CN104649912A - Method for efficiently separating primary amine and purifying secondary amine by using micro reactor - Google Patents
Method for efficiently separating primary amine and purifying secondary amine by using micro reactor Download PDFInfo
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Abstract
The invention discloses a method for efficiently separating primary amine and purifying secondary amine by using a micro reactor. The method comprises the following steps: 1, dissolving primary amine and secondary amine mixture in an organic solvent, respectively conveying a mixed solution and benzene sulfonyl chloride into two inlets of a micro-channel reactor by virtue of a high-pressure constant flow pump, mixing, reacting, and allowing the reaction solution to flow into a collection tank from the outlet of the reactor; 2, introducing the reaction solution in the collection tank and NaOH dilute solution into the two inlets of the micro-channel reactor by virtue of the high-pressure constant flow pump, mixing, reacting, and separating the organic phase; and 3, respectively introducing the separated organic phase and NaOH concentrated solution into the two inlets of the micro-channel reactor by virtue of the high-pressure constant flow pump again, heating, mixing, reacting, separating the organic phase after the reaction is ended, performing reduced pressure distillation, thereby obtaining the secondary amine. The invention relates to a method for separating the primary amine and purifying the secondary amine by using the micro reactor; and compared with the conventional reactor, the micro reactor has large specific surface area, the heat exchange efficiency in the reaction process is high, and short reaction time and convenient operation are integrated into a whole.
Description
Technical field
The present invention relates to a kind of method of microreactor high efficiency separation primary amine purification secondary amine, prepare dinitroaniline herbicide synthesis in be of great immediate significance.
Background technology
Micro-reacting tcchnology is a kind of emerging technology, belongs to the forward position of modern chemical industry subject, and microreactor, more properly should be called microstructure or micro passage reaction, be exactly the utilization of micro-reacting tcchnology in reality.
Microreactor has geometrical property diverse with large reactor: the accurate control of temperature of reaction, the accurate proportioning of material ratio, mix instantaneously, be swift in response.
Existing many scholars complete various dissimilar reaction in microreactor both at home and abroad.
The Chen Guangwen of Dalian Inst of Chemicophysics, Chinese Academy of Sciences etc. [200810010797.8] disclose a kind of nitrifying method of one-step synthesis dinitrotoluene (DNT) in micro passage reaction.Be initial action material with the mixing acid of toluene and nitric acid/sulfuric acid (n/s), streams is synchronously input in microreactor by volume pump, and in reaction channel, complete mixing mass transfer and reaction process; In reaction mixing acid, amount consists of: 0.1 ~ 1.0n/s, and lower than the water of 15% (quality); Liquid hourly space velocity in reactor is 500 ~ 50000h
-1.In normal temperature to 80 DEG C reactor service temperature, toluene conversion is higher than 98%, and dinitrotoluene (DNT) yield is higher than 95%.Chen Guangwen etc. disclose again a kind of associating nitrofication process of synthesizing nitryl benzene in micro passage reaction at [200810011998.X].Building-up process operate continuously under the nitration mixture condition of High water cut, benzene transformation efficiency is 99.85%, product oil of mirbane housing choice behavior 99.8%.
Shao ancestor equality of Nanjing University of Technology discloses a kind of method utilizing microreactor spontaneous combustion synthesis nano lithium ion power cell negative pole material in [200710191915.5].With the nano-powder of the soluble salt of metal or other compounds for raw material, and prepare burden according to the stoichiometric of material, add a certain amount of ignition dope again, formation solution soluble in water or homodisperse emulsion, and plant the cotton of matter with fiber or solution all absorbs by stationery, make its spontaneous combustion obtain presoma, then presoma is sintered in stove and can obtain negative material.This method technique is simple, substantially reduces the reaction times, reduces sintering temperature, and meet environmental requirement, is applicable to scale operation.
The people such as Wilms D, Klos J utilize microreactor to carry out multistep synthesis diazomethane presoma, and employ different solvents, yield is greater than 90%, apparently higher than conventional reactor; The people such as Hisamoto H, Saito T carry out the coupling reaction of oreinol diphenol and 4-nitrobenzene diazonium tetrafluoride in microreactor, and transformation efficiency, up to 100%, avoids side reaction.
But, in microreactor, be separated primary amine purification secondary amine but yet there are no report.
Summary of the invention
The object of the present invention is to provide a kind of method of microreactor high efficiency separation primary amine purification secondary amine, described microreactor at least has two imports, an outlet.
A method for microreactor high efficiency separation primary amine purification secondary amine, said method comprising the steps of:
The first step, is dissolved in organic solvent by primary amine secondary amine mixture, respectively this mixed solution and benzene sulfonyl chloride is delivered to two entrances of micro passage reaction via high pressure constant flow pump, reacts after mixing, and reaction solution flows out from the exit of reactor and enters receiving tank;
Second step, passes into two entrances of micro passage reaction again respectively via high pressure constant flow pump by the reaction solution in receiving tank and NaOH dilute solution, after hybrid reaction, be separated organic phase;
3rd step, passes into two entrances of micro passage reaction, intensification hybrid reaction again respectively via high pressure constant flow pump by the organic phase after separation and NaOH strong solution, reaction terminates rear separation organic phase, namely obtains secondary amine after underpressure distillation.
Wherein, in the first step, described organic solvent is the one in hexanaphthene, normal hexane.
In the first step, the mol ratio of the primary amine secondary amine mixture in described benzene sulfonyl chloride and mixed solution is (1 ~ 1.3): 1, and the reaction times is 15s.
In second step, in the primary amine secondary amine mixture in described reaction solution and NaOH dilute solution, the mol ratio of NaOH is (4 ~ 10): 1, NaOH dilute solution massfraction is 2%, and the reaction times is 10s.
In 3rd step, the mol ratio of the NaOH in described NaOH strong solution and the primary amine secondary amine mixture in organic phase is (1 ~ 1.15): 1, and described NaOH strong solution massfraction is 10%.
In 3rd step, react and carry out at 45 ~ 75 DEG C, the reaction times is 35 ~ 65s.
The present invention is core reaction with Hinsberg reaction, and reaction equation is as follows:
Primary amine and benzene sulfonyl chloride (the first step) react:
Secondary amine and benzene sulfonyl chloride (the first step) react:
The reaction of sulphonamide and the NaOH rare (second step) of primary amine is because the hydrogen atom on amino is subject to the impact of alkylsulfonyl to be slightly acidic, so can be dissolved in alkali to become salt.
Sulphonamide alkaline hydrolysis (the 3rd step) reaction of secondary amine:
Hinsberg reaction utilizes benzene sulfonyl chloride to differentiate and is separated reaction that is primary, secondary, tertiary amine.One-level, secondary amine in the presence of a base, also can follow benzene sulfonyl chloride effect, generate benzsulfamide.The benzsulfamide that primary amine generates, the impact being subject to alkylsulfonyl because of the hydrogen atom on amino is slightly acidic, so can be dissolved in alkali to become salt.The benzsulfamide that secondary amine generates, amino does not have hydrogen atom can not generate salt.Tertiary amine and benzene sulfonyl chloride can not work.So often utilize benzene sulfonyl chloride (or Tosyl chloride) to be separated the mixture of three kinds of amine, this is called Hinsberg reaction.Of the present invention is benzene sulfonyl chloride, because it has feature cheap and easy to get.
Compared with prior art, its remarkable advantage is in the present invention:
(1) owing to the present invention relates to the method being separated primary amine purification secondary amine with microreactor, and microreactor has larger specific surface area compared to conventional reactor, and the heat exchanger effectiveness in reaction process is high, and the collection reaction times is short, and simple operation.
(2) present invention employs hexanaphthene, normal hexane as solvent, the sulphonamide avoided because of secondary amine is insoluble to NaOH solution and produces the operation of filtration, at utmost reduces the loss of experimentation.
(3) compared to the reaction kit of routine, need 10 ~ 12h even more time backflow, the reaction of the present invention the 3rd step, only needs the reaction times to be 35 ~ 65s, greatly reduces the reaction times, in production application, has huge industrial practical prospect.
(4) method of separation primary amine purification secondary amine of the present invention, drastically increases the purity of secondary amine, can reach more than 98% (GC).
Accompanying drawing explanation
The method flow diagram of Fig. 1 microreactor high efficiency separation of the present invention primary amine purification secondary amine.
Embodiment
The present invention is used for the micro passage reaction of realization response, is glass material, due to its reactor good corrosion resistance, has two intake vents and an exit passageway be attached thereto.Inlet microchannel size and microchannel size inconsistent, intake vent size is comparatively large, is more beneficial to and improves microring array efficiency, in the microchannel that micro passage reaction has, large drop can be separated into uniform milk sap, mixed effect is better, is conducive to the carrying out of two phase reaction.
In following each embodiment, the method flow diagram of microreactor high efficiency separation primary amine purification secondary amine is as Fig. 1.
Embodiment 1
The first step, get 3,4 xylidines and N-(1-methylethyl)-3,4-xylidine (containing 90%) mixture is dissolved in hexanaphthene or normal hexane, this mixed solution and benzene sulfonyl chloride are delivered to respectively two entrances of micro passage reaction via high pressure constant flow pump with the mol ratio of 1:1, react after mixing, reaction solution flows out from the exit of reactor and enters receiving tank, and the reaction times is 15s.
Second step, reaction solution in receiving tank and NaOH dilute solution are passed into again respectively two entrances of micro passage reaction with the mol ratio of 10:1 via high pressure constant flow pump, after hybrid reaction, be separated organic phase, NaOH dilute solution massfraction is 2%, and the reaction times is 10s.
3rd step, organic phase after being separated and NaOH strong solution are passed into again respectively two entrances of micro passage reaction via high pressure constant flow pump with the mol ratio of 1:1, intensification hybrid reaction, reaction terminates rear separation organic phase, namely obtain secondary amine after underpressure distillation, described NaOH strong solution massfraction is 10%.
React the mixed solution terminated in rear receiving tank, be separated organic phase, after underpressure distillation, namely obtain secondary amine.
Obtaining N-(1-methylethyl)-3,4-xylidine purity is after testing 98.1% (GC).
Embodiment 2
Process is with embodiment 1, and only change the first step reaction mixture and benzene sulfonyl chloride mol ratio are 1.1:1, and remaining reaction condition is constant, and obtaining secondary amine N-(1-methylethyl)-3,4-xylidine purity is after testing 98.8% (GC).
Embodiment 3
Process is with embodiment 1, and only change the first step reaction mixture and benzene sulfonyl chloride mol ratio are 1.2:1, and remaining reaction condition is constant, and obtaining secondary amine N-(1-methylethyl)-3,4-xylidine purity is after testing 98.3% (GC).
Embodiment 4
Process is with embodiment 1, and only change the first step reaction mixture and benzene sulfonyl chloride mol ratio are 1.3:1, and remaining reaction condition is constant, and obtaining secondary amine N-(1-methylethyl)-3,4-xylidine purity is after testing 98.9% (GC).
Embodiment 5
Process is with embodiment 1, the mol ratio only changing NaOH in primary amine secondary amine mixture in second step reaction solution and dilute NaOH solution is 8:1, remaining reaction condition is constant, and obtaining secondary amine N-(1-methylethyl)-3,4-xylidine purity is after testing 98.7% (GC).
Embodiment 6
Process is with embodiment 1, the mol ratio only changing NaOH in primary amine secondary amine mixture in second step reaction solution and dilute NaOH solution is 6:1, remaining reaction condition is constant, and obtaining secondary amine N-(1-methylethyl)-3,4-xylidine purity is after testing 99.1% (GC).
Embodiment 7
Process is with embodiment 1, the mol ratio only changing NaOH in primary amine secondary amine mixture in second step reaction solution and dilute NaOH solution is 4:1, remaining reaction condition is constant, and obtaining secondary amine N-(1-methylethyl)-3,4-xylidine purity is after testing 99.3% (GC).
Embodiment 8
Process is with embodiment 1, the mol ratio only changing the primary amine secondary amine mixture in three-step reaction NaOH strong solution and organic phase is 1.05:1, remaining reaction condition is constant, and obtaining secondary amine N-(1-methylethyl)-3,4-xylidine purity is after testing 99.1% (GC).
Embodiment 9
Process is with embodiment 1, the mol ratio only changing the primary amine secondary amine mixture in three-step reaction NaOH strong solution and organic phase is 1.1:1, remaining reaction condition is constant, and obtaining secondary amine N-(1-methylethyl)-3,4-xylidine purity is after testing 99.6% (GC).
Embodiment 10
Process is with embodiment 1, the mol ratio only changing the primary amine secondary amine mixture in three-step reaction NaOH strong solution and organic phase is 1.15:1, remaining reaction condition is constant, and obtaining secondary amine N-(1-methylethyl)-3,4-xylidine purity is after testing 98.2% (GC).
Embodiment 11
Process is with embodiment 1, and only changing the three-step reaction time is 45s, and remaining reaction condition is constant, and obtaining secondary amine N-(1-methylethyl)-3,4-monomethylaniline purity is after testing 99.6% (GC).
Embodiment 12
Process is with embodiment 1, and only changing the three-step reaction time is 55s, and remaining reaction condition is constant, and obtaining secondary amine N-(1-methylethyl)-3,4-monomethylaniline purity is after testing 99.8% (GC).
Embodiment 13
Process is with embodiment 1, and only changing the three-step reaction time is 65s, and remaining reaction condition is constant, and obtaining secondary amine N-(1-methylethyl)-3,4-monomethylaniline purity is after testing 99.2% (GC).
Embodiment 14
Process is with embodiment 1, and only changing three-step reaction temperature is 55 DEG C, and remaining reaction condition is constant, and obtaining secondary amine N-(1-methylethyl)-3,4-monomethylaniline purity is after testing 99.1% (GC).
Embodiment 15
Process is with embodiment 1, and only changing three-step reaction temperature is 65 DEG C, and remaining reaction condition is constant, and obtaining secondary amine N-(1-methylethyl)-3,4-monomethylaniline purity is after testing 98.8% (GC).
Embodiment 16
Process is with embodiment 1, and only changing three-step reaction temperature is 75 DEG C, and remaining reaction condition is constant, and obtaining secondary amine N-(1-methylethyl)-3,4-monomethylaniline purity is after testing 99.4% (GC).
Claims (6)
1., by a method for microreactor high efficiency separation primary amine purification secondary amine, it is characterized in that, said method comprising the steps of:
The first step, is dissolved in organic solvent by primary amine secondary amine mixture, respectively this mixed solution and benzene sulfonyl chloride is delivered to two entrances of micro passage reaction via high pressure constant flow pump, reacts after mixing, and reaction solution flows out from the exit of reactor and enters receiving tank;
Second step, passes into two entrances of micro passage reaction again respectively via high pressure constant flow pump by the reaction solution in receiving tank and NaOH dilute solution, after hybrid reaction, be separated organic phase;
3rd step, passes into two entrances of micro passage reaction, intensification hybrid reaction again respectively via high pressure constant flow pump by the organic phase after separation and NaOH strong solution, reaction terminates rear separation organic phase, namely obtains secondary amine after underpressure distillation.
2. the method with microreactor high efficiency separation primary amine purification secondary amine as claimed in claim 1, it is characterized in that, in the first step, described organic solvent is the one in hexanaphthene, normal hexane.
3. the method with microreactor high efficiency separation primary amine purification secondary amine as claimed in claim 1, it is characterized in that, in the first step, the mol ratio of the primary amine secondary amine mixture in described benzene sulfonyl chloride and mixed solution is (1 ~ 1.3): 1, and the reaction times is 15s.
4. the method with microreactor high efficiency separation primary amine purification secondary amine as claimed in claim 1, it is characterized in that, in second step, in primary amine secondary amine mixture in described reaction solution and NaOH dilute solution, the mol ratio of NaOH is (4 ~ 10): 1, NaOH dilute solution massfraction is 2%, and the reaction times is 10s.
5. the method with microreactor high efficiency separation primary amine purification secondary amine as claimed in claim 1, it is characterized in that, in 3rd step, the mol ratio of the NaOH in described NaOH strong solution and the primary amine secondary amine mixture in organic phase is (1 ~ 1.15): 1, and described NaOH strong solution massfraction is 10%.
6. the method with microreactor high efficiency separation primary amine purification secondary amine as claimed in claim 1, it is characterized in that, in the 3rd step, react and carry out at 45 ~ 75 DEG C, the reaction times is 35 ~ 65s.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110687235A (en) * | 2019-10-18 | 2020-01-14 | 贵州省烟草科学研究院 | Derivatization and back-extraction method for removing interference of primary amine and secondary amine in tertiary amine chiral chromatographic analysis |
| CN112266347A (en) * | 2020-11-13 | 2021-01-26 | 西安近代化学研究所 | Preparation method of high-purity ethylene imine |
| CN113563274A (en) * | 2021-07-27 | 2021-10-29 | 南京硕达生物科技有限公司 | Synthesis method of N- (2, 6-difluorophenyl) -5-amino-1, 2, 4-triazole-3-sulfonamide |
| CN115650891A (en) * | 2022-10-27 | 2023-01-31 | 常熟市滨江化工有限公司 | Method for purifying tert-butyl peroxybenzoate by using microchannel reactor |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110687235A (en) * | 2019-10-18 | 2020-01-14 | 贵州省烟草科学研究院 | Derivatization and back-extraction method for removing interference of primary amine and secondary amine in tertiary amine chiral chromatographic analysis |
| CN112266347A (en) * | 2020-11-13 | 2021-01-26 | 西安近代化学研究所 | Preparation method of high-purity ethylene imine |
| CN112266347B (en) * | 2020-11-13 | 2022-11-15 | 西安近代化学研究所 | Preparation method of high-purity ethylene imine |
| CN113563274A (en) * | 2021-07-27 | 2021-10-29 | 南京硕达生物科技有限公司 | Synthesis method of N- (2, 6-difluorophenyl) -5-amino-1, 2, 4-triazole-3-sulfonamide |
| CN115650891A (en) * | 2022-10-27 | 2023-01-31 | 常熟市滨江化工有限公司 | Method for purifying tert-butyl peroxybenzoate by using microchannel reactor |
| CN115650891B (en) * | 2022-10-27 | 2024-05-03 | 常熟市滨江化工有限公司 | Method for purifying tert-butyl peroxybenzoate by using microchannel reactor |
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