CN104860829A - Rubber vulcanization accelerator CBS mother liquor treatment and application method - Google Patents
Rubber vulcanization accelerator CBS mother liquor treatment and application method Download PDFInfo
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- CN104860829A CN104860829A CN201510180441.9A CN201510180441A CN104860829A CN 104860829 A CN104860829 A CN 104860829A CN 201510180441 A CN201510180441 A CN 201510180441A CN 104860829 A CN104860829 A CN 104860829A
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Abstract
The invention discloses a rubber vulcanization accelerator CBS mother liquor treatment and application method. The method comprises the following steps: the CBS mother liquor is subjected to standing under a temperature of 20-35 DEG C; when the mother liquor is preliminarily stratified into 3 layers, the temperature is reduced to 0-15 DEG C, and standing is continued, until the boundaries between the layers of the CBS mother liquor are clear; the CBS mother liquor at a middle part is extracted, and is marked as middle-layer mother liquor; the middle-layer mother liquor is subjected to standing under a normal temperature; an upper layer of the middle-layer mother liquor is subjected to rectification for recovering cyclohexylamine; and the lower layer of the middle-layer mother liquor is used as a recovered mother liquor and is directly applied in a synthesis method of the rubber vulcanization accelerator CBS. The method provided by the invention has the advantages of simple process and easy operation. With the method, CBS dissolved in the mother liquor is recovered, the water amount of one usage is saved; the energy needed for post-stage mother liquor rectification is saved; production cost is reduced; and sewage and residue discharge are reduced. The method accords with the national environmental policy.
Description
Technical field
The present invention relates to a kind of process and using method of rubber vulcanizing accelerator CBS mother liquor, belong to rubber vulcanizing accelerator CBS production technical field.
Background technology
(chemical name is N-cyclohexyl-2-benzothiazole sulfonamide to rubber vulcanizing accelerator CBS, molecular formula is C13H16N2S2) be a kind of late effect property thiofide conventional both at home and abroad, physicals and the ageing-resistant performance of rubber item can be significantly improved, scorching quality is excellent, process safety, curing time is short, and be applicable to various rubber, variable color is slight, no blooming, cross-linked rubber is ageing-resistant, tensile strength, and ability of surely stretching is all better, mainly for the manufacture of tire, sebific duct, rubber overshoes, the industrial rubber articles such as electric wire.Because it does not exist the carcinogenic problem of nitrosamine, be therefore one of principal item of sulfenamide type accelerators both at home and abroad at present, the market requirement increases very fast.
The method of existing production CBS is that (chemical name is 2-thiol benzothiazole with captax, molecular formula is C7H5NS2) with excessive hexahydroaniline salify, then obtained CBS under oxygenant effect, after filtration, wash, dry up, dry (or granulation) rubber vulcanizing accelerator CBS finished product, finally more remaining for filtration mother liquor is carried out rectifying, reclaim the hexahydroaniline having neither part nor lot in reaction.Owing to containing hexahydroaniline in mother liquor, and accelerator CBS can be dissolved in hexahydroaniline, if therefore discharge after direct for mother liquor rectifying can be caused the loss of CBS, have impact on product yield, adds production cost; Meanwhile, if by direct for mother liquor rectifying, rectifying operates at more than 100 DEG C, accelerator CBS can be decomposed to form the resinous impurities of complicated component at this temperature, becomes solid waste, causes waste, also add processing cost, have impact on environment, do not meet national environmental protection policy.
Summary of the invention
The object of this invention is to provide a kind for the treatment of process of rubber vulcanizing accelerator CBS mother liquor, the method processes CBS mother liquor, is separated by CBS before mother liquor rectifying, has fully reclaimed ring amine and CBS, decrease the generation of solid waste, decrease the quantity discharged of waste water.
Another object of the present invention is to provide a kind of using method of rubber vulcanizing accelerator CBS mother liquor, the method in CBS synthesis is used for by CBS disposing mother liquor cover, disposing mother liquor is applied mechanically by the method, decrease a water (namely without the pure water used, use down together), decrease the quantity discharged of waste water, improve product yield, reduce production cost.
For achieving the above object, the present invention is achieved by following technical proposals:
A treatment process for rubber vulcanizing accelerator CBS mother liquor, comprises the following steps:
(1) CBS mother liquor is left standstill at 20 ~ 35 DEG C, after mother liquor is tentatively divided into three layers, is cooled to 0 ~ 15 DEG C again leaves standstill, until CBS mother liquor each interlayer boundary line is clear;
(2) extract the CBS mother liquor being positioned at middle part, be designated as middle layer mother liquor, it left standstill at normal temperatures, leave standstill CBS in process and be enriched to the lower floor of middle layer mother liquor, hexahydroaniline is then enriched to the upper strata of middle layer mother liquor;
(3) rectifying is carried out on the upper strata of middle layer mother liquor, reclaim hexahydroaniline, by lower floor's direct reuse of middle layer mother liquor in CBS produces.
In above-mentioned treatment process, by the adjustment to mother liquor temperature, make the various compositions in mother liquor carry out enrichment and be separated, then by diverse ways, available composition is recycled respectively, avoid the waste of resource.Wherein in step (1), mother liquor is divided into three layers, the first layer is the superiors of mother liquor, for the Gugulipid that proportion is lighter, the second layer is positioned at the centre of mother liquor, is aqueous phase, ring amine and CBS mainly concentrates on this layer, third layer is positioned at the bottom of mother liquor, is the viscous materials such as the resin that proportion is larger, and their agglomerating caking ground exists.
Further, after CBS mother liquor extracts middle layer mother liquor, the resin of CBS mother liquor upper strata and bottom merges together, and can reclaim by distillation after steam heating the hexahydroaniline wherein contained.Because the hexahydroaniline concentration obtained is low, need can be back in production by the content side of rectifying concentrate to regulation again.After reclaiming hexahydroaniline, remaining resin becomes the oily liquids of flowing at high operating temperatures, then is for further processing.
In aforesaid method, in the lower floor's (be designated as and reclaim mother liquor) processing the middle layer mother liquor obtained, hexahydroaniline content is 4 ~ 10wt%, and accelerator CBS content is 2 ~ 5wt%.By the recycled of this recovery mother liquor, the CBS in mother liquor can be reclaimed, improve CBS yield.
Present invention also offers a kind of method of mother liquid recycle synthetic rubber aniline fluid bed, the method first carries out pre-treatment according to the treatment process of above-mentioned rubber vulcanizing accelerator CBS mother liquor to CBS mother liquor, then gets the lower floor of middle layer mother liquor as reclaiming mother liquid recycle in the synthetic method of rubber vulcanizing accelerator CBS.
In above-mentioned mother liquid recycle method, step comprises: water, tensio-active agent, captax, a recovery mother liquor are mixed, then add hexahydroaniline and carry out salt-forming reaction, add clorox in the mode dripped again after reaction and carry out oxidizing reaction, after reaction, reaction solution is processed, obtain rubber vulcanizing accelerator CBS.
In above-mentioned mother liquid recycle method, react in hexahydroaniline used and have the hexahydroaniline of 50 ~ 65% molecular volumes for reclaiming hexahydroaniline.
In above-mentioned mother liquid recycle method, captax: tensio-active agent a: water: the mass ratio reclaiming mother liquor is 1:0.002 ~ 0.005:0.6 ~ 1.2:1 ~ 2, preferred 1:0.002 ~ 0.004:0.8 ~ 1.2:1.2 ~ 1.5.
In above-mentioned mother liquid recycle method, captax: hexahydroaniline: the mol ratio of clorox is 1:2.0 ~ 2.6:1.0 ~ 1.3, preferred 1:2.0 ~ 2.6:1.2.
In above-mentioned mother liquid recycle method, described tensio-active agent is aliphatic alcohol polyoxyethylene or alkylphenol polyoxyethylene.
In above-mentioned mother liquid recycle method, the mixing time of water, tensio-active agent, captax and a recovery mother liquor is 30 ~ 60 minutes.
In above-mentioned mother liquid recycle method, captax and hexahydroaniline will when heat up stir abundant salify, control salt time at 30 ~ 60 minutes.
In above-mentioned mother liquid recycle method, the temperature of oxidizing reaction is 20 ~ 50 DEG C, is preferably 30 ~ 40 DEG C.
In above-mentioned mother liquid recycle method, the time that dropping clorox carries out reacting is 150 ~ 240 minutes, preferred 180-240 minute.
In above-mentioned mother liquid recycle method, specifically comprise the following steps:
(1) in still with slurry, a water is added, and tensio-active agent, open and stir;
(2) add captax making beating, and then add recovery mother liquor, continue stirring to pulp;
(3) the slip dnockout pump after making beating proceeds to synthesis reactor, adds the recovery hexahydroaniline of reaction integral molar quantity 50 ~ 65%, and then adds fresh hexahydroaniline and supply, and stirs and heats up, make captax and the abundant salify of hexahydroaniline;
(4) at 20 ~ 50 DEG C, drip clorox, control time for adding at 150 ~ 240 minutes, after dropping clorox reaches 90% of specified amount, frequent sampling and testing reaction end, reach terminal to stop dripping clorox, and in continuation stirring after 15 minutes, remaining unchanged of terminal;
(5) filter after completion of the reaction, filter and mother liquid obtainedly to process according to above-mentioned mother liquor processing method, to make recycled, filter gained material through wash, drying up, dry or wash, dry up, must rubber vulcanizing accelerator CBS product after granulation.
In aforesaid method, first with a moistening captax of water containing tensio-active agent, solve due to use merely reclaim mother liquor with slurry time easily make M unite the shortcoming of caking, mother liquid recycle amount can be reached react to add more than 50% of the water yield.
CBS mother liquor carries out processing and carries out recycled to the mother liquor after process by the present invention, process is simple, easy handling, again rectifying is carried out to mother liquor after first isolating CBS in mother liquid disposal process and reclaim ring amine, alleviate the pressure that hexahydroaniline is reclaimed in rectifying, reduce energy consumption, decrease the waste residue amount produced in rectifying, meet national environmental protection policy.The present invention is by mother liquor reuse, by the hexahydroaniline recycling in mother liquor, not only reduce the quantity discharged of waste water, also correspondingly reduce the consumption of a water and ring amine, reduce production cost, the CBS being dissolved in and reclaiming in mother liquor has been reclaimed in mother liquor reuse simultaneously, product average yield improves 2.5%, and the accelerator CBS steady quality synthesized, content reaches more than 98.0%, meets the requirements.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described, and following embodiment is only exemplary, does not limit its content.
embodiment 1
1, remaining CBS mother liquor after getting filtering product CBS, added in standing tank, stratification at 20 ~ 35 DEG C, after mother liquor is tentatively divided into three layers, then be cooled to 0 ~ 15 DEG C leave standstill, make mother liquor layering obvious, the viscous materials such as the division is clearly demarcated for each interlayer, the resin that proportion is larger are separated out from mother liquor agglomerating caking, are positioned at the lowest layer, and the lighter Gugulipid of proportion swims in the superiors of mother liquor, water layer is positioned at middle layer.
2, middle mother liquor is extracted, by this middle mother liquor stratification at normal temperatures again, the clear liquid separated and collected that upper strata CBS content is less, after concentrating, hexahydroaniline reuse is reclaimed in rectifying, the liquid of lower floor CBS enrichment is as recovery mother liquor, be back in CBS production, reclaiming hexahydroaniline content in mother liquor is 4 ~ 10wt%, and accelerator CBS content is 2 ~ 5wt%.
3, by hexahydroaniline that Distillation recovery after remaining mother liquor steam heating after having extracted middle mother liquor in standing tank wherein contains, the content that the hexahydroaniline of the lower concentration obtained reaches regulation through rectifying concentrate is again back to production, and the resin remained in still kettle bottom then becomes the oily liquids of flowing to release bottom still kettle at high operating temperatures.
embodiment 2
450 liters, water and 1.2 kilograms, tensio-active agent (aliphatic alcohol polyoxyethylene) is added in still with slurry, open and stir, add 500 kilograms of raw material captax making beating, and then add recovery 750 liters, mother liquor, continue stirring to pulp, amounting to beating time is 50 ~ 60 minutes; Slip dnockout pump proceeds to synthesis reactor, add reaction integral molar quantity 50%(pure) recovery hexahydroaniline, and then add calculate according to reaction ratio gauge add industrial hexahydroaniline, stir and heat up, make M and the abundant salify of hexahydroaniline, control salt time at 50 ~ 60 minutes, the reaction mol ratio of captax and hexahydroaniline is 1:2.3; At oxidizing temperature 30 DEG C, clorox is dripped after reaction, the reaction mol ratio of captax and clorox is 1:1.20, control time for adding at 200 ~ 240 minutes, after dropping clorox reaches 90% of specified amount, frequent sampling and testing reaction end, less than reaction end, then continue to add clorox, until stop after reaching reaction end dripping clorox, and continue stirring after 15 minutes, remaining unchanged of terminal.Filter after completion of the reaction, collect mother liquor and also process according to the method for embodiment 1, to recycle, material must rubber vulcanizing accelerator CBS product through wash, drying up, after dry (or granulation).The accelerator CBS content synthesized reaches 98.2%, yield 95.8%.
embodiment 3
500 liters, water and 1.5 kilograms, tensio-active agent (alkylphenol polyoxyethylene) is added in still with slurry, open and stir, add 500 kilograms of raw material captax making beating, and then add recovery 700 liters, mother liquor, continue stirring to pulp, amounting to beating time is 50 ~ 60 minutes; Slip dnockout pump proceeds to synthesis reactor, add reaction integral molar quantity 55%(pure) recovery hexahydroaniline, and then add calculate according to reaction ratio gauge add industrial hexahydroaniline, stir and heat up, make M and the abundant salify of hexahydroaniline, control salt time at 40 ~ 60 minutes, the reaction mol ratio of captax and hexahydroaniline is 1:2.5; At oxidizing temperature 35 DEG C, clorox is dripped after reaction, the reaction mol ratio of captax and clorox is 1:1.20, control time for adding at 180 ~ 210 minutes, after dropping clorox reaches 90% of specified amount, frequent sampling and testing reaction end, less than reaction end, then continue to add clorox, until stop after reaching reaction end dripping clorox, and continue stirring after 15 minutes, remaining unchanged of terminal.Filter after completion of the reaction, collect mother liquor and also process according to the method for embodiment 1, material must rubber vulcanizing accelerator CBS product through wash, drying up, after dry (or granulation).The accelerator CBS content synthesized reaches 98.3%, yield 95.6%.
embodiment 4
550 liters, water and 1.8 kilograms, tensio-active agent (aliphatic alcohol polyoxyethylene) is added in still with slurry, open and stir, add 500 kilograms of raw material captax making beating, and then add recovery 650 liters, mother liquor, continue stirring to pulp, amounting to beating time is 40 ~ 50 minutes; Slip dnockout pump proceeds to synthesis reactor, add reaction integral molar quantity 60%(pure) recovery hexahydroaniline, and then add calculate according to reaction ratio gauge add industrial hexahydroaniline, stir and heat up, make M and the abundant salify of hexahydroaniline, control salt time at 50 ~ 60 minutes, the reaction mol ratio of captax and hexahydroaniline is 1:2.2; At oxidizing temperature 40 DEG C, clorox is dripped after reaction, the reaction mol ratio of captax and clorox is 1:1.20, control time for adding at 160 ~ 200 minutes, after dropping clorox reaches 90% of specified amount, frequent sampling and testing reaction end, less than reaction end, then continue to add clorox, until stop after reaching reaction end dripping clorox, and continue stirring after 15 minutes, remaining unchanged of terminal.Filter after completion of the reaction, collect mother liquor and also process according to the method for embodiment 1, material must rubber vulcanizing accelerator CBS product through wash, drying up, after dry (or granulation).The accelerator CBS content synthesized reaches 98.5%, yield 95.5%.
embodiment 5
600 liters, water and 2.0 kilograms, tensio-active agent (alkylphenol polyoxyethylene) is added in still with slurry, open and stir, add 500 kilograms of raw material captax making beating, and then add recovery 600 liters, mother liquor, continue stirring to pulp, amounting to beating time is 30 ~ 40 minutes; Slip dnockout pump proceeds to synthesis reactor, add reaction integral molar quantity 55%(pure) recovery hexahydroaniline, and then add calculate according to reaction ratio gauge add industrial hexahydroaniline, stir and heat up, make M and the abundant salify of hexahydroaniline, control salt time at 30 ~ 40 minutes, the reaction mol ratio of captax and hexahydroaniline is 1:2.1; At oxidizing temperature 28 DEG C, clorox is dripped after reaction, the reaction mol ratio of captax and clorox is 1:1.20, control time for adding at 150 ~ 180 minutes, after dropping clorox reaches 90% of specified amount, frequent sampling and testing reaction end, less than reaction end, then continue to add clorox, until stop after reaching reaction end dripping clorox, and continue stirring after 15 minutes, remaining unchanged of terminal.Filter after completion of the reaction, collect mother liquor and also process according to the method for embodiment 1, material must rubber vulcanizing accelerator CBS product through wash, drying up, after dry (or granulation).The accelerator CBS content synthesized reaches 98.6%, yield 95.2%.
comparative example 1
In still with slurry, add 1200 liters, water and 2.0 kilograms, tensio-active agent (alkylphenol polyoxyethylene), open and stir, add 500 kilograms of raw material captaxs making beating, beating time is 30 ~ 40 minutes; Slip dnockout pump proceeds to synthesis reactor, add reaction total amount 55%(pure) recovery hexahydroaniline, and then add calculate according to reaction ratio gauge add industrial hexahydroaniline, stir and heat up, make M and the abundant salify of hexahydroaniline, control salt time at 30 ~ 40 minutes, the reaction mol ratio of captax and hexahydroaniline is 1:2.1; At oxidizing temperature 28 DEG C, clorox is dripped after reaction, the reaction mol ratio of captax and clorox is 1:1.20, control time for adding at 150 ~ 180 minutes, after dropping clorox reaches 90% of specified amount, frequent sampling and testing reaction end, less than reaction end, then continue to add clorox, until stop after reaching reaction end dripping clorox, and continue stirring after 15 minutes, remaining unchanged of terminal.Filter after completion of the reaction, collect mother liquor, material must rubber vulcanizing accelerator CBS product through wash, drying up, after dry (or granulation).The accelerator CBS content 99.3% synthesized, yield 93.5%.
Other are identical with comparative example except using the mother liquor reclaimed and replacing part water for embodiment 5, and viewed from result, embodiment 5 products obtained therefrom purity is slightly lower than comparative example, but increases on yield, and the consumption of a water reduces greatly.
comparative example 2
In still with slurry, add 600 liters, water, open and stir, add 500 kilograms of raw material captaxs making beating, and then add and reclaim 600 liters, mother liquor, continue stirring to pulp, amounting to beating time is 30 ~ 40 minutes; Slip dnockout pump proceeds to synthesis reactor, add reaction total amount 55%(pure) recovery hexahydroaniline, and then add calculate according to reaction ratio gauge add industrial hexahydroaniline, stir and heat up, make M and the abundant salify of hexahydroaniline, control salt time at 30 ~ 40 minutes, the reaction mol ratio of captax and hexahydroaniline is 1:2.1; At oxidizing temperature 28 DEG C, clorox is dripped after reaction, the reaction mol ratio of captax and clorox is 1:1.20, control time for adding at 150 ~ 180 minutes, after dropping clorox reaches 90% of specified amount, frequent sampling and testing reaction end, less than reaction end, then continue to add clorox, until stop after reaching reaction end dripping clorox, and continue stirring after 15 minutes, remaining unchanged of terminal.Filter after completion of the reaction, collect mother liquor, material must rubber vulcanizing accelerator CBS product through wash, drying up, after dry (or granulation).The accelerator CBS content synthesized 97.2%, yield 90.5%.Product appearance color and luster is partially yellow, and wherein carry minute quantity unreacted M particulate completely secretly, poor quality, yield is low.
Claims (10)
1. a treatment process for rubber vulcanizing accelerator CBS mother liquor, is characterized in that comprising the following steps:
(1) CBS mother liquor is left standstill at 20 ~ 35 DEG C, after mother liquor is tentatively divided into three layers, is cooled to 0 ~ 15 DEG C again leaves standstill, until CBS mother liquor each interlayer boundary line is clear;
(2) extract the CBS mother liquor being positioned at middle part, be designated as middle layer mother liquor, it left standstill at normal temperatures, leave standstill CBS in process and be enriched to the lower floor of middle layer mother liquor, hexahydroaniline is enriched to the upper strata of middle layer mother liquor;
(3) rectifying is carried out on the upper strata of middle layer mother liquor, reclaim hexahydroaniline, by lower floor's direct reuse of middle layer mother liquor in CBS produces.
2. treatment process according to claim 1, is characterized in that: remaining CBS mother liquor Distillation recovery hexahydroaniline after the mother liquor of extraction middle layer.
3. the method for a mother liquid recycle synthetic rubber aniline fluid bed, it is characterized in that: according to the treatment process of rubber vulcanizing accelerator CBS mother liquor according to claim 1, pre-treatment is carried out to CBS mother liquor, using the lower floor of middle layer mother liquor as reclaiming mother liquid recycle in the synthetic method of rubber vulcanizing accelerator CBS.
4. method according to claim 3, it is characterized in that: water, tensio-active agent, captax, a recovery mother liquor are mixed, then add hexahydroaniline and carry out salt-forming reaction, add clorox in the mode dripped again after reaction and carry out oxidizing reaction, after reaction, reaction solution is processed, obtain rubber vulcanizing accelerator CBS.
5. method according to claim 4, is characterized in that: react in hexahydroaniline used and have the hexahydroaniline of 50 ~ 65% molecular volumes for reclaiming hexahydroaniline.
6. method according to claim 4, is characterized in that: captax: tensio-active agent: a water: the mass ratio reclaiming mother liquor is 1:0.002 ~ 0.005:0.6 ~ 1.2:1 ~ 2; Captax: hexahydroaniline: the mol ratio of clorox is 1:2.0 ~ 2.6:1.0 ~ 1.3.
7. method according to claim 4, is characterized in that: described tensio-active agent is aliphatic alcohol polyoxyethylene or alkylphenol polyoxyethylene.
8. method according to claim 4, is characterized in that: the mixing time of water, tensio-active agent, captax and a recovery mother liquor is 30 ~ 60 minutes; Captax and hexahydroaniline will when heat up stir abundant salify, control salt time at 30 ~ 60 minutes.
9. method according to claim 4, is characterized in that: the temperature of oxidizing reaction is 20 ~ 50 DEG C.
10. method according to claim 4, is characterized in that: the time that dropping clorox carries out reacting is 150 ~ 240 minutes.
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Cited By (2)
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| CN105399702A (en) * | 2015-12-17 | 2016-03-16 | 科迈化工股份有限公司 | Recycling and reusing method of solid matters in rubber vulcanization accelerator CBS production mother liquor |
| CN110577502A (en) * | 2019-09-16 | 2019-12-17 | 山东尚舜化工有限公司 | Method for improving yield of rubber accelerator TBBS |
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| CN105399702A (en) * | 2015-12-17 | 2016-03-16 | 科迈化工股份有限公司 | Recycling and reusing method of solid matters in rubber vulcanization accelerator CBS production mother liquor |
| CN110577502A (en) * | 2019-09-16 | 2019-12-17 | 山东尚舜化工有限公司 | Method for improving yield of rubber accelerator TBBS |
| CN110577502B (en) * | 2019-09-16 | 2021-03-23 | 山东尚舜化工有限公司 | Method for improving yield of rubber accelerator TBBS |
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| CN104860829B (en) | 2017-06-06 |
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