CN109503417A - The continuous preparation method of diazonium salt of aniline and phenylhydrazine hydrochloride based on microreactor - Google Patents
The continuous preparation method of diazonium salt of aniline and phenylhydrazine hydrochloride based on microreactor Download PDFInfo
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- CN109503417A CN109503417A CN201710826339.0A CN201710826339A CN109503417A CN 109503417 A CN109503417 A CN 109503417A CN 201710826339 A CN201710826339 A CN 201710826339A CN 109503417 A CN109503417 A CN 109503417A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C241/00—Preparation of compounds containing chains of nitrogen atoms singly-bound to each other, e.g. hydrazines, triazanes
- C07C241/02—Preparation of hydrazines
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C245/00—Compounds containing chains of at least two nitrogen atoms with at least one nitrogen-to-nitrogen multiple bond
- C07C245/20—Diazonium compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00781—Aspects relating to microreactors
- B01J2219/00788—Three-dimensional assemblies, i.e. the reactor comprising a form other than a stack of plates
- B01J2219/00792—One or more tube-shaped elements
- B01J2219/00795—Spiral-shaped
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00781—Aspects relating to microreactors
- B01J2219/00889—Mixing
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Abstract
A kind of continuous preparation method of diazonium salt of aniline based on microreactor, it is continuously injected into microreactor in the aniline salt and acid blend and nitrite aqueous solution for configuring room temperature and carries out diazo-reaction, then again through reduction step, via obtaining phenylhydrazine hydrochloride after acid out, filtering.Operation of the present invention is simple, and diazo-reaction temperature is high, and for reactant dosage close to stoichiometric ratio, the diazo-reaction time is short, and yield is high, can be continuously produced diazonium salt of aniline and increases process safety with phenylhydrazine hydrochloride, reduction energy consumption, can be used for industrialized production.
Description
Technical field
The present invention relates to a kind of technology of field of fine chemical, specifically a kind of aniline diazonium based on microreactor
Salt and the continuous preparation method of phenylhydrazine hydrochloride.
Background technique
Phenylhydrazine hydrochloride is important industrial chemicals and pesticide, medicine intermediate.The preparation of phenylhydrazine hydrochloride need aniline diazotising,
Diazonium salt restores two-step reaction preparation.In traditional tank reactor, diazo-reaction time of aniline in 30min or more,
Reaction temperature is at -5-0 DEG C, and generating aniline hydrochloride need to be further across the reduction reaction of diazonium salt of aniline, the reaction temperature of use
Degree is generally at 60 DEG C or more.The temperature difference of diazotising and reduction reaction between the two is larger, and leading to process, energy consumption is high.The diazonium of aniline
Salt is extremely unstable at high temperature, and diazo is easy to be replaced by other atoms and atomic group, and releases nitrogen simultaneously.Diazonium salt
The phenol of hydrolyzable generation is gone back under high temperature, hydrolysate can continue that coupling reaction occurs with diazonium salt.In addition, aniline can also be with benzene
Coupling reaction occurs for the diazonium salt of amine, reduces the yield of final product.It will increase nitrite and strong acid dosage in practical operation
Inhibit side reaction to increase the yield of aniline conversion and phenylhydrazine hydrochloride.It is worth noting that, if diazo-reaction is released
Heat remove not in time, reaction process will have the possibility of explosion.Good mixed performance possessed by microreactor not only may be used
To inhibit the generation of diazoamino compound, and quickly rate of heat transfer reduces the decomposition and hydrolysis of diazonium salt, makes room temperature system
Standby diazonium salt is possibly realized.In fact, microreactor is with its efficient mixing efficiency, quick mass transfer/heat transfer property, safety
Can height, flexible operation, be easy to the advantages that amplifying parallel and obtain researcher and greatly pay close attention to, be extremely applicable to strongly exothermic instantaneous
Or fast reaction.The diazo-reaction of aniline belongs to strongly exothermic fast reaction, good mixed performance and heat transfer in microreactor
Rate can guarantee that aniline diazo-reaction efficiently carries out.Simultaneously make diazonium salt preparation realize serialization, convenient for operation and
The safety of increase process.
Summary of the invention
The present invention is long for the prior art preparation phenylhydrazine hydrochloride reaction time, energy consumption is high for process, reaction is discontinuous, reaction is former
The defects of material is superfluous proposes a kind of diazonium salt of aniline based on microreactor and the continuous preparation method of phenylhydrazine hydrochloride,
The present invention is achieved by the following technical solutions:
The present invention is using the mixed liquor containing strong acid and aniline as first fluid, using nitrite solution as second fluid, two streams
Body enters in micro-mixer after constant temperature diazo-reaction via fluid pump control, and products therefrom is passed through ammonium sulfite and sulfurous acid
Sour hydrogen ammonium mixed liquor carries out reduction reaction, most through acid out and is separated by filtration to obtain phenylhydrazine hydrochloride afterwards.
Nitrite in the second fluid uses: sodium nitrite, potassium nitrite, calcium nitrite or combinations thereof.
In the mixed liquor containing strong acid and aniline, strong acid is used: hydrochloric acid, sulfuric acid or combinations thereof.
The molar ratio of the diazo-reaction material is aniline: nitrite: acid=1:(1-1.2): (2-2.3).
The volume flow ratio of the first fluid and second fluid is (0.01-100): 1, the wherein volume flow of single fluid
Amount range is 2-20mL/min.
The isothermal reaction refers to: it is reacted at 10-40 DEG C, preferred diazo-reaction temperature is lower than 40 DEG C,
Reaction time is lower than 8s.
The reduction reaction, preferably the reduction reaction kettle by being built-in with ammonium sulfite and sulfurous acid acid hydrogen ammonium mixed liquor
Middle carry out reduction reaction.
The acid out, using but be not limited to that strong acid is further added into reaction kettle.
Described is separated by filtration, using but be not limited to decrease temperature crystalline filter realize.
It is not required to that other solvents other than water are added in the fluid of the micro-mixer.
For the micro-mixer band there are two input port and an output port, the microreactor is micro- logical by capillary
Road is connected with the reduction reaction kettle with heat-exchanger rig.
The internal diameter of the micro-mixer and the internal diameter of capillary microchannels are 0.25mm-3mm.
The length of the capillary microchannels is 0.4-4m.
The arrangement mode of the capillary microchannels is straight line arrangement, helical arrangement or broken line arrangement, in which: spiral row
The screw pitch of cloth is 1.59mm-10mm, screw diameter 20-100mm；The bent angle of broken line arrangement is greater than 90 degree, and the spacing of bent angle is small
In 100mm.
Technical effect
Compared with prior art, the reaction time of the invention is greatly shortened, it is not necessary that remaining solvent than water, reaction is added
Material is close to stoichiometric ratio, and product yield improves significantly to 93%, and diazo-reaction temperature significantly improves, can serialization preparation
Phenylhydrazine hydrochloride and process safety is improved.
Detailed description of the invention
Fig. 1 is the device of the invention schematic diagram；
In figure: Q1, Q2 are respectively the first and second fluids, 1 microreactor input channel, 2 constant temperature water baths, 3 microring arrays
Capillary microchannels that device, 4 are connect with micro-mixer, 5 condensing water inlets, 6 condenser pipes, 7 condensation-water drains, 8 fill reducing solution
Reaction kettle, 9 thermostat water baths；
Fig. 2 is the helical arrangement schematic diagram of capillary microchannels of the present invention；
P is screw pitch in figure, D is screw diameter；
Fig. 3 is capillary broken line arrangement schematic diagram in micro-mixer outlet end of the present invention；
α is the bent angle of broken line in figure, L is bent angle spacing；
Fig. 4 is the straight line arrangement schematic diagram that the present invention is capillary microchannels；
L is length of straight pipe in figure.
Specific embodiment
Embodiment 1
In reactor 1 as shown in the figure, long capillary tube 1000mm arranges at broken line, and the bent angle of broken line is 120 °, curved
Angular separation is 80mm.As Fig. 1, sodium nitrite Q1 are via fluid pump injection internal diameter respectively with aniline salt and hydrochloric acid mixed solution Q 2
In the T-type micro-mixer of 0.5mm, injected slurry volume flow is 8mL/min, and molar ratio is sodium nitrite: aniline: hydrochloric acid=1:
1.01:2.15.Capillary microchannels, which are built in 15 DEG C of water baths, makes reaction process reach state, and the diazo liquid of acquisition is direct
Subsequent reactions are carried out in injection reduction reaction kettle.Reaction kettle includes configured ammonium sulfite in advance and the mixing of sulfurous acid acid hydrogen ammonium
Liquid.After reaction kettle collects enough a certain amount of fluid-mixings from microreactor, continuation is kept the temperature under 80 DEG C of temperature conditions
1h is eventually adding strong acid and continues to keep the temperature 15min.Sample is obtained after decrease temperature crystalline filters.Obtained sample is through high-efficient liquid phase color
The yield of spectrum analysis, final phenylhydrazine hydrochloride reaches 90%.
Embodiment 2
In reactor 2 as shown in the figure, long capillary tube 1000mm is spiral.The diameter of spiral is 80mm, screw pitch
30mm.Such as Fig. 1, sodium nitrite Q1 and aniline salt and hydrochloric acid mixed solution Q 2 are respectively the T of 0.5mm via fluid pump injection internal diameter
In type micro-mixer, injected slurry volume flow is 10mL/min, and molar ratio is sodium nitrite: aniline: hydrochloric acid=1:1.01:
2.15.Capillary microchannels, which are built in 20 DEG C of water baths, makes reaction process reach state, and the diazo liquid of acquisition is directly injected into
Subsequent reactions are carried out in reduction reaction kettle.Reaction kettle includes configured ammonium sulfite in advance and sulfurous acid acid hydrogen ammonium mixed liquor.
After reaction kettle collects enough a certain amount of fluid-mixings from microreactor, continuation keeps the temperature 1h under 80 DEG C of temperature conditions,
Strong acid is eventually adding to continue to keep the temperature 15min.Sample is obtained after decrease temperature crystalline filters.Obtained sample is through high performance liquid chromatography point
Analysis, the yield of final phenylhydrazine hydrochloride reach 93%.
Embodiment 3
In reactor 3 as shown in the figure, long capillary tube 1000mm is in line, such as Fig. 1, sodium nitrite Q1 and aniline
Salt and hydrochloric acid mixed solution Q2 are respectively in the T-type micro-mixer of 0.5mm via fluid pump injection internal diameter, and injected slurry volume flow is
8mL/min, molar ratio are sodium nitrite: aniline: hydrochloric acid=1:1.01:2.15.Capillary microchannels are built in 30 DEG C of water-baths
Reaction process is made to reach state in slot, the diazo liquid of acquisition, which is directly injected into reduction reaction kettle, carries out subsequent reactions.Reaction kettle
Include configured ammonium sulfite in advance and sulfurous acid acid hydrogen ammonium mixed liquor.When reaction kettle collection is enough a certain amount of from micro- reaction
After the fluid-mixing of device, continuation keeps the temperature 1h under 80 DEG C of temperature conditions, is eventually adding strong acid and continues to keep the temperature 15min.Through cooling down
Crystallization obtains sample after filtering.Obtained sample reaches 80% through efficient liquid phase chromatographic analysis, the yield of final phenylhydrazine hydrochloride.
Above-mentioned specific implementation can by those skilled in the art under the premise of without departing substantially from the principle of the invention and objective with difference
Mode carry out local directed complete set to it, protection scope of the present invention is subject to claims and not by above-mentioned specific implementation institute
Limit, each implementation within its scope is by the constraint of the present invention.
Claims (10)
1. a kind of continuous preparation method of diazonium salt of aniline and phenylhydrazine hydrochloride based on microreactor, which is characterized in that contain strong acid
Mixed liquor with aniline is first fluid, and using nitrite solution as second fluid, two fluids enter micro- via fluid pump control
In mixer after constant temperature diazo-reaction, products therefrom restore instead by ammonium sulfite and sulfurous acid acid hydrogen ammonium mixed liquor
Answer, most afterwards through acid out, be separated by filtration to obtain phenylhydrazine hydrochloride.
2. according to the method described in claim 1, it is characterized in that, nitrite in the second fluid uses: nitrous acid
Sodium, potassium nitrite, calcium nitrite or combinations thereof.
3. according to the method described in claim 1, it is characterized in that, in the mixed liquor containing strong acid and aniline, strong acid use:
Hydrochloric acid, sulfuric acid or combinations thereof.
4. according to the method described in claim 1, it is characterized in that, the molar ratio of the diazo-reaction material is aniline: sub-
Nitrate: acid=1:(1-1.2): (2-2.3).
5. according to the method described in claim 1, it is characterized in that, the volume flow ratio of the first fluid and second fluid is
(0.01-100): 1, wherein the volumetric flow rates of single fluid are 2-20mL/min.
6. according to the method described in claim 1, it is characterized in that, the isothermal reaction refers to: carrying out at 10-40 DEG C anti-
It answers, preferred diazo-reaction temperature is lower than 40 DEG C, and the reaction time is lower than 8s.
7. according to the method described in claim 1, it is characterized in that, the reduction reaction, preferably by being built-in with ammonium sulfite
Reduction reaction is carried out in the reduction reaction kettle of sulfurous acid acid hydrogen ammonium mixed liquor.
8. according to the method described in claim 1, it is characterized in that, the micro-mixer band there are two input port and one it is defeated
Exit port, the microreactor are connected by capillary microchannels with the reduction reaction kettle with heat-exchanger rig.
9. according to the method described in claim 1, it is characterized in that, the internal diameter of the micro-mixer and capillary microchannels it is interior
Diameter is 0.25mm-3mm；The length of the capillary microchannels is 0.4-4m.
10. according to the method described in claim 1, it is characterized in that, the arrangement modes of the capillary microchannels is straight line row
Cloth, helical arrangement or broken line arrangement, in which: spiral-distributed screw pitch is 1.59mm-10mm, screw diameter 20-100mm；Folding
The bent angle of line arrangement is greater than 90 degree, and the spacing of bent angle is less than 100mm.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710826339.0A CN109503417A (en) | 2017-09-14 | 2017-09-14 | The continuous preparation method of diazonium salt of aniline and phenylhydrazine hydrochloride based on microreactor |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710826339.0A CN109503417A (en) | 2017-09-14 | 2017-09-14 | The continuous preparation method of diazonium salt of aniline and phenylhydrazine hydrochloride based on microreactor |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111440114A (en) * | 2020-04-16 | 2020-07-24 | 宿迁市万和泰化工有限公司 | Method for continuously synthesizing melatonine intermediate by using microreactor |
| CN114160073A (en) * | 2021-11-12 | 2022-03-11 | 启东亚太药业有限公司 | High-purity phenylhydrazine synthesis method and device |
| CN114160066A (en) * | 2021-12-03 | 2022-03-11 | 启东亚太药业有限公司 | Equipment and method for producing diazotized phenylhydrazine hydrochloride based on microreactor |
| CN114195677A (en) * | 2021-12-23 | 2022-03-18 | 上海交通大学 | Continuous preparation method of 4-NBDT and 4-NBP based on microreactor |
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| CN1169423A (en) * | 1996-06-20 | 1998-01-07 | 张海林 | Method fro preparing phenylhydrazine hydrochloride |
| CN104610093A (en) * | 2015-02-05 | 2015-05-13 | 江苏艾科维科技有限公司 | Synthetic method of phenylhydrazine |
| CN106316879A (en) * | 2015-06-19 | 2017-01-11 | 中国石油化工股份有限公司 | Method for preparing hydrazinobenzene in continuous micro-channel reactor |
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Patent Citations (3)
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| CN1169423A (en) * | 1996-06-20 | 1998-01-07 | 张海林 | Method fro preparing phenylhydrazine hydrochloride |
| CN104610093A (en) * | 2015-02-05 | 2015-05-13 | 江苏艾科维科技有限公司 | Synthetic method of phenylhydrazine |
| CN106316879A (en) * | 2015-06-19 | 2017-01-11 | 中国石油化工股份有限公司 | Method for preparing hydrazinobenzene in continuous micro-channel reactor |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111440114A (en) * | 2020-04-16 | 2020-07-24 | 宿迁市万和泰化工有限公司 | Method for continuously synthesizing melatonine intermediate by using microreactor |
| CN114160073A (en) * | 2021-11-12 | 2022-03-11 | 启东亚太药业有限公司 | High-purity phenylhydrazine synthesis method and device |
| CN114160066A (en) * | 2021-12-03 | 2022-03-11 | 启东亚太药业有限公司 | Equipment and method for producing diazotized phenylhydrazine hydrochloride based on microreactor |
| CN114195677A (en) * | 2021-12-23 | 2022-03-18 | 上海交通大学 | Continuous preparation method of 4-NBDT and 4-NBP based on microreactor |
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