CN109320475A - The method of the direct synthetic rubber aniline fluid bed of resin in waste water - Google Patents
The method of the direct synthetic rubber aniline fluid bed of resin in waste water Download PDFInfo
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- CN109320475A CN109320475A CN201811243799.1A CN201811243799A CN109320475A CN 109320475 A CN109320475 A CN 109320475A CN 201811243799 A CN201811243799 A CN 201811243799A CN 109320475 A CN109320475 A CN 109320475A
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/45—Heterocyclic compounds having sulfur in the ring
- C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring
- C08K5/47—Thiazoles
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to field of waste water treatment, and in particular to a kind of method of the direct synthetic rubber aniline fluid bed of resin in waste water includes the following steps: under 1) room temperature, resin is mixed under stirring with the aqueous solution of NaOH, prepares M-Na salting liquid；2) by 1.5-3 parts by weight cyclohexylamine and 2-3 parts by weight water investment reactor in, be uniformly mixing to obtain Aqueous Solution of Cyclohexylamine；3) it is instilled in the reactor in step 2) after mixing M-Na salt, acid obtained in step 1) and oxidant；4) after the material after reacting first passes around sedimentation layering 0.5-1h, lower layer's material is obtained into product after centrifuge dripping.The invention saves high-temperature solvent dissolution infall process, it is simple easy to operate, because reducing environmental pollution caused by the volatilization of solvent without heating and while not necessary solvent reduces the energy, and target product CBS yield is more than 99.0% (with the content meter of MBT).
Description
Technical field
The invention belongs to field of waste water treatment, and in particular to the direct synthetic rubber vulcanization accelerator of resin in a kind of waste water
The method of CBS.
Background technique
Rubber vulcanizing accelerator CBS (chemical name N cyclohexyl 2 benzothiazole sulfenamide, also known as CZ) is time sulphonyl
One of important species 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.Mainly for the manufacture of industrial rubber articles such as tire, sebific duct, rubber overshoes, electric wires.
The big proportioning process production CBS of cyclohexylamine, cyclohexylamine: MBT=industrially are all made of in order to improve CBS mass at present
2-4 (molar ratio), extra cyclohexylamine are recycled by way of distillation.Although improving the quality of product in this way,
A problem is brought, is exactly that MBT, intermediate product and final product CBS have one in reacting hexamethylene amine aqueous solution to the end
Fixed solubility, and these mother liquors for having dissolved material have to pass through high temperature distillation and could recycle back as far as possible extra cyclohexylamine
Come, general vapo(u)rizing temperature will at 100-104 DEG C, and at this temperature MBT, intermediate product, CBS can occur denaturation generate its
His black resin.It changes and there was only 90% or so according to MBT conversion ratio highest at present, that is, remaining 10% is unreacted
MBT is dissolved in waste water with this or other forms, and the viscosity that the available MBT content of wastewater treatment process is about 60% is organic
Object (hereinafter referred to as resin).It is as follows that the resin of the MBT content 60% or so recycled from waste water recycles mode: stirring
In the case where, solvent such as toluene, ammonium hydroxide, aniline is added in resin investment reactor and is heated to 60-90 DEG C of dissolution, is then filtered
Undissolved substance is removed, the solution being obtained by filtration cools down the purer MBT for being recrystallized to give MBT content 85% or so again,
Then cyclohexylamine is added for synthesis accelerant CBS, and the method puts into cyclohexylamine: resin (according to MBT content)=3-4:1
(molar ratio), reaction yield only have 85% or so (on the basis of MBT content in resin).The method is very troublesome, first CBS
The resin recycled in waste water is heating up, and the solubility very little in these types of solvent, course of dissolution needs the time longer, and high temperature is molten
It is grume liquid-solid mixture after solution, when filtering, is more complicated, with filtering and centrifuge dripping is easy blocking filter cloth and strainer hole,
It generally needs to be placed in settling tank, extracts upper solution after cooling sedimentation, but even if still some floating in this way
Tackifying resin can enter pipeline, and blocking pipeline can be precipitated for a long time.And purifying obtained material in this way is that comparison is glutinous, is suspended to equipment
And pipe surface, temperature-fall period heat exchange efficiency is influenced, needs heat more and periodic cleaning, generally at least wants cleaning one in one week
It is secondary.Then then a large amount of cyclohexylamine is added by mashing in the material of the MBT purity 85% obtained, by be added dropwise time sodium or
Hydrogen peroxide oxidation synthesis accelerant CBS, very low only 90% or so (being converted according to MBT) of the yield of the method, the COD of waste water
High disposal is complicated.
Summary of the invention
The purpose of the present invention is to overcome the defects in the prior art, provides the direct synthetic rubber sulphur of resin in a kind of waste water
Change the method for accelerator CBS.
The present invention to achieve the above object, using following technical scheme:
The method of the direct synthetic rubber aniline fluid bed of resin, includes the following steps: in a kind of waste water
1) under room temperature, resin is mixed under stirring with the aqueous solution of NaOH, prepares M-Na salting liquid, sedimentation is extracted
Upper layer M-Na salting liquid is spare；
2) by 1.5-3 parts by weight cyclohexylamine and 2-3 parts by weight water investment reactor in, be uniformly mixing to obtain cyclohexylamine
Aqueous solution；
3) by 2-3.5 parts by weight M-Na salt, the acid of 1-2 parts by weight obtained in step 1) and 2-3 parts by weight oxidant
It is instilled in the reactor containing Aqueous Solution of Cyclohexylamine in step 2) in 1-2.5h after mixing；The oxidant is sodium hypochlorite
Or hydrogen peroxide.
4) after the material after reacting first passes around sedimentation layering 0.5-1h, lower layer's material is produced after centrifuge dripping
Object.
The mass concentration of NaOH is 25-35% in step 1), and the mass ratio of resin and NaOH are 1:0.5-1.5；M-Na salt
Setup time be 1-3h, configuration temperature be 0-100 DEG C, sedimentation time 1-2h.
Acid in step 3) is hydrochloric acid, sulfuric acid or nitric acid.
Product in step 4) after centrifuge dripping washs removal impurity with hexamethylene amine aqueous solution.
Mother liquor is separately separated sedimentation to step 4) at the middle and upper levels, upper after sedimentation by short grained CBS material by sedimentation recycling
The extra cyclohexylamine of layer mother liquor redistillation recycling unreacted.
The acid of 1/10 mass parts, is instilling M-Na salt, residual acid and oxidant later in being first added dropwise in step 3).
The reactor is reaction kettle, tubular reactor, micro passage reaction or tower reactor
Compared with prior art, the beneficial effects of the present invention are:
The invention saves high-temperature solvent dissolution infall process, simple easy to operate, because not having to heating and being not required
Reduce environmental pollution caused by the volatilization of solvent while reducing the energy with solvent, and target product CBS yield is more than
99.0% (with the content meter of MBT)；Simultaneously by technique adjustment, so that by-product organic matter (mostlys come from non-in raw material MBT
MBT ingredient) hardly enter in waste water during the reaction, waste water COD is only 5000ppm or so after the reaction was completed, more traditional
Autoclave batch technology waste water COD reduces by 80% or more.The technique also greatly improved reaction and receive in addition to changing reactive mode
Rate, so that the effective component in original MBT has almost been completely converted into product, while it is organic to realize by-product during the reaction
The separation of object and water, significantly reduces waste water COD, reduces wastewater treatment difficulty, realizes the greenization progress of technique.
Specific embodiment
In order to make those skilled in the art more fully understand technical solution of the present invention, implement below with reference to best
The present invention is described in further detail for example.
Embodiment 1: a kind of method of the direct synthetic rubber aniline fluid bed of resin in waste water includes the following steps:
1) under room temperature, resin is uniformly mixed system according to mass ratio 1:1 with the aqueous solution of 32%NaOH under stirring
Standby M-Na salting liquid, mixing temperature are 50 DEG C, setup time 2h, and it is spare that upper layer M-Na salting liquid is extracted in sedimentation；
2) by the cyclohexylamine of 1.5 parts by weight and 2 parts by weight water investment reactor, it is water-soluble to be uniformly mixing to obtain cyclohexylamine
Liquid；
3) 2 parts by weight M-Na salt, the hydrochloric acid of 1.5 parts by weight obtained in step 1) and 2.5 parts by weight oxidants are mixed
It is instilled in the reactor containing Aqueous Solution of Cyclohexylamine in step 2) after conjunction.The acid of 1/10 mass parts, exists again later in being first added dropwise
M-Na salt, residual acid and oxidant are instilled in 1h.
4) after the material after reacting first passes around sedimentation layering 0.5h, lower layer's material is produced after centrifuge dripping
Object, the product after centrifuge dripping wash removal impurity with hexamethylene amine aqueous solution and obtain product.Upper layer mother liquor is separately separated sedimentation, will be small
For the CBS material of particle by sedimentation recycling, the extra cyclohexylamine of unreacted is recycled in the upper layer mother liquor redistillation after sedimentation, recycles ring
Waste water after hexylamine is by sedimentation 1h, waste water COD 4800mg/L.Product CBS yield is more than 99.2% (with the content of MBT
Meter).
Embodiment 2: a kind of method of the direct synthetic rubber aniline fluid bed of resin in waste water includes the following steps:
1) under room temperature, resin is uniformly mixed with the aqueous solution of 35%NaOH according to mass ratio 1:0.5 under stirring
M-Na salting liquid is prepared, mixing temperature is 0 DEG C, setup time 3h, and it is spare that sedimentation 1h extracts upper layer M-Na salting liquid；
2) by 3 parts by weight cyclohexylamine and 3 parts by weight water investment reactor in, it is water-soluble to be uniformly mixing to obtain cyclohexylamine
Liquid；
3) after 3 parts by weight M-Na salt, the sulfuric acid of 1 parts by weight obtained in step 1) and 2 parts by weight hydrogen peroxide being mixed
It instills in the reactor containing Aqueous Solution of Cyclohexylamine in step 2).The acid of 1/10 mass parts is first added dropwise, later again in 1.5h
Instill M-Na salt, residual acid and oxidant.
4) after the material after reacting first passes around sedimentation layering 1h, lower layer's material is obtained into product after centrifuge dripping,
Product after centrifuge dripping washs removal impurity with hexamethylene amine aqueous solution and obtains product.Upper layer mother liquor is separately separated sedimentation, by small
For the CBS material of grain by sedimentation recycling, the extra cyclohexylamine of unreacted is recycled in the upper layer mother liquor redistillation after sedimentation.Recycle hexamethylene
Waste water after amine is by sedimentation 1h, waste water COD 5000mg/L.Product CBS yield is more than 99.2% (with the content meter of MBT).
Target product CBS yield is more than 99.0% (with the content meter of MBT).
Embodiment 3:
The method of the direct synthetic rubber aniline fluid bed of resin, includes the following steps: in a kind of waste water
1) under room temperature, resin is uniformly mixed with the aqueous solution of 25%NaOH according to mass ratio 1:1.5 under stirring
M-Na salting liquid is prepared, mixing temperature is 100 DEG C, setup time 1h, and it is spare that upper layer M-Na salting liquid is extracted in sedimentation；
2) by 2 parts by weight cyclohexylamine and 2.5 parts by weight water investment reactor in, it is water-soluble to be uniformly mixing to obtain cyclohexylamine
Liquid；
3) 3.5 parts by weight M-Na salt, the nitric acid of 2 parts by weight obtained in step 1) and 3 parts by weight sodium hypochlorite are mixed
It is instilled in the reactor containing Aqueous Solution of Cyclohexylamine in step 2) after conjunction.The acid of 1/10 mass parts, exists again later in being first added dropwise
2.5h instills M-Na salt, residual acid and oxidant.
4) after the material after reacting first passes around sedimentation layering 0.75h, lower layer's material is produced after centrifuge dripping
Object, the product after centrifuge dripping wash removal impurity with hexamethylene amine aqueous solution and obtain product.Upper layer mother liquor is separately separated sedimentation, will be small
For the CBS material of particle by sedimentation recycling, the extra cyclohexylamine of unreacted is recycled in the upper layer mother liquor redistillation after sedimentation, recycles ring
Waste water after hexylamine is by sedimentation 1h, waste water COD 5000mg/L.Product CBS yield is more than 99.1% (with the content of MBT
Meter).
The above is only a preferred embodiment of the present invention, for those of ordinary skill in the art, according to the present invention
Thought, there will be changes in the specific implementation manner and application range, and the content of the present specification should not be construed as to the present invention
Limitation.
Claims (7)
1. a kind of method of the direct synthetic rubber aniline fluid bed of resin in waste water, which is characterized in that include the following steps:
1) under room temperature, resin is mixed under stirring with the aqueous solution of NaOH, prepares M-Na salting liquid, upper layer is extracted in sedimentation
M-Na salting liquid is spare；
2) by 1.5-3 parts by weight cyclohexylamine and 2-3 parts by weight water investment reactor in, it is water-soluble to be uniformly mixing to obtain cyclohexylamine
Liquid；
3) 2-3.5 parts by weight M-Na salt, the acid of 1-2 parts by weight obtained in step 1) and 2-3 parts by weight oxidant are mixed
It is instilled in the reactor containing Aqueous Solution of Cyclohexylamine in step 2) in 1-2.5h afterwards；
4) after the material after reacting first passes around sedimentation layering 0.5-1h, lower layer's material is obtained into product after centrifuge dripping.
2. the method for the direct synthetic rubber aniline fluid bed of resin, feature exist in waste water according to claim 1
In the mass concentration of NaOH is 25-35% in step 1), and the mass ratio of resin and NaOH are 1:0.5-1.5；The configuration of M-Na salt
Time is 1-3h, and configuration temperature is 0-100 DEG C, sedimentation time 1-2h.
3. the method for the direct synthetic rubber aniline fluid bed of resin, feature exist in waste water according to claim 1
In the acid in step 3) is hydrochloric acid, sulfuric acid or nitric acid.
4. the method for the direct synthetic rubber aniline fluid bed of resin, feature exist in waste water according to claim 1
In the product in step 4) after centrifuge dripping washs removal impurity with hexamethylene amine aqueous solution.
5. the method for the direct synthetic rubber aniline fluid bed of resin, feature exist in waste water according to claim 1
In mother liquor is separately separated sedimentation to step 4) at the middle and upper levels, and by short grained CBS material by sedimentation recycling, the upper layer after sedimentation is female
The extra cyclohexylamine of unreacted is recycled in liquid redistillation.
6. the method for the direct synthetic rubber aniline fluid bed of resin, feature exist in waste water according to claim 1
In, be first added dropwise in step 3) in 1/10 mass parts acid, instilling M-Na salt, residual acid and oxidant later.
7. the method for the direct synthetic rubber aniline fluid bed of resin, feature exist in waste water according to claim 1
In the reactor is reaction kettle, tubular reactor, micro passage reaction or tower reactor.
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| CN201811243799.1A CN109320475A (en) | 2018-10-24 | 2018-10-24 | The method of the direct synthetic rubber aniline fluid bed of resin in waste water |
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| CN201811243799.1A CN109320475A (en) | 2018-10-24 | 2018-10-24 | The method of the direct synthetic rubber aniline fluid bed of resin in waste water |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000042099A1 (en) * | 1999-01-12 | 2000-07-20 | Uniroyal Chemical Company, Inc. | In situ preparation of a bis-(benzothiazolesulfen)amide in a polymeric matrix |
| CN102838564A (en) * | 2012-09-25 | 2012-12-26 | 科迈化工股份有限公司 | Preparation method of rubber vulcanization accelerator DCBS |
| CN108570021A (en) * | 2018-05-23 | 2018-09-25 | 科迈化工股份有限公司 | A kind of aniline fluid bed and its continuous production method |
-
2018
- 2018-10-24 CN CN201811243799.1A patent/CN109320475A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000042099A1 (en) * | 1999-01-12 | 2000-07-20 | Uniroyal Chemical Company, Inc. | In situ preparation of a bis-(benzothiazolesulfen)amide in a polymeric matrix |
| CN102838564A (en) * | 2012-09-25 | 2012-12-26 | 科迈化工股份有限公司 | Preparation method of rubber vulcanization accelerator DCBS |
| CN108570021A (en) * | 2018-05-23 | 2018-09-25 | 科迈化工股份有限公司 | A kind of aniline fluid bed and its continuous production method |
Non-Patent Citations (1)
| Title |
|---|
| 陈俊强等: "从生产促进剂M废树脂中制取促进剂DM", 《河南科学》 * |
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Application publication date: 20190212 |
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