CN112354495B - Continuous flow reaction system and method for parachlorophenylhydrazine hydrochloride - Google Patents
Continuous flow reaction system and method for parachlorophenylhydrazine hydrochloride Download PDFInfo
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Abstract
The invention discloses a p-chlorophenylhydrazine hydrochloride continuous flow reaction system and a p-chlorophenylhydrazine hydrochloride continuous flow reaction method. The p-chlorophenylhydrazine hydrochloride continuous flow reaction system comprises a p-chloroaniline acid aqueous solution feeding pipeline, a sodium nitrite aqueous solution feeding pipeline, a diazotization reaction region, a diazonium salt intermediate discharging pipeline, a diazonium salt intermediate solution storage tank, a diazonium salt intermediate liquid feeding pipeline, a reducing agent liquid feeding pipeline, a reduction reaction region, a hydrochloric acid liquid feeding pipeline, a hydrolysis reaction region and a product liquid outlet. The p-chlorophenylhydrazine hydrochloride continuous flow reaction system has short reaction time, can reduce energy consumption, saves cost, and has no problems of wastewater treatment, environmental pollution and the like; the operation is simple, and the stability is high; 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%.
Description
Technical Field
The invention relates to a p-chlorophenylhydrazine hydrochloride continuous flow reaction system and a p-chlorophenylhydrazine hydrochloride continuous flow reaction method.
Background
The p-chlorophenylhydrazine hydrochloride is an important intermediate of medicines and pesticides, and the synthetic route is mainly to take p-chloroaniline, diazotizing reagent, reducing agent and hydrochloric acid as raw materials, and the p-chlorophenylhydrazine hydrochloride is prepared by three steps of reactions of diazotization, reduction and hydrolysis in sequence.
In the prior art, the above synthetic route mainly adopts an intermittent process, after raw materials are added into a reactor, the time for each step of reaction, the time for cooling, the time for heating, the time for heat preservation, the time for each operation interval and the like need to be waited, and after the reaction reaches the requirement, the products are discharged at one time. In addition, during the operation of the batch process, the composition of materials such as intermediate products and final products in the reactor, the temperature and other state parameters can change with time, and the batch process is an unsteady state process. It can be seen that there is a large uncertainty in both the production process and the product quality, which is difficult to control.
At present, in the synthetic process of p-chlorophenylhydrazine hydrochloride, the synthetic method of diazonium salt intermediates is mainly a batch process. Sodium nitrite is generally added dropwise into hydrochloric acid solution of p-chloroaniline for diazotization. However, the process has large wastewater production amount, high treatment cost and poor environmental friendliness; and has the defects of long reaction time, low yield, large industrialization difficulty, incapability of realizing large-scale continuous production and the like.
CN106316879a discloses a method for preparing phenylhydrazine hydrochloride by using a continuous reaction kettle type operation mode, which can be used for industrial production, although the diazotization stage is continuously operated, and the safety risk faced by the diazotization reaction is partially solved, reaction kettles are still used in the reduction reaction stage and the acidolysis reaction stage, the two steps of reactions are still batch processes, and the whole process flow for synthesizing phenylhydrazine hydrochloride is still substantially batch reaction processes. The two steps of reduction and acidolysis require several hours in total, resulting in longer total reaction time in the process; furthermore, the acid precipitation is followed by purification steps such as neutralization and distillation. Therefore, the process is still a batch reaction process, 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.
Accordingly, there is a need to provide a system and method for continuous flow reactions of p-chlorophenylhydrazine hydrochloride.
Disclosure of Invention
The invention aims to overcome the defects that a p-chlorophenylhydrazine hydrochloride reaction system in the prior art has long reaction time, low production efficiency, low product purity, high production energy consumption, high cost, increased industrialization difficulty, incapability of realizing large-scale continuous production and the like, and provides the p-chlorophenylhydrazine hydrochloride continuous flow reaction system and method.
The invention solves the technical problems by the following technical scheme:
the invention provides a p-chlorophenylhydrazine hydrochloride continuous flow reaction system which comprises a p-chloroaniline acid aqueous solution feeding pipeline, a sodium nitrite aqueous solution feeding pipeline, a diazotization reaction zone, a diazonium salt intermediate discharging pipeline, a diazonium salt intermediate solution storage tank, a diazonium salt intermediate liquid feeding pipeline, a reducing agent liquid feeding pipeline, a reduction reaction zone, a hydrochloric acid liquid feeding pipeline, a hydrolysis reaction zone and a product liquid outlet, wherein the diazonium salt intermediate liquid feeding pipeline is connected with the diazonium salt intermediate liquid feeding pipeline;
wherein the diazotization reaction area comprises n continuous flow reactors which are sequentially connected in series; n is more than or equal to 4;
the para-chloroaniline acid aqueous solution feeding pipeline and the sodium nitrite aqueous solution feeding pipeline are respectively connected with a first continuous flow reactor in the diazotization reaction region;
an nth continuous flow reactor in the diazotization reaction region is sequentially connected with the diazonium salt intermediate discharging pipeline and the diazonium salt intermediate solution liquid storage tank;
the diazonium salt intermediate solution liquid 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 zone; 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 diazotisation reaction may be a diazotisation mixing reaction conventional in the art.
The diazotisation reaction may be carried out in the diazotisation reaction zone. Preferably, the diazotisation reaction is carried out sequentially in the n consecutive continuous flow reactors connected in series.
In the invention, the first continuous flow reactor can be provided with a first feed inlet and a second feed inlet. The first feed port is preferably provided in an upper portion of the first continuous flow reactor. The second feed port is preferably provided in the lower portion of the first continuous flow reactor.
Wherein, the para-chloroaniline acid aqueous solution feeding pipeline can be connected with the first continuous flow reactor through the first feeding port and is used for inputting para-chloroaniline acid aqueous solution into the diazotization reaction zone. And the sodium nitrite aqueous solution feeding pipeline can be connected with the first continuous flow reactor through the second feeding port and is used for inputting sodium nitrite aqueous solution into the diazotization reaction region.
The nth continuous flow reactor can be provided with a diazonium salt intermediate solution discharge port. The diazonium salt intermediate solution discharge port is preferably located in the upper portion of the nth continuous flow reactor.
Wherein, diazonium salt intermediate discharge conduit may be connected with the nth continuous flow reactor through the diazonium salt intermediate solution discharge port. Preferably, n=4.
In the invention, the diazonium salt intermediate solution liquid storage tank is used for storing the diazonium salt intermediate solution obtained by the diazotization reaction. The diazonium salt intermediate solution liquid storage tank is provided with a diazonium salt intermediate solution inlet and a diazonium salt intermediate solution outlet. Wherein, diazonium salt intermediate solution import can with diazonium salt intermediate discharge pipeline connection.
In the invention, the p-chlorophenylhydrazine hydrochloride continuous flow reaction system preferably comprises a water storage tank. The water storage tank can be connected with the diazotization reaction area and is used for cleaning the n continuous flow reactors which are sequentially connected in series.
In the present invention, the reduction reaction may be performed in the reduction reaction zone. The reduction reaction may be a reduction reaction in a p-chlorophenylhydrazine hydrochloride synthesis process conventional in the art. Preferably, the reduction reaction is carried out in the m reduction reaction units and the 2 continuous flow reactors.
In the reduction reaction zone, diazonium salt intermediate liquid inlets are arranged on m reduction reaction kettles in m reduction reaction units. Preferably, the diazonium salt intermediate liquid inlet pipeline comprises m diazonium salt intermediate liquid inlet pipelines which are connected in parallel, and the diazonium salt intermediate liquid inlet pipelines are 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 further 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 reduction intermediate liquid storage tank in sequence through a reduction 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 be subjected to hydrolysis reaction. The hydrolysis reaction may be that in the art conventional p-chlorophenylhydrazine hydrochloride synthesis process. 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 reduction intermediate liquid inlet is arranged on the hydrolysis reaction kettle and is used for being connected with a liquid storage outlet on the reduction intermediate liquid storage tank, and a reduction intermediate solution is input into the hydrolysis reaction kettle; the hydrochloric acid liquid inlet is used for inputting hydrochloric acid solution into the hydrolysis reaction kettle; and a hydrolysis reaction liquid outlet for inputting the hydrolysis reaction liquid into the first continuous flow reactor among the 4 continuous flow reactors.
And a product outlet for outputting p-chlorophenylhydrazine hydrochloride can be arranged on the fourth continuous flow reactor in the 4 continuous flow reactors.
In the present invention, the continuous flow reactor may be any one or more reactors that can realize 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 p-chlorophenylhydrazine hydrochloride continuous flow reaction system can also comprise a slurry delivery pump and a diaphragm metering pump.
And the slurry conveying pump and the diaphragm metering pump are respectively and sequentially arranged on the p-chloroaniline acid aqueous solution feeding pipeline, the sodium nitrite aqueous solution feeding pipeline, the diazonium salt intermediate liquid feeding pipeline, the reducing agent liquid feeding pipeline and the hydrochloric acid liquid feeding pipeline.
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 p-chlorophenylhydrazine hydrochloride continuous flow reaction system can also comprise a heat conducting oil heating device.
Preferably, the conduction oil heating device is connected with the diazotization reaction area, the reduction reaction area and the hydrolysis reaction area respectively through a conduction oil liquid inlet pipeline and a conduction oil liquid outlet pipeline and is used for heating the continuous flow reactor. Wherein, the heat conduction oil can be recycled.
The application method of the parachlorophenylhydrazine hydrochloride continuous flow reaction system can comprise the following steps: inputting heat conducting oil into the diazotization reaction region through the heat conducting oil liquid inlet pipeline, and continuously inputting an aqueous solution of p-chloroaniline acid and an aqueous solution of sodium nitrite into the diazotization reaction region through the aqueous solution of p-chloroaniline acid and the aqueous solution of sodium nitrite respectively to carry out diazotization reaction to obtain a diazonium salt intermediate solution;
inputting heat conducting oil into the reduction reaction zone and the hydrolysis reaction zone respectively through the heat conducting oil liquid inlet pipeline, and continuously inputting diazonium salt intermediate solution and reducing agent into the reduction reaction zone respectively through the diazonium salt intermediate liquid inlet pipeline and the reducing agent liquid inlet pipeline for reduction reaction to obtain a reduction intermediate solution; and continuously inputting the hydrochloric acid solution into the hydrolysis reaction zone through the hydrochloric acid liquid inlet pipeline to carry out hydrolysis reaction to obtain the p-chlorophenylhydrazine hydrochloride.
Preferably, the para-chloroaniline acid aqueous solution and the sodium nitrite aqueous solution are respectively and continuously input into the first continuous flow reactor for reaction through the para-chloroaniline acid aqueous solution feeding pipeline and the sodium nitrite aqueous solution feeding pipeline, and after the reaction is completed, the para-chloroaniline acid aqueous solution and the sodium nitrite aqueous solution enter the next continuous flow reactor for reaction until the para-chloroaniline acid aqueous solution and the sodium nitrite aqueous solution enter the n continuous flow reactor for reaction, and after the reaction is completed, the reaction solution enters the diazonium salt intermediate solution liquid storage tank through the diazonium salt intermediate discharging pipeline.
Preferably, the diazonium salt intermediate solution and the reducing agent are respectively and continuously input into the first reduction reaction unit for reaction through the diazonium salt intermediate liquid inlet pipeline and the reducing agent liquid inlet pipeline, after the reaction is finished, the first reduction reaction liquid 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 liquid enters the 2 continuous flow reactors which are sequentially connected in series for reaction, after the reaction is finished, the reducing intermediate solution enters the plate heat exchanger, then enters the reducing intermediate liquid storage tank, and is input into the hydrolysis reaction kettle through the liquid storage outlet.
Preferably, hydrochloric acid solution is continuously input into the hydrolysis reaction kettle through the hydrochloric acid liquid inlet pipeline, hydrolysis reaction is carried out on the hydrochloric acid solution and the reduction intermediate solution, p-chlorophenylhydrazine hydrochloride is obtained, 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, such as sodium sulfite solution.
On the basis of conforming to the common knowledge in the field, the above preferred conditions can be arbitrarily combined to obtain the preferred examples of the invention.
The reagents and materials used in the present invention are commercially available.
The invention has the positive progress effects that:
(1) The p-chlorophenylhydrazine hydrochloride continuous flow reaction system overcomes the defects of long reaction time, low yield, large 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 p-chlorophenylhydrazine hydrochloride continuous flow reaction system has the advantages of few operation steps, simple process and high stability.
(3) The p-chlorophenylhydrazine hydrochloride continuous flow reaction system can be used for industrial production and has high production efficiency; meanwhile, the p-chlorophenylhydrazine hydrochloride prepared by adopting the p-chlorophenylhydrazine hydrochloride continuous flow reaction system does not contain diazonium amino compounds or reaction byproducts such as reduction reaction intermediates; in addition, when the p-chlorophenylhydrazine hydrochloride continuous flow reaction system is adopted to prepare the p-chlorophenylhydrazine hydrochloride, no step of removing reaction byproducts such as organic solvent extraction or recrystallization is 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 the continuous flow reaction system of parachlorophenylhydrazine hydrochloride in example 1.
Description of the reference numerals
Diazonium salt intermediate feed liquor pipeline 1
First diazonium salt intermediate feed liquor pipe 11
Second diazonium salt intermediate liquid inlet conduit 12
Third diazonium salt intermediate liquid inlet pipe 13
First diazonium salt intermediate liquid inlet 111
Second diazonium salt intermediate liquid inlet 121
Third diazonium salt intermediate liquid inlet 131
Reducing agent liquid inlet pipeline 2
Reducing agent inlet 21
Hydrochloric acid liquid inlet pipeline 3
Hydrochloric acid inlet 31
Reduction reaction zone 4
First reduction reactor 41
Fifth continuous flow reactor 411
Sixth continuous flow reactor 412
First reaction liquid outlet 413
Second reduction reactor 42
Seventh continuous flow reactor 421
Eighth continuous flow reactor 422
First reduction reaction liquid inlet 423
Third reduction reactor 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 solution outlet 437
Reduction intermediate solution inlet 471
Plate heat exchanger 44
Reduction intermediate liquid storage tank 45
Liquid storage inlet 451
Liquid storage outlet 452
Hydrolysis reaction zone 5
Hydrolysis reactor 51
Thirteenth continuous flow reactor 511
Fourteenth continuous flow reactor 512
Fifteenth continuous flow reactor 513
Sixteenth continuous flow reactor 514
Reduction intermediate feed 515
Hydrolysis reaction liquid outlet 516
Product outlet 6
A p-chloroaniline acid aqueous solution feed line 7;
first slurry transfer pump 71
First diaphragm metering pump 721
Second diaphragm metering pump 722
First feed inlet 73
Sodium nitrite aqueous solution feed pipe 8
Second slurry transfer pump 81
Third diaphragm metering pump 821
Fourth diaphragm metering pump 822
Second feed inlet 83
Diazotisation 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 conduit 10
Diazonium salt intermediate solution discharge port 101
Diazonium salt intermediate solution reservoir 14
Diazonium salt intermediate solution inlet 141
Diazonium salt intermediate solution outlet 142
Conduction oil heating device 15
Conduction oil liquid inlet pipe 151
Conduction oil outlet pipe 152
Water storage tank 16
Detailed Description
The invention is further illustrated by means of the following examples, which are not intended to limit the scope of the invention. The experimental methods, in which specific conditions are not noted in the following examples, were selected according to conventional methods and conditions, or according to the commercial specifications.
Example 1
The continuous flow reaction system of the parachloroaniline hydrochloride in the embodiment 1 is shown in fig. 1, and comprises a parachloroaniline acid aqueous solution feeding pipeline 7, a sodium nitrite aqueous solution feeding pipeline 8, a diazotization reaction zone 9, a diazonium salt intermediate discharging pipeline 10, a diazonium salt intermediate solution liquid storage tank 14, a diazonium salt intermediate liquid feeding pipeline 1, a reducing agent liquid feeding pipeline 2, a reduction reaction zone 4, a hydrochloric acid feeding pipeline 3, a hydrolysis reaction zone 5 and a product liquid outlet 6;
wherein the diazotization reaction zone 9 comprises 4 continuous flow reactors which are sequentially connected in series;
the parachloroaniline acid aqueous solution feeding pipe 7 and the sodium nitrite aqueous solution feeding pipe 8 are respectively connected with a first continuous flow reactor 91 in the diazotization reaction area 9;
a fourth continuous flow reactor 94 in the diazotization reaction region 9 is connected with a diazonium salt intermediate discharging pipeline 10 and a diazonium salt intermediate solution liquid storage tank 14 in sequence;
the diazonium salt intermediate solution liquid 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 zone 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 sequentially connected;
the first reduction reaction unit, the second reduction reaction unit and the third reduction reaction unit comprise 1 reduction reaction kettle and 2 continuous flow reactors which are sequentially connected in series;
hydrolysis reaction zone 5 comprises hydrolysis reaction kettle 51 and 4 continuous flow reactors;
the reduction intermediate liquid tank 45 is connected in series with the hydrolysis reaction vessel 51, thirteenth continuous flow reactor 511, fourteenth continuous flow reactor 512, fifteenth continuous flow reactor 513, sixteenth continuous flow reactor 514 in this order.
The diazotisation reaction in example 1 is a diazotisation mixing reaction.
The diazotization reaction is performed in 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, which are sequentially connected in series in the diazotization reaction region 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 an upper portion of the first continuous flow reactor 91. The second feed port 83 is provided in the lower portion of the first continuous flow reactor 91.
Wherein the supply line 7 for the aqueous solution of para-chloroaniline is connected to the first continuous flow reactor 91 through the first feed port 73 for supplying the aqueous solution of para-chloroaniline to the diazotization reaction zone 9. The sodium nitrite aqueous solution feed pipe 8 is connected to the first continuous flow reactor 91 through the second feed port 83 for feeding the sodium nitrite aqueous solution into the diazotization reaction region 9.
The fourth continuous flow reactor 94 is provided with a diazonium salt intermediate solution outlet 101. A diazonium salt intermediate solution outlet 101 is provided in the upper portion of the fourth continuous flow reactor 94.
Wherein diazonium salt intermediate discharge conduit 10 is coupled to fourth continuous flow reactor 94 through diazonium salt intermediate solution discharge port 101.
In example 1, a diazonium salt intermediate solution reservoir 14 was used to store the diazonium salt intermediate solution obtained from the diazotisation reaction. The diazonium salt intermediate solution reservoir 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 to the diazonium salt intermediate discharge conduit 10.
The p-chlorophenylhydrazine hydrochloride continuous flow reaction system of example 1 also includes a water storage tank 16. The water storage tank 16 is connected to the diazotization reaction region 9 for cleaning 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 which are sequentially connected in series.
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 parachlorophenylhydrazine 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 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 respectively.
Wherein, the first reduction reaction kettle 41 in the first reduction reaction unit is also provided with a reducing agent liquid inlet 21 for inputting 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 tank 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 in series through the reduction reaction liquid outlet 437.
The eleventh and twelfth continuous flow reactors 46 and 47 are connected in sequence to the plate heat exchanger 44 and the reducing intermediate liquid reservoir 45 through the reducing intermediate solution inlet 471.
Wherein the reducing intermediate liquid tank 45 is provided with a liquid storage inlet 451 and a liquid storage outlet 452. The liquid storage inlet 451 is connected to the plate heat exchanger 44. The liquid storage outlet 452 is connected with the hydrolysis reaction kettle 51.
In example 1, hydrolysis reaction zone 5 was subjected to hydrolysis reaction. The hydrolysis reaction is that in the synthesis process of the p-chlorophenylhydrazine hydrochloride. The hydrolysis reaction is performed in hydrolysis reaction kettle 51, thirteenth continuous flow reactor 511, fourteenth continuous flow reactor 512, fifteenth continuous flow reactor 513, and sixteenth continuous flow reactor 514.
In the hydrolysis reaction zone 5, a reduction intermediate liquid inlet 515 is arranged on the hydrolysis reaction kettle 51 and is used for being connected with a liquid storage outlet 452 on the reduction intermediate liquid storage tank 45, and a reduction intermediate solution is input 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 outlet 6 is also provided in the sixteenth continuous flow reactor 514 for the output of p-chlorophenylhydrazine hydrochloride.
The continuous flow reactor in example 1 is a microreactor.
The parachlorophenylhydrazine hydrochloride continuous flow reaction system of example 1 further comprises a slurry transfer pump and a diaphragm metering pump.
The first slurry transfer pump 71, and the first diaphragm metering pump 721 and the second diaphragm metering pump 722 which are arranged in parallel are sequentially arranged on the p-chloroaniline acid aqueous solution feeding pipe 7. When one of the diaphragm metering pumps fails, the other diaphragm metering pump may be used.
The second slurry conveying pump 81, the third diaphragm metering pump 821 and the fourth diaphragm metering pump 822 which are arranged in parallel are sequentially arranged on the sodium nitrite aqueous solution feeding pipeline 8. When one of the diaphragm metering pumps fails, the other diaphragm metering pump may be used.
The parachlorophenylhydrazine hydrochloride continuous flow reaction system of example 1 further comprises a conduction oil heating apparatus 15.
The conduction oil heating device 15 is connected to the diazotization reaction region 9 through a conduction oil feed pipe 151 and a conduction oil discharge pipe 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 conduction oil can be recycled.
The method of using the parachlorophenylhydrazine hydrochloride continuous flow reaction system of example 1 comprises the steps of: conducting oil is input into the diazotization reaction region 9 through a conducting oil liquid inlet pipeline 151, and an aqueous solution of p-chloroaniline acid and an aqueous solution of sodium nitrite are respectively and continuously input into the diazotization reaction region 9 through an aqueous solution of p-chloroaniline acid and an aqueous solution of sodium nitrite feeding pipeline 7 and an aqueous solution of sodium nitrite feeding pipeline 8 for diazotization reaction to obtain a diazonium salt intermediate solution;
the method comprises the steps of respectively inputting heat conduction oil into a reduction reaction zone 4 and a hydrolysis reaction zone 5 through heat conduction oil liquid inlet pipelines, and continuously inputting 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 respectively for reduction reaction to obtain a reduction intermediate solution; the hydrochloric acid solution is continuously input into a hydrolysis reaction zone 5 through a hydrochloric acid liquid inlet pipeline 3 for hydrolysis reaction, and p-chlorophenylhydrazine hydrochloride is obtained.
Specifically, the aqueous solution of the para-chloroaniline acid and the aqueous solution of the sodium nitrite are respectively and continuously input into the first continuous flow reactor 91 for reaction through the aqueous solution of the para-chloroaniline acid and the aqueous solution of the sodium nitrite feed pipe 8, after the reaction is completed, the mixture enters the next continuous flow reactor for reaction until the mixture enters the fourth continuous flow reactor 94 for reaction, and after the reaction is completed, the reaction solution enters the diazonium salt intermediate solution liquid storage tank 14 through the diazonium salt intermediate discharge pipe 10.
Continuously inputting diazonium salt intermediate solution and reducing agent into a first reduction reaction unit through a diazonium salt intermediate liquid inlet pipeline 1 and a reducing agent liquid inlet pipeline 2 respectively for reaction, 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 sequentially connected in series for continuous reaction; after the reaction is finished, the reaction solution enters a ninth continuous flow reactor 431 and a tenth continuous flow reactor 432 which are sequentially connected in series, and after the reaction is finished, the reaction solution enters an eleventh continuous flow reactor 46 and a twelfth continuous flow reactor 47 which are sequentially connected in series for continuous reaction; after the reaction is completed, the reduced intermediate solution enters the plate heat exchanger 44, then enters the reduced intermediate liquid storage tank 45, and is input into the hydrolysis reaction kettle 51 through the liquid storage outlet 452.
Hydrochloric acid solution is continuously input into a hydrolysis reaction kettle 51 through a hydrochloric acid liquid inlet pipeline 3, hydrolysis reaction is carried out on the hydrochloric acid solution and the reduction intermediate solution, p-chlorophenylhydrazine hydrochloride is obtained, and the p-chlorophenylhydrazine hydrochloride is output through a product liquid outlet 6.
Wherein the reducing agent is sodium sulfite solution.
The parachlorophenylhydrazine hydrochloride continuous flow reaction system in the embodiment 1 overcomes the defects that the batch process has long reaction time, low yield and large industrialization difficulty and cannot realize large-scale continuous production, can stably run, has the reaction time of less than 10 minutes, reduces the energy consumption, saves the cost, and has no problems of wastewater treatment, environmental pollution and the like. In addition, the p-chlorophenylhydrazine hydrochloride continuous flow reaction system in the embodiment 1 has the advantages of few operation steps, simple process and high stability. Further, the parachlorophenylhydrazine hydrochloride continuous flow reaction system in the embodiment 1 can be used for industrial production, and the production efficiency is high; meanwhile, the p-chlorophenylhydrazine hydrochloride prepared by adopting the p-chlorophenylhydrazine hydrochloride continuous flow reaction system in the embodiment 1 does not contain diazonium amino compounds or reaction byproducts such as reduction reaction intermediates; in addition, when the parachlorophenylhydrazine hydrochloride is prepared by adopting the parachlorophenylhydrazine hydrochloride continuous flow reaction system in the embodiment 1, no step of removing reaction byproducts such as organic solvent extraction or recrystallization is included in the reaction process or the treatment of reaction products, thus the parachlorophenylhydrazine hydrochloride with the purity of up to 99.9 percent can be prepared, and equipment, reagents and time required by the purification process are saved.
Claims (24)
1. The continuous flow reaction system for the parachloroaniline hydrochloride is characterized by comprising a parachloroaniline acid 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 liquid storage tank, a diazonium salt intermediate liquid feeding pipeline, a reducing agent liquid feeding pipeline, a reduction reaction area, a hydrochloric acid liquid feeding pipeline, a hydrolysis reaction area and a product liquid outlet;
wherein the diazotization reaction area comprises n continuous flow reactors which are sequentially connected in series; n is more than or equal to 4;
the para-chloroaniline acid aqueous solution feeding pipeline and the sodium nitrite aqueous solution feeding pipeline are respectively connected with a first continuous flow reactor in the diazotization reaction region; the first continuous flow reactor is provided with a first feed inlet and a second feed inlet; the first feeding port is arranged at the upper part of the first continuous flow reactor; the second feeding port is arranged at the lower part of the first continuous flow reactor; the diazotisation reaction is carried out in the diazotisation reaction zone; the p-chloroaniline acid aqueous solution feeding pipeline is connected with the first continuous flow reactor through the first feeding port; the sodium nitrite aqueous solution feeding pipeline is connected with the first continuous flow reactor through the second feeding port;
an nth continuous flow reactor in the diazotization reaction region is sequentially connected with the diazonium salt intermediate discharging pipeline and the diazonium salt intermediate solution liquid storage tank;
the diazonium salt intermediate solution liquid 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 zone; 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;
in the reduction reaction zone, diazonium salt intermediate liquid inlets are arranged on m reduction reaction kettles in m reduction reaction units;
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 p-chlorophenylhydrazine hydrochloride continuous flow reaction system of claim 1, wherein the nth continuous flow reactor is provided with a diazonium salt intermediate solution outlet; and the diazonium salt intermediate discharging pipeline is connected with the nth continuous flow reactor through the diazonium salt intermediate solution discharging port.
3. The continuous flow p-chlorophenylhydrazine hydrochloride reaction system of claim 1, wherein the diazonium salt intermediate solution reservoir is provided with a diazonium salt intermediate solution inlet and a diazonium salt intermediate solution outlet.
4. The continuous flow reaction system of p-chlorophenylhydrazine hydrochloride according to claim 2,
the diazonium salt intermediate solution discharge port is arranged at the upper part of the nth continuous flow reactor; the n=4.
5. The continuous flow reaction system of parachlorophenylhydrazine hydrochloride according to claim 3,
and the diazonium salt intermediate solution inlet is connected with the diazonium salt intermediate discharging pipeline.
6. The continuous flow p-chlorophenylhydrazine hydrochloride reaction system of claim 1, comprising a water storage tank connected to the diazotisation reaction zone for cleaning the n consecutive series of continuous flow reactors.
7. The continuous flow p-chlorophenylhydrazine hydrochloride reaction system of claim 1, wherein a reduction reaction is carried out in said reduction reaction zone;
and/or the diazonium salt intermediate liquid inlet pipeline comprises m diazonium salt intermediate liquid inlet pipelines which are connected in parallel and are respectively used for inputting diazonium salt intermediate solutions into the m reduction reaction kettles.
8. The continuous flow p-chlorophenylhydrazine hydrochloride reaction system of claim 7, wherein the reduction reaction is carried out in the m reduction reaction units and the 2 continuous flow reactors.
9. The continuous flow reaction system of p-chlorophenylhydrazine hydrochloride according to claim 1, wherein a reducing agent inlet is provided on a first reduction reactor in a first reduction reaction unit for inputting a reducing agent into the first reduction reactor; and a first reaction liquid outlet for inputting the reaction liquid into the first continuous flow reactor in the first reduction reaction unit.
10. The continuous flow reaction system of parachlorophenylhydrazine hydrochloride according to claim 1, wherein the second continuous flow reactor in the first reduction reaction unit is connected to the second reduction reaction kettle in the second reduction reaction unit through the first reduction reaction liquid inlet; the m-th reduction reaction unit is connected with the 2 continuous flow reactors through a reduction reaction liquid outlet.
11. The p-chlorophenylhydrazine hydrochloride continuous flow reaction system of claim 10, wherein the 2 continuous flow reactors are connected in series with the plate heat exchanger and the reducing intermediate reservoir via a reducing intermediate solution inlet.
12. The continuous flow reaction system of p-chlorophenylhydrazine hydrochloride according to claim 1, wherein the reduction intermediate reservoir is provided with a reservoir inlet and a reservoir outlet, the reservoir inlet being connected to the plate heat exchanger; the liquid storage outlet is connected with the hydrolysis reaction kettle.
13. The continuous flow reaction system of p-chlorophenylhydrazine hydrochloride according to claim 1, wherein in the hydrolysis reaction zone, a reducing intermediate liquid inlet is arranged on the hydrolysis reaction kettle and is used for being connected with a liquid storage outlet on the reducing intermediate liquid storage tank, and reducing intermediate solution is input into the hydrolysis reaction kettle; the hydrochloric acid liquid inlet is used for inputting hydrochloric acid solution into the hydrolysis reaction kettle; and a hydrolysis reaction liquid outlet for inputting a hydrolysis reaction liquid into a first continuous flow reactor among the 4 continuous flow reactors; and 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.
14. The continuous flow reaction system of p-chlorophenylhydrazine hydrochloride according to claim 1,
the continuous flow reactor is one or more of a microreactor, a tubular reactor, a cascade mixer and a static mixer.
15. The continuous flow p-chlorophenylhydrazine hydrochloride reaction system of claim 14, wherein the continuous flow reactor is a microreactor.
16. The continuous flow p-chlorophenylhydrazine hydrochloride reaction system of claim 1, wherein the continuous flow p-chlorophenylhydrazine hydrochloride reaction system comprises a slurry transfer pump and a diaphragm metering pump.
17. The continuous flow reaction system of p-chlorophenylhydrazine hydrochloride according to claim 1,
the p-chlorophenylhydrazine hydrochloride continuous flow reaction system comprises a heat conducting oil heating device.
18. The continuous flow reaction system of parachloroaniline hydrochloride according to claim 16, wherein the slurry transfer pump and the diaphragm metering pump are respectively and sequentially arranged on the parachloroaniline acid aqueous solution feeding pipeline, the sodium nitrite aqueous solution feeding pipeline, the diazonium salt intermediate liquid feeding pipeline, the reducing agent liquid feeding pipeline and the hydrochloric acid liquid feeding pipeline.
19. The p-chlorophenylhydrazine hydrochloride continuous flow reaction system of claim 17, wherein the conduction oil heating apparatus is separately connected to the diazotization reaction zone, the reduction reaction zone, and the hydrolysis reaction zone by a conduction oil feed conduit and a conduction oil exit conduit for heating a continuous flow reactor.
20. The continuous flow p-chlorophenylhydrazine hydrochloride reaction system of claim 18, wherein the diaphragm metering pump is two diaphragm metering pumps arranged in parallel.
21. A method of using the parachlorophenylhydrazine hydrochloride continuous flow reaction system of any one of claims 1 to 20, comprising the steps of: inputting heat conduction oil into the diazotization reaction region through a heat conduction oil liquid inlet pipeline, and continuously inputting an aqueous solution of p-chloroaniline acid and an aqueous solution of sodium nitrite into the diazotization reaction region through the aqueous solution of p-chloroaniline acid and the aqueous solution of sodium nitrite respectively to carry out diazotization reaction to obtain a diazonium salt intermediate solution;
the method comprises the steps of respectively inputting heat conduction oil into a reduction reaction zone and a hydrolysis reaction zone through heat conduction oil liquid inlet pipelines, and continuously inputting diazonium salt intermediate solution and reducing agent into the reduction reaction zone through diazonium salt intermediate liquid inlet pipelines and reducing agent liquid inlet pipelines respectively for reduction reaction to obtain a reduction intermediate solution; and continuously inputting the hydrochloric acid solution into the hydrolysis reaction zone through the hydrochloric acid liquid inlet pipeline to carry out hydrolysis reaction to obtain the p-chlorophenylhydrazine hydrochloride.
22. The method of claim 21, wherein the aqueous solution of p-chloroaniline hydrochloride and the aqueous solution of sodium nitrite are continuously fed into the first continuous flow reactor in the diazotization reaction zone through the feeding pipeline of the aqueous solution of p-chloroaniline hydrochloride and the feeding pipeline of the aqueous solution of sodium nitrite respectively for reaction, and after the reaction is completed, the mixture is fed into the next continuous flow reactor for reaction until the mixture is fed into the nth continuous flow reactor for reaction, and after the reaction is completed, the mixture is fed into the diazonium salt intermediate solution liquid storage tank through the discharging pipeline of the diazonium salt intermediate.
23. The method of claim 21, wherein the diazonium salt intermediate solution and the reducing agent are continuously fed into the first reduction reaction unit through the diazonium salt intermediate liquid inlet pipeline and the reducing agent liquid inlet pipeline respectively, after the reaction is completed, the first reduction reaction liquid enters the second reduction reaction unit to the nth reduction reaction unit which are sequentially connected in series to react, after the reaction is completed, the nth reduction reaction liquid enters the 2 continuous flow reactors which are sequentially connected in series to react, after the reaction is completed, the reduction intermediate solution enters the plate heat exchanger, then enters the reduction intermediate liquid storage tank and is fed into the hydrolysis reaction kettle through the liquid storage outlet.
24. The method of claim 21, wherein the hydrochloric acid solution is continuously fed into the hydrolysis reactor through the hydrochloric acid feed pipe, and the hydrochloric acid solution and the reducing intermediate solution undergo hydrolysis reaction to obtain p-chlorophenylhydrazine hydrochloride, and the p-chlorophenylhydrazine hydrochloride is output through the product outlet.
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| DE1148236B (en) * | 1958-11-27 | 1963-05-09 | Hoechst Ag | Process for the continuous production of phenols by boiling diazonium salt solutions |
| FR1419092A (en) * | 1963-11-28 | 1965-11-26 | Basf Ag | Process for continuous diazotization of amines |
| CN102993044A (en) * | 2012-12-31 | 2013-03-27 | 天津市天川化工有限公司 | Preparation method of 4-chlorophenylhydrazine hydrochloride |
| CN104744295B (en) * | 2015-03-23 | 2016-11-23 | 浙江工业大学 | The method of the adjacent ethylo benzene hydrazine hydrochloride of pipelineization preparation and device thereof |
| 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 |
| CN107663161B (en) * | 2016-07-27 | 2020-04-10 | 上海惠和化德生物科技有限公司 | Continuous flow synthesis process of phenylhydrazine salt and substituted phenylhydrazine salt |
| CN206980725U (en) * | 2017-07-13 | 2018-02-09 | 启东亚太化工厂有限公司 | A kind of diazo-reaction device for producing phenylhydrazine hydrochloride |
| CN107573256B (en) * | 2017-09-26 | 2020-02-21 | 安徽国星生物化学有限公司 | Continuous production method and device for p-chlorophenylhydrazine hydrochloride |
| CN213699808U (en) * | 2020-11-10 | 2021-07-16 | 上海惠和化德生物科技有限公司 | P-chlorophenylhydrazine hydrochloride continuous flow reaction system |
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