CN106699526A - Method of preparing 2,4-dichlorobenzaldehyde through continuous oxidation of 2,4-dichlorotoluene - Google Patents
Method of preparing 2,4-dichlorobenzaldehyde through continuous oxidation of 2,4-dichlorotoluene Download PDFInfo
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- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
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Abstract
The invention relates to a method of preparing 2,4-dichlorobenzaldehyde through continuous oxidation of 2,4-dichlorotoluene, and belongs to the technical field of organic synthetic process. The method includes the steps that a 2,4-dichlorotoluene compound is used as a raw material, one or more metal ion complexes of cobalt, molybdenum and bromine are used as catalysts, hydrogen peroxide is used as an oxidizing agent, acetic acid is used as solvent, and 2,4-dichlorotoluene is continuously oxidized in a tubular reactor to prepare 2,4-dichlorobenzaldehyde. The method is mild in condition, short in reaction time, high in raw material use ratio, safe, stable and high in production efficiency and can achieve effect control in the reaction process and continuous operation.
Description
Technical field
The invention belongs to organic synthesis technology field, it is related to one kind under liquid-phase reaction condition by 2,4-DCT
The method that continuous oxidation prepares 2,4- dichlorobenzaldehydes, is more specifically that, with 2,4-DCT as substrate, hydrogen peroxide is oxidation
Agent, one or more metal ion complexs of cobalt, molybdenum, bromine are catalyst, and monocarboxylic acid is solvent, with different micro-structurals
Tubular reactor in continuously prepare 2,4 dichloro benzene formaldehyde products.
Background technology
2,4- dichlorobenzaldehydes, are very important fine chemicals, and it is the intermediate for synthesizing many important chemicals,
2,4- dichlorobenzaldehydes are used to produce dyestuff intermediate benzaldehyde -2,4- disulfonic acid, and benzaldehyde -2, and 4- disulfonic acid is used to synthesize
Reactive blue K-FGR, acid sky blue A, acid sky blue v, 2,4- dichlorobenzaldehydes are additionally operable to produce agricultural chemicals olefin conversion.As can be seen here,
2,4 dichloro benzene formaldehyde has presented very wide application prospect.But, so far, 2, the 4- dichlorobenzaldehydes of China are needed
Portion demand perfection by import, and it is expensive, largely influence and limit the development of each side.
The synthetic process that current 2,4 dichloro benzene formaldehyde is reported has following several：
(1) synthetic route with 2,4 di chloro toluene as raw material
The D.A. Xiao Lai in the U.S. were once introduced can produce α by 2,4-DCT through bromination, the bromo- 2,4-DCTs of α-two,
2,4- dichlorobenzaldehydes are produced through single step reaction again, specific course of reaction is as follows：
Although the product yield and purity of above-mentioned route are higher, and synthesis is simple, due to needing a large amount of few valencys of consumption thing
High bromine, this is just difficult to industrially realize large-scale application.
(2) chlorination reaction on side chain
Black grace into et al. in study on the synthesis, it is contemplated that raw material, catalyst and industrialized possibility, also employ directly
The method that chlorination is hydrolyzed again, specific reaction method is as follows：
The above method in process of production, it is necessary to strictly control chlorination depth, in case the generation of side reaction；And
In the production of two steps, it is necessary to strict control reaction temperature and time, too harsh to reaction condition, it is difficult to industrially, really
Implement.
Approach described above prepares 2,4 dichloro benzene formaldehyde and optimizes to 2,4 di chloro toluene oxidation from different angles
And improvement, but still suffer from some problems need solve：It is still main using the production of batch still batch first in large-scale production；Its
Secondary a large amount of of catalyst use in process of production, the control of chlorination degree and the monitoring of subsequent reactions, all to industrialized production
Propose strict requirements.And closed using the continuous oxidation that the continuous flow tubular reactor of ad hoc structure carries out 2,4 di chloro toluene
Into 2,4- dichlorobenzaldehydes, can many-sided many deficiencies for solving existing process technology.
Tubular reactor is the general designation of the mini-reactor with micro-structural, compared with conventional reactor, tubular reactor
With small volume, specific surface area is big, easily amplifies, and process is continuous, and quick good mixing effect, heat-transfer effect is good, high temperature high voltage resistant etc.
Feature, the continuous flow tubular reactor using ad hoc structure can have to the mixing of reaction mass and mass transfer, diabatic process
Effect control.By the control of length and reaction time to tubular reactor, can further make the distribution of raw material and product
More optimize controllable；Can realize that substrate 2,4 di chloro toluene enters tubular type in proportion with oxidant by the flow velocity for adjusting raw material pump
Reactor carries out reaction and greatly reduces back-mixing, further reduces the generation of side reaction, and the stability and target of oxidant are produced
The selectivity of thing is also greatly improved；By setting pressure safety valve in tubular reactor, in can in time giving off reactor
Excessive oxidant, it is ensured that the safety of reaction is carried out, and level of significance is minimized.The present invention uses the pipe reaction of ad hoc structure
Device carries out 2,4 di chloro toluene continuous oxidation and prepares the method for 2,4 dichloro benzene formaldehyde relative to conventional batch production method tool
There is unrivaled advantage, and an important approach can be provided for it industrializes quantity-produced improvement.
The content of the invention
The present invention is directed to not enough present on, there is provided one kind is in tubular reactor by the continuous oxygen of 2,4-DCT
The method that change prepares 2,4 dichloro benzene formaldehyde.This method reaction time is short, and production efficiency is high, and mass transfer, heat transfer are optimized significantly,
Course of reaction is more stablized controllable.Further object of the present invention is, by process of the invention, realizes 2,4- bis-
Stablizing for chlorotoluene continuous oxidation is controllable, reduces the generation of accessory substance.Carried by the reinforcing and process optimization of mass-and heat-transfer process
The effective rate of utilization of reaction mass high, further reduces the usage amount of oxidant and catalyst and avoids during the course of the reaction
The use of co-catalyst, so that effectively save production cost and then the existing industrialized preparing process of improvement.
To achieve the above object, the technical solution adopted by the present invention is：
2,4 di chloro toluene continuous oxidation is prepared 2,4 dichloro benzene formaldehyde by a kind of tubular reactor of use special construction
Method, carry out as steps described below：
(1) first at room temperature, by substrate 2,4-DCT and part carboxylic acid solvent with volume ratio 1:1 stirring mixing is equal
It is even, by oxidant and part carboxylic acid solvent with volume ratio 1:1 is well mixed, and then mixes metal complex and pours into 2,4- dichloros
Toluene-carboxylic acid solution, sodium salt is poured into hydrogen peroxide-carboxylic acid solution；By the required reaction time, two kinds of materials are calculated
It is different in flow rate, continuously squeezed into tubular reactor through measuring pump reacted into reaction zone after preheated mixing respectively, instead
Temperature is answered to be controlled by outer loop heat-exchange system；
(2) mol ratio of reaction mass is controlled by adjusting the method for flow velocity and weight calculation, by changing tubular reactor
0.5~15mm of internal diameter of the pipeline, 25~750ml of volume carry out the 60~1800s of residence time of control material hybrid reaction；Reacting
Cheng Hou, product exits into collecting tank from reactor end, and product rectification is separated, and unreacted 2,4-DCT circulation is anti-
Should, product 2,4- dichlorobenzaldehyde rectifying is collected after purification, wherein target product 2, and the yield of 4- dichlorobenzaldehydes is up to 20%
~35%.
Wherein described catalyst is cobalt, molybdenum, bromine one or more metal complex catalysts, and it mainly includes：Acetic acid
Cobalt, cobalt oxalate, cobalt carbonate, cobalt naphthenate, sodium molybdate, ammonium molybdate, sodium bromide, ammonium bromide etc., wherein being with oil-soluble catalyst
It is main, can fully be dissolved in 2,4-DCT, the mol ratio of its consumption and substrate 2,4-DCT is in (0.001~0.15)
: 1, wherein preferred molar ratio is (0.01~0.08): 1.
Wherein described oxidant is hydrogen peroxide, and its solution concentration is calculated as 5%~80% with mass concentration, and preferred concentration is
5%~60%.Hydrogen peroxide is (1.0~8.0) with the preferred molar ratio of substrate 2,4 di chloro toluene: 1.
Wherein described hydrogen peroxide, in tubular reactor, when hydrogen peroxide passes through reactor volume 50ml, hydrogen peroxide
Start it is rapid decompose, discharge a large amount of molecular oxygens, when it passes through 100ml, almost molecular oxygen form now should be anti-in 100ml
Answer the hydrogen peroxide that isoconcentration is additionally supplemented at volume to enter, reaction is participated in again.
Wherein described carboxylic acid solvent includes:Formic acid, acetic acid, propionic acid, butyric acid, caproic acid, octanoic acid etc..Wherein solvent and 2,4-
The volume ratio of dichlorotoleune is in (1~15): 1.
Wherein described reaction temperature is 60~160 DEG C, and preferable reaction temperature is 100~135 DEG C, and reaction time is
60s~1800s.
In further technical scheme, the oxidant for having neither part nor lot in reaction is first quenched with dichloromethane sodium after completion of the reaction,
Then extracted by organic solvent, separated obtains target product after purification.
In above-mentioned technical proposal, the described reaction system difference in functionality such as including raw material storage tank, reaction zone, collection of products area
Region.Channel of reactor structure includes：Pipe once-through type channel design, cake formula pulse diameter varied narrow rectangular tube road structure, tiltedly
Square cake formula pulse diameter varied narrow rectangular tube road structure, enhancing mixed type cake formula narrow rectangular tube road structure and Corning's
Heart Cell channel designs.
The present invention has advantages below：
1st, the present invention uses a kind of mode of production of serialization, and the reaction time is short, and reaction condition is gentle, and process safety can
Control, production efficiency is high.
2nd, the present invention is capable of achieving the effective control to course of reaction by the tubular reactor made using different structure, makes
Product rests on the step of aldehyde alcohol one.
3rd, by the way that the utilization rate of its reaction rate and raw material greatly improved to mass transfer in course of reaction, heat transfer intensification,
And the usage amount of oxidant and catalyst is effectively reduced, and the use of co-catalyst is avoided, there is production cost
Effect is saved.
4th, the present invention is easy to operate, applied widely, and production is flexible, can be advised by the expanding production in parallel of reaction unit
Mould.
Brief description of the drawings
Fig. 1 is the process chart that 2,4 di chloro toluene continuous oxidation of the present invention prepares 2,4 dichloro benzene formaldehyde.
Fig. 2 is continuous flow tubular reactor installation drawing used in the present invention：1st, 2- head tanks, 3,4- raw material measuring pumps,
5- preheating zones, 6,7- reaction zones, 8- products are quenched collecting region.
Fig. 3 is tubular reactor channel design schematic diagram used in the present invention, wherein a- once-through types channel design, b- circles
Cake formula pulse diameter varied narrow rectangular tube road, the oblique side cake formula pulse diameter varied narrow rectangular tube roads of c-, d- enhancings mixed type cake formula is flat
Pipeline, the Heart Cell structures microchannel of e-Corning.
Specific embodiment
Cobalt acetate and sodium molybdate are dissolved in the 1# tanks equipped with 2,4-DCT and acetic acid, being pumped into 5# by 3# preheats
In reactor, pre- thermal reactor is heated to 50 DEG C；Sodium bromide is dissolved in the 2# tanks equipped with hydrogen peroxide and acetic acid, is pumped by 4#
Enter in the pre- thermal reactors of 6#, pre- thermal reactor is heated to 50 DEG C, then by two strands of preheating materials, be delivered in 7#, 8# reactor,
Temperature of reactor is set in temperature needed for reaction, and product flows out by 8# reactors, using 0 DEG C of cooling, collects products therefrom.
The present invention is described in detail with reference to embodiment, but the following examples are only the present invention preferably implementation method,
Protection scope of the present invention is not limited thereto, technology model of any one skilled in the art in present disclosure
In enclosing, technology according to the present invention scheme and its inventive concept are subject to equivalent substitute or change, should all cover in guarantor of the invention
Within the scope of shield.
Embodiment 1
(1) device：Reference picture 2 determines the connected mode of tubular reactor, and conduit types are：(3a+3b) once-through type passage+
Cake formula pulse diameter varied narrow rectangular tube road, internal diameter of the pipeline is with volume according to flow velocity and reaction time determination, heat transferring medium
It is conduction oil.
(2) 1.01g cobalt acetates and 1.01g sodium molybdates are dissolved in 200ml2,4- dichlorotoleune and 200ml acetic acid shapes respectively
Into mixed solution, now n (cobalt acetate)：N (2,4 di chloro toluene)=0.0025:1,1.01g sodium bromides are dissolved in 15%H2O2
Form H2O2- acetic acid solution, now n (sodium bromide)：N (2,4 di chloro toluene)=0.0025:1,2,4-DCT-acetic acid is molten
Liquid and and H2O2- acetic acid solution injects lasting heat exchange with the flow velocity of 5.33ml/min and 10.67ml/min by constant flow pump respectively
In tubular reactor, now n (H2O2)：N (2,4 di chloro toluene)=2:1, using Fig. 2 micro passage reactions, controlling reaction temperature
60 DEG C, residence time 60s.0 DEG C of cooling of outlet material, reaction solution is quenched with dichloromethane.Analyzed by GC, 2,4-DCT
Conversion ratio is 45.3%, and 2,4- dichlorobenzaldehyde yields are 23.1%.
Embodiment 2
(1) device：Reference picture 2 determines the connected mode of tubular reactor, and conduit types are：(3a+3c) once-through type passage+
Oblique side cake formula pulse diameter varied narrow rectangular tube road, internal diameter of the pipeline determines according to flow velocity and reaction time with volume, exchanges heat and be situated between
Matter is conduction oil.
(2) 6.06g cobalt acetates and 6.06g sodium molybdates are dissolved in 200ml2,4- dichlorotoleune and 200ml acetic acid shapes respectively
Into mixed solution, now n (cobalt acetate)：N (2,4 di chloro toluene)=0.015:1,6.06g sodium bromides are dissolved in 15%H2O2
Form H2O2- acetic acid solution, now n (sodium bromide)：N (2,4 di chloro toluene)=0.015:1,2,4-DCT-acetic acid solution
With and H2O2- acetic acid solution injects the pipe of lasting heat exchange with the flow velocity of 8.33ml/min and 16.67ml/min by constant flow pump respectively
In formula reactor, now n (H2O2)：N (2,4 di chloro toluene)=3:1, using Fig. 2 micro passage reactions, controlling reaction temperature 75
DEG C, residence time 200s.0 DEG C of cooling of outlet material, reaction solution is quenched with dichloromethane.Analyzed by GC, 2,4-DCT
Conversion ratio is 50.0%, and 2,4- dichlorobenzaldehyde yields are 28.7%.
Embodiment 3
(1) device：Reference picture 2 determines the connected mode of tubular reactor, and conduit types are：(3a+3d) once-through type passage+
Enhancing mixed type cake formula narrow rectangular tube road, internal diameter of the pipeline is with volume according to flow velocity and reaction time determination, heat transferring medium
It is conduction oil.
(2) 6.06g cobalt acetates and 6.06g sodium molybdates are dissolved in 200ml2,4- dichlorotoleune and 200ml acetic acid shapes respectively
Into mixed solution, now n (cobalt acetate)：N (2,4 di chloro toluene)=0.015:1,6.06g sodium bromides are dissolved in 15%H2O2
Form H2O2- acetic acid solution, now n (sodium bromide)：N (2,4 di chloro toluene)=0.015:1,2,4-DCT-acetic acid solution
With and H2O2- acetic acid solution injects the pipe of lasting heat exchange with the flow velocity of 8.33ml/min and 16.67ml/min by constant flow pump respectively
In formula reactor, now n (H2O2)：N (2,4 di chloro toluene)=3:1, using Fig. 2 micro passage reactions, controlling reaction temperature 95
DEG C, residence time 300s.0 DEG C of cooling of outlet material, reaction solution is quenched with dichloromethane.Analyzed by GC, 2,4-DCT
Conversion ratio is 45.8%, and 2,4- dichlorobenzaldehyde yields are 28.2%.
Embodiment 4
(1) device：Reference picture 2 determines the connected mode of tubular reactor, and conduit types are：(3a+3b) once-through type passage+
Cake formula pulse diameter varied narrow rectangular tube road, internal diameter of the pipeline is with volume according to flow velocity and reaction time determination, heat transferring medium
It is conduction oil.
(2) 6.06g cobalt acetates and 6.06g sodium molybdates are dissolved in 200ml2,4- dichlorotoleune and 200ml acetic acid shapes respectively
Into mixed solution, now n (cobalt acetate)：N (2,4 di chloro toluene)=0.015:1,6.06g sodium bromides are dissolved in 25%H2O2
Form H2O2- acetic acid solution, now n (sodium bromide)：N (2,4 di chloro toluene)=0.015:1,2,4-DCT-acetic acid solution
With and H2O2- acetic acid solution injects the pipe of lasting heat exchange with the flow velocity of 5.33ml/min and 10.67ml/min by constant flow pump respectively
In formula reactor, now n (H2O2)：N (2,4 di chloro toluene)=2:1, using Fig. 2 micro passage reactions, controlling reaction temperature
100 DEG C, residence time 500s.0 DEG C of cooling of outlet material, reaction solution is quenched with dichloromethane.Analyzed by GC, 2,4- dichloromethanes
Benzene conversion ratio is 51.5%, and 2,4- dichlorobenzaldehyde yields are 28.1%.
Embodiment 5
(1) device：Reference picture 2 determines the connected mode of tubular reactor, and conduit types are：(3a+3c) once-through type passage+
Oblique side cake formula pulse diameter varied narrow rectangular tube road, internal diameter of the pipeline determines according to flow velocity and reaction time with volume, exchanges heat and be situated between
Matter is conduction oil.
(2) 6.06g cobalt acetates and 6.06g sodium molybdates are dissolved in 200ml2,4- dichlorotoleune and 200ml acetic acid shapes respectively
Into mixed solution, now n (cobalt acetate)：N (2,4 di chloro toluene)=0.015:1,6.06g sodium bromides are dissolved in 25%H2O2
Form H2O2- acetic acid solution, now n (sodium bromide)：N (2,4 di chloro toluene)=0.015:1,2,4-DCT-acetic acid solution
With and H2O2- acetic acid solution injects the pipe of lasting heat exchange with the flow velocity of 8.33ml/min and 16.67ml/min by constant flow pump respectively
In formula reactor, now n (H2O2)：N (2,4 di chloro toluene)=3:1, using Fig. 2 micro passage reactions, controlling reaction temperature
105 DEG C, residence time 600s.0 DEG C of cooling of outlet material, reaction solution is quenched with dichloromethane.Analyzed by GC, 2,4- dichloromethanes
Benzene conversion ratio is 41.7%, and 2,4- dichlorobenzaldehyde yields are 30.1%.
Embodiment 6
(1) device：Reference picture 2 determines the connected mode of tubular reactor, and conduit types are：(3a+3d) once-through type passage+
Enhancing mixed type cake formula narrow rectangular tube road, internal diameter of the pipeline is with volume according to flow velocity and reaction time determination, heat transferring medium
It is conduction oil.
(2) 6.06g cobalt acetates and 6.06g sodium molybdates are dissolved in 200ml2,4- dichlorotoleune and 200ml acetic acid shapes respectively
Into mixed solution, now n (cobalt acetate)：N (2,4 di chloro toluene)=0.015:1,6.06g sodium bromides are dissolved in 25%H2O2
Form H2O2- acetic acid solution, now n (sodium bromide)：N (2,4 di chloro toluene)=0.015:1,2,4-DCT-acetic acid solution
With and H2O2- acetic acid solution injects the pipe of lasting heat exchange with the flow velocity of 5.56ml/min and 11.11ml/min by constant flow pump respectively
In formula reactor, now n (H2O2)：N (2,4 di chloro toluene)=2:1, using Fig. 2 micro passage reactions, controlling reaction temperature
135 DEG C, residence time 900s.0 DEG C of cooling of outlet material, reaction solution is quenched with dichloromethane.Analyzed by GC, 2,4- dichloromethanes
Benzene conversion ratio is 35.7%, and 2,4- dichlorobenzaldehyde yields are 20.5%.
Embodiment 7
(1) device：Reference picture 2 determines the connected mode of tubular reactor, and conduit types are：(3a+3e) once-through type passage+
Corningde Heart Cell structures, internal diameter of the pipeline determines that heat transferring medium is with volume according to flow velocity and reaction time
Conduction oil.
(2) 6.06g cobalt acetates and 6.06g sodium molybdates are dissolved in 200ml2,4- dichlorotoleune and 200ml acetic acid shapes respectively
Into mixed solution, now n (cobalt acetate)：N (2,4 di chloro toluene)=0.015:1,6.06g sodium bromides are dissolved in 25%H2O2
Form H2O2- acetic acid solution, now n (sodium bromide)：N (2,4 di chloro toluene)=0.015:1,2,4-DCT-acetic acid solution
With and H2O2- acetic acid solution injects the pipe of lasting heat exchange with the flow velocity of 5.56ml/min and 11.11ml/min by constant flow pump respectively
In formula reactor, now n (H2O2)：N (2,4 di chloro toluene)=2:1, using Fig. 2 micro passage reactions, controlling reaction temperature 90
DEG C, residence time 1200s.0 DEG C of cooling of outlet material, reaction solution is quenched with dichloromethane.Analyzed by GC, 2,4-DCT
Conversion ratio is 35.8%, and 2,4- dichlorobenzaldehyde yields are 20.0%.
Embodiment 8
(1) device：Reference picture 2 determines the connected mode of tubular reactor, and conduit types are：(3a+3d) once-through type passage+
Enhancing mixed type cake formula narrow rectangular tube road, internal diameter of the pipeline is with volume according to flow velocity and reaction time determination, heat transferring medium
It is conduction oil.
(2) 6.06g cobalt acetates and 6.06g sodium molybdates are dissolved in 200ml2,4- dichlorotoleune and 200ml acetic acid shapes respectively
Into mixed solution, now n (cobalt acetate)：N (2,4 di chloro toluene)=0.015:1,6.06g sodium bromides are dissolved in 35%H2O2
Form H2O2- acetic acid solution, now n (sodium bromide)：N (2,4 di chloro toluene)=0.015:1,2,4-DCT-acetic acid solution
With and H2O2- acetic acid solution injects the pipe of lasting heat exchange with the flow velocity of 5.56ml/min and 11.11ml/min by constant flow pump respectively
In formula reactor, now n (H2O2)：N (2,4 di chloro toluene)=2:1, using Fig. 2 micro passage reactions, controlling reaction temperature
150 DEG C, residence time 1500s.0 DEG C of cooling of outlet material, reaction solution is quenched with dichloromethane.Analyzed by GC, 2,4- dichloros
Toluene conversion is 39.9%, and 2,4- dichlorobenzaldehyde yields are 24.1%.
Embodiment 9
(1) device：Reference picture 2 determines the connected mode of tubular reactor, and conduit types are：(3a+3c) once-through type passage+
Oblique side cake formula pulse diameter varied narrow rectangular tube road, internal diameter of the pipeline determines according to flow velocity and reaction time with volume, exchanges heat and be situated between
Matter is conduction oil.
(2) 6.06g cobalt acetates and 6.06g sodium molybdates are dissolved in 200ml2,4- dichlorotoleune and 200ml acetic acid shapes respectively
Into mixed solution, now n (cobalt acetate)：N (2,4 di chloro toluene)=0.015:1,6.06g sodium bromides are dissolved in 35%H2O2
Form H2O2- acetic acid solution, now n (sodium bromide)：N (2,4 di chloro toluene)=0.015:1,2,4-DCT-acetic acid solution
With and H2O2- acetic acid solution injects the pipe of lasting heat exchange with the flow velocity of 5.56ml/min and 11.11ml/min by constant flow pump respectively
In formula reactor, now n (H2O2)：N (2,4 di chloro toluene)=2:1, using Fig. 2 micro passage reactions, controlling reaction temperature
160 DEG C, residence time 1800s.0 DEG C of cooling of outlet material, reaction solution is quenched with dichloromethane.Analyzed by GC, 2,4- dichloros
Toluene conversion is 52.1%, and 2,4- dichlorobenzaldehyde yields are 29.2%.
Claims (6)
1. a kind of method that 2,4-DCT continuous oxidation prepares 2,4- dichlorobenzaldehydes, it is characterised in that as steps described below
Carry out：
（1）At room temperature, by substrate 2,4-DCT and part carboxylic acid solvent with volume ratio 1:1 is uniformly mixed, and will aoxidize
Agent and part carboxylic acid solvent are with volume ratio 1:1 is well mixed, and then mixes metal complex and pours into 2,4-DCT-carboxylic acid
Solution, sodium salt is poured into hydrogen peroxide-carboxylic acid solution；By the required reaction time, two kinds of not cocurrent flows of material are calculated
Speed, continuously squeezes into tubular reactor through measuring pump reacted into reaction zone after preheated mixing respectively, reaction temperature by
Outer loop heat-exchange system is controlled；
（2）The mol ratio of reaction mass is controlled by the method for adjusting flow velocity and weight calculation, by the pipeline for changing tubular reactor
0.5 ~ 15mm of internal diameter, 25 ~ 750ml of volume carrys out the residence time of control material hybrid reaction；After completion of the reaction, product is from reaction
Device end exits into collecting tank, and product rectification is separated, unreacted 2,4-DCT circular response, product 2,4- dichloro-benzenes
Formaldehyde rectification is collected after purification.
2. the method that a kind of 2,4-DCT continuous oxidation according to claims 1 prepares 2,4- dichlorobenzaldehydes,
It is characterized in that described catalyst is cobalt, molybdenum, sodium one or more metal complex catalysts, it mainly includes：Cobalt acetate,
Cobalt oxalate, cobalt carbonate, cobalt naphthenate, sodium molybdate, ammonium molybdate, sodium bromide, ammonium bromide etc., wherein based on oil-soluble catalyst,
Can fully be dissolved in 2,4-DCT, its consumption exists with the mol ratio of substrate 2,4-DCT（0.001~0.15）: 1,
Wherein preferred molar ratio is（0.01~0.08）∶1.
3. the method that a kind of 2,4-DCT continuous oxidation according to claims 1 prepares 2,4- dichlorobenzaldehydes,
It is characterized in that described oxidant is hydrogen peroxide, its solution concentration is calculated as 5% ~ 80% with mass concentration, preferred concentration is 5% ~
60%, hydrogen peroxide is with the preferred molar ratio of substrate 2,4-DCT（1.0~8.0）∶1.
4. the method that a kind of 2,4-DCT continuous oxidation according to claims 1 prepares 2,4- dichlorobenzaldehydes,
It is characterized in that described carboxylic acid solvent includes：Formic acid, acetic acid, propionic acid, butyric acid, caproic acid, octanoic acid；Wherein solvent and 2,4- dichloros
The volume ratio of toluene exists（1~15）∶1.
5. the method that a kind of 2,4-DCT continuous oxidation according to claims 1 prepares 2,4- dichlorobenzaldehydes,
It is characterized in that：Reaction temperature is 60 ~ 160 DEG C, and preferable reaction temperature is 100 ~ 135 DEG C, reaction time 60s ~ 1800s.
6. the method that a kind of 2,4-DCT continuous oxidation according to claims 1 prepares 2,4- dichlorobenzaldehydes,
It is characterized in that total overall reaction process is carried out continuously in the tubular reactor of ad hoc structure, the reaction system is stored up including raw material
The difference in functionality such as tank, reaction zone, collection of products region；Channel of reactor structure includes：Pipe once-through type channel design, cake formula
Pulse diameter varied narrow rectangular tube road structure, tiltedly side cake formula pulse diameter varied narrow rectangular tube road structure, enhancing mixed type cake formula square
The flat pipeline configuration of shape, cardioid channel design.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610972042.0A CN106699526A (en) | 2016-11-07 | 2016-11-07 | Method of preparing 2,4-dichlorobenzaldehyde through continuous oxidation of 2,4-dichlorotoluene |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107051366A (en) * | 2017-06-09 | 2017-08-18 | 山东诺为制药流体系统有限公司 | A kind of continuous stream tubular reactor system and reaction control system |
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| CN107051366B (en) * | 2017-06-09 | 2018-06-29 | 山东诺为制药流体系统有限公司 | A kind of continuous flow tubular reactor system and reaction control system |
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