CN106316879A - Method for preparing hydrazinobenzene in continuous micro-channel reactor - Google Patents
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- HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical compound NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 66
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims abstract description 62
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 37
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 235000010288 sodium nitrite Nutrition 0.000 claims abstract description 31
- MMCPOSDMTGQNKG-UHFFFAOYSA-N anilinium chloride Chemical compound Cl.NC1=CC=CC=C1 MMCPOSDMTGQNKG-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000002253 acid Substances 0.000 claims abstract description 18
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 claims abstract description 15
- 229940067157 phenylhydrazine Drugs 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 13
- 230000009467 reduction Effects 0.000 claims description 11
- 230000035484 reaction time Effects 0.000 claims description 6
- 230000006641 stabilisation Effects 0.000 claims description 6
- 238000011105 stabilization Methods 0.000 claims description 6
- 230000033228 biological regulation Effects 0.000 claims description 2
- 239000000243 solution Substances 0.000 abstract description 35
- 238000003756 stirring Methods 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 8
- 238000002156 mixing Methods 0.000 abstract description 7
- 238000001914 filtration Methods 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 5
- 238000006193 diazotization reaction Methods 0.000 abstract description 2
- 239000002341 toxic gas Substances 0.000 abstract description 2
- 230000003472 neutralizing effect Effects 0.000 abstract 1
- 238000013021 overheating Methods 0.000 abstract 1
- 238000005086 pumping Methods 0.000 abstract 1
- 239000012266 salt solution Substances 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 10
- 239000003513 alkali Substances 0.000 description 9
- JOVOSQBPPZZESK-UHFFFAOYSA-N phenylhydrazine hydrochloride Chemical compound Cl.NNC1=CC=CC=C1 JOVOSQBPPZZESK-UHFFFAOYSA-N 0.000 description 9
- 238000013019 agitation Methods 0.000 description 8
- 239000000706 filtrate Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 230000004044 response Effects 0.000 description 7
- 235000010265 sodium sulphite Nutrition 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 239000004519 grease Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- FHIVAFMUCKRCQO-UHFFFAOYSA-N diazinon Chemical compound CCOP(=S)(OCC)OC1=CC(C)=NC(C(C)C)=N1 FHIVAFMUCKRCQO-UHFFFAOYSA-N 0.000 description 2
- 239000012954 diazonium Substances 0.000 description 2
- 150000001989 diazonium salts Chemical class 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- FGODPVCKFLEVFG-UHFFFAOYSA-N (2-methoxyphenyl)hydrazine Chemical compound COC1=CC=CC=C1NN FGODPVCKFLEVFG-UHFFFAOYSA-N 0.000 description 1
- BHXVYTQDWMQVBI-UHFFFAOYSA-N 1h-indazole-3-carboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=NNC2=C1 BHXVYTQDWMQVBI-UHFFFAOYSA-N 0.000 description 1
- -1 2H-Pyridazin-3-one thiadiazole Chemical compound 0.000 description 1
- QAZRMNRWRMTORL-UHFFFAOYSA-N C1=CC=NN=C1.O=C1C=CN=N1 Chemical class C1=CC=NN=C1.O=C1C=CN=N1 QAZRMNRWRMTORL-UHFFFAOYSA-N 0.000 description 1
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical class [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 1
- 208000008601 Polycythemia Diseases 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- CAYORDAREPKRGI-UHFFFAOYSA-N aniline phenylhydrazine Chemical compound C1(=CC=CC=C1)NN.NC1=CC=CC=C1 CAYORDAREPKRGI-UHFFFAOYSA-N 0.000 description 1
- 230000001430 anti-depressive effect Effects 0.000 description 1
- 239000000935 antidepressant agent Substances 0.000 description 1
- 229940005513 antidepressants Drugs 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- QELUYTUMUWHWMC-UHFFFAOYSA-N edaravone Chemical compound O=C1CC(C)=NN1C1=CC=CC=C1 QELUYTUMUWHWMC-UHFFFAOYSA-N 0.000 description 1
- 229950009041 edaravone Drugs 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 235000021050 feed intake Nutrition 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- WDRYRZXSPDWGEB-UHFFFAOYSA-N lonidamine Chemical compound C12=CC=CC=C2C(C(=O)O)=NN1CC1=CC=C(Cl)C=C1Cl WDRYRZXSPDWGEB-UHFFFAOYSA-N 0.000 description 1
- 229960003538 lonidamine Drugs 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical class O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 description 1
- 150000003217 pyrazoles Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- APJYDQYYACXCRM-UHFFFAOYSA-N tryptamine Chemical class C1=CC=C2C(CCN)=CNC2=C1 APJYDQYYACXCRM-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for preparing highly pure hydrazinobenzene by using continuous flow micro-channel reactor. The method concretely comprises the following steps: preparing aniline hydrochloride from hydrochloric acid and aniline, respectively pumping the aniline hydrochloride and a sodium nitrite solution into the micro-channel reactor by two metering pumps to obtain a diazo salt solution, reducing the obtained reaction solution, carrying out acid separation on the reduced solution, filtering the obtained solution, neutralizing the filtered solution, and distilling the neutralized solution to obtain the highly pure hydrazinobenzene. The diazotization process is a strong exothermic reaction, and the generated diazo salt easily decomposes after standing at a high temperature for a long time, and generates toxic gases which pollute environment and even blast. The mixing effect of the heart-shaped micro-channel reactor is far better than the mass transfer effect generated by stirring, so the aniline conversion rate can reach 99%, the mixing mass transfer effect is good, and heat conduction is fast to avoid local overheating phenomenon; and the reaction can be carried out at constant temperature conditions, so the temperature runaway blast danger of general reactors is eliminated, and the safety is improved.
Description
Technical field
The present invention relates to the synthesis of phenylhydrazine, particular content includes utilizing " heart " type micro passage reaction (the high flux micro passage reaction of Corning Incorporated) that prepared by aniline diazotising phenylhydrazine, belongs to Field of Fine Chemicals category, is a kind of novel method preparing phenylhydrazine.
Background technology
Phenylhydrazine is a kind of important dyestuff, medicine, pesticide intermediate, can be used for treating erythrocytosis as antidepressant, for synthesizing sugar osazone, phenylhydrazone, alkyl-indol, 1H-indazole-3 monocarboxylic acid, drug lonidamine, Edaravone, pyrazole derivatives, pyrazolone derivative, tryptamine derivatives 2H-Pyridazin-3-one thiadiazole and pyridazine pyrazolone derivative etc., also coordination compound can be formed with metal.
The synthesis technique of phenylhydrazine mainly uses aniline diazotising, reduces, hydrolyzes, distills technique, and the progress of its technology focuses primarily upon aniline diazotising.Owing to diazo-reaction is strong exothermal reaction, and the diazol generated long-time easily decomposition at a higher temperature, produce toxic gas, pollute environment, even explode.Therefore must in time substantial amounts of reaction heat be removed.
Chinese patent CN1169423 discloses the preparation method of a kind of hydrazinobenzene hydrochloride salt, it is characterized in that taking hydrochloric acid, sodium nitrite is sequentially added in aniline, wherein aniline, hydrochloric acid, sodium nitrite mol ratio is 1: 2.3～3.2: 1～1.1, and sodium nitrite starts to feed intake when 0～5 DEG C, reaction temperature is 0～22 DEG C, response time is 30～90 min, again by the mol ratio with aniline be 1: 2～3.5: 2.5～3.0 add ammonium sulfites, hydrochloric acid, reduce, hydrolysis, acid out, again through sucking filtration or drying, , this technique is interval diazotisation methods, response time is long, product yield is low.
Chinese patent CN102807505A, CN102807506A of SUMITOMO CHEMICAL Co., Ltd. application discloses a kind of method producing phenylhydrazine comprised the steps: reacted in presence of water with at least one material in sulphite and bisulfites by diazol；And the reactant mixture of gained is mixed at 0 to 10 DEG C with hydrogen chloride, holds the mixture in 10 to 30 DEG C subsequently.What this patent was also adopted by is interval diazotisation methods, gives the synthesis example of O-methoxy phenylhydrazine.
German patent DE 2758027 and indian patent In142812 also disclose that the synthetic method of phenylhydrazine, and what it used is also interval diazotization process.
More than inventing and all use traditional batch tank reactor, feed way uses and dropwise drips, and energy consumption is high, and equipment corrosion is serious, and diazo-reaction is strong exothermal reaction, reacts the drastically rising along with temperature, therefore is difficult to control for reaction safety.
Summary of the invention
The present invention be directed to traditional batch tank reactor and produce a kind of novel high-efficiency and continuous stream production technology that the problems such as phenylhydrazine process time length, yield is low, course of reaction safety is difficult to control to propose.Use novel " heart " type micro passage reaction, raw material dosing pump is squeezed in reactor, and liquid relies on " heart " type structure to complete to mix mass transfer, and mixed effect is far superior to stir produced mass transfer effect, aniline conversion can reach 99%, greatly improves product yield；" heart " type structural response plate mixing mass transfer effect is good, and heat conduction is fast, it is to avoid hot-spot phenomenon, and reaction can be carried out under the conditions of constant temperature, eliminate the temperature runaway explosion danger of General reactions device, improve safety.
The method that the present invention prepares phenylhydrazine at continuous micro passage reaction, specifically comprises the following steps that
1)
Anilinechloride configures: under room temperature, hydrochloric acid and the aniline of 30% are made into anilinechloride；
2)
Sodium nitrite solution configures: sodium nitrite and water are made into the sodium nitrite solution of 40%；
3)
Use circulator's cooler that " heart " type micro passage reaction is freezed, after temperature stabilization, the sodium nitrite solution of anilinechloride solution and 40% is squeezed in reactor, reaction temperature is-5 ~ 15 DEG C, reaction time is 5 ~ 60s, reaction pressure 0.1 ~ 1.8 MPa, diazo liquid continuously flows in catcher from reactor, the diazo liquid that obtains through reduction, acid out, filter, neutralize, distill and obtain product.
Usually, step of the present invention is as follows:
1) configuration of anilinechloride: under room temperature, by aniline and the hydrochloric acid mix and blend by a certain percentage of 30%, is configured to homogeneous phase solution, stand-by.
2) by above-mentioned gained anilinechloride solution and 40% sodium nitrite solution via two dosing pumps, squeeze into micro passage reaction by a certain percentage, by a series of quality transmission type module sustained responses, obtain diazo liquid solution, finally enter dislodger.The time of staying in micro passage reaction at 5 ~ 60s, reaction temperature at-5 ~ 15 DEG C, pressure 0.1 ~ 1.8 Mpa.
3) diazonium salt solution obtained through sodium sulfite and the reduction of 30% alkali liquor, 30% hydrochloric acid acid out, filter, neutralize, distill, obtain the phenylhydrazine of content more than 99%.
" heart " the type micro passage reaction that the present invention relates to is formed by polylith module assembled, and this module is a kind of three-decker plate.First and third layer is heat transfer layer, and intermediate reaction plate is for strengthening mixing cardioid channel design.Material is special glass, can acid corrosion-resistant, maximum pressure is 5 ~ 10 bar.
Aniline of the present invention, hydrochloric acid, sodium nitrite mol ratio are 1: 2.3～3.2: 1～1.5.
What the present invention provided carry out diazotising with stream reactive mode continuously in continuously stream micro passage reaction prepares phenylhydrazine, and raw material is squeezed into by dosing pump, and reactor accurately regulates the temperature needed for reaction by recirculation cooler.In course of reaction, carried out the mol ratio of feed change by the flow of regulation dosing pump, after the time of staying of tens seconds to a few minutes, obtain diazonium salt solution.
Use and prepare the technique of phenylhydrazine compared with prior art at micro passage reaction, have the advantage that
1) " heart " type structural response plate mixing mass transfer effect is high, and heat conduction is fast, is accurately controlled reaction temperature by recirculation cooler, and process keeps temperature constant, eliminates the temperature runaway explosion danger of General reactions device；
2) reaction is for flowing reaction continuously, and the response time is only tens seconds, substantially reduces the response time；
3) Sptting plate is for strengthening mixing cardioid channel design, mass transfer good mixing effect, adds the conversion ratio of reaction.
Accompanying drawing explanation
Fig. 1 is " heart " type micro passage reaction Sptting plate conversion zone structure.
Fig. 2 is " heart " type micro passage reaction Sptting plate heat transfer layer structure.
Fig. 3 is the process flow diagram of aniline phenylhydrazine in embodiment.
Fig. 4 is two strands of material feeding manner schematic diagrams simultaneously in embodiment.
Detailed description of the invention
The Sptting plate of " heart " type micro passage reaction of the embodiment of the present invention is three-decker, and intermediate layer is conversion zone, and first and third layer is heat transfer layer (seeing Fig. 1 and 2).The preparation process of embodiment sees Fig. 3 and 4.
Embodiment
1
Device: Coring cardioid micro passage reaction, reaction module selects 6 blocks of plates, and feedstock mode determines with reference to Fig. 3, and heat transferring medium is conduction oil.
Anilinechloride configures: under room temperature, the hydrochloric acid (3.0 mol) of 310 ml 30%, 200 mL water are added in 1000 mL there-necked flasks, in 30 min, dropping aniline 93 g (1.0 mol), adds and is stirred for 30 min, be made into anilinechloride.
Sodium nitrite solution configures: sodium nitrite 64 g (1.0 mol) and 300 mL water are made into the sodium nitrite solution solution of 40%.
Diazotising: use circulator's cooler that reactor is freezed, by reactor design temperature 5 DEG C, after temperature stabilization, by dosing pump, anilinechloride solution is squeezed in reactor, flow speed control 20 mL/min, by dosing pump, the sodium nitrite solution of 40% is squeezed in reactor, flow speed control 40 mL/min, material reacts in micro passage reaction, and reaction time is 30 s, reaction pressure 0.2 MPa, diazo liquid continuously flows in catcher from reactor.
Reduction: add water in reduction kettle, sodium sulfite and 30% alkali liquor, is heated up to 80 DEG C, controls 80～115 DEG C, pH=6.2～6.7, in 20 min, above-mentioned diazo liquid thread is added, continue stirring 1.5 h, add zinc powder, kieselguhr, agitation and filtration, filtrate puts into acid out still.
Acid out: in above-mentioned filtrate, adds 30% hydrochloric acid in 70 DEG C and carries out acid out, and control temperature, at 85～110 DEG C, stirs 10min, is cooled to less than 20 DEG C, and suction strainer obtains hydrazinobenzene hydrochloride salt.
Neutralize: in reaction pot, add alkali liquor, under agitation add above-mentioned hydrazinobenzene hydrochloride salt and appropriate water, be warming up to 50 DEG C, stir 1 h at 50～80 DEG C, stand 8 more than h, separate lower aqueous solution, obtaining upper strata grease and be phenylhydrazine, distillation obtains the phenylhydrazine of purity 99.1%, yield 85.8%.
Embodiment
2
Anilinechloride configures: under room temperature, the hydrochloric acid (2.3 mol) of 237 ml 30%, 200 mL water are added in 1000 mL there-necked flasks, in 30 min, dropping aniline 93 g (1.0 mol), adds and is stirred for 30 min, be made into anilinechloride.
Sodium nitrite solution configures: sodium nitrite 64g (1.0 mol) and 300 mL water are made into the sodium nitrite solution solution of 40%.
Diazotising: use circulator's cooler that reactor is freezed, by reactor design temperature 0 DEG C, after temperature stabilization, by dosing pump, anilinechloride solution is squeezed in reactor, flow speed control 20 mL/min, by dosing pump, the sodium nitrite solution of 40% is squeezed in reactor, flow speed control 44 mL/min, material reacts in micro passage reaction, and reaction time is 28 s, reaction pressure 0.2 MPa, diazo liquid continuously flows in catcher from reactor.
Reduction: add water in reduction kettle, sodium sulfite and 30% alkali liquor, is heated up to 80 DEG C, controls 80～115 DEG C, pH=6.2～6.7, in 20 min, above-mentioned diazo liquid thread is added, continue stirring 1.5 h, add zinc powder, kieselguhr, agitation and filtration, filtrate puts into acid out still.
Acid out: in above-mentioned filtrate, adds 30% hydrochloric acid in 70 DEG C and carries out acid out, and control temperature, at 85～110 DEG C, stirs 10min, is cooled to less than 20 DEG C, and suction strainer obtains hydrazinobenzene hydrochloride salt.
Neutralize: in reaction pot, add alkali liquor, under agitation add above-mentioned hydrazinobenzene hydrochloride salt and appropriate water, be warming up to 50 DEG C, stir 1 h at 50～80 DEG C, stand 8 more than h, separate lower aqueous solution, obtaining upper strata grease and be phenylhydrazine, distillation obtains the phenylhydrazine of purity 98.7%, yield 74.2%.
Embodiment
3
Anilinechloride configures: under room temperature, the hydrochloric acid (3.2 mol) of 330 ml 30%, 200 mL water are added in 1000 mL there-necked flasks, in 30 min, dropping aniline 93 g (1.0 mol), adds and is stirred for 30 min, be made into anilinechloride.
Sodium nitrite solution configures: sodium nitrite 64 g (1.0mol) and 300 mL water are made into the sodium nitrite solution solution of 40%.
Diazotising: use circulator's cooler that reactor is freezed, by reactor design temperature 10 DEG C, after temperature stabilization, by dosing pump, anilinechloride solution is squeezed in reactor, flow speed control 20 mL/min, by dosing pump, the sodium nitrite solution of 40% is squeezed in reactor, flow speed control 48 mL/min, material reacts in micro passage reaction, and reaction time is 26 s, reaction pressure 0.2 MPa, diazo liquid continuously flows in catcher from reactor.
Reduction: add water in reduction kettle, sodium sulfite and 30% alkali liquor, is heated up to 80 DEG C, controls 80～115 DEG C, pH=6.2～6.7, in 20 min, above-mentioned diazo liquid thread is added, continue stirring 1.5 h, add zinc powder, kieselguhr, agitation and filtration, filtrate puts into acid out still.
Acid out: in above-mentioned filtrate, adds 30% hydrochloric acid in 70 DEG C and carries out acid out, and control temperature, at 85～110 DEG C, stirs 10min, is cooled to less than 20 DEG C, and suction strainer obtains hydrazinobenzene hydrochloride salt.
Neutralize: in reaction pot, add alkali liquor, under agitation add above-mentioned hydrazinobenzene hydrochloride salt and appropriate water, be warming up to 50 DEG C, stir 1 h at 50～80 DEG C, stand 8 more than h, separate lower aqueous solution, obtaining upper strata grease and be phenylhydrazine, distillation obtains the phenylhydrazine of purity 99.3%, yield 87.4%.
Embodiment
4
Anilinechloride configures: under room temperature, the hydrochloric acid (3.0 mol) of 310 ml 30%, 200 mL water are added in 1000 mL there-necked flasks, in 30 min, dropping aniline 93 g (1.0 mol), adds and is stirred for 30 min, be made into anilinechloride.
Sodium nitrite solution configures: sodium nitrite 64 g (1.0 mol) and 300 mL water are made into the sodium nitrite solution solution of 40%.
Diazotising: use circulator's cooler that reactor is freezed, by reactor design temperature 15 DEG C, after temperature stabilization, by dosing pump, anilinechloride solution is squeezed in reactor, flow speed control 20 mL/min, by dosing pump, the sodium nitrite solution of 40% is squeezed in reactor, flow speed control 52 mL/min, material reacts in micro passage reaction, and reaction time is 25 s, reaction pressure 0.1 MPa, diazo liquid continuously flows in catcher from reactor.
Reduction: add water in reduction kettle, sodium sulfite and 30% alkali liquor, is heated up to 80 DEG C, controls 80～115 DEG C, pH=6.2～6.7, in 20 min, above-mentioned diazo liquid thread is added, continue stirring 1.5 h, add zinc powder, kieselguhr, agitation and filtration, filtrate puts into acid out still.
Acid out: in above-mentioned filtrate, adds 30% hydrochloric acid in 70 DEG C and carries out acid out, and control temperature, at 85～110 DEG C, stirs 10min, is cooled to less than 20 DEG C, and suction strainer obtains hydrazinobenzene hydrochloride salt.
Neutralize: in reaction pot, add alkali liquor, under agitation add above-mentioned hydrazinobenzene hydrochloride salt and appropriate water, be warming up to 50 DEG C, stir 1 h at 50～80 DEG C, stand 8 more than h, separate lower aqueous solution, obtaining upper strata grease and be phenylhydrazine, distillation obtains the phenylhydrazine of content 98.1%, yield 88.8%.
Protection scope of the present invention is not limited only to above example, and every claims are mentioned, and the deformation that those skilled in the art can be extrapolated to is all in protection domain.
Claims (5)
1. the method preparing phenylhydrazine in stream micro passage reaction continuously, it is characterised in that comprise the steps:
Anilinechloride configures: under room temperature, hydrochloric acid and the aniline of 30% are made into anilinechloride；Sodium nitrite solution configures: sodium nitrite and water are made into the sodium nitrite solution of 40%；Use circulator's cooler that " heart " type micro passage reaction is freezed, after temperature stabilization, the sodium nitrite solution of anilinechloride solution and 40% is squeezed in reactor, reaction temperature is-5 ~ 15 DEG C, reaction time is 5 ~ 60s, reaction pressure 0.1 ~ 1.8 MPa, diazo liquid continuously flows in catcher from reactor, the diazo liquid that obtains through reduction, acid out, filter, neutralize, distill and obtain product.
2. according to the method shone described in claim 1, it is characterized in that described " heart " type micro passage reaction, this reactor reaction plate is made up of three sheaf spaces, and first and third layer is heat transfer layer, intermediate layer is conversion zone, and conversion zone is cascaded by the multiple reaction compartment of heart shape.
Method the most according to claim 1, it is characterised in that diazotizing temperature is-5 ~ 15 DEG C.
Method the most according to claim 1, it is characterised in that aniline and 30% the mol ratio of hydrochloric acid be 1:2.3 ~ 3.2.
Method the most according to claim 1, it is characterised in that control anilinechloride by the flow velocity of regulation feed pump and 40% sodium nitrite solution mol ratio is 1:1.0 ~ 1.5.
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| CN107573266A (en) * | 2017-09-19 | 2018-01-12 | 黑龙江鑫创生物科技开发有限公司 | A kind of synthetic method of 4-hydrazinobenzene-1-sulfonamide hydrochloride |
| WO2018019250A1 (en) * | 2016-07-27 | 2018-02-01 | 上海惠和化德生物科技有限公司 | Continuous flow synthesis process for phenylhydrazine salt and substituted phenylhydrazine salt |
| CN107739313A (en) * | 2017-11-29 | 2018-02-27 | 黑龙江鑫创生物科技开发有限公司 | A kind of method of the multi-temperature zone continuous stream micro passage reaction synthesis chlorophenol of 4 amino 3 |
| CN107879927A (en) * | 2017-11-17 | 2018-04-06 | 中国药科大学 | A kind of method for preparing α chlorinated carboxylic acids |
| CN109503417A (en) * | 2017-09-14 | 2019-03-22 | 上海交通大学 | The continuous preparation method of diazonium salt of aniline and phenylhydrazine hydrochloride based on microreactor |
| CN110016001A (en) * | 2019-05-30 | 2019-07-16 | 武汉创新特科技有限公司 | A kind of continuous synthetic method of benzotriazole |
| CN110105296A (en) * | 2019-05-10 | 2019-08-09 | 江苏扬农化工集团有限公司 | The synthetic method of benzotriazole sodium salt and benzotriazole |
| CN110590687A (en) * | 2019-11-07 | 2019-12-20 | 山东豪迈化工技术有限公司 | Preparation method of benzotriazole |
| CN111662207A (en) * | 2020-06-08 | 2020-09-15 | 广东广康生化科技股份有限公司 | Method for synthesizing 4-methoxy-3-biphenylhydrazine hydrochloride by adopting micro-channel |
| CN111848438A (en) * | 2020-07-29 | 2020-10-30 | 浙江鼎龙科技有限公司 | Preparation method of 4,6-diphenylazoresorcinol and 4,6-diaminoresorcinol |
| CN112028788A (en) * | 2020-09-09 | 2020-12-04 | 上海试四赫维化工有限公司 | Preparation method for continuously preparing tert-butyl hydrazine hydrochloride |
| CN112225677A (en) * | 2020-11-10 | 2021-01-15 | 上海惠和化德生物科技有限公司 | Reaction system and method for p-chlorophenylhydrazine hydrochloride |
| CN112354495A (en) * | 2020-11-10 | 2021-02-12 | 上海惠和化德生物科技有限公司 | Continuous flow reaction system and method for p-chlorophenylhydrazine hydrochloride |
| CN113769675A (en) * | 2021-09-18 | 2021-12-10 | 株洲时代新材料科技股份有限公司 | Heart-shaped micro-reactor, continuous polymerization device and device for preparing modified meta-aramid fiber through continuous polymerization-dry-wet spinning |
| CN113956187A (en) * | 2021-11-08 | 2022-01-21 | 山东省药学科学院 | A kind of synthetic method of p-sulfonamidophenylhydrazine hydrochloride |
| CN114082209A (en) * | 2021-12-08 | 2022-02-25 | 启东亚太药业有限公司 | Negative pressure distillation phenylhydrazine separation and purification equipment and method |
| CN114195677A (en) * | 2021-12-23 | 2022-03-18 | 上海交通大学 | Continuous Preparation of 4-NBDT and 4-NBP Based on Microreactor |
| CN115073385A (en) * | 2022-07-04 | 2022-09-20 | 湖北欧立制药有限公司 | Application of microchannel continuous flow reaction technology in synthesis of rizatriptan benzoate |
| CN115385853A (en) * | 2022-10-17 | 2022-11-25 | 山东友道化学有限公司 | Production method of 2-hydrazino-3-chloropyridine |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050002835A1 (en) * | 2001-11-01 | 2005-01-06 | Astrazeneca Ab | Micro-engineered reactor |
| CN104478730A (en) * | 2014-12-31 | 2015-04-01 | 浙江永太科技股份有限公司 | 2-4-dichloronitrobenzene synthesis method utilizing micro-channel reactor |
| CN104478731A (en) * | 2014-12-31 | 2015-04-01 | 浙江永太科技股份有限公司 | Method for synthesizing 2, 4-dichloro-3-fluoronitrobenzene by means of micro-channel reactors |
-
2015
- 2015-06-19 CN CN201510343697.7A patent/CN106316879A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050002835A1 (en) * | 2001-11-01 | 2005-01-06 | Astrazeneca Ab | Micro-engineered reactor |
| CN104478730A (en) * | 2014-12-31 | 2015-04-01 | 浙江永太科技股份有限公司 | 2-4-dichloronitrobenzene synthesis method utilizing micro-channel reactor |
| CN104478731A (en) * | 2014-12-31 | 2015-04-01 | 浙江永太科技股份有限公司 | Method for synthesizing 2, 4-dichloro-3-fluoronitrobenzene by means of micro-channel reactors |
Non-Patent Citations (3)
| Title |
|---|
| ROBIN FORTT等: "On chip generation and reaction of unstable intermediates: monolithic microreactors for diazonium chemistries", 《MICRO TOTAL ANALYSIS SYSTEMS 》 * |
| 付春: "高纯度苯肼的合成", 《精细与专用化学品》 * |
| 胡云根等: "苯肼的合成工艺研究", 《江西化工》 * |
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2018019250A1 (en) * | 2016-07-27 | 2018-02-01 | 上海惠和化德生物科技有限公司 | Continuous flow synthesis process for phenylhydrazine salt and substituted phenylhydrazine salt |
| CN109503417A (en) * | 2017-09-14 | 2019-03-22 | 上海交通大学 | The continuous preparation method of diazonium salt of aniline and phenylhydrazine hydrochloride based on microreactor |
| CN107573266A (en) * | 2017-09-19 | 2018-01-12 | 黑龙江鑫创生物科技开发有限公司 | A kind of synthetic method of 4-hydrazinobenzene-1-sulfonamide hydrochloride |
| CN107879927A (en) * | 2017-11-17 | 2018-04-06 | 中国药科大学 | A kind of method for preparing α chlorinated carboxylic acids |
| CN107739313A (en) * | 2017-11-29 | 2018-02-27 | 黑龙江鑫创生物科技开发有限公司 | A kind of method of the multi-temperature zone continuous stream micro passage reaction synthesis chlorophenol of 4 amino 3 |
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| CN111662207B (en) * | 2020-06-08 | 2023-01-10 | 广东广康生化科技股份有限公司 | Method for synthesizing 4-methoxy-3-biphenylhydrazine hydrochloride by adopting micro-channel |
| CN111662207A (en) * | 2020-06-08 | 2020-09-15 | 广东广康生化科技股份有限公司 | Method for synthesizing 4-methoxy-3-biphenylhydrazine hydrochloride by adopting micro-channel |
| CN111848438A (en) * | 2020-07-29 | 2020-10-30 | 浙江鼎龙科技有限公司 | Preparation method of 4,6-diphenylazoresorcinol and 4,6-diaminoresorcinol |
| CN112028788A (en) * | 2020-09-09 | 2020-12-04 | 上海试四赫维化工有限公司 | Preparation method for continuously preparing tert-butyl hydrazine hydrochloride |
| CN112225677A (en) * | 2020-11-10 | 2021-01-15 | 上海惠和化德生物科技有限公司 | Reaction system and method for p-chlorophenylhydrazine hydrochloride |
| CN112354495A (en) * | 2020-11-10 | 2021-02-12 | 上海惠和化德生物科技有限公司 | Continuous flow reaction system and method for p-chlorophenylhydrazine hydrochloride |
| CN113769675A (en) * | 2021-09-18 | 2021-12-10 | 株洲时代新材料科技股份有限公司 | Heart-shaped micro-reactor, continuous polymerization device and device for preparing modified meta-aramid fiber through continuous polymerization-dry-wet spinning |
| CN113956187A (en) * | 2021-11-08 | 2022-01-21 | 山东省药学科学院 | A kind of synthetic method of p-sulfonamidophenylhydrazine hydrochloride |
| CN114082209A (en) * | 2021-12-08 | 2022-02-25 | 启东亚太药业有限公司 | Negative pressure distillation phenylhydrazine separation and purification equipment and method |
| CN114195677A (en) * | 2021-12-23 | 2022-03-18 | 上海交通大学 | Continuous Preparation of 4-NBDT and 4-NBP Based on Microreactor |
| CN115073385A (en) * | 2022-07-04 | 2022-09-20 | 湖北欧立制药有限公司 | Application of microchannel continuous flow reaction technology in synthesis of rizatriptan benzoate |
| CN115385853A (en) * | 2022-10-17 | 2022-11-25 | 山东友道化学有限公司 | Production method of 2-hydrazino-3-chloropyridine |
| CN115385853B (en) * | 2022-10-17 | 2024-02-02 | 山东友道化学有限公司 | Production method of 2-hydrazino-3-chloropyridine |
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