CN108570021A - A kind of aniline fluid bed and its continuous production method - Google Patents
A kind of aniline fluid bed and its continuous production method Download PDFInfo
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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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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The present invention provides a kind of aniline fluid bed and its continuous production methods, the described method comprises the following steps：The salting liquid of accelerant MBT, the acid solution of cyclohexylamine, solvent and oxidant are passed through in reactor and carry out oxidation reaction, reacting rear material obtains CBS products through processing；Wherein, reactor is any one in tubular reactor, micro passage reaction or tower reactor or at least two combination.The present invention is using the salting liquid of 2 mercaptobenzothiazolers (MBT), the acid solution of cyclohexylamine, oxidant and suitable solvent as raw material, in flow reactor, prepare aniline fluid bed, reaction yield can be greatly improved, and after waste water obtained by the reaction carries out air-distillation recycling cyclohexylamine, COD can be reduced to 2000ppm hereinafter, being convenient for subsequent processing in remaining water.
Description
Technical field
The invention belongs to rubber chemicals field, it is related to a kind of aniline fluid bed and its continuous production method.
Background technology
During with various rubber products such as rubber production tire, sebific duct and rubber overshoes, it is necessary to five big analog assistants are used,
They are thiofide, rubber antioxidant, the vulcanization of rubber and vulcanizing activator, processing type rubber chemicals and features
Property auxiliary agent.Wherein, thiofide abbreviation accelerating agent can promote the substance of sulfurization.Vulcanization time can be shortened, reduced
Curing temperature reduces vulcanizing agent dosage and improves the physical mechanical property etc. of rubber.
Rubber vulcanizing accelerator CBS (chemical name N cyclohexyl 2 benzothiazole sulfenamide, also known as CZ) is time sulphonyl
One of important kind of amine type accelerator, he is that a kind of common delayed vulcanization promoter, scorching quality are excellent both at home and abroad
Good, process safety, vulcanization time is short, can improve the stretching strength and tensile strength of vulcanizate, is suitable for various rubber, and discoloration is light
It is micro-, no blooming.Thiofide is mainly for the manufacture of industrial rubber articles such as tire, sebific duct, rubber overshoes and electric wires.
Currently, the industrialization method of rubber vulcanizing accelerator CBS is using sodium hypochlorite or hydrogen peroxide as oxidant, will promote
Agent MBT generates accelerator CBS with cyclohexylamine oxidation.Wherein, sodium hypochlorite oxidization have technical maturity, reaction condition it is mild,
Product quality is preferable and the higher advantage of yield (generally in 90%-92% or so).But its production wastewater flow rate is big, 1 ton of product
About produce 8 tons of waste water, and salt content and COD higher (generally in 30000ppm or more) in waste water, it is difficult to which (there are lifes for biochemical treatment
Object toxicity), it is unfavorable to environmental protection.And hydrogen peroxide rule can avoid the problem that salt content is high in waste water, but hydrogen peroxide activity
By force, side reaction is more compared with sodium hypochlorite oxidization in oxidation process, and product yield also decreases compared with sodium hypochlorite oxidization.
Oxygen Catalytic Oxidation rule is conducive to environmental protection, in recent years by colleges and universities and enterprise since waste water yield is greatly reduced
Industry research.But then there is the problems such as conversion ratio is low, and reaction speed is slow, and process dangerous is high, and equipment investment is big in dioxygen oxidation technique,
All affect the feasibility of its further industrialization conversion.
In addition, at present mainstream CBS industrialized manufacturing techniques based on autoclave intermittent reaction, between batch and batch no matter
There is certain fluctuation in the control in terms of the technological parameters such as inventory, the temperature of reaction process and rate of feeding, and then right
Between batch there is more apparent influence in the yield of product, quality, and then reduce the stability of industrialization production.Also, by
Raw material MBT in existing market is mainly refined using emerging solvent method, and somewhat lower purity is in traditional acid-base method essence
The MBT rather than MBT of system are also changed greatly with MBT batches difference at being grouped as, and further increase stable accelerator CBS interval
The difficulty of production technology, so that reaction evaluating yield further decreases, waste water COD further increases, while product quality
Fluctuation is also more obvious.And the processing mode of waste water is produced, also it is a problem for perplexing CBS manufacturers.
Patent CN 106800540A disclose a kind of side preparing rubber vulcanizing accelerator CBS using micro passage reaction
Method is used as reaction raw materials after using excessive hexamethylene amine solvent raw material MBT, and is being urged using hydrogen peroxide, sodium hypochlorite or oxygen
Under agent effect, the synthesis accelerant CBS in micro passage reaction.Although this method provides another serialization and prepares rubber sulphur
Change the method for accelerator CBS, but the reaction time in this method in micro passage reaction is long, and single reactor
Flux peak is only 15L/h so that the technology does not have capability of industrialization completely, and reaction yield is relatively low (only in 87%-
Between 95%), reaction product purity is also unable to get guarantee.
Invention content
The problem of for existing rubber vulcanizing accelerator CBS production process, the present invention provides a kind of vulcanization rush
Into agent CBS and its continuous production method.The present invention with the salting liquid of 2-mercaptobenzothiazole (MBT), cyclohexylamine acid solution,
Oxidant and suitable solvent are that raw material prepares aniline fluid bed in flow reactor, can greatly improve reaction yield,
And after waste water obtained by the reaction carries out air-distillation recycling cyclohexylamine, COD can be reduced to 2000 hereinafter, convenient for follow-up in remaining water
Processing.
For this purpose, the present invention uses following technical scheme：
In a first aspect, the present invention provides a kind of continuous production method of aniline fluid bed, the method includes with
Lower step：
The salting liquid of accelerant MBT, the acid solution of cyclohexylamine, solvent and oxidant are passed through in reactor and aoxidize instead
It answers, reacting rear material obtains CBS products through processing；
Wherein, reactor is any one in tubular reactor, micro passage reaction or tower reactor or at least two
Combination.
In the present invention, the accelerant MBT, that is, 2-mercaptobenzothiazole, abbreviation MBT.
In the present invention, the acid solution of the salting liquid and cyclohexylamine that use MBT selects suitable solvent and oxidation for raw material
Agent carries out oxidative synthesis reaction in flow reactor, substantially reduces in reactor in the case where not using catalyst
Reaction time, it is only 0.5s~10s to make the optimal residence time.In equating volume equipment, single devices flux peak
Up to 1.8m3/ h, production capacity maximum can be extended to 1200 times, more industrialization value.
In the present invention, (DCBS productions, such as CN are generally common in for traditional M-Na salt technique for preparing vulcanization accelerator
Method involved in 102838564A), it is molten with liquor natrii hypochloritis, M-Na salt to change inorganic acid (sulfuric acid, hydrochloric acid etc.) needs
Liquid synchronizes the mode being added dropwise, prepare respectively the salting liquid (below by taking M-Na salt as an example) of MBT, cyclohexylamine acid solution (below with
For the hydrochloric acid solution of cyclohexylamine), mainly there is following purpose：
On the one hand, the salting liquid for first preparing the hydrochloric acid solution and MBT of cyclohexylamine respectively keeps hydrochloric acid mixed with cyclohexylamine first
It closes, can play the role of neutralizing cyclohexylamine, reduce the risk of esters solvent hydrolysis；And not with autoclave or vial-type dropwise reaction
Together, in the continuous flow reactors such as tubular reactor, micro passage reaction or tower reactor, if directly by hydrochloric acid, M-
Na salt is mixed with cyclohexylamine, other than it will appear hydrochloric acid and react generation cyclohexylamine hydrochloride with cyclohexylamine, while also will appear M-
Na salt reacts the reaction for generating sodium chloride and MBT with hydrochloric acid, and MBT is contacted with oxidant, and side reaction can occur, and generates 2,2'-
Dithio-bis-benzothiazole (abbreviation MBTS) or other resinae by-products improve line clogging while reducing yield
Risk.Therefore, it is necessary to first prepare the hydrochloric acid solution of M-Na salting liquids and cyclohexylamine respectively, then carry out subsequent reaction；
On the other hand, M-Na salting liquids are prepared respectively, the hydrochloric acid solution of cyclohexylamine also simplifies feeding mode, by script
Five kinds of cyclohexylamine, hydrochloric acid, solvent, M-Na salting liquids, oxidant raw materials are fed respectively, have made four kinds of chargings into, are reduced continuous
Control points when metaplasia is produced, improve the stability of technique.
It is used as currently preferred technical solution below, but not as the limitation of technical solution provided by the invention, passes through
Following technical scheme can preferably reach and realize the technical purpose and advantageous effect of the present invention.
As currently preferred technical solution, the preparation method of the salting liquid of the accelerant MBT includes the following steps：
Accelerant MBT is mixed with aqueous slkali under agitation, the salting liquid of MBT is made.
Preferably, the aqueous slkali includes NaOH solution, KOH solution or NH3·H2Any one in O solution or at least two
The mixing of kind, the combination is typical but non-limiting examples have：The combination of NaOH solution and KOH solution, KOH solution and NH3·
H2The combination etc. of O solution, preferably NaOH solution.With the MBT salting liquids prepared by NaOH solution for M-Na salting liquids.
As currently preferred technical solution, a concentration of 1wt%~50wt% of the aqueous slkali, such as 3wt%,
5wt%, 10wt%, 15wt%, 25wt% or 40wt% etc., it is not limited to cited numerical value, in the numberical range its
His unrequited numerical value is equally applicable.
Preferably, the mass ratio of the accelerant MBT and aqueous slkali is 1:(0.3~4.0), such as 1:0.5、1:1.1、1:
1.5、1:2.0、1:2.5、1:2.8 or 1:3.0 etc., it is not limited to cited numerical value, interior other of the numberical range do not arrange
The numerical value of act is equally applicable, and preferably 1:(0.5~1.5).
Preferably, accelerant MBT under agitation with the incorporation time of aqueous slkali be 0~4h, such as 0.5h, 1h,
1.5h, 2h, 2.5h, 3h, 3.5h or 4h etc., it is not limited to cited numerical value, other are unrequited in the numberical range
Numerical value is equally applicable, preferably 0~2h.
Preferably, accelerant MBT under agitation with the mixing temperature of aqueous slkali be 0~100 DEG C, such as 5 DEG C, 10
DEG C, 20 DEG C, 30 DEG C, 40 DEG C, 50 DEG C, 60 DEG C, 70 DEG C, 80 DEG C, 90 DEG C or 100 DEG C etc., it is not limited to cited numerical value,
Other unrequited numerical value are equally applicable in the numberical range, preferably 40 DEG C~60 DEG C.
As currently preferred technical solution, the preparation method of the acid solution of the cyclohexylamine includes the following steps：It will
Cyclohexylamine mixes under agitation with acid, and is diluted, and obtains the acid solution of cyclohexylamine.
Preferably, mixing of the acid including any one in hydrochloric acid, sulfuric acid, nitric acid or phosphoric acid or at least two, it is described
Combination is typical but non-limiting examples have：The combination of the combination of hydrochloric acid and sulfuric acid, nitric acid and phosphoric acid, sulfuric acid, nitric acid and phosphoric acid
Combination etc..
As currently preferred technical solution, a concentration of 1wt%~98wt% of the acid, such as 1wt%,
11wt%, 21wt%, 51wt% or 71wt% etc., it is not limited to cited numerical value, interior other of the numberical range do not arrange
The numerical value of act is equally applicable.
Preferably, the molar ratio of the cyclohexylamine and solute in acid solution is 1:(0.1~2), such as 1:0.2、1:0.4、
1:0.6、1:0.8、1:1、1:1.2、1:1.4、1:1.6、1:1.8 or 2 etc., it is not limited to cited numerical value, the numerical value
Other unrequited numerical value are equally applicable in range, and preferably 1:(0.3~1).
Preferably, solvent for use is water in the dilution.
Preferably, the acid solution of cyclohexylamine is 1 with the mass ratio of solvent for use in dilution:(0~2), such as 1:0.5、
1:0.8、1:1、1:1.2、1:1.4、1:1.6、1:1.8 or 2 etc., it is not limited to cited numerical value, in the numberical range
Other unrequited numerical value are equally applicable, and preferably 1:(0.5~1).
Preferably, cyclohexylamine and the temperature that mixes under agitation of acid are 0~100 DEG C, for example, 5 DEG C, 10 DEG C, 20 DEG C,
30 DEG C, 40 DEG C, 50 DEG C, 60 DEG C, 70 DEG C, 80 DEG C, 90 DEG C or 100 DEG C etc., it is not limited to cited numerical value, the numerical value model
Other unrequited numerical value are equally applicable in enclosing, preferably 40~45 DEG C.
As currently preferred technical solution, the solvent is methyl formate, methyl acetate, Ethyl formate, acetic acid second
Any one in ester, acetic acid triglyceride, chloroform, carbon tetrachloride, benzene, toluene, ethylbenzene, isopropylbenzene or hexamethylene or at least
Two kinds of combination, the combination is typical but non-limiting examples have：The combination of methyl formate and methyl acetate, Ethyl formate and second
The combination of acetoacetic ester, the combination of acetic acid triglyceride and chloroform, the combination of carbon tetrachloride and benzene, the group of toluene and ethylbenzene
It closes, the combination of methyl formate, methyl acetate, Ethyl formate and ethyl acetate, ethyl acetate, acetic acid triglyceride and chloroform
Combination, the combination etc. of benzene, toluene, ethylbenzene, isopropylbenzene and hexamethylene, preferably ethyl acetate and/or toluene.
In the present invention, the effect reached using ethyl acetate and/or toluene as solvent is optimal.
In the present invention, the salting liquid technique using the solvent and traditional MBT for preparing vulcanization accelerator is (general common
Produced in DCBS, such as the method involved in CN 102838564A) in solvent for use (such as isopropanol) have essential difference.
If reaction involved in CN 102838564A is solid-liquid heterogeneous reaction, which is raw material M-Na salt
Intermediate product (mainly the complex salt to be formed is complexed with dicyclohexyl amine in MBT) and the oxidant (hypochlorous acid formed with dicyclohexyl amine
Sodium) redox reaction is carried out, generate target product DCBS.Final product DCBS can be suspended in reaction system in solid form
In, and the main purpose for being introduced into this water-soluble solvent of isopropanol is to increase solubility of the reaction intermediate in water phase,
So that the redox reaction of partial intermediate and oxidant becomes being contrary in water from solid-liquid heterogeneous reaction
Answer, and then improve reaction speed and reaction yield, reduce due to oxidant for a long time in solid phase intermediate product contact process because
Deep oxidation and the side reaction caused.But the isopropanol solvent of introducing, it is only capable of part and improves reaction speed, it can not be from this
The process that DCBS is prepared as solid-liquid heterogeneous reaction is solved in matter.Therefore, most industrialized implementation situations are found, the technical industry
After change, the conversion ratio of raw material MBT is even lower substantially 90% or so.Also, since final product DCBS can be in solid form
It suspends in the reaction system, cannot achieve and carry out continuous production in flow reactor.
And in the building-up process of aniline fluid bed, Aqueous Solution of Cyclohexylamine not only plays the role of raw material, simultaneously
It can play the role of solvent, (MBT is complexed with cyclohexylamine to be formed for the intermediate product that can make to be formed in reaction process in this way
Salt) and final product CBS be dissolved into reaction system, avoid the generation of heterogeneous reaction so that the reaction can tubular type very
To in micro passage reaction, progress is without blocking pipeline, the technology as described in patent CN 106800540A.
But since cyclohexylamine is stronger compared with dicyclohexyl amine alkalinity, and the bridge-type cyclic structure of cyclohexylamine make cyclohexylamine with
MBT is complexed the salt to be formed and is easier by oxidation even deep oxidation, and then the yield of product CBS can be made to reduce.In this regard, with ring
Hexylamine aqueous solution is solvent, and intermediate product is made to be in together in water phase with oxidant, then deep oxidation generation has been further amplified
Possibility.And the CBS that reaction generates can be dissolved in the aqueous solution of cyclohexylamine, be in homogeneous state with oxidant for a long time, also
Can by-product be converted by deep oxidation so that reaction yield further decreases.Reality of this phenomenon from CN 106800540A
It applies in example and is not difficult to find out, yield maintains essentially in 90% or less.Meanwhile this phenomenon also has in the synthesis of accelerator TBBS
It embodies, but since tert-butylamine does not have the special bridge-type cyclic structure of cyclohexylamine, so its salt generated with MBT complexings is gone back
Originality is less than cyclohexylamine, so the yield of synthesis TBBS is higher than CBS in this way, but still can not turn close to 100% theory
Rate, this is not difficult to find out from the embodiment in CN 106866578A.
Thus in view of the above-mentioned problems, present invention introduces solvent, i.e. methyl formate, methyl acetate, Ethyl formate, acetic acid second
Any one in ester, acetic acid triglyceride, chloroform, carbon tetrachloride, benzene, toluene, ethylbenzene, isopropylbenzene or hexamethylene or at least
Two kinds of combination.Its purpose is not only only that instead of cyclohexylamine as solvent, while can make raw material cyclohexylamine, intermediate product
(salt to be formed is complexed with cyclohexylamine by MBT) from being moved in water phase in solvent phase, and then make oxidation process by single water phase into
Row becomes the reaction of the liquid-liquid diphase between water phase and oil phase.Compared to CN 102838564A, CN 106866578A and CN
Homogeneous reaction in 106800540A, present invention introduces oil/water liquid-liquid diphase reaction occur mainly on boundary, aoxidized
Journey becomes more mild controllable, and the generation of side reaction can be greatly reduced.
Meanwhile the target product CBS of generation then can be very good dissolving in a solvent, avoid excessively contacting with oxidant,
To reduce the secondary oxidation of the product generated, and then further increase product yield.Therefore, reaction involved in the present invention
Process goal product can reach 99.6% or more, you can think the generation of side reaction substantially completely evaded.
But the reaction of oil/water liquid-liquid diphase needs better two-phase mixtures that can be carried in the case where not changing reaction yield
High reaction speed.In this regard, the present invention uses flow reactor (such as micro passage reaction), the material mixing in reactor is strong
Spend bigger, mass-transfer efficiency higher.So reaction process according to the present invention, reaction time is only 0.5-10s, significantly low
In currently reported all reaction technologies.
And this is also the feature that the present invention is better than other prior arts, oil/water liquid-liquid diphase reactant is in continuous reaction
Mixing in device (such as micro passage reaction), during strengthening mixing, without considering the problems of side reaction.It therefore, can be with
In the case where keeping product yield, the reaction time is greatly reduced so that the present invention has more industrialization value.Although existing preparation
Micro passage reaction is used in the method for aniline fluid bed, but homogeneous reaction yield is uncontrollable, the shortening reaction time can make
Target product yield is reduced at deep oxidation, so the characteristics play of the high mass-and heat-transfer efficiency of micro passage reaction can not be gone out
Come.And longer reaction time then represents lower reaction efficiency so that its industrialization value is greatly reduced.
Preferably, the oxidant is oxygen, hydrogen peroxide, liquor natrii hypochloritis, dimethyl sulfoxide (DMSO), chlorine, potassium permanganate
Any one in solution or potassium chlorate solution or at least two combination, the combination is typical but non-limiting examples have：Oxygen
With the combination of hydrogen peroxide, the combination of oxygen and liquor natrii hypochloritis, the combination of oxygen and chlorine, liquor natrii hypochloritis and potassium chlorate
The combination etc. of the combination of solution, chlorine and liquor natrii hypochloritis, preferably liquor natrii hypochloritis.
Preferably, in the liquor natrii hypochloritis available chlorine content be 8wt%~17wt%, such as 8wt%, 10wt%,
12wt%, 14wt%, 16wt% or 17wt% etc., it is not limited to cited numerical value, interior other of the numberical range do not arrange
The numerical value of act is equally applicable.
Preferably, the charge-mass ratio of the acid solution of the salting liquid and cyclohexylamine of MBT is 1:(0.5~5), such as 1:0.5、
1:1、1:1.5、1:2、1:2.5、1:3、1:3.5、1:4、1:4.5 or 1:5 etc., it is not limited to cited numerical value, the number
It is equally applicable to be worth other unrequited numerical value in range, preferably 1:(1~2.5).
Preferably, the charge-mass ratio of the salting liquid of MBT and solvent is 1:(1~5), such as 1:1、1:1.5、1:2、1:
2.5、1:3、1:3.5、1:4、1:4.5 or 1:5 etc., it is not limited to cited numerical value, interior other of the numberical range do not arrange
The numerical value of act is equally applicable, and preferably 1:(1.5~3).
Preferably, the charge-mass ratio of the salting liquid of MBT and oxidant is 1:(1~8), such as 1:1、1:2、1:3、1:4、
1:5、1:6、1:7 or 1:8 etc., it is not limited to cited numerical value, other interior unrequited numerical value of the numberical range are same
It is applicable in, preferably 1:(1.2~4).
Preferably, the reaction temperature of the oxidation reaction be 10 DEG C~100 DEG C, such as 10 DEG C, 20 DEG C, 30 DEG C, 40 DEG C, 50
DEG C, 60 DEG C, 70 DEG C, 80 DEG C, 90 DEG C or 100 DEG C etc., it is not limited to cited numerical value, other are not arranged in the numberical range
The numerical value of act is equally applicable, preferably 20 DEG C~50 DEG C.
Preferably, the reactor is micro passage reaction.
Preferably, the residence time reacted in the reactor be 0.5s~2400s, such as 0.5s, 1s, 3s, 10s,
50s, 100s, 300s, 500s, 1000s, 1500s, 2000s, 2200s or 2400s etc., it is not limited to cited numerical value,
Other unrequited numerical value are equally applicable in the numberical range, preferably 0.5s~10s.
As currently preferred technical solution, reacting rear material obtains CBS products through processing, specifically includes：Reaction
Through solvent recovery and CBS crude products are obtained by filtration in material afterwards, and CBS products are obtained after CBS crude products are washed and dry.
As currently preferred technical solution, the solvent recovery is to be evaporated under reduced pressure.
Preferably, it is evaporated under reduced pressure until solvent-free steam.
Preferably, the temperature of the solvent recovery be 20 DEG C~80 DEG C, such as 20 DEG C, 30 DEG C, 40 DEG C, 50 DEG C, 60 DEG C, 70
DEG C or 80 DEG C etc., it is not limited to cited numerical value, other unrequited numerical value are equally applicable in the numberical range, preferably
It is 40 DEG C~80 DEG C.
Preferably, in the solvent recovery control vacuum degree be 10kPa~80kPa, such as 10kPa, 20kPa, 30kPa,
40kPa, 50kPa, 60kPa, 70kPa or 80kPa etc., it is not limited to cited numerical value, in the numberical range, other are not
The numerical value enumerated is equally applicable, preferably 10kPa~50kPa.
Preferably, include organic solvent washing and washing successively to the washing of CBS crude products；
Preferably, organic solvent used includes methanol, ethyl alcohol, isopropanol, methyl formate, second in the organic solvent washing
Any one in sour methyl esters, Ethyl formate, ethyl acetate, acetic acid triglyceride, acetone, tert-butylamine, cyclohexylamine or aniline or extremely
Few two kinds of aqueous solution, the combination is typical but non-limiting examples have：The aqueous solution of methanol and ethyl alcohol, methyl formate and acetic acid
The aqueous solution of the aqueous solution of methyl esters, Ethyl formate and ethyl acetate, Ethyl formate, ethyl acetate and acetic acid triglyceride group
It closes, the combination etc. of acetone, tert-butylamine, cyclohexylamine and aniline, the preferably aqueous solution of cyclohexylamine.
As currently preferred technical solution, the described method comprises the following steps：
(a) M-Na salting liquids are configured：By the accelerant MBT NaOH with a concentration of 20wt%~35wt% under agitation
Solution mixes, and M-Na salting liquids are made；Wherein, accelerant MBT and the mass ratio of NaOH solution are 1:(0.5~1.5), when mixing
Between be 0~2h, mixing temperature be 40 DEG C~60 DEG C；
Configure the hydrochloric acid solution of cyclohexylamine：By the hydrochloric acid of cyclohexylamine and a concentration of 20wt~30wt% under agitation in
40 DEG C~45 DEG C mixing, and water is diluted, and obtains the hydrochloric acid solution of cyclohexylamine；Wherein, cyclohexylamine and solute in acid solution
Molar ratio is 1:The mass ratio of (0.3~1), cyclohexylamine and water is 1:(0.5~1)；
(b) by M-Na salting liquids, the hydrochloric acid solution of cyclohexylamine, solvent ethyl acetate and/or toluene and oxidant hypochlorous acid
Sodium solution, which is passed through in micro passage reaction at 20 DEG C~50 DEG C, carries out oxidation reaction, and the residence time of reaction is 0.5s~10s；
Wherein, the charge-mass ratio of the hydrochloric acid solution of M-Na salting liquids and cyclohexylamine is 1:(1~2.5), M-Na salting liquids and solvent
Charge-mass ratio is 1:The feedstock quality of (1.5~3), M-Na salting liquids and oxidant is 1:(1.2~4)；
(c) material is evaporated under reduced pressure back under conditions of 40 DEG C~80 DEG C and vacuum degree are 10kPa~50kPa after oxidation reaction
Solvent is received, obtains CBS crude products using filter, CBS crude products obtain after the washing of the aqueous solution of cyclohexylamine, washing and drying successively
To CBS products.
Second aspect, the present invention provides the aniline fluid beds that above-mentioned continuous production method is prepared.
Compared with prior art, the invention has the advantages that：
(1) present invention is with the M-Na salting liquids of 2-mercaptobenzothiazole (MBT), hydrochloric acid solution, solvent and the oxygen of cyclohexylamine
Agent is raw material, in flow reactor, prepares aniline fluid bed, product yield is up to 99.6% (with the content of MBT
Meter) more than, product purity is up to 99.6wt% or more；
(2) after the method for the invention waste water obtained by the reaction carries out air-distillation recycling cyclohexylamine, COD can in remaining water
It is reduced to 2000ppm or less；
(3) the method for the invention has reaction speed fast, and product yield high, waste water COD is low, disposable etc. many excellent
Point is a kind of new technology of more industrialization value.
Specific implementation mode
For the present invention is better described, it is easy to understand technical scheme of the present invention, below further specifically to the present invention
It is bright.But following embodiments is only the simple example of the present invention, does not represent or limit the scope of the present invention, this
Invention protection domain is subject to claims.
Specific embodiment of the invention part provides a kind of continuous production method of aniline fluid bed, the side
Method includes the following steps：
The M-Na salting liquids of accelerant MBT, the hydrochloric acid solution of cyclohexylamine, solvent and oxidant are passed through in reactor and carried out
Oxidation reaction, reacting rear material obtain CBS products through processing；
Wherein, reactor is any one in tubular reactor, micro passage reaction or tower reactor or at least two
Combination.
It is present invention typical case but non-limiting embodiment below：
Embodiment 1：
A kind of continuous production method of aniline fluid bed is present embodiments provided, the described method comprises the following steps：
(1) M-Na salting liquids are configured：The accelerant MBT of 400g is mixed with the NaOH solution of a concentration of 32wt% of 360g,
2h is stirred at 50 DEG C, M-Na salting liquids are made；
Configure the hydrochloric acid solution of cyclohexylamine：316g cyclohexylamine is mixed with the technical hydrochloric acid of a concentration of 31wt% of 376g, is added
Enter 224g water, stirred at 35 DEG C, obtains the hydrochloric acid solution of cyclohexylamine；
(2) the secondary chlorine for being 17% by M-Na salting liquids, the hydrochloric acid solution of cyclohexylamine, solvent ethyl acetate and available chlorine content
Acid sodium solution according to M-Na salting liquids 72mL/min, the hydrochloric acid solution 115mL/min of cyclohexylamine, ethyl acetate 154mL/min and
The speed of liquor natrii hypochloritis 96mL/min, which is passed through in micro passage reaction, carries out oxidation reaction, reaction time 2s, instead
It is 30 DEG C to answer temperature, and micro passage reaction is that 4 reactors are connected, and every reactor volume is 3.2mL, and series connection post-reactor is total
Volume is 12.8mL；
(4) material flowed out in reactor is collected, is evaporated under reduced pressure at vacuum degree -0.05MPa, 40 DEG C~50 DEG C
Ethyl acetate is recycled, until no distillate, remaining solidliquid mixture obtains crude product after filtering；The thick production being obtained by filtration
Product washed once with 200mL Aqueous Solution of Cyclohexylamine, after 200mL water washings 2 times, you can obtain CBS wet feeds, after drying, i.e.,
CBS finished products can be obtained.
After measured, the present embodiment CBS yields are 99.6% (with the content meter of MBT), and CBS purity is 99.6wt%, appearance
For white micro-crystals powder, for waste water after normal pressure is distilled to recover cyclohexylamine, remaining COD is 1900ppm.
Embodiment 2：
A kind of continuous production method of aniline fluid bed is present embodiments provided, the described method comprises the following steps：
(1) M-Na salting liquids are configured：The accelerant MBT of 2t is mixed with the NaOH solution of a concentration of 30wt% of 2.4t,
2h is stirred at 60 DEG C, M-Na salting liquids are made；
(2) hydrochloric acid solution of cyclohexylamine is configured：By the technical hydrochloric acid of 1.8t cyclohexylamine and a concentration of 30wt% of 2.2t, 1.2t
Water mixes, and is stirred at 40 DEG C, obtains the hydrochloric acid solution of cyclohexylamine；
(3) sodium hypochlorite for being 17% by M-Na salting liquids, the hydrochloric acid solution of cyclohexylamine, solvent toluene and available chlorine content
Solution is according to M-Na salting liquids 0.74m3/ h, cyclohexylamine hydrochloride salting liquid 1m3/ h, toluene 2.2m3/ h, liquor natrii hypochloritis
1.07m3The speed of/h, which is passed through in micro passage reaction, carries out oxidation reaction, reaction time 2s, and reaction temperature is 40 DEG C,
Micro passage reaction is that 10 monomer reaction devices are connected, and every reactor volume is 270mL, and series connection post-reactor total measurement (volume) is
2700mL；
(4) material flowed out in reactor is collected, is evaporated under reduced pressure at vacuum degree -0.09MPa, 65 DEG C~75 DEG C
Toluene is recycled, until no distillate, remaining solidliquid mixture obtains crude product after filtering；The crude product being obtained by filtration is used
1t Aqueous Solution of Cyclohexylamine washed once, after 1t water washings 2 times, you can obtain CBS wet feeds, after drying, you can obtain CBS at
Product.
After measured, CBS yields are 99.6% (with the content meter of MBT), and CBS purity is 99.7wt%, and appearance is that white is micro-
Crystalline flour end, for waste water after normal pressure is distilled to recover cyclohexylamine, remaining COD is 1830ppm.
Embodiment 3：
A kind of continuous production method of aniline fluid bed is present embodiments provided, the described method comprises the following steps：
(1) M-K salting liquids are configured：400g accelerant MBTs and the KOH solution of a concentration of 30wt% of 536g are stirred at 40 DEG C
3h is mixed, M-K salting liquids are made；
(2) sulfuric acid solution of cyclohexylamine is configured：By the sulfuric acid of 427g cyclohexylamine and a concentration of 20wt% of 469g at 50 DEG C
Stirring, obtains the sulfuric acid solution of cyclohexylamine；
(3) by M-K salting liquids, the sulfuric acid solution of cyclohexylamine, solvent acetic acid methyl esters and a concentration of 17% hydrogen peroxide solution
According to M-K salting liquids 14mL/min, cyclohexylamine sulfate liquor 19mL/min, methyl acetate 80mL/min, hydrogen peroxide solution
The speed of 21mL/min, which is passed through in micro passage reaction, carries out oxidation reaction, reaction time 5s, and reaction temperature is 50 DEG C,
Micro passage reaction is that 5 monomer reaction devices are connected, and every reactor volume is 1.86mL, and series connection post-reactor total measurement (volume) is
9.3mL；
(4) material flowed out in reactor is collected, is evaporated under reduced pressure at vacuum degree -0.01MPa, 20 DEG C~30 DEG C
Methyl acetate is recycled, until no distillate, remaining solidliquid mixture obtains crude product after filtering；The thick production being obtained by filtration
Product washed once with 200ml Aqueous Solution of Cyclohexylamine, after 200ml water washings 2 times, you can obtain CBS wet feeds, after drying, i.e.,
CBS finished products can be obtained.
After measured, CBS yields are 95.3% (with the content meter of MBT), and CBS purity is 98.9wt%, and appearance is that white is micro-
Crystalline flour end, for waste water after normal pressure is distilled to recover cyclohexylamine, remaining COD is 1950ppm.
Embodiment 4：
A kind of continuous production method of aniline fluid bed is present embodiments provided, the described method comprises the following steps：
(1) M-NH is configured3Salting liquid：400g accelerant MBTs and the ammonia of a concentration of 25wt% of 244g are stirred at 60 DEG C
M-NH is made in 4h3Salting liquid；
(2) salpeter solution of cyclohexylamine is configured：By the nitric acid of 356g cyclohexylamine and a concentration of 50wt% of 452g, 356g water exists
It is stirred at 45 DEG C, obtains the nitrate solution of cyclohexylamine；
(3) by M-NH3Salting liquid, the nitrate solution of cyclohexylamine, solvent hexamethylene and concentration 3% potassium chlorate solution press
According to M-NH3Salting liquid 10ml/min, the nitrate solution 17ml/min of cyclohexylamine, hexamethylene 23ml/min, potassium chlorate solution
The charge-mass ratio of 62ml/min, which is passed through in micro passage reaction, carries out oxidation reaction, reaction time 10s, reaction temperature
It it is 20 DEG C, micro passage reaction is that 10 monomer reaction devices are connected, and every reactor volume is 1.86mL, and series connection post-reactor is total
Volume is 18.6mL；
(4) material flowed out in reactor is collected, is evaporated under reduced pressure at vacuum degree -0.07MPa, 30 DEG C~40 DEG C
Hexamethylene is recycled, until no distillate, remaining solidliquid mixture obtains crude product after filtering；The crude product being obtained by filtration
It washed once with 200ml Aqueous Solution of Cyclohexylamine, after 200ml water washings 2 times, you can obtain CBS wet feeds, after drying, you can
Obtain CBS finished products.
After measured, CBS yields are 89.5% (with the content meter of MBT), and CBS purity is 98.3wt%, and appearance is that white is micro-
Crystalline flour end, for waste water after normal pressure is distilled to recover cyclohexylamine, remaining COD is 2080ppm.
Embodiment 5：
A kind of continuous production method of aniline fluid bed is present embodiments provided, the described method comprises the following steps：
(1) M-Na salting liquids are configured：The accelerant MBT of 400g is mixed with the NaOH solution of a concentration of 32wt% of 360g,
2h is stirred at 50 DEG C, M-Na salting liquids are made；
(2) hydrochloric acid solution of cyclohexylamine is configured：316g cyclohexylamine is mixed with the technical hydrochloric acid of a concentration of 31wt% of 376g,
224g water is added, is stirred at 35 DEG C, obtains the hydrochloric acid solution of cyclohexylamine；
(3) the secondary chlorine for being 17% by M-Na salting liquids, the hydrochloric acid solution of cyclohexylamine, solvent ethyl acetate and available chlorine content
Acid sodium solution according to M-Na salting liquids 72mL/min, the hydrochloric acid solution 115mL/min of cyclohexylamine, ethyl acetate 154mL/min and
The speed of liquor natrii hypochloritis 96mL/min, which is passed through in micro passage reaction, carries out oxidation reaction, reaction time 10s, instead
It is 45 DEG C to answer temperature, and tower reactor volume is 64mL；
(4) material flowed out in reactor is collected, is evaporated under reduced pressure at vacuum degree -0.05MPa, 40 DEG C~50 DEG C
Ethyl acetate is recycled, until no distillate, remaining solidliquid mixture obtains crude product after filtering；The thick production being obtained by filtration
Product washed once with 200mL Aqueous Solution of Cyclohexylamine, after 200mL water washings 2 times, you can obtain CBS wet feeds, after drying, i.e.,
CBS finished products can be obtained.
After measured, the present embodiment CBS yields are 99.2% (with the content meter of MBT), and CBS purity is 99.3wt%, appearance
For white micro-crystals powder, for waste water after normal pressure is distilled to recover cyclohexylamine, remaining COD is 1980ppm.
Comparative example 1：
This comparative example provides a kind of continuous production method of aniline fluid bed, the described method comprises the following steps
Method in reference embodiment 1, difference lies in：The hydrochloric acid solution for not configuring cyclohexylamine in step (1), by M-Na in step (2)
The liquor natrii hypochloritis that salting liquid, cyclohexylamine, hydrochloric acid, solvent ethyl acetate and available chlorine content are 17% presses embodiment 1 respectively
In consumption proportion be added micro passage reaction in；
In this comparative example, due to not configuring the hydrochloric acid solution of cyclohexylamine, repeatedly there is equipment stopping state in reaction process,
After measured, CBS yields are 85.9% (with the content meter of MBT), and CBS purity is 98.7wt%, and waste water is distilled to recover ring through normal pressure
After hexylamine, remaining COD is 8500ppm.
Comparative example 2：
This comparative example provides a kind of continuous production method of aniline fluid bed, and the method does not configure M-Na salt
The hydrochloric acid solution of solution and cyclohexylamine, but captax is dissolved in cyclohexylamine and forms solution, captax is dissolved in cyclohexylamine
The liquor natrii hypochloritis that the solution and available chlorine content of middle formation are 17% is added in micro passage reaction, i.e. CN106800540A
In reaction condition.
In this comparative example, due to not configuring the acid solution of cyclohexylamine, after measured, CBS yields are only 89.1% (with MBT's
Content meter), CBS purity is 98.3wt%, and for waste water after normal pressure is distilled to recover cyclohexylamine, remaining COD is 9500ppm.
It is molten with the M-Na salt of 2-mercaptobenzothiazole (MBT) that the present invention is can be seen that with comparative example based on the above embodiments
Liquid, the hydrochloric acid solution of cyclohexylamine, solvent and oxidant are that raw material prepares aniline fluid bed in flow reactor, are produced
Object yield up to 99.6% (with the content meter of MBT) more than, product purity is up to 99.6wt% or more；
After the method for the invention waste water obtained by the reaction carries out air-distillation recycling cyclohexylamine, COD can drop in remaining water
Down to 2000ppm or less；
The method of the invention have reaction speed it is fast, product yield high, waste water COD is low, it is disposable many advantages, such as, be
A kind of new technology of more industrialization value.
Applicant states that the present invention illustrates the method detailed of the present invention, but the present invention not office by above-described embodiment
It is limited to above-mentioned method detailed, that is, does not mean that the present invention has to rely on above-mentioned method detailed and could implement.Technical field
Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to each raw material of product of the present invention
Addition, the selection etc. of concrete mode, all fall within protection scope of the present invention and the open scope.
Claims (10)
1. a kind of continuous production method of aniline fluid bed, which is characterized in that the described method comprises the following steps：
The salting liquid of accelerant MBT, the acid solution of cyclohexylamine, solvent and oxidant are passed through in reactor and carry out oxidation reaction,
Reacting rear material obtains CBS products through processing；
Wherein, reactor is any one in tubular reactor, micro passage reaction or tower reactor or at least two group
It closes.
2. continuous production method according to claim 1, which is characterized in that the system of the salting liquid of the accelerant MBT
Preparation Method includes the following steps：Accelerant MBT is mixed with aqueous slkali under agitation, the salting liquid of MBT is made；
Preferably, the aqueous slkali includes NaOH solution, KOH solution or NH3·H2Any one in O solution or at least two
Mixing, preferably NaOH solution.
3. continuous production method according to claim 2, which is characterized in that a concentration of 1wt% of the aqueous slkali~
50wt%, preferably 20wt%~35wt%；
Preferably, the mass ratio of the accelerant MBT and aqueous slkali is 1:(0.3~4.0), preferably 1:(0.5~1.5)；
Preferably, accelerant MBT is under agitation 0~4h, preferably 0~2h with the incorporation time of aqueous slkali；
Preferably, accelerant MBT under agitation with the mixing temperature of aqueous slkali be 0~100 DEG C, preferably 40 DEG C~60
℃。
4. according to claim 1-3 any one of them continuous production methods, which is characterized in that the acid solution of the cyclohexylamine
Preparation method include the following steps：Cyclohexylamine is mixed under agitation with acid, and is diluted, the acid of cyclohexylamine is obtained
Solution.
Preferably, the acid includes any one in hydrochloric acid, sulfuric acid, nitric acid or phosphoric acid or at least two mixing.
5. continuous production method according to claim 4, which is characterized in that a concentration of 1wt% of the acid~
98wt%, preferably 20wt%~30wt%；
Preferably, the molar ratio of the cyclohexylamine and solute in acid is 1:(0.1~2), preferably 1:(0.3~1)；
Preferably, solvent for use is water in the dilution；
Preferably, the mass ratio of solvent for use is 1 in the dilution of the acid solution of cyclohexylamine:(0~2), preferably 1:(0.5~1)；
Preferably, cyclohexylamine is 0~100 DEG C, preferably 40~45 DEG C with the temperature that acid mixes under agitation.
6. according to claim 1-5 any one of them continuous production methods, which is characterized in that the solvent is formic acid first
It is ester, methyl acetate, Ethyl formate, ethyl acetate, acetic acid triglyceride, chloroform, carbon tetrachloride, benzene, toluene, ethylbenzene, different
Any one in propyl benzene or hexamethylene or at least two combination, preferably ethyl acetate and/or toluene；
Preferably, the oxidant is oxygen, hydrogen peroxide, liquor natrii hypochloritis, dimethyl sulfoxide (DMSO), chlorine, liquor potassic permanganate
Any one in potassium chlorate solution or at least two combination, preferably liquor natrii hypochloritis；
Preferably, available chlorine content is 8wt%~17wt% in the liquor natrii hypochloritis；
Preferably, the charge-mass ratio of the acid solution of the salting liquid and cyclohexylamine of MBT is 1:(0.5~5), preferably 1:(1~
2.5)；
Preferably, the charge-mass ratio of the salting liquid of MBT and solvent is 1:(1~5), preferably 1:(1.5~3)；
Preferably, the charge-mass ratio of the salting liquid of MBT and oxidant is 1:(1~8), preferably 1:(1.2~4)；
Preferably, the reaction temperature of the oxidation reaction is 10 DEG C~100 DEG C, preferably 20 DEG C~50 DEG C；
Preferably, the reactor is micro passage reaction；
Preferably, the residence time reacted in the reactor is 0.5s~2400s, preferably 0.5s~10s.
7. according to claim 1-6 any one of them continuous production methods, which is characterized in that reacting rear material is through handling
To CBS products, specifically include：Reacting rear material is through solvent recovery and CBS crude products are obtained by filtration, and CBS crude products are washed
With CBS products are obtained after drying.
8. continuous production method according to claim 7, which is characterized in that the solvent recovery is to be evaporated under reduced pressure；
Preferably, it is evaporated under reduced pressure until solvent-free steam；
Preferably, the temperature of the solvent recovery is 20 DEG C~80 DEG C, preferably 40 DEG C~80 DEG C；
Preferably, it is 10kPa~80kPa, preferably 10kPa~50kPa that vacuum degree is controlled in the solvent recovery；
Preferably, include organic solvent washing and washing successively to the washing of CBS crude products；
Preferably, organic solvent used includes methanol, ethyl alcohol, isopropanol, methyl formate, acetic acid first in the organic solvent washing
Any one in ester, Ethyl formate, ethyl acetate, acetic acid triglyceride, acetone, tert-butylamine, cyclohexylamine or aniline or at least two
The aqueous solution of kind, the preferably aqueous solution of cyclohexylamine.
9. according to claim 1-8 any one of them continuous production methods, which is characterized in that the method includes following steps
Suddenly：
(a) M-Na salting liquids are configured：By the accelerant MBT NaOH solution with a concentration of 20wt%~35wt% under agitation
M-Na salting liquids are made in mixing；Wherein, accelerant MBT and the mass ratio of NaOH solution are 1:(0.5~1.5), incorporation time are
0~2h, mixing temperature are 40 DEG C~60 DEG C；
Configure the acid solution of cyclohexylamine：By the acid of cyclohexylamine and a concentration of 20wt~30wt% under agitation in 40 DEG C~45
DEG C mixing, and water is diluted, and obtains the acid solution of cyclohexylamine；Wherein, the molar ratio of cyclohexylamine and solute in acid solution is 1:
The mass ratio of (0.3~1), cyclohexylamine and water is 1:(0.5~1)；
(b) by M-Na salting liquids, the acid solution of cyclohexylamine, solvent ethyl acetate and/or toluene and oxidizing agent sodium hypochlorite's solution
It is passed through in micro passage reaction at 20 DEG C~50 DEG C and carries out oxidation reaction, the residence time of reaction is 0.5s~10s；Wherein,
The charge-mass ratio of the acid solution of M-Na salting liquids and cyclohexylamine is 1:(1~2.5), the feedstock quality of M-Na salting liquids and solvent
Than being 1:The feedstock quality of (1.5~3), M-Na salting liquids and oxidant is 1:(1.2~4)；
(c) material reduction vaporization recycling under conditions of 40 DEG C~80 DEG C and vacuum degree are 10kPa~50kPa is molten after oxidation reaction
Agent obtains CBS crude products using filter, and CBS crude products obtain after the washing of the aqueous solution of cyclohexylamine, washing and drying successively
CBS products.
10. a kind of aniline fluid bed being prepared such as claim 1-9 any one of them continuous production methods.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109320475A (en) * | 2018-10-24 | 2019-02-12 | 科迈化工股份有限公司 | The method of the direct synthetic rubber aniline fluid bed of resin in waste water |
| CN110105303A (en) * | 2019-06-21 | 2019-08-09 | 科迈化工股份有限公司 | A method of using liquid chlorine as oxidant continuous production aniline fluid bed |
| CN111072595A (en) * | 2020-01-19 | 2020-04-28 | 山东尚舜化工有限公司 | Novel method for preparing rubber accelerator DCBS |
| CN112624945A (en) * | 2020-12-30 | 2021-04-09 | 山东尚舜化工有限公司 | Method and equipment for continuously synthesizing rubber vulcanization accelerator S |
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| CN102827104A (en) * | 2012-09-25 | 2012-12-19 | 科迈化工股份有限公司 | Method for synthesizing rubber vulcanization accelerator CZ by two-step process by using sodium hypochlorite as oxidizer |
| CN106800540A (en) * | 2017-03-30 | 2017-06-06 | 山东斯递尔化工科技有限公司 | A kind of method that utilization micro passage reaction prepares rubber vulcanizing accelerator CBS |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102827104A (en) * | 2012-09-25 | 2012-12-19 | 科迈化工股份有限公司 | Method for synthesizing rubber vulcanization accelerator CZ by two-step process by using sodium hypochlorite as oxidizer |
| CN106800540A (en) * | 2017-03-30 | 2017-06-06 | 山东斯递尔化工科技有限公司 | A kind of method that utilization micro passage reaction prepares rubber vulcanizing accelerator CBS |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109320475A (en) * | 2018-10-24 | 2019-02-12 | 科迈化工股份有限公司 | The method of the direct synthetic rubber aniline fluid bed of resin in waste water |
| CN110105303A (en) * | 2019-06-21 | 2019-08-09 | 科迈化工股份有限公司 | A method of using liquid chlorine as oxidant continuous production aniline fluid bed |
| CN111072595A (en) * | 2020-01-19 | 2020-04-28 | 山东尚舜化工有限公司 | Novel method for preparing rubber accelerator DCBS |
| CN112624945A (en) * | 2020-12-30 | 2021-04-09 | 山东尚舜化工有限公司 | Method and equipment for continuously synthesizing rubber vulcanization accelerator S |
| CN112624945B (en) * | 2020-12-30 | 2023-04-25 | 山东尚舜化工有限公司 | Method and equipment for continuously synthesizing rubber vulcanization accelerator S |
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