CN112354495A - Continuous flow reaction system and method for p-chlorophenylhydrazine hydrochloride - Google Patents
Continuous flow reaction system and method for p-chlorophenylhydrazine hydrochloride Download PDFInfo
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Abstract
The invention discloses a continuous flow reaction system and a continuous flow reaction method for p-chlorophenylhydrazine hydrochloride. The continuous flow reaction system for p-chlorophenylhydrazine hydrochloride comprises a p-chlorophenylhydrazine hydrochloride aqueous solution feeding pipeline, a sodium nitrite aqueous solution feeding pipeline, a diazotization reaction area, a diazonium salt intermediate discharging pipeline, a diazonium salt intermediate solution storage tank, a diazonium salt intermediate liquid inlet pipeline, a reducing agent liquid inlet pipeline, a reduction reaction area, a hydrochloric acid liquid inlet pipeline, a hydrolysis reaction area and a product liquid outlet. The continuous flow reaction system of the p-chlorophenylhydrazine hydrochloride has short reaction time, can reduce energy consumption, save cost, and has no problems of wastewater treatment, environmental pollution and the like; the operation is simple, and the stability is high; the method can be used for industrial production, and has high production efficiency; and the purity of the prepared p-chlorophenylhydrazine hydrochloride is up to more than 99 percent.
Description
Technical Field
The invention relates to a continuous flow reaction system and a continuous flow reaction method for p-chlorophenylhydrazine hydrochloride.
Background
The p-chlorophenylhydrazine hydrochloride is an important intermediate of medicines and pesticides, and the synthetic route mainly takes p-chlorophenylhydrazine, a diazotization reagent, a reducing agent and hydrochloric acid as raw materials to prepare the p-chlorophenylhydrazine hydrochloride through three steps of reactions of diazotization, reduction and hydrolysis.
In the prior art, the synthesis route mainly adopts an intermittent process, after raw materials are added into a reactor, the reaction time, the cooling time, the heating time, the heat preservation time, the interval time of each operation and the like of each step need to be waited, after the reaction meets the requirement, the product is discharged at one time, the production mode of intermittent process products is divided into batches, and the quantity of the products produced in each batch is limited by the volume of the reactor. In addition, in the operation process of the batch process, the state parameters of the composition, the temperature and the like of materials such as intermediate products, final products and the like in the reactor can change along with time, so that the batch process is an unstable process. Therefore, both the production process and the product quality have large uncertainty and are difficult to control.
At present, in the synthesis process of p-chlorophenylhydrazine hydrochloride, the synthesis method of a diazonium salt intermediate is mainly a batch process. The diazotization reaction is generally carried out by dropwise adding sodium nitrite into hydrochloric acid solution of p-chloroaniline. However, the process has the disadvantages of large wastewater generation amount, high treatment cost and poor environmental friendliness; and the method has the defects of long reaction time, low yield, high industrialization difficulty, incapability of realizing large-scale continuous production and the like.
CN106316879A discloses a method for preparing phenylhydrazine hydrochloride by a continuous reaction kettle type operation method, which can be used in industrial production, wherein the diazotization stage is a continuous operation, and partially solves the safety risk faced by the diazotization reaction, but the reduction reaction stage and the acidolysis reaction stage still use reaction kettles, the two reactions are still batch processes, and the whole process flow for synthesizing phenylhydrazine hydrochloride is still a batch process in essence. The two reactions of reduction and acidolysis take several hours in total, resulting in a long total reaction time in the process; furthermore, after the acid precipitation, purification steps such as neutralization and distillation are required. Therefore, the process is still a batch reaction process in essence, and the problems of long reaction time, low production efficiency, low product purity, high production energy consumption and high cost of the batch process cannot be fundamentally solved.
Therefore, it is desirable to provide a continuous flow reaction system and method for p-chlorophenylhydrazine hydrochloride.
Disclosure of Invention
The invention aims to overcome the defects that in the prior art, a p-chlorophenylhydrazine hydrochloride reaction system has long reaction time, low production efficiency, low product purity, high production energy consumption and high cost, increases the industrialization difficulty, cannot realize large-scale continuous production and the like, and provides a p-chlorophenylhydrazine hydrochloride continuous flow reaction system and a p-chlorophenylhydrazine hydrochloride continuous flow reaction method.
The invention solves the technical problems through the following technical scheme:
the invention provides a continuous flow reaction system for p-chlorophenylhydrazine hydrochloride, which comprises a p-chlorophenylhydrazine hydrochloride aqueous solution feeding pipeline, a sodium nitrite aqueous solution feeding pipeline, a diazotization reaction area, a diazonium salt intermediate discharging pipeline, a diazonium salt intermediate solution storage tank, a diazonium salt intermediate liquid inlet pipeline, a reducing agent liquid inlet pipeline, a reduction reaction area, a hydrochloric acid liquid inlet pipeline, a hydrolysis reaction area and a product liquid outlet;
wherein the diazotization reaction zone comprises n continuous flow reactors connected in series in sequence; n is more than or equal to 4;
the p-chloroaniline hydrochloric acid aqueous solution feeding pipeline and the sodium nitrite aqueous solution feeding pipeline are respectively connected with the first continuous flow reactor in the diazotization reaction zone;
the nth continuous flow reactor in the diazotization reaction zone is sequentially connected with the diazonium salt intermediate discharge pipeline and the diazonium salt intermediate solution storage tank;
the diazonium salt intermediate solution storage tank is connected with the reduction reaction zone through the diazonium salt intermediate liquid inlet pipeline; the reducing agent liquid inlet pipeline is connected with the reduction reaction zone; the hydrochloric acid liquid inlet pipeline is connected with the hydrolysis reaction area; the product liquid outlet is connected with the hydrolysis reaction zone;
the reduction reaction zone comprises m reduction reaction units, 2 continuous flow reactors, a plate heat exchanger and a reduction intermediate liquid storage tank which are connected in sequence; m is more than or equal to 3;
each m reduction reaction units comprise 1 reduction reaction kettle and 2 continuous flow reactors which are sequentially connected in series;
the hydrolysis reaction zone comprises 1 hydrolysis reaction kettle and 4 continuous flow reactors;
the reduction intermediate liquid storage tank is connected with the hydrolysis reaction kettle and the 4 continuous flow reactors in series in sequence.
In the present invention, the diazotization reaction may be a diazotization mixing reaction which is conventional in the art.
The diazotization reaction may be carried out in the diazotization reaction zone. Preferably, the diazotization reactions are carried out sequentially in the n successive series of continuous flow reactors.
In the present invention, the first continuous flow reactor may be provided with a first feeding port and a second feeding port. The first feed port is preferably located in the upper portion of the first continuous flow reactor. The second feed port is preferably located in the lower portion of the first continuous flow reactor.
The p-chloroaniline hydrochloric acid aqueous solution feeding pipeline can be connected with the first continuous flow reactor through the first feeding hole and is used for inputting p-chloroaniline hydrochloric acid aqueous solution into the diazotization reaction zone. The sodium nitrite aqueous solution feeding pipeline can be connected with the first continuous flow reactor through the second feeding hole and is used for inputting the sodium nitrite aqueous solution into the diazotization reaction zone.
And a diazonium salt intermediate solution discharge port can be arranged on the nth continuous flow reactor. The diazonium salt intermediate solution discharge port is preferably provided at the upper part of the nth continuous flow reactor.
Wherein the diazonium salt intermediate discharge pipeline can be connected with the nth continuous flow reactor through the discharge hole of the diazonium salt intermediate solution. Preferably, n is 4.
In the invention, the diazonium salt intermediate solution storage tank is used for storing the diazonium salt intermediate solution obtained by the diazotization reaction. The diazonium salt intermediate solution storage tank is provided with a diazonium salt intermediate solution inlet and a diazonium salt intermediate solution outlet. Wherein the diazonium salt intermediate solution inlet can be connected with the diazonium salt intermediate discharge pipeline.
In the invention, the continuous flow reaction system of the p-chlorophenylhydrazine hydrochloride preferably comprises a water storage tank. The water storage tank can be connected with the diazotization reaction zone and is used for cleaning the n continuous flow reactors which are sequentially connected in series.
In the present invention, a reduction reaction may be performed in the reduction reaction zone. The reduction reaction can be a reduction reaction in a p-chlorophenylhydrazine hydrochloride synthesis process which is conventional in the field. Preferably, the reduction reaction is carried out in the m reduction reaction units and the 2 continuous flow reactors.
In the reduction reaction zone, m reduction reaction kettles in m reduction reaction units are respectively provided with a diazonium salt intermediate liquid inlet. Preferably, the diazonium salt intermediate liquid inlet pipeline comprises m diazonium salt intermediate liquid inlet pipelines connected in parallel and respectively used for inputting diazonium salt intermediate solutions into the m reduction reaction kettles.
The first reduction reaction kettle in the first reduction reaction unit can be also provided with a reducing agent liquid inlet for inputting a reducing agent into the first reduction reaction kettle; and a first reaction liquid outlet for inputting the reaction liquid into the fifth continuous flow reactor in the first reduction reaction unit.
Preferably, the sixth continuous flow reactor in the first reduction reaction unit is connected with the second reduction reaction kettle in the second reduction reaction unit through the first reduction reaction liquid inlet.
Preferably, the mth reduction reaction unit is connected to the 2 continuous flow reactors through a reduction reaction liquid outlet.
The 2 continuous flow reactors are preferably connected with the plate heat exchanger and the reducing intermediate liquid storage tank in sequence through a reducing intermediate solution inlet.
Wherein, the reduction intermediate liquid storage tank is provided with a liquid storage inlet and a liquid storage outlet. The liquid storage inlet can be connected with the plate heat exchanger. The liquid storage outlet can be connected with the hydrolysis reaction kettle.
In the present invention, the hydrolysis reaction zone may perform a hydrolysis reaction. The hydrolysis reaction can be a hydrolysis reaction in a p-chlorophenylhydrazine hydrochloride synthesis process which is conventional in the field. Preferably, the hydrolysis reaction is carried out in the 1 hydrolysis reaction kettle and the 4 continuous flow reactors.
In the hydrolysis reaction zone, a reducing intermediate liquid inlet can be formed in the hydrolysis reaction kettle and is used for being connected with a liquid storage outlet in the reducing intermediate liquid storage tank and inputting a reducing intermediate solution into the hydrolysis reaction kettle; a hydrochloric acid liquid inlet for inputting a hydrochloric acid solution into the hydrolysis reaction kettle; and a hydrolysis reaction liquid outlet for inputting hydrolysis reaction liquid into the first continuous flow reactor in the 4 continuous flow reactors.
And a product liquid outlet can be arranged on the fourth continuous flow reactor in the 4 continuous flow reactors and is used for outputting the p-chlorophenylhydrazine hydrochloride.
In the present invention, the continuous flow reactor may be any one or more reactors capable of realizing continuous flow reaction, such as one or more of a microreactor, a tubular reactor, a cascade mixer, and a static mixer; preferably a microreactor.
In the invention, the continuous flow reaction system of the p-chlorophenylhydrazine hydrochloride can also comprise a slurry delivery pump and a diaphragm metering pump.
The parachloroaniline hydrochloric acid aqueous solution feeding pipeline, the sodium nitrite aqueous solution feeding pipeline, the diazonium salt intermediate liquid inlet pipeline, the reducing agent liquid inlet pipeline and the hydrochloric acid liquid inlet pipeline are respectively and sequentially provided with the slurry delivery pump and the diaphragm metering pump.
Preferably, the diaphragm metering pump may be two diaphragm metering pumps arranged in parallel. When one of the diaphragm metering pumps fails, the other diaphragm metering pump may be used.
In the invention, the continuous flow reaction system of the p-chlorophenylhydrazine hydrochloride can also comprise a heat-conducting oil heating device.
Preferably, the heat-conducting oil heating device is respectively connected with the diazotization reaction zone, the reduction reaction zone and the hydrolysis reaction zone through a heat-conducting oil inlet pipeline and a heat-conducting oil outlet pipeline, and is used for heating the continuous flow reactor. Wherein the heat transfer oil can be recycled.
The application method of the continuous flow reaction system for the p-chlorophenylhydrazine hydrochloride in the invention can comprise the following steps: inputting heat conduction oil into the diazotization reaction area through the heat conduction oil liquid inlet pipeline, and continuously inputting p-chloroaniline hydrochloric acid aqueous solution and sodium nitrite aqueous solution into the diazotization reaction area through the p-chloroaniline hydrochloric acid aqueous solution feeding pipeline and the sodium nitrite aqueous solution feeding pipeline respectively to carry out diazotization reaction so as to obtain diazonium salt intermediate solution;
respectively inputting heat conduction oil into the reduction reaction zone and the hydrolysis reaction zone through the heat conduction oil liquid inlet pipeline, and continuously inputting a diazonium salt intermediate solution and a reducing agent into the reduction reaction zone through the diazonium salt intermediate liquid inlet pipeline and the reducing agent liquid inlet pipeline to carry out reduction reaction so as to obtain a reduction intermediate solution; and continuously inputting a hydrochloric acid solution into the hydrolysis reaction zone through the hydrochloric acid liquid inlet pipeline for hydrolysis reaction to obtain the p-chlorophenylhydrazine hydrochloride.
Preferably, the p-chloroaniline hydrochloric acid aqueous solution and the sodium nitrite aqueous solution are continuously input into the first continuous flow reactor through the p-chloroaniline hydrochloric acid aqueous solution feeding pipeline and the sodium nitrite aqueous solution feeding pipeline respectively for reaction, after the reaction is finished, the reaction solution enters the next continuous flow reactor for reaction until the reaction solution enters the nth continuous flow reactor for reaction, and after the reaction is finished, the reaction solution enters the diazonium salt intermediate solution storage tank through the diazonium salt intermediate discharging pipeline.
Preferably, a diazonium salt intermediate solution and a reducing agent are continuously input into the first reduction reaction unit through the diazonium salt intermediate liquid inlet pipeline and the reducing agent liquid inlet pipeline respectively for reaction, after the reaction is finished, the first reduction reaction solution enters the second reduction reaction unit to the nth reduction reaction unit which are sequentially connected in series for reaction, after the reaction is finished, the nth reduction reaction solution enters the 2 continuous flow reactors which are sequentially connected in series for reaction, after the reaction is finished, the reduction intermediate solution enters the plate heat exchanger, then enters the reduction intermediate liquid storage tank, and is input into the hydrolysis reaction kettle through the liquid storage outlet.
Preferably, a hydrochloric acid solution is continuously input into the hydrolysis reaction kettle through the hydrochloric acid liquid inlet pipeline, the hydrochloric acid solution and the reduction intermediate solution perform hydrolysis reaction to obtain p-chlorophenylhydrazine hydrochloride, and the p-chlorophenylhydrazine hydrochloride is output through a product liquid outlet.
In the present invention, the reducing agent may be a reducing agent conventional in the art, for example, a sodium sulfite solution.
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows:
(1) the continuous flow reaction system of p-chlorophenylhydrazine hydrochloride overcomes the defects of long reaction time, low yield, high industrialization difficulty and incapability of realizing large-scale continuous production of an intermittent process, can stably run, can control the reaction time to be less than 10 minutes, reduces energy consumption, saves cost, and has no problems of wastewater treatment, environmental pollution and the like.
(2) The continuous flow reaction system of the p-chlorophenylhydrazine hydrochloride has the advantages of few operation steps, simple process and high stability.
(3) The continuous flow reaction system of the p-chlorophenylhydrazine hydrochloride can be used for industrial production, and has high production efficiency; meanwhile, the p-chlorophenylhydrazine hydrochloride prepared by the continuous flow reaction system of the p-chlorophenylhydrazine hydrochloride does not contain reaction byproducts such as diazoamino compounds or reduction reaction intermediates; moreover, when the continuous flow reaction system for p-chlorophenylhydrazine hydrochloride is adopted to prepare the p-chlorophenylhydrazine hydrochloride, the steps of removing reaction byproducts such as organic solvent extraction or recrystallization and the like are not included in the reaction process or the treatment of reaction products, so that the p-chlorophenylhydrazine hydrochloride with the purity of more than 99 percent can be prepared, and equipment, reagents and time required by the purification process are saved.
Drawings
FIG. 1 is a schematic diagram of a continuous flow reaction system for p-chlorophenylhydrazine hydrochloride in example 1.
Description of the reference numerals
Diazonium salt intermediate liquid inlet pipeline 1
First diazonium salt intermediate liquid inlet pipeline 11
Second diazonium salt intermediate liquid inlet pipeline 12
Third diazonium salt intermediate liquid inlet pipeline 13
First diazonium salt intermediate inlet 111
Second diazonium salt intermediate liquid inlet 121
Third diazonium salt intermediate liquid inlet 131
Reducing agent inlet pipe 2
Liquid inlet 21 for reducing agent
Hydrochloric acid inlet pipe 3
Hydrochloric acid inlet 31
Reduction reaction zone 4
First reduction reaction vessel 41
Fifth continuous flow reactor 411
Sixth continuous flow reactor 412
First reaction liquid outlet 413
Second reduction reaction vessel 42
Seventh continuous flow reactor 421
Eighth continuous flow reactor 422
First reduction reaction liquid inlet 423
Third reduction reaction kettle 43
Ninth continuous flow reactor 431
Tenth continuous flow reactor 432
Eleventh continuous flow reactor 46
Twelfth continuous flow reactor 47
Second reduction reaction liquid inlet 435
Reduction reaction liquid outlet 437
Reducing intermediate solution inlet 471
Plate heat exchanger 44
Reducing intermediate liquid storage tank 45
Liquid storage inlet 451
Reservoir outlet 452
Hydrolysis reaction zone 5
Hydrolysis reaction kettle 51
Thirteenth continuous flow reactor 511
Fourteenth continuous flow reactor 512
Fifteenth continuous flow reactor 513
Sixteenth continuous flow reactor 514
Reduction intermediate liquid inlet 515
Hydrolysis reaction liquid outlet 516
Product outlet 6
A p-chloroaniline hydrochloric acid aqueous solution feed pipeline 7;
first slurry feed pump 71
First diaphragm metering pump 721
Second diaphragm metering pump 722
First feed port 73
Sodium nitrite aqueous solution feed line 8
Second slurry transport pump 81
Third diaphragm metering pump 821
Fourth diaphragm metering pump 822
Second feed port 83
Diazotization reaction zone 9
First continuous flow reactor 91
Second continuous flow reactor 92
Third continuous flow reactor 93
Fourth continuous flow reactor 94
Diazonium salt intermediate discharge pipeline 10
Discharge port 101 of diazonium salt intermediate solution
Diazonium salt intermediate solution storage tank 14
Diazonium salt intermediate solution inlet 141
Diazonium salt intermediate solution outlet 142
Heat conducting oil heating device 15
Heat conducting oil inlet pipeline 151
Heat conducting oil liquid outlet pipeline 152
A water storage tank 16
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
Example 1
A continuous flow reaction system of p-chlorophenylhydrazine hydrochloride in example 1 is shown in fig. 1, and includes a p-chlorophenylhydrazine hydrochloride aqueous solution feed pipe 7, a sodium nitrite aqueous solution feed pipe 8, a diazotization reaction zone 9, a diazonium salt intermediate discharge pipe 10, a diazonium salt intermediate solution storage tank 14, a diazonium salt intermediate liquid inlet pipe 1, a reducing agent liquid inlet pipe 2, a reduction reaction zone 4, a hydrochloric acid liquid inlet pipe 3, a hydrolysis reaction zone 5, and a product liquid outlet 6;
wherein, the diazotization reaction zone 9 comprises 4 continuous flow reactors connected in series in sequence;
a p-chloroaniline hydrochloric acid aqueous solution feeding pipeline 7 and a sodium nitrite aqueous solution feeding pipeline 8 are respectively connected with a first continuous flow reactor 91 in the diazotization reaction zone 9;
the fourth continuous flow reactor 94 in the diazotization reaction zone 9 is connected with a diazonium salt intermediate discharge pipeline 10 and a diazonium salt intermediate solution storage tank 14 in sequence;
a diazonium salt intermediate solution storage tank 14 is connected with the reduction reaction zone 4 through a diazonium salt intermediate liquid inlet pipeline 1; the reducing agent liquid inlet pipeline 2 is connected with the reduction reaction zone 4; the hydrochloric acid liquid inlet pipeline 3 is connected with the hydrolysis reaction area 5; the product liquid outlet 6 is connected with the hydrolysis reaction zone 5;
the reduction reaction zone 4 comprises a first reduction reaction unit, a second reduction reaction unit, a third reduction reaction unit, an eleventh continuous flow reactor 46, a twelfth continuous flow reactor 47, a plate heat exchanger 44 and a reduction intermediate liquid storage tank 45 which are connected in sequence;
the first reduction reaction unit, the second reduction reaction unit and the third reduction reaction unit respectively comprise 1 reduction reaction kettle and 2 continuous flow reactors which are sequentially connected in series;
the hydrolysis reaction zone 5 comprises a hydrolysis reaction kettle 51 and 4 continuous flow reactors;
the reducing intermediate storage tank 45 is connected in series with the hydrolysis reaction kettle 51, the thirteenth continuous flow reactor 511, the fourteenth continuous flow reactor 512, the fifteenth continuous flow reactor 513 and the sixteenth continuous flow reactor 514 in this order.
The diazotization reaction in example 1 is a diazotization mixing reaction.
The diazotization reaction is carried out in sequence in a first continuous flow reactor 91, a second continuous flow reactor 92, a third continuous flow reactor 93 and a fourth continuous flow reactor 94 which are connected in series in the diazotization reaction zone 9.
Wherein the first continuous flow reactor 91 is provided with a first feed port 73 and a second feed port 83. The first feed port 73 is provided in the upper part of the first continuous flow reactor 91. The second feed port 83 is provided in the lower part of the first continuous flow reactor 91.
Wherein, the p-chloroaniline hydrochloric acid water solution feeding pipeline 7 is connected with the first continuous flow reactor 91 through the first feeding hole 73 and is used for inputting the p-chloroaniline hydrochloric acid water solution into the diazotization reaction zone 9. A sodium nitrite aqueous solution feed conduit 8 is connected to the first continuous flow reactor 91 through the second feed port 83 for feeding an aqueous sodium nitrite solution into the diazotization reaction zone 9.
A diazonium salt intermediate solution outlet 101 is arranged on the fourth continuous flow reactor 94. A diazonium salt intermediate solution outlet 101 is provided at the upper portion of the fourth continuous flow reactor 94.
Wherein the diazonium salt intermediate discharge pipeline 10 is connected with the fourth continuous flow reactor 94 through a diazonium salt intermediate solution discharge port 101.
In example 1, the diazonium salt intermediate solution receiver 14 is used to store the diazonium salt intermediate solution obtained by the diazotization reaction. The diazonium salt intermediate solution storage tank 14 is provided with a diazonium salt intermediate solution inlet 141 and a diazonium salt intermediate solution outlet 142. Wherein, the diazonium salt intermediate solution inlet 141 is connected with the diazonium salt intermediate discharging pipeline 10.
The continuous flow reaction system for p-chlorophenylhydrazine hydrochloride in example 1 further comprises a water storage tank 16. The water storage tank 16 is connected with the diazotization reaction zone 9 and is used for cleaning a first continuous flow reactor 91, a second continuous flow reactor 92, a third continuous flow reactor 93 and a fourth continuous flow reactor 94 which are connected in series in sequence.
Wherein the reduction reaction is carried out in the reduction reaction zone 4. The reduction reaction is the reduction reaction in the synthesis process of the p-chlorophenylhydrazine hydrochloride. The reduction reaction is performed in the first reduction reaction unit, the second reduction reaction unit, the third reduction reaction unit, the eleventh continuous flow reactor 46, and the twelfth continuous flow reactor 47 in this order.
In the reduction reaction zone 4, a first diazonium salt intermediate liquid inlet 111, a second diazonium salt intermediate liquid inlet 121 and a third diazonium salt intermediate liquid inlet 131 are respectively arranged on the first reduction reaction kettle 41, the second reduction reaction kettle 42 and the third reduction reaction kettle 43. The diazonium salt intermediate liquid inlet pipeline 1 comprises a first diazonium salt intermediate liquid inlet pipeline 11, a second diazonium salt intermediate liquid inlet pipeline 12 and a third diazonium salt intermediate liquid inlet pipeline 13 which are connected in parallel and are respectively used for inputting diazonium salt intermediate solutions into a first reduction reaction kettle 41, a second reduction reaction kettle 42 and a third reduction reaction kettle 43.
Wherein, a reducing agent liquid inlet 21 is also arranged on the first reduction reaction kettle 41 in the first reduction reaction unit and is used for inputting a reducing agent into the first reduction reaction kettle 41; and a first reaction liquid outlet 413 for inputting the reaction liquid into the fifth continuous flow reactor 411 in the first reduction reaction unit.
The sixth continuous flow reactor 412 in the first reduction reaction unit is connected to the second reduction reaction tank 42 in the second reduction reaction unit through the first reduction reaction liquid inlet 423.
The eighth continuous flow reactor 422 in the second reduction reaction unit is connected to the third reduction reaction vessel 43 in the third reduction reaction unit through the second reduction reaction liquid inlet 435.
The tenth continuous flow reactor 432 in the third reduction reaction unit is connected to the eleventh continuous flow reactor 46 and the twelfth continuous flow reactor 47 connected in series in this order through the reduction reaction liquid outlet 437.
The eleventh continuous flow reactor 46 and the twelfth continuous flow reactor 47 are connected in series to the plate heat exchanger 44 and the reducing intermediate storage tank 45 through the reducing intermediate solution inlet 471.
Wherein, the reducing intermediate liquid storage tank 45 is provided with a liquid storage inlet 451 and a liquid storage outlet 452. The reservoir inlet 451 is connected to the plate heat exchanger 44. The outlet 452 of the liquid storage is connected to the hydrolysis reactor 51.
In example 1, the hydrolysis reaction zone 5 was subjected to hydrolysis reaction. The hydrolysis reaction is the hydrolysis reaction in the synthesis process of the p-chlorophenylhydrazine hydrochloride. The hydrolysis reaction is carried out in the hydrolysis reaction kettle 51, the thirteenth continuous flow reactor 511, the fourteenth continuous flow reactor 512, the fifteenth continuous flow reactor 513 and the sixteenth continuous flow reactor 514.
In the hydrolysis reaction zone 5, a reducing intermediate liquid inlet 515 is arranged on the hydrolysis reaction kettle 51 and is used for connecting with a liquid storage outlet 452 on the reducing intermediate liquid storage tank 45 and inputting a reducing intermediate solution into the hydrolysis reaction kettle 51; a hydrochloric acid inlet 31 for inputting a hydrochloric acid solution into the hydrolysis reaction kettle 51; and a hydrolysis reaction liquid outlet 516 for inputting a hydrolysis reaction liquid into the thirteenth continuous flow reactor 511.
A product liquid outlet 6 is further disposed on the sixteenth continuous flow reactor 514 and is used for outputting p-chlorophenylhydrazine hydrochloride.
The continuous flow reactor in example 1 is a microreactor.
The continuous flow reaction system for p-chlorophenylhydrazine hydrochloride of example 1 further comprises a slurry delivery pump and a diaphragm metering pump.
The p-chloroaniline aqueous acid solution feed pipe 7 is provided with a first slurry feed pump 71, and a first diaphragm metering pump 721 and a second diaphragm metering pump 722 which are arranged in parallel in this order. When one of the diaphragm metering pumps fails, the other diaphragm metering pump may be used.
The sodium nitrite aqueous solution feed pipe 8 is provided with a second slurry feed pump 81, a third diaphragm metering pump 821 and a fourth diaphragm metering pump 822 which are arranged in parallel in this order. When one of the diaphragm metering pumps fails, the other diaphragm metering pump may be used.
The continuous flow reaction system for p-chlorophenylhydrazine hydrochloride of embodiment 1 further comprises a heat conducting oil heating device 15.
The heat-conducting oil heating device 15 is connected with the diazotization reaction zone 9 through a heat-conducting oil liquid inlet pipeline 151 and a heat-conducting oil liquid outlet pipeline 152, and is used for heating the first continuous flow reactor 91, the second continuous flow reactor 92, the third continuous flow reactor 93 and the fourth continuous flow reactor 94. Wherein, the heat conducting oil can be recycled.
The application method of the continuous flow reaction system of the p-chlorophenylhydrazine hydrochloride in the embodiment 1 comprises the following steps: inputting heat conducting oil into a diazotization reaction area 9 through a heat conducting oil liquid inlet pipeline 151, and continuously inputting p-chloroaniline hydrochloric acid aqueous solution and sodium nitrite aqueous solution into the diazotization reaction area 9 through a p-chloroaniline hydrochloric acid aqueous solution feeding pipeline 7 and a sodium nitrite aqueous solution feeding pipeline 8 respectively to carry out diazotization reaction to obtain diazonium salt intermediate solution;
respectively inputting heat conducting oil into a reduction reaction zone 4 and a hydrolysis reaction zone 5 through a heat conducting oil liquid inlet pipeline, and continuously inputting a diazonium salt intermediate solution and a reducing agent into the reduction reaction zone 4 through a diazonium salt intermediate liquid inlet pipeline 1 and a reducing agent liquid inlet pipeline 2 to carry out reduction reaction to obtain a reduction intermediate solution; and continuously inputting the hydrochloric acid solution into a hydrolysis reaction zone 5 through a hydrochloric acid liquid inlet pipeline 3 for hydrolysis reaction to obtain the p-chlorophenylhydrazine hydrochloride.
Specifically, the p-chloroaniline hydrochloric acid aqueous solution and the sodium nitrite aqueous solution are continuously input into the first continuous flow reactor 91 through a p-chloroaniline hydrochloric acid aqueous solution feed pipeline 7 and a sodium nitrite aqueous solution feed pipeline 8 respectively for reaction, after the reaction is completed, the reaction solution enters the next continuous flow reactor for reaction until the reaction solution enters the fourth continuous flow reactor 94 for reaction, and after the reaction is completed, the reaction solution enters the diazonium salt intermediate solution storage tank 14 through the diazonium salt intermediate discharge pipeline 10.
Continuously inputting a diazonium salt intermediate solution and a reducing agent into a first reduction reaction unit for reaction through a diazonium salt intermediate liquid inlet pipeline 1 and a reducing agent liquid inlet pipeline 2 respectively, after the reaction is finished, enabling reaction liquid to enter a second reduction reaction unit to a third reduction reaction unit which are sequentially connected in series for reaction, and enabling the reaction liquid to enter a fifth continuous flow reactor 411 and a sixth continuous flow reactor 412 which are sequentially connected in series for continuous reaction; after the reaction is finished, the reaction solution enters a second reduction reaction kettle 42 for reaction, and after the reaction is finished, the reaction solution enters a seventh continuous flow reactor 421 and an eighth continuous flow reactor 422 which are connected in series in sequence for continuous reaction; after the reaction, the reaction solution enters the third reduction reaction kettle 43 for reaction, after the reaction is completed, the reaction solution enters the ninth continuous flow reactor 431 and the tenth continuous flow reactor 432 which are connected in series in sequence, and after the reaction is completed, the reaction solution enters the eleventh continuous flow reactor 46 and the twelfth continuous flow reactor 47 which are connected in series in sequence for continuous reaction; after the reaction is completed, the reducing intermediate solution enters the plate heat exchanger 44, then enters the reducing intermediate storage tank 45, and is input into the hydrolysis reaction kettle 51 through the storage outlet 452.
And continuously inputting the hydrochloric acid solution into the hydrolysis reaction kettle 51 through a hydrochloric acid liquid inlet pipeline 3, and performing hydrolysis reaction on the hydrochloric acid solution and the reduction intermediate solution to obtain the p-chlorophenylhydrazine hydrochloride, and outputting the p-chlorophenylhydrazine hydrochloride through a product liquid outlet 6.
Wherein the reducing agent is sodium sulfite solution.
The continuous flow reaction system of p-chlorophenylhydrazine hydrochloride in the embodiment 1 overcomes the defects of long reaction time, low yield, high industrialization difficulty and incapability of realizing large-scale continuous production of an intermittent process, can stably run, has the reaction time of less than 10min, reduces energy consumption, saves cost, and has no problems of wastewater treatment, environmental pollution and the like. In addition, the continuous flow reaction system of p-chlorophenylhydrazine hydrochloride in the embodiment 1 has the advantages of few operation steps, simple process and high stability. Further, the continuous flow reaction system of p-chlorophenylhydrazine hydrochloride in the embodiment 1 can be used for industrial production, and the production efficiency is high; meanwhile, the p-chlorophenylhydrazine hydrochloride prepared by the continuous flow reaction system of the p-chlorophenylhydrazine hydrochloride in the embodiment 1 does not contain reaction byproducts such as diazoamino compounds or reduction reaction intermediates; moreover, when the continuous flow reaction system of p-chlorophenylhydrazine hydrochloride in example 1 is used to prepare p-chlorophenylhydrazine hydrochloride, the removal steps of organic solvent extraction or recrystallization and the like on reaction byproducts are not included in the reaction process or the treatment of reaction products, so that the p-chlorophenylhydrazine hydrochloride with the purity as high as 99.9% can be prepared, and the equipment, reagents and time required by the purification process are saved.
Claims (10)
1. A continuous flow reaction system of p-chlorophenylhydrazine hydrochloride is characterized by comprising a p-chlorophenylhydrazine hydrochloride aqueous solution feeding pipeline, a sodium nitrite aqueous solution feeding pipeline, a diazotization reaction area, a diazonium salt intermediate discharging pipeline, a diazonium salt intermediate solution storage tank, a diazonium salt intermediate liquid inlet pipeline, a reducing agent liquid inlet pipeline, a reduction reaction area, a hydrochloric acid liquid inlet pipeline, a hydrolysis reaction area and a product liquid outlet;
wherein the diazotization reaction zone comprises n continuous flow reactors connected in series in sequence; n is more than or equal to 4;
the p-chloroaniline hydrochloric acid aqueous solution feeding pipeline and the sodium nitrite aqueous solution feeding pipeline are respectively connected with the first continuous flow reactor in the diazotization reaction zone;
the nth continuous flow reactor in the diazotization reaction zone is sequentially connected with the diazonium salt intermediate discharge pipeline and the diazonium salt intermediate solution storage tank;
the diazonium salt intermediate solution storage tank is connected with the reduction reaction zone through the diazonium salt intermediate liquid inlet pipeline; the reducing agent liquid inlet pipeline is connected with the reduction reaction zone; the hydrochloric acid liquid inlet pipeline is connected with the hydrolysis reaction area; the product liquid outlet is connected with the hydrolysis reaction zone;
the reduction reaction zone comprises m reduction reaction units, 2 continuous flow reactors, a plate heat exchanger and a reduction intermediate liquid storage tank which are connected in sequence; m is more than or equal to 3;
each m reduction reaction units comprise 1 reduction reaction kettle and 2 continuous flow reactors which are sequentially connected in series;
the hydrolysis reaction zone comprises 1 hydrolysis reaction kettle and 4 continuous flow reactors;
the reduction intermediate liquid storage tank is connected with the hydrolysis reaction kettle and the 4 continuous flow reactors in series in sequence.
2. The continuous flow reaction system of para-chlorophenylhydrazine hydrochloride according to claim 1, wherein the diazotization reaction is carried out in the diazotization reaction zone;
preferably, a first feeding hole and a second feeding hole are arranged on the first continuous flow reactor; the first feeding hole is arranged at the upper part of the first continuous flow reactor; the second feeding hole is arranged at the lower part of the first continuous flow reactor;
more preferably, the p-chloroaniline hydrochloric acid aqueous solution feed conduit is connected with the first continuous flow reactor through the first feed port; and the sodium nitrite aqueous solution feeding pipeline is connected with the first continuous flow reactor through the second feeding hole.
3. The continuous flow reaction system of para-chlorophenylhydrazine hydrochloride as claimed in claim 1 wherein the nth continuous flow reactor is provided with a diazonium salt intermediate solution outlet; the diazonium salt intermediate solution discharge port is preferably arranged at the upper part of the nth continuous flow reactor;
and/or the diazonium salt intermediate discharging pipeline is connected with the nth continuous flow reactor through the diazonium salt intermediate solution discharging port; preferably, said n-4;
and/or the diazonium salt intermediate solution storage tank is provided with a diazonium salt intermediate solution inlet and a diazonium salt intermediate solution outlet; wherein the diazonium salt intermediate solution inlet is preferably connected with the diazonium salt intermediate discharge pipeline;
and/or the continuous flow reaction system of the p-chlorophenylhydrazine hydrochloride comprises a water storage tank; the water storage tank is preferably connected with the diazotization reaction zone and is used for cleaning the n continuous flow reactors which are sequentially connected in series.
4. The continuous flow reaction system of para-chlorophenylhydrazine hydrochloride as claimed in claim 1 wherein the reduction reaction is carried out in the reduction reaction zone; the reduction reaction is preferably carried out in the m reduction reaction units and the 2 continuous flow reactors;
and/or in the reduction reaction zone, m reduction reaction kettles in m reduction reaction units are respectively provided with a diazonium salt intermediate liquid inlet;
and/or the diazonium salt intermediate liquid inlet pipeline comprises m diazonium salt intermediate liquid inlet pipelines connected in parallel and is respectively used for inputting diazonium salt intermediate solutions into the m reduction reaction kettles.
5. The continuous flow reaction system of p-chlorophenylhydrazine hydrochloride as claimed in claim 1, wherein the first reduction reaction kettle in the first reduction reaction unit is provided with a reducing agent inlet for inputting a reducing agent into the first reduction reaction kettle; and a first reaction liquid outlet for inputting the reaction liquid into the fifth continuous flow reactor in the first reduction reaction unit.
6. The continuous flow reaction system of p-chlorophenylhydrazine hydrochloride as claimed in claim 1, wherein the sixth continuous flow reactor in the first reduction reaction unit is connected with the second reduction reaction kettle in the second reduction reaction unit through the first reduction reaction liquid inlet;
and/or the m reduction reaction unit is connected with the 2 continuous flow reactors through a reduction reaction liquid outlet;
the 2 continuous flow reactors are preferably connected with the plate heat exchanger and the reduction intermediate liquid storage tank in sequence through a reduction intermediate solution inlet;
and/or the reduction intermediate liquid storage tank is provided with a liquid storage inlet and a liquid storage outlet; the liquid storage inlet is preferably connected with the plate heat exchanger; the liquid storage outlet is preferably connected with the hydrolysis reaction kettle.
7. The continuous flow reaction system of p-chlorophenylhydrazine hydrochloride as claimed in claim 1, wherein in the hydrolysis reaction zone, the hydrolysis reaction kettle is provided with a reducing intermediate liquid inlet for connecting with a liquid storage outlet on the reducing intermediate liquid storage tank and inputting a reducing intermediate solution into the hydrolysis reaction kettle; a hydrochloric acid liquid inlet for inputting a hydrochloric acid solution into the hydrolysis reaction kettle; and a hydrolysis reaction liquid outlet for inputting hydrolysis reaction liquid into the first continuous flow reactor of the 4 continuous flow reactors;
and/or a product liquid outlet is arranged on the fourth continuous flow reactor in the 4 continuous flow reactors and is used for outputting p-chlorophenylhydrazine hydrochloride;
and/or the continuous flow reactor is one or more of a microreactor, a tubular reactor, a stacked mixer and a static mixer; preferably a microreactor.
8. The continuous flow reaction system of para-chlorophenylhydrazine hydrochloride according to claim 1, wherein the continuous flow reaction system of para-chlorophenylhydrazine hydrochloride comprises a slurry delivery pump and a diaphragm metering pump;
preferably, the p-chloroaniline hydrochloric acid aqueous solution feeding pipeline, the sodium nitrite aqueous solution feeding pipeline, the diazonium salt intermediate liquid inlet pipeline, the reducing agent liquid inlet pipeline and the hydrochloric acid liquid inlet pipeline are respectively and sequentially provided with the slurry conveying pump and the diaphragm metering pump;
more preferably, the diaphragm metering pump is two diaphragm metering pumps arranged in parallel;
and/or the continuous flow reaction system of the p-chlorophenylhydrazine hydrochloride comprises a heat conduction oil heating device;
preferably, the heat-conducting oil heating device is respectively connected with the diazotization reaction zone, the reduction reaction zone and the hydrolysis reaction zone through a heat-conducting oil inlet pipeline and a heat-conducting oil outlet pipeline, and is used for heating the continuous flow reactor.
9. A method for using the continuous flow reaction system of the chlorophenylhydrazine hydrochloride as claimed in any one of claims 1 to 8, which comprises the following steps: inputting heat conduction oil into the diazotization reaction area through a heat conduction oil liquid inlet pipeline, and continuously inputting a p-chloroaniline hydrochloric acid aqueous solution and a sodium nitrite aqueous solution into the diazotization reaction area through the p-chloroaniline hydrochloric acid aqueous solution feeding pipeline and the sodium nitrite aqueous solution feeding pipeline respectively to carry out diazotization reaction so as to obtain a diazonium salt intermediate solution;
respectively inputting heat conducting oil into the reduction reaction zone and the hydrolysis reaction zone through a heat conducting oil liquid inlet pipeline, and continuously inputting a diazonium salt intermediate solution and a reducing agent into the reduction reaction zone through the diazonium salt intermediate liquid inlet pipeline and the reducing agent liquid inlet pipeline respectively to carry out reduction reaction so as to obtain a reduction intermediate solution; and continuously inputting a hydrochloric acid solution into the hydrolysis reaction zone through the hydrochloric acid liquid inlet pipeline for hydrolysis reaction to obtain the p-chlorophenylhydrazine hydrochloride.
10. The use method of the continuous flow reaction system of p-chlorophenylhydrazine hydrochloride as claimed in claim 9, wherein the aqueous solution of p-chlorophenylhydrazine hydrochloride and the aqueous solution of sodium nitrite are continuously fed into the first continuous flow reactor for reaction through the feed line of the aqueous solution of p-chlorophenylhydrazine hydrochloride and the feed line of the aqueous solution of sodium nitrite, and after the reaction is completed, the reaction solution enters the next continuous flow reactor for reaction until the reaction solution enters the nth continuous flow reactor for reaction, and after the reaction is completed, the reaction solution enters the diazonium salt intermediate solution storage tank through the discharge line of the diazonium salt intermediate;
and/or continuously inputting a diazonium salt intermediate solution and a reducing agent into the first reduction reaction unit through the diazonium salt intermediate liquid inlet pipeline and the reducing agent liquid inlet pipeline respectively for reaction, after the reaction is finished, enabling the first reduction reaction solution to enter the second reduction reaction unit to the nth reduction reaction unit which are sequentially connected in series for reaction, after the reaction is finished, enabling the nth reduction reaction solution to enter 2 continuous flow reactors which are sequentially connected in series for reaction, after the reaction is finished, enabling the reduction intermediate solution to enter a plate heat exchanger, then enter the reduction intermediate liquid storage tank, and inputting the reduction intermediate solution into the hydrolysis reaction kettle through a liquid storage outlet;
and/or continuously inputting a hydrochloric acid solution into the hydrolysis reaction kettle through the hydrochloric acid liquid inlet pipeline, and performing hydrolysis reaction on the hydrochloric acid solution and the reduction intermediate solution to obtain p-chlorophenylhydrazine hydrochloride, and outputting the p-chlorophenylhydrazine hydrochloride through a product liquid outlet.
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