower and carry out fractionation by distillation, controlling vacuum tightness in distillation tower is 0.07Mpa; The tower top temperature of distillation tower is 60～115 ℃, and the gained fraction collection, obtain fraction B, 10kg, be the mixture of toluene and water altogether, and the tower top temperature of distillation tower is 115～190 ℃, collect the gained cut, obtain cut C, 40kg, be the miscellany of aniline and benzothiazole altogether, tower top temperature starts to reduce and stops distilling while without cut, flowing out, open drain hole and emit residue in still kettle, residue, through cooling, obtains bituminous substances D; The hydrogen sulfide produced in the fractionation by distillation process absorbs with sodium hydroxide solution, makes sodium hydrosulfide, then through the concentrated Sodium sulfhydrate solid 11kg that obtains;
(3) rectification process: cut C is added in the rectifying still of rectifying tower and carry out rectifying separation, controlling vacuum tightness in rectifying tower is 0.07Mpa; The tower top temperature of rectifying tower is 175～180 ℃, and the gained fraction collection, obtain aniline, and the tower top temperature of rectifying tower is 180～190 ℃, and the gained fraction collection, obtain benzothiazole, and tower top temperature starts to reduce and stop while without cut, flowing out rectifying.The heavy 3.6kg of the aniline obtained, purity is 99.6%.The heavy 36.4kg of the benzothiazole obtained, purity is 98.6%.Fraction B in step (2), through stratification, is therefrom isolated toluene, obtains toluene 5kg.
Claims (3)
1. the treatment process of a 2-mercaptobenzothiazole processing waste, is characterized in that, comprises the following steps:
(1) solid-liquid separation: the 2-mercaptobenzothiazole processing waste is heated to 90～95 ℃, puts into afterwards whizzer and carry out solid-liquid separation, obtain solid substance and liquid A, described solid substance returns to the captax workshop and makes with extra care purification, obtains the product captax;
(2) liquid distillation: described liquid A is added in the still kettle of distillation tower and carry out fractionation by distillation, controlling vacuum tightness in distillation tower is more than 0.07MPa; The tower top temperature of distillation tower is 60～115 ℃, the gained fraction collection, for fraction B, the tower top temperature of distillation tower is 115～190 ℃, collects the gained cut, obtains cut C, tower top temperature starts to reduce and stops distilling while without cut, flowing out, open drain hole and emit residue in still kettle, described residue, through cooling, obtains bituminous substances D; The hydrogen sulfide produced in the fractionation by distillation process absorbs with sodium hydroxide solution, makes sodium hydrosulfide, then through the concentrated Sodium sulfhydrate solid that obtains;
(3) rectification process: described cut C is the miscellany of aniline and benzothiazole, described cut C is added in the rectifying still of rectifying tower and carries out rectifying separation, and controlling vacuum tightness in rectifying tower is more than 0.07MPa; The tower top temperature of rectifying tower is 175～180 ℃, and the gained fraction collection, obtain aniline, and the tower top temperature of rectifying tower is 180～190 ℃, and the gained fraction collection, obtain benzothiazole, and tower top temperature starts to reduce and stop while without cut, flowing out rectifying;
It is high-pressure process production that above-mentioned 2-dredges base benzothiazole processing waste, and the refining synthesis 2-of acid-base method or Toluene Extraction dredges the processing waste that the base benzothiazole produces.
2. the treatment process of 2-mercaptobenzothiazole processing waste according to claim 1, is characterized in that, the purity of the aniline obtained is greater than 99.5%.
3. the treatment process of 2-mercaptobenzothiazole processing waste according to claim 1, is characterized in that, the purity of the benzothiazole obtained is greater than 98%.
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| CN106243059A (en) * | 2016-07-26 | 2016-12-21 | 濮阳蔚林化工股份有限公司 | A kind of method extracting benzothiazole from 2 benzothiazolyl mercaptans production by-products |
| CN106518803A (en) * | 2016-10-08 | 2017-03-22 | 扬中市橡胶塑料厂有限公司 | Rubber vulcanization accelerator for high-abrasion-resistance rubber sealing piece production |
| CN106967007A (en) * | 2017-03-06 | 2017-07-21 | 山东尚舜化工有限公司 | A kind of processing method of rubber accelerator M resins |
| CN107286910A (en) * | 2017-06-29 | 2017-10-24 | 可名芸 | A kind of harmless treatment process of spent resin |
| CN107721947A (en) * | 2017-12-05 | 2018-02-23 | 河南恒瑞橡塑科技股份有限公司 | A kind of green clean synthesis process for producing benzothiazole |
| CN109111410B (en) * | 2018-10-11 | 2022-05-03 | 科迈化工股份有限公司 | Treatment method of waste material produced by acid-base method 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 |
| CN109608417B (en) * | 2018-10-24 | 2023-04-07 | 科迈化工股份有限公司 | Method for directly synthesizing accelerator MBTS by recovering crude MBT from resin |
| 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 |
| 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 |
| CN114805241B (en) * | 2022-06-24 | 2023-08-18 | 山东戴瑞克新材料有限公司 | Benzothiazole and preparation method thereof |
| CN115403539A (en) * | 2022-08-11 | 2022-11-29 | 山东戴瑞克新材料有限公司 | M resin stripping method containing aniline and benzothiazole |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4780540A (en) * | 1986-02-14 | 1988-10-25 | Bayer Aktiengesellschaft | Process for working up tars containing 2-mercaptobenzothiazole |
| CN101215271A (en) * | 2008-01-16 | 2008-07-09 | 天津市科迈化工有限公司 | Method of separating rubber vulcanization accelerator MBT |
| CN101245052A (en) * | 2008-03-14 | 2008-08-20 | 何连峰 | Method for extracting benzothiazole with by-product for producing 2-mercaptobenzothiazole |
| 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) |
| CN101693701A (en) * | 2009-10-21 | 2010-04-14 | 山东阳谷华泰化工股份有限公司 | Purification process for vulcanization accelerator 2-mercaptobenzothiazole |
-
2012
- 2012-02-21 CN CN2012100399188A patent/CN102603668B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4780540A (en) * | 1986-02-14 | 1988-10-25 | Bayer Aktiengesellschaft | Process for working up tars containing 2-mercaptobenzothiazole |
| CN101215271A (en) * | 2008-01-16 | 2008-07-09 | 天津市科迈化工有限公司 | Method of separating rubber vulcanization accelerator MBT |
| CN101245052A (en) * | 2008-03-14 | 2008-08-20 | 何连峰 | Method for extracting benzothiazole with by-product for producing 2-mercaptobenzothiazole |
| 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) |
| CN101693701A (en) * | 2009-10-21 | 2010-04-14 | 山东阳谷华泰化工股份有限公司 | Purification process for vulcanization accelerator 2-mercaptobenzothiazole |
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Effective date of registration: 20220629 Address after: 458000 jijiashan Industrial Park, Heshan District, Hebi City, Henan Province Patentee after: HEBI HENGLI RUBBER CO.,LTD. Address before: 456250 No. 276, Gongren lane, Jiefang Road, Daokou Town, Hua county, Hebi City, Henan Province Patentee before: Liu Zhao |