CN108484444B - Utilize the method for bromine and Hydrogen Peroxide Production azodiisobutyronitrile - Google Patents
Utilize the method for bromine and Hydrogen Peroxide Production azodiisobutyronitrile Download PDFInfo
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- bromine
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
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Abstract
The invention belongs to chemical technology fields, and in particular to a method of utilize bromine and Hydrogen Peroxide Production azodiisobutyronitrile.This method: bromine solution, organic solvent, bis-isobutyronitrile hydrazine being added into reaction kettle, form three-phase；Stirring, bis-isobutyronitrile hydrazine is reacted with bromine generates azodiisobutyronitrile and hydrobromic acid, azodiisobutyronitrile is by organic extractant phase, and hydrobromic acid reacts with the hydrogen peroxide being added dropwise later and generates bromine, bromine is further continued for generating azodiisobutyronitrile and hydrobromic acid with bis-isobutyronitrile hydrazine reaction, when in solution without bis-isobutyronitrile hydrazine, reaction terminating ultimately forms organic phase and water phase containing azodiisobutyronitrile.The present invention does not use acid as raw material and solvent, avoids the generation of saliferous acid waste water, reaction process is mild, and the mother liquor after reaction can be recycled.In addition, there will not be the generation of extra substance the invention avoids while other materials addition, realizing the recycling of material, save cost, economy is excellent.
Description
Technical field
The invention belongs to chemical technology fields, and in particular to a kind of using bromine and Hydrogen Peroxide Production azodiisobutyronitrile
Method.
Background technique
Following two method is mainly used in the production of azodiisobutyronitrile at present:
One, chlorine: being first passed through in reaction kettle by chlorine oxidation process, reacts with sodium bromide and generates simple substance bromine, then with bromine and two
Isobutyronitrile hydrazine reaction, prepares azodiisobutyronitrile.The major defect of this production method is: (1) process is relative complex, control point
It is more；Reaction process is unstable, and reaction end is not easy to control, be easy to cause peroxidating, and device therefor is more；(2) it produces
The utilization rate of chlorine is lower in the process, and a part of chlorine causes to waste because that cannot react in time, and is easy to produce tri-chlorination
Nitrogen by-product, risk are high；(3) solvent is made with hydrochloric acid solution in production process, dissolubility is poor, and the reaction time is too long；(4) anti-
A large amount of liquid alkaline should be needed to consume in the process to handle useless tail gas, waste chemical reagent；(5) product is washed, 1 ton of production
Product are washed with 20-30 tons of water, serious waste water resource, but also can generate a large amount of waste acid waters.
Two, sulfuric acid oxidation method: first configuring the dilute sulfuric acid of 30-40%, and bis-isobutyronitrile hydrazine is then added, and stirring is dissolved in dilute sulphur
Acid, dripping hydrogen peroxide is reacted with sodium bromide generates simple substance bromine, then captures the hydrogen in bis-isobutyronitrile hydrazine with bromine, and preparation takes azo two
Isobutyronitrile.The major defect of this production method is: (1) reaction process is unstable, and concentration is be easy to cause to react, and generates a large amount of
Heat causes the azodiisobutyronitrile generated to decompose, and causes production accident；(2) raw material and product are mixed in together, and reaction end is not
It is easy to control；(3) utilization rate of hydrogen peroxide is lower, and a part of hydrogen peroxide is wasted because that cannot react in time；(4) it is used in production process
Dilute sulfuric acid makees solvent, and dissolubility is poor, and the reaction time is too long；(5) solid containing a large amount of sulfuric acid in the waste water generated in reaction process
Body salt and dilute sulfuric acid, are not easily recycled, and processing cost is higher.A kind of hydrogen peroxide oxidation is used as Chinese patent CN101134735A is disclosed
The method that method produces azodiisobutyronitrile, this method is to configure sulfuric acid solution in a kettle, is then added into reaction kettle
Bis-isobutyronitrile hydrazine adds sodium bromide, and after stirring to bis-isobutyronitrile hydrazine dissolution, dripping hydrogen peroxide is stirred to react, and azo is made
Bis-isobutyronitrile.When the patent is reacted, only water phase, all reactants are only existed in water phase, are only being reacted in reaction system
Can just there are water phase and solid phase two-phase after the completion.So the patent reaction process is unstable, reaction end is not easy to control, Suo Youyuan
Material and product mix together, be easy to cause concentration to react, generate big calorimetric, cause the azodiisobutyronitrile generated to decompose, draw
Send out production accident；In addition, obtained azodiisobutyronitrile needs are washed with water, waste water resource, but also can generate a large amount of useless
Sour water；Importantly, there is a large amount of solid sodium sulfate salt to generate in the patent reaction process, solid sodium sulfate salt will enter useless
In water, it is difficult to handle, and processing cost is higher.
Summary of the invention
The object of the present invention is to provide a kind of methods using bromine and Hydrogen Peroxide Production azodiisobutyronitrile, do not use acid
As raw material and solvent, the generation of saliferous acid waste water is avoided, reaction process is mild, and the mother liquor after reaction, which can recycle, to be made
With.
Method of the present invention using bromine and Hydrogen Peroxide Production azodiisobutyronitrile: bromine is added into reaction kettle
Solution, organic solvent, bis-isobutyronitrile hydrazine form three-phase；Lower layer is the water phase that bromine solution is formed, and middle layer is organic solvent shape
At organic phase, upper layer be bis-isobutyronitrile hydrazine formed solid phase；Stirring, bis-isobutyronitrile hydrazine is reacted with bromine generates two isobutyl of azo
Nitrile and hydrobromic acid, azodiisobutyronitrile is by organic extractant phase, and hydrobromic acid reacts with the hydrogen peroxide being added dropwise later and generates bromine, bromine
Element is further continued for generating azodiisobutyronitrile and hydrobromic acid with bis-isobutyronitrile hydrazine reaction, and when in solution without bis-isobutyronitrile hydrazine, reaction is eventually
Only, two-phase is ultimately formed, upper layer is the organic phase containing azodiisobutyronitrile, and lower layer is the water phase or contain that bromine solution is formed
The water phase for thering is the bromine solution of hydrobromic acid to be formed.Organic phase crystallization containing azodiisobutyronitrile, obtains azodiisobutyronitrile.
Wherein:
Bis-isobutyronitrile hydrazine and the mass ratio of bromine solution are 1:4-6, and the mass percentage concentration of bromine solution is 0.1-10%；
The solvent of bromine solution is water or reaction mother liquor.
The mass ratio of bis-isobutyronitrile hydrazine and organic solvent is 1:3-5.
The density of organic solvent is less than the density of water.
Organic solvent is the mixture of toluene or methylene chloride and ether.Methylene chloride is mixed with ether with arbitrary proportion
Can, as long as mixed density is less than the density of water.
The mass ratio of bis-isobutyronitrile hydrazine and hydrogen peroxide is 1:0.2-0.5, preferably 1:0.2-0.3.For production safety, dioxygen
Water in the reaction cannot be excessive, therefore contains hydrobromic acid when end of reaction in water phase.
In the entire reaction process of bromine and Hydrogen Peroxide Production azodiisobutyronitrile, reaction temperature control 20-28 DEG C it
Between, when hydrogen peroxide is added dropwise, rate of addition controls reaction temperature also to be advisable between 20-28 DEG C, and entire reaction is mild, controllable.
Reaction time controlled at 5-15 hours, was equally divided into twice, including reaction leading portion and reaction back segment, and when hydrogen peroxide addition
Between according to the case where actual production determine, generally after the reaction section add.
Preferably, the method for the present invention using bromine and Hydrogen Peroxide Production azodiisobutyronitrile:
When bromine solution, organic solvent, bis-isobutyronitrile hydrazine being added into reaction kettle, first into bromine solution, addition reaction is helped
Agent hydrobromic acid solution forms three-phase；Lower layer is bromine solution and the water phase that hydrobromic acid solution is formed, and middle layer is organic solvent shape
At organic phase, upper layer be bis-isobutyronitrile hydrazine formed solid phase；Stirring, bis-isobutyronitrile hydrazine is reacted with bromine generates two isobutyl of azo
Nitrile and hydrobromic acid, azodiisobutyronitrile is by organic extractant phase, and hydrobromic acid reacts with the hydrogen peroxide being added dropwise later and generates bromine, bromine
Element is further continued for generating azodiisobutyronitrile and hydrobromic acid with bis-isobutyronitrile hydrazine reaction, and when in solution without bis-isobutyronitrile hydrazine, reaction is eventually
Only, two-phase is ultimately formed, upper layer is the organic phase containing azodiisobutyronitrile, and lower layer is the water phase or contain that bromine solution is formed
The water phase for thering is the bromine solution of hydrobromic acid to be formed.Organic phase crystallization containing azodiisobutyronitrile, obtains azodiisobutyronitrile.
Wherein:
The ratio of the quality of bis-isobutyronitrile hydrazine and bromine solution and hydrobromic acid solution gross mass is 1:4-6, bromine solution with
The mass ratio of hydrobromic acid solution is 1-2:1.
The mass percentage concentration of bromine solution is 0.1-3%, and the solvent of bromine solution is water or reaction mother liquor；
The mass percentage concentration of hydrobromic acid solution is 0.5-30%, and the solvent of hydrobromic acid solution is water or reaction mother liquor.
Hydrobromic acid solution can be added as auxiliary agent in the present invention in bromine solution.When in reaction system bromine solution it is dense
When spending lower, reaction speed is slower, and the hydrobromic acid of generation is less, after the reaction section be added hydrogen peroxide after, the hydrobromic acid of generation with
The bromine that hydrogen peroxide reaction generates is also less, so that reaction efficiency is low；Hydrobromic acid solution work is added in the present invention in bromine solution
Hydrobromic acid for auxiliary agent, generation is reacted with hydrogen peroxide simultaneously with the hydrobromic acid of addition, generates more bromine, promotion react into
Row, so that reaction efficiency improves.
It is of the invention that the reaction mechanism is as follows:
(1)C8H14N4+Br2=C8H12N4+2HBr；
(2)H2O2+ 2HBr=Br2+2H2O。
Beneficial effects of the present invention are as follows:
Bromine solution, organic solvent, bis-isobutyronitrile hydrazine in the present invention form three-phase；Lower layer is the water that bromine solution is formed
Phase, middle layer are the organic phase that organic solvent is formed, and upper layer is the solid phase that bis-isobutyronitrile hydrazine is formed；Under stirring, bromine is different with two
Butyronitrile hydrazine reaction generates azodiisobutyronitrile and hydrobromic acid, azodiisobutyronitrile and is extracted by organic solvent, hydrobromic acid with drip later
The hydrogen peroxide reaction added generates bromine, and bromine is further continued for generating azodiisobutyronitrile and hydrobromic acid with bis-isobutyronitrile hydrazine reaction, molten
When in liquid without bis-isobutyronitrile hydrazine, reaction terminating ultimately forms two-phase, and upper layer is the organic phase containing azodiisobutyronitrile, lower layer
The water phase that the water phase formed for bromine solution or the bromine solution containing hydrobromic acid are formed.Contain the organic of azodiisobutyronitrile
It mutually crystallizes, obtains azodiisobutyronitrile.
It before present invention stirring, because of the interval of organic phase between water phase, solid phase, will not react, reaction is controllable.Stirring
Afterwards, just start to react, generate azodiisobutyronitrile, and it is different to realize azo two into organic phase for the azodiisobutyronitrile generated
The separation of butyronitrile and reactant is avoided because the phenomenon that azodiisobutyronitrile decomposes caused by concentrating reaction；Contain two isobutyl of azo
The organic phase of nitrile crystallizes, that is, may separate out azodiisobutyronitrile, without washing, generates without saliferous acid waste water, saves water
Resource reduces the discharge of waste water, waste residue.
Bromine of the invention and bis-isobutyronitrile hydrazine reaction generate hydrobromic acid, and hydrobromic acid react with hydrogen peroxide, generation bromine with
Water, bromine again be produce azodiisobutyronitrile reactant, then with bis-isobutyronitrile hydrazine reaction, circulation production azodiisobutyronitrile.
Bromine is mutually converted with hydrobromic acid in the present invention, while avoiding other materials addition, there will not be the generation of extra substance,
The recycling for realizing material, saves cost, and economy is excellent.
In addition, reducing production cost the invention avoids the generation of saliferous acid waste water, reduce three waste discharge.This
The yield > 98.0% of azodiisobutyronitrile, purity >=99.5% in invention.
Specific embodiment
The present invention is described further with reference to embodiments.
Embodiment 1
Bromine solution, the 1000g toluene, 200g bis-isobutyronitrile that 800g mass percentage concentration is 4% are added into reaction kettle
Hydrazine forms three-phase, and lower layer is the water phase that bromine solution is formed, and middle layer is the organic phase that toluene is formed, and upper layer is bis-isobutyronitrile
The solid phase that hydrazine is formed；Whole temperature control is reacted at 25 ± 2 DEG C.
Stirring, bis-isobutyronitrile hydrazine is reacted with bromine generates azodiisobutyronitrile and hydrobromic acid, and azodiisobutyronitrile, which enters, to be had
Machine phase, after reacting 6h；50g hydrogen peroxide is added into reaction kettle again, dioxygen water management is added dropwise in 2h, keeps the temperature 4h；Herein
In the process, hydrobromic acid is reacted with hydrogen peroxide generates bromine, and bromine is further continued for generating azodiisobutyronitrile with bis-isobutyronitrile hydrazine reaction
And hydrobromic acid, azodiisobutyronitrile enter back into organic phase.
After keeping the temperature 4h, reaction terminating ultimately forms two-phase, and upper layer is the organic phase containing azodiisobutyronitrile, and lower layer is
The water phase that bromine solution containing hydrobromic acid is formed；Separation organic phase and water phase, water phase i.e. mother liquor can be recycled, have
Machine is mutually refined, and is crystallized, and is centrifuged, dry, obtains 195.0g azodiisobutyronitrile, and the yield of azodiisobutyronitrile is 98.2%,
Purity is 99.5%.
Embodiment 2
Mixed solution, 900g toluene, bis- isobutyl of 300g of 1500g bromine solution and hydrobromic acid solution are added into reaction kettle
Nitrile hydrazine forms three-phase, and lower layer is the water phase of the mixed solution formation of bromine solution and hydrobromic acid solution, and middle layer is formed for toluene
Organic phase, upper layer be bis-isobutyronitrile hydrazine formed solid phase；Whole temperature control is reacted at 28 ± 2 DEG C.Wherein, bromine solution and
In the mixed solution of hydrobromic acid solution comprising 1000g mass percentage concentration be 1% bromine solution, 500g mass percentage concentration be
10% hydrobromic acid solution.
Stirring, bis-isobutyronitrile hydrazine is reacted with bromine generates azodiisobutyronitrile and hydrobromic acid, and azodiisobutyronitrile, which enters, to be had
Machine phase, after reacting 7h；90g hydrogen peroxide is added into reaction kettle again, dioxygen water management is added dropwise in 2h, keeps the temperature 5h；Herein
In the process, hydrobromic acid is reacted with hydrogen peroxide generates bromine, and bromine is further continued for generating azodiisobutyronitrile with bis-isobutyronitrile hydrazine reaction
And hydrobromic acid, azodiisobutyronitrile enter back into organic phase.
After keeping the temperature 5h, reaction terminating ultimately forms two-phase, and upper layer is the organic phase containing azodiisobutyronitrile, and lower layer is
The water phase that bromine solution containing hydrobromic acid is formed；Separation organic phase and water phase, water phase i.e. mother liquor can be recycled, have
Machine is mutually refined, and is crystallized, and is centrifuged, dry, obtains 294.0g azodiisobutyronitrile, and the yield of azodiisobutyronitrile is 98.8%,
Purity is 99.6%.
Embodiment 3
Bromine solution, 1000g methylene chloride and the ether that 1250g mass percentage concentration is 8% are added into reaction kettle
Mixture, 250g bis-isobutyronitrile hydrazine form three-phase, and lower layer is the water phase that bromine solution is formed, and middle layer is methylene chloride and second
The organic phase that the mixture of ether is formed, upper layer are the solid phase that bis-isobutyronitrile hydrazine is formed；The mass ratio of methylene chloride and ether is 1:
1, whole temperature control is reacted at 23 ± 2 DEG C.
Stirring, bis-isobutyronitrile hydrazine is reacted with bromine generates azodiisobutyronitrile and hydrobromic acid, and azodiisobutyronitrile, which enters, to be had
Machine phase, after reacting 3h；100g hydrogen peroxide is added into reaction kettle again, dioxygen water management is added dropwise in 1h, keeps the temperature 2h；Herein
In the process, hydrobromic acid is reacted with hydrogen peroxide generates bromine, and bromine is further continued for generating azodiisobutyronitrile with bis-isobutyronitrile hydrazine reaction
And hydrobromic acid, azodiisobutyronitrile enter back into organic phase.
After keeping the temperature 2h, reaction terminating ultimately forms two-phase, and upper layer is the organic phase containing azodiisobutyronitrile, and lower layer is
The water phase that bromine solution containing hydrobromic acid is formed；Separation organic phase and water phase, water phase i.e. mother liquor can be recycled, have
Machine is mutually refined, and is crystallized, and is centrifuged, dry, obtains 245.8g azodiisobutyronitrile, and the yield of azodiisobutyronitrile is 99.0%,
Purity is 99.5%.
Claims (10)
1. a kind of method using bromine and Hydrogen Peroxide Production azodiisobutyronitrile, it is characterised in that: bromine is added into reaction kettle
Plain solution, organic solvent, bis-isobutyronitrile hydrazine form three-phase；Lower layer is the water phase that bromine solution is formed, and middle layer is organic solvent
The organic phase of formation, upper layer are the solid phase that bis-isobutyronitrile hydrazine is formed；Stirring, it is different that bis-isobutyronitrile hydrazine reacts generation azo two with bromine
Butyronitrile and hydrobromic acid, azodiisobutyronitrile is by organic extractant phase, and hydrobromic acid reacts with the hydrogen peroxide being added dropwise later and generates bromine,
Bromine is further continued for generating azodiisobutyronitrile and hydrobromic acid with bis-isobutyronitrile hydrazine reaction, when in solution without bis-isobutyronitrile hydrazine, reaction
Terminate, ultimately form two-phase, upper layer is the organic phase containing azodiisobutyronitrile, lower layer be the water phase that bromine solution is formed or
The water phase that bromine solution containing hydrobromic acid is formed.
2. the method according to claim 1 using bromine and Hydrogen Peroxide Production azodiisobutyronitrile, it is characterised in that: two
Isobutyronitrile hydrazine and the mass ratio of bromine solution are 1:4-6, and the mass percentage concentration of bromine solution is 0.1-10%；Bromine solution
Solvent is water.
3. the method according to claim 1 using bromine and Hydrogen Peroxide Production azodiisobutyronitrile, it is characterised in that: two
The mass ratio of isobutyronitrile hydrazine and organic solvent is 1:3-5.
4. the method according to claim 1 or 3 using bromine and Hydrogen Peroxide Production azodiisobutyronitrile, feature exist
In: the density of organic solvent is less than the density of water.
5. the method according to claim 4 using bromine and Hydrogen Peroxide Production azodiisobutyronitrile, it is characterised in that: have
Solvent is the mixture of toluene or methylene chloride and ether.
6. the method according to claim 1 using bromine and Hydrogen Peroxide Production azodiisobutyronitrile, it is characterised in that: two
The mass ratio of isobutyronitrile hydrazine and hydrogen peroxide is 1:0.2-0.5.
7. the method according to claim 1 using bromine and Hydrogen Peroxide Production azodiisobutyronitrile, it is characterised in that: anti-
Answer temperature control between 20-28 DEG C, the reaction time is 5-15 hours.
8. the method according to claim 1 using bromine and Hydrogen Peroxide Production azodiisobutyronitrile, it is characterised in that: to
When bromine solution, organic solvent, bis-isobutyronitrile hydrazine being added in reaction kettle, it is molten that reaction promoter hydrobromic acid is first added into bromine solution
Liquid.
9. the method according to claim 8 using bromine and Hydrogen Peroxide Production azodiisobutyronitrile, it is characterised in that: two
The quality and bromine solution of isobutyronitrile hydrazine and the ratio of hydrobromic acid solution gross mass are 1:4-6.
10. the method according to claim 8 using bromine and Hydrogen Peroxide Production azodiisobutyronitrile, it is characterised in that:
The mass percentage concentration of bromine solution is 0.1-3%, and the solvent of bromine solution is water；The mass percentage concentration of hydrobromic acid solution is
0.5-30%, the solvent of hydrobromic acid solution are water；The mass ratio of bromine solution and hydrobromic acid solution is 1-2:1.
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| CN111018742A (en) * | 2019-11-01 | 2020-04-17 | 辽宁双旗精细化工有限公司 | Device for producing azobisisobutyronitrile through continuous chlorination reaction |
| CN111744544B (en) * | 2020-08-05 | 2023-03-10 | 上海大学 | Catalyst for synthesizing azobisisobutyronitrile and preparation method and application thereof |
| CN112851548A (en) * | 2020-12-31 | 2021-05-28 | 孙晓伟 | Method for producing azobisisobutyronitrile by using hydrobromic acid and hydrogen peroxide under action of catalyst |
| CN113773234A (en) * | 2021-09-13 | 2021-12-10 | 台州学院 | Method for oxidizing hydrazine compound into azo compound |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101134735A (en) * | 2006-09-03 | 2008-03-05 | 山东海明化工有限公司 | Method for producing azo-diisobutyronitrile by using hydroperoxide oxidation process |
| CN103896808A (en) * | 2014-04-12 | 2014-07-02 | 唐山晨虹实业有限公司 | Method of preparing azodiisobutyronitrile |
-
2018
- 2018-05-23 CN CN201810498046.9A patent/CN108484444B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101134735A (en) * | 2006-09-03 | 2008-03-05 | 山东海明化工有限公司 | Method for producing azo-diisobutyronitrile by using hydroperoxide oxidation process |
| CN103896808A (en) * | 2014-04-12 | 2014-07-02 | 唐山晨虹实业有限公司 | Method of preparing azodiisobutyronitrile |
Non-Patent Citations (1)
| Title |
|---|
| Two-phase dehydrogenation of 1,2-substituted hydrazines to 1,2-substituted diazenes (azo compounds);Karl Dimroth et al;《Synthesis》;19770531;339-340 |
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Effective date of registration: 20200623 Address after: Room 902, unit 2, building 2, sunshine zone, 171 Dongyue Road, Huantai County, Zibo City, Shandong Province Patentee after: Pang Xuefeng Address before: 256400 Unit 302, Building 40, Beiyuan District, Jianjie, Huantai County, Shandong Province Patentee before: Cui Lifang |
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| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20221128 Address after: 256600 South side of Beihai Street, Beihai Economic Development Zone, Binzhou, Shandong Province West side of the solid waste plant Patentee after: Shandong Keshang Fine Chemical Co.,Ltd. Address before: Room 902, unit 2, building 2, sunshine zone, 171 Dongyue Road, Huantai County, Zibo City, Shandong Province, 256400 Patentee before: Pang Xuefeng |