CN107445918A - Solvent purifications method rubber accelerator M synthesis sulfenamide type accelerators CBS method - Google Patents
Solvent purifications method rubber accelerator M synthesis sulfenamide type accelerators CBS method Download PDFInfo
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- CN107445918A CN107445918A CN201710690442.7A CN201710690442A CN107445918A CN 107445918 A CN107445918 A CN 107445918A CN 201710690442 A CN201710690442 A CN 201710690442A CN 107445918 A CN107445918 A CN 107445918A
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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
- C07D277/76—Sulfur atoms attached to a second hetero atom
- C07D277/80—Sulfur atoms attached to a second hetero atom to a nitrogen atom
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- Organic Chemistry (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention discloses solvent purifications method rubber accelerator M synthesis sulfenamide type accelerators CBS method, using rubber accelerator M, cyclohexylamine as raw material, using hydrogen peroxide, sodium hypochlorite as oxidant, using sulfuric acid as catalyst, reacts synthesis accelerant CBS；Optimal manufacturing condition is：(1) mol ratio between each raw material, oxidant is as follows：n(M):N (cyclohexylamine)=1：2.2；n(M):N (20% hydrogen peroxide):N (15% sodium hypochlorite)=1:0.6:0.65~0.75；(2) reaction temperature is：35~40 DEG C；(3) reaction time:2.0~2.5h.The comprehensive technical barrier for solving solvent method rubber accelerator M synthesis sulfenamide type accelerators CBS of the present invention, product quality indicator are higher than national standard level, and consumption indicators reach industry reduced levels, and solve waste water, solid waste, odorant pollutant process problem.
Description
Technical field
The invention belongs to Chemical Engineering Technology, more particularly to solvent purifications method rubber accelerator M synthesis sulfenamide type accelerators
CBS method.
Background technology
Rubber accelerator M (chemical name is 2- sulfurio benzo thiazoles) is a kind of important rubber accelerator in itself,
It is the important intermediate for synthesizing other accelerator, it has excellent vulcanization accelerator performance, and purposes is wider, and consumption is maximum, is
Synthesize the parent of other delayed action accelerators (such as thiazole accelerator, sulfenamide type accelerators), such as rubber accelerator DM,
MZ, CBS (CZ), TBBS (NS), NOBS, DZ etc. derive from parent M.
It is acid-base method that rubber accelerator M, which produces most widely used purifying technique, is produced in the art production process a large amount of
Waste water (per ton product produce 20 tons of waste water).And waste water has the characteristics of high salinity, pollutant concentration height and difficult degradation, waste water
Intractability is big.As country is to the pay attention to day by day of environmental issue, wastewater discharge standard it is increasingly strict, such wastewater treatment is set
The height for applying investment cost and facility operation expense is that enterprise is difficult to bear.Therefore one enterprise of presence yoke of such waste water
Development and growth, turn into each development bottleneck for facing problems enterprise and whole industry.
Researched and developed successively in industry from 2012 and the rubber accelerator M solvent purifications method projects that start, use toluene as solvent
Purification by liquid extraction, realizes solvent purifications method rubber accelerator M industrialized production, without any discharge of wastewater in production process, no
Enterprise wastewater problem is address only, and solves the vital conjuncture of Rubber Chemicals Industries；Not only save every environmental protection investments and
Operating cost, reduces the production cost of enterprise, and realizes the unification of economic benefit, environmental benefit and social benefit, carries
The market competitiveness of high enterprise.
But solvent purifications method rubber accelerator M is deposited when using Conventional processing methods synthesis sulfenamide type accelerators
It can not break through in more technical barrier, as quality index do not reach Standard, cost is much higher than industry average water and leads flat, lead
Solvent method rubber accelerator M application is caused to be restricted, large-scale rubber accelerator manufacturing enterprise still continues to use acid-base method M conjunctions
Into accelerant CZ, to ensure product quality and production cost, the propulsion of accelerator industry clean manufacturing work is hindered.
The content of the invention
Goal of the invention：The defects of to overcome prior art, the present invention provide solvent purifications method rubber accelerator M synthesis time
The method of sulfonamides accelerator CBS, improve product quality indicator, reduce raw material and energy consumption levels and can solve waste water,
Solid waste, odorant pollutant process problem.
Technical scheme：To achieve the above object, the technical scheme is that：
Solvent purifications method rubber accelerator M synthesis sulfenamide type accelerators CBS method, with rubber accelerator M, hexamethylene
Amine is raw material, using hydrogen peroxide, sodium hypochlorite as oxidant, using sulfuric acid as catalyst, reacts synthesis accelerant CBS；
The reaction equation is：
And it is determined through experimentation optimal manufacturing condition and is：
(1) mol ratio between each raw material, oxidant is as follows：
n(M):N (cyclohexylamine)=1：2.2；
n(M):N (20% hydrogen peroxide):N (15% sodium hypochlorite)=1:0.6:0.65~0.75；
(2) reaction temperature is：35~40 DEG C；
(3) reaction time:2.0~2.5h.
Products obtained therefrom chemical name is N- cyclohexyl-2-benzothiazole sulfonamides, English name CBS, abbreviation CZ, matter
Amount is stable, and outward appearance is white or faint yellow；Fusing point >=99 DEG C, yield is based on main raw material(s) unit consumption, and captax unit consumption is 0.68
~0.682t/t products, cyclohexylamine unit consumption is in 0.408~0.413t/t products.
This method replaces the dehydrating operations of traditional centrifuge+suction strainer groove using multi-functional pressure filter.And conventional dehydration is grasped
As；Semi-finished product suspension reclaims accelerator CBS through suction strainer again through centrifuge dewatering, mother liquor, centrifuges post and suction strainer post is waved
The amine gas of hair, then lead to absorption system recovery cyclohexylamine through air-introduced machine.Centrifuge is high-power dynamic device, and vibration is big, pair is set
Standby fundamental importance is strict, admittedly can not be arranged in high-order aspect, cause that the semi-finished product after centrifugal dehydration and suction strainer reclaim half into
Product, boosted transfer is needed, could realize that screening operation is dried in granulation engagement etc..I.e. conventional dehydration operating process is complicated, linking, turns
During shifting presence material exposure, shed, volatilize, pollute environment, continuous operation can not be realized.And multi-functional pressure filter should
With, solve above-mentioned problem, multi-functional pressure filter is closed static device, by the discrepancy in elevation be arranged at reactor and drying system it
Between high-order aspect.Semi-finished product suspension is through in pipeline to multi-functional filter press, material is after filter-press water-washing, and mother liquor is through steaming
System recovery cyclohexylamine is evaporated, is recycled.Semi-finished product are directly entered dry screening system and finished product are made.Gas enters through emptying pipeline
Enter absorption system recycling.That is the seal of multi-functional pressure filter ensure that the inorganization volatile emission of amine gas is zero, thing
Expect that the transfer amount of shedding is zero, reduce environmental pollution.Multi-functional pressure filter is static equipment, realizes reaction post and is sieved with drying
The seamless connection in post, improve serialization degree.The press filtration principle of multi-functional pressure filter, instead of the complexity of centrifugation+suction strainer
Dehydrating operations, simplify operating process.
In addition, traditional CBS methods are in process of production, mother liquor is after being distilled to recover cyclohexylamine, and main waste is with raffinate shape
Formula is discharged, and the salts such as NaCL and a small amount of accessory substance are mainly contained in raffinate, after residual liquid discharge to Sewage Disposal is handled, waste water row
Put, sludge is as solidification disposal of waste.And the present invention recycles to the accessory substance in vinasse, raffinate is varied, neutralize,
Solid byproducts are filtrated to get, in reuse to reactor.M can be reduced and consume 22 kgs/tonne of products, reduce by 54% sewage chemical
Oxygen demand CODcr, the solid suspension SS and soluble solid for reducing by 80%, reduce the generation of dewatered sludge.
The advantages of the present invention：The present invention is comprehensive to solve solvent method rubber accelerator M synthesis time sulphonyl
Amine type accelerator CBS technical barrier, product quality indicator are higher than national standard level, and consumption indicators reach industry reduced levels, and
Solve waste water, solid waste, odorant pollutant process problem；The solvent method rubber accelerator M that the program provides through more suppliers
Experimental demonstration is carried out, indices are stable, and repeatability is strong, realized big industrial production, and product has applied to international large-scale rubber
Glue product industry；This method will change industry rubber accelerator M production waste water generations and processing problem after promoting, realize that rubber promotees
The cleaning for entering agent M is carried out production strictly in line with rules and regulations.
Brief description of the drawings
Fig. 1 is technological process of production schematic diagram of the present invention；
Fig. 2 is that by-product recovery of the present invention utilizes process flow diagram.
Embodiment
In order that the object, technical solutions and advantages of the present invention are clearer, with reference to specific embodiment and experiment number
According to the present invention will be described in detail.
Solvent purifications method rubber accelerator M synthesis sulfenamide type accelerators CBS method, with rubber accelerator M, hexamethylene
Amine is raw material, using hydrogen peroxide, sodium hypochlorite as oxidant, using sulfuric acid as catalyst, reacts synthesis accelerant CBS.
The reaction equation is：
Embodiment：
First, optimal manufacturing condition is determined by following experiment：
(1) influence of the raw material proportioning to product quality and yield
Controlling reaction temperature is at 35~40 DEG C, and the reaction time, experimental raw was with comparison product in the case of 2.0~3.0h
The influence of quality and yield：
Note：Using dual oxidizer system, sodium hypochlorite usage amount is defined by end point determination.
Empirically data analysis, M and cyclohexylamine in molar ratio 1:When 1.8, product appearance is faint yellow, and yield, fusing point are equal
Relatively low, with the reduction of M and cyclohexylamine mol ratio, outward appearance, yield, fusing point improve, when cyclohexylamine is excessive, because product is molten
Solution causes yield to reduce in hexamethylene amine aqueous solution, and causes cyclohexylamine post processing recovery complicated.Gu M and cyclohexylamine minimum mole
Than 1:2.2.As M and H2O2In molar ratio 1:When 0.4, with sodium hypochlorite oxidization product quality and yield without significant difference, with
M and H2O2Reduce in molar ratio, product appearance, yield, fusing point have downward trend.H2O2The use of oxidant can reduce reaction
Accessory substance NaCL generation, reaches green clean manufacturing, reduces wastewater treatment difficulty, therefore minimum M and H2O2It is 1 in molar ratio:
0.6。
(2) influence of the reaction temperature to product quality and yield
By M：Cyclohexylamine：H2O2=1:2.2:0.6 proportioning is tested
Pass through experimental data：With the growth in reaction time, product yield has downward trend, and product fusing point progressively carries
Height, when reaction temperature is more than 40 DEG C, product appearance burnt hair, obfuscation, fusing point have declined.
(3) influence of the reaction time to product quality and yield
Reaction temperature is controlled at 35~40 DEG C, by M：Cyclohexylamine：H2O2=1:2.2:0.6 proportioning is tested, (H2O2
Concentration is 20%, and sodium hypochlorite is efficient for 15%)
| Reaction time h | Outward appearance | Average yield/% | Average fusing point DEG C |
| 1 | Yellowish white powder | 92.3 | 95.4 |
| 1.5 | White powder | 93.5 | 98.2 |
| 2 | White powder | 94.5 | 99.6 |
| 2.5 | Pale powder | 94.2 | 99.1 |
| 3 | Pale powder | 93.7 | 98.8 |
(4) influence of the oxidant concentration to product quality and yield
Reaction temperature is controlled at 35~40 DEG C, by M：Cyclohexylamine：H2O2=1:2.2:0.6 proportioning is tested (during reaction
Between be 2.0~2.5h)
Pass through experimental data：Work as H2O2When concentration is 15%, product yield, fusing point are relatively low, with H2O2Concentration carries
Height, product appearance, yield, fusing point improve.When sodium hypochlorite is efficient relatively low, product fusing point, yield are relatively low, with secondary chlorine
Sour sodium is efficient to be improved, and product fusing point, yield improve therewith.When sodium hypochlorite is efficient is more than 16%, reaction temperature is difficult to
Control, product fusing point, yield have downward trend.
In summary, it is determined that optimal manufacturing condition is：
n(M):N (cyclohexylamine)=1：2.2；
n(M):N (20% hydrogen peroxide):N (15% sodium hypochlorite)=1:0.6:0.65~0.75；
Reaction temperature is：35~40 DEG C；
Reaction time:2.0~2.5h.
Gained chemical name is N- cyclohexyl-2-benzothiazole sulfonamides, English name CBS, abbreviation CZ, and quality is steady
Fixed, outward appearance is white or faint yellow；Fusing point >=99 DEG C, yield based on main raw material(s) unit consumption, captax unit consumption 0.68~
0.682t/t products, cyclohexylamine unit consumption is in 0.408~0.413t/t products.
2nd, process equipment and flow
Program flow is completely embedded, process is succinctly reasonable, and serialization degree is high, solves in industry between traditional each operation
(the invention technological process of production schematic diagram is as schemed for odorant pollutant control emission caused by material transfer, gas uncontrollable discharge
1)。
This programme replaces the dehydrating operations of traditional centrifuge+suction strainer groove using multi-functional pressure filter.And conventional dehydration is grasped
As；Semi-finished product suspension reclaims accelerator CBS through suction strainer again through centrifuge dewatering, mother liquor, centrifuges post and suction strainer post is waved
The amine gas of hair, then lead to absorption system recovery cyclohexylamine through air-introduced machine.Centrifuge is high-power dynamic device, and vibration is big, pair is set
Standby fundamental importance is strict, admittedly can not be arranged in high-order aspect, cause that the semi-finished product after centrifugal dehydration and suction strainer reclaim half into
Product, boosted transfer is needed, could realize that screening operation is dried in granulation engagement etc..I.e. conventional dehydration operating process is complicated, linking, turns
During shifting presence material exposure, shed, volatilize, pollute environment, continuous operation can not be realized.And multi-functional pressure filter should
With, solve above-mentioned problem, multi-functional pressure filter is closed static device, by the discrepancy in elevation be arranged at reactor and drying system it
Between high-order aspect.Semi-finished product suspension is through in pipeline to multi-functional filter press, material is after filter-press water-washing, and mother liquor is through steaming
System recovery cyclohexylamine is evaporated, is recycled.Semi-finished product are directly entered dry screening system and finished product are made.Gas enters through emptying pipeline
Enter absorption system recycling.That is the seal of multi-functional pressure filter ensure that the inorganization volatile emission of amine gas is zero, thing
Expect that the transfer amount of shedding is zero, reduce environmental pollution.Multi-functional pressure filter is static equipment, realizes reaction post and is sieved with drying
The seamless connection in post, improve serialization degree.The press filtration principle of multi-functional pressure filter, instead of the complexity of centrifugation+suction strainer
Dehydrating operations, simplify operating process.
3rd, by-product recovery utilizes technique
Traditional CBS methods in process of production, after being distilled to recover cyclohexylamine, arranged mother liquor in the form of raffinate by main waste
Go out, the salts such as NaCL and a small amount of accessory substance are mainly contained in raffinate, after residual liquid discharge to Sewage Disposal is handled, discharge of wastewater,
Sludge is as solidification disposal of waste.
The present invention recycles to the accessory substance in vinasse, and raffinate is varied, neutralize, is filtrated to get solid-state pair
Product, in reuse to reactor (the invention by-product recovery utilizes process flow diagram such as Fig. 2).
The recovered utilization of byproduct of reaction, M can be reduced and consume 22 kgs/tonne of products, reduce by 54% sewage chemical oxygen consumption
CODcr, the solid suspension SS and soluble solid of reduction by 80% are measured, reduces the generation of dewatered sludge.
For to sum up, the beneficial effect of this method includes：
1st, solvent purifications method M synthesis accelerants CBS industrialized production is realized.
2nd, hydrogen peroxide, the industrial applications of sodium hypochlorite combination oxidant are realized, realize green, cleaning procedure production.
3rd, promote upstream product rubber accelerator M production cleanings to civilise, reduce rubber accelerator M productions and produce waste water 20
Ton/ton product.
4th, the recycling of accessory substance in vinasse is realized, M is reduced and consumes 22 kgs/tonne of products, reduce by 54%
Chemical oxygen consumption of sewage CODcr, the solid suspension SS and soluble solid for reducing by 80%, reduce the generation of dewatered sludge.
5th, the separation of solid and liquid for replacing centrifugation+suction strainer using advanced multi-functional pressure filter operates, and has prevented inorganization gas
Discharge, when reducing material transfer, exposure, the influence of impurity, foreign matter to quality, improve pipeline, serialization degree.
Claims (5)
1. solvent purifications method rubber accelerator M synthesis sulfenamide type accelerators CBS method, it is characterised in that promoted with rubber
Enter agent M, cyclohexylamine is raw material, using hydrogen peroxide, sodium hypochlorite as oxidant, using sulfuric acid as catalyst, react synthesis accelerant
CBS。
2. solvent purifications method rubber accelerator M synthesis sulfenamide type accelerators CBS according to claim 1 method,
Characterized in that, the reaction equation is：
3. solvent purifications method rubber accelerator M synthesis sulfenamide type accelerators CBS according to claim 1 method,
Characterized in that, optimal manufacturing condition is：
(1) mol ratio between each raw material, oxidant is as follows：
n(M):N (cyclohexylamine)=1：2.2；
n(M):N (20% hydrogen peroxide):N (15% sodium hypochlorite)=1:0.6:0.65~0.75；
(2) reaction temperature is：35~40 DEG C；
(3) reaction time:2.0~2.5h.
4. solvent purifications method rubber accelerator M synthesis sulfenamide type accelerators CBS according to claim 1 method,
Characterized in that, replacing the dehydrating operations of traditional centrifuge+suction strainer groove using multi-functional pressure filter, multi-functional pressure filter is close
The static device closed, the high-order aspect being arranged at by the discrepancy in elevation between reactor and drying system；Semi-finished product suspension is defeated through pipeline
Deliver in multi-functional pressure filter, for material after filter-press water-washing, mother liquor reclaims cyclohexylamine through Distallation systm, recycles；Semi-finished product
It is directly entered dry screening system and finished product is made；Gas recycles through emptying pipeline into absorption system.
5. solvent purifications method rubber accelerator M synthesis sulfenamide type accelerators CBS according to claim 1 method,
Characterized in that, being recycled to the accessory substance in vinasse, raffinate is varied, neutralize, is filtrated to get solid-state by-product
Thing, in reuse to reactor；The recovered utilization of byproduct of reaction, M can be reduced and consume 22 kgs/tonne of products, reduce by 54% dirt
Water chemistry oxygen demand CODcr, the solid suspension SS and soluble solid for reducing by 80%, reduce the generation of dewatered sludge.
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Citations (8)
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|---|---|---|---|---|
| US2419283A (en) * | 1944-01-27 | 1947-04-22 | Us Rubber Co | Manufacture of sulfenamides |
| CN1523020A (en) * | 2003-02-20 | 2004-08-25 | Process for preparing storage-stable benzothiazolyl sulfenamides | |
| CN101717381A (en) * | 2009-11-16 | 2010-06-02 | 天津市科迈化工有限公司 | Method for synthesizing thiofide CZ by taking hydrogen peroxide as oxidant |
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| CN103539757A (en) * | 2013-09-30 | 2014-01-29 | 科迈化工股份有限公司 | Method for synthesizing rubber vulcanization accelerator CZ |
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2017
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| US2419283A (en) * | 1944-01-27 | 1947-04-22 | Us Rubber Co | Manufacture of sulfenamides |
| CN1523020A (en) * | 2003-02-20 | 2004-08-25 | Process for preparing storage-stable benzothiazolyl sulfenamides | |
| CN101717381A (en) * | 2009-11-16 | 2010-06-02 | 天津市科迈化工有限公司 | Method for synthesizing thiofide CZ by taking hydrogen peroxide as oxidant |
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| CN103539757A (en) * | 2013-09-30 | 2014-01-29 | 科迈化工股份有限公司 | Method for synthesizing rubber vulcanization accelerator CZ |
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Application publication date: 20171208 |