CN106588602A - Method for preparing 2,6-dichlorobenzaldehyde through continuous oxidization of 2,6-dichlorotoluene - Google Patents
Method for preparing 2,6-dichlorobenzaldehyde through continuous oxidization of 2,6-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 discloses a method for preparing 2,6-dichlorobenzaldehyde through continuous oxidization of 2,6-dichlorotoluene, and belongs to the technical field of organic synthesis. The method is a technology that a 2,6-dichlorotoluene compound is adopted as a raw material, a metal ion complex of one or more of cobalt, molybdenum and bromine is adopted as a catalyst, hydrogen peroxide is adopted as an oxidizing agent, acetic acid is adopted as a solvent, and 2,6-dichlorotoluene is continuously oxidized in a tubular reactor to prepare 2,6-dichlorobenzaldehyde. The method is mild in condition, short in reaction time, high in raw material utilization rate, capable of achieving effective control in the reacting process, safe, stable, continuous in operation and high in production efficiency.
Description
Technical field
The invention belongs to organic synthesiss Technology field, is related to one kind under liquid-phase reaction condition by 2,6-DCT
The method that continuous oxidation prepares 2,6- dichlorobenzaldehydes, is more specifically that, with 2,6-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 structures
Tubular reactor in continuous prepare 2,6- dichlorobenzaldehyde products.
Background technology
2,6- dichlorobenzaldehydes, molecular formula：C7H4Cl2O, molecular weight are 175.01, and finished product is tied for white to yellow needles
Crystalline substance, with overpowering odor, fusing point is 67-71 DEG C, is dissolved in the organic solvents such as ethanol, ether, petroleum ether, and 2,6- dichlorobenzaldehydes are
One of important raw material of synthesis fine chemicals, for synthetic dyestuffs, pesticide and medicine intermediate.It is mainly used in pesticide industry
The intermediate of synthetic herbicide dichlobenil and insecticide d ichlorbenzuron；It is mainly used in the drift of synthetic dyestuffs acidic intermedium in dye industry blue
The intermediate of B；It is mainly used in synthesizing Dicloxaeillin Sodium in medical industry.
The synthetically produced method of current 2,6- dichlorobenzaldehydes has toluene direct chlorination method, Methylnitrobenzene method, adjacent nitro
Toluene method, p-tert-butyltoluene method, toluene-2-sulfonyl chloride decomposition method etc. are following several：
(1) chlorinolysis
It is that initiation material synthesizes 2,6- dichlorobenzaldehydes using chlorination, Hydrolyze method with 2,6- dichlorotoleune.The reaction lack
Point is that time of chlorinating is long, and chlorination degree is difficult to control to, and easily produces substantial amounts of by-product.
(2) Methylnitrobenzene chlorinolysis
With 2-chloro-6-nitrotoluene as initiation material, heated up with oil bath heating and melted, be passed through dry chlorine under light illumination
Gas, at 180～200 DEG C, the response time is about 15h for reaction temperature control, obtains the mixture of 2,6- dichloro benzal chlorides.Then
By said mixture, one is hydrated p-methyl benzenesulfonic acid and zinc chloride adds reactor by appropriate proportioning, is heated under stirring
110～120 DEG C, then post-treated acquisition 2,6- dichlorobenzaldehydes.But there is obvious defect in production method described above：It is raw
Produce that control is difficult, yield poorly, high cost, its market demand can not be adapted to.
Approach described above prepares 2,6- dichlorobenzaldehydes to the oxidation of 2,6- dichlorotoleune from different angles and is optimized
And improvement, but still suffer from some problems need solve：Still mainly produced using batch still batch first in large-scale production；Its
It is secondary in the above-mentioned methods still with extensive chlorination then hydrolyze prepare based on, chlorination degree therein is difficult to control to, and easily makes
Into the increase of by-product.And the continuous oxidation synthesis of 2,6- dichlorotoleune is carried out using the continuous flow tubular reactor of ad hoc structure
2,6- dichlorobenzaldehydes, can many-sided many deficiencies for solving existing process technology.
Tubular reactor is the general designation of the mini-reactor with micro structure, 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 are good, high temperature high voltage resistant etc.
Feature, can be had to the mixing of reaction mass and mass transfer, diabatic process using the continuous flow tubular reactor of ad hoc structure
Effect control.By the control of length and reaction time to tubular reactor, the distribution of raw material and product can be further made
More optimize controllable；Substrate 2,6- dichlorotoleune is capable of achieving with oxidant in proportion into tubular type by adjusting the flow velocity of raw material pump
Reactor carries out reaction and greatly reduces back-mixing, further reduces the generation of side reaction, and the stability of oxidant and target are produced
The selectivity of thing is also greatly improved；By pop off valve is arranged in tubular reactor, can be given off in reactor in time
Excessive oxidant, it is ensured that the safety of reaction is carried out, and risk is minimized.Pipe reaction of the present invention using ad hoc structure
Device carries out 2,6- dichlorotoleune continuous oxidations and prepares the method for 2,6- dichlorobenzaldehydes relative to conventional batch production method tool
There is unrivaled advantage, and an important approach can be provided for its industrialization quantity-produced improvement.
The content of the invention
The present invention is for not enough with present on, there is provided one kind is in tubular reactor by 2,6-DCT continuous oxygen
The method that change prepares 2,6- dichlorobenzaldehydes.This method response 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 the process of the present invention, to realize 2,6- bis-
Stablizing for chlorotoluene continuous oxidation is controllable, reduces the generation of by-product.Carried by the reinforcing and process optimization of mass-and heat-transfer process
The effective rate of utilization of high reaction mass, further reduces the usage amount of oxidant and catalyst and avoids during the course of the reaction
The use of promoter, so as to effectively save production cost further improves existing industrialized preparing process.
For achieving the above object, the technical solution used in the present invention is：
2,6- dichlorotoleune continuous oxidation is prepared 2,6- dichlorobenzaldehydes by a kind of tubular reactor of employing special construction
Method, carry out as steps described below：
(1) first at room temperature, by substrate 2,6-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 mix homogeneously, then pours metal complex mixing into 2,6- dichloros
Toluene-carboxylic acid solution, sodium salt is poured in hydrogen peroxide-carboxylic acid solution；By the required response time, two kinds of materials are calculated
It is different in flow rate, continuously squeeze in tubular reactor Jing dosing pump respectively and reacted into reaction zone after preheated mixing, instead
Temperature is answered to be controlled by outer loop heat-exchange system；
(2) method by adjusting flow velocity and weight calculation controls the mol ratio of reaction mass, by changing tubular reactor
0.5～15mm of internal diameter of the pipeline, 25～750ml of volume carry out the 60～1800s of the time of staying of control material hybrid reaction；Reacting
Cheng Hou, product exit into collecting tank from reactor end, and product rectification is separated, and unreacted 2,6-DCT circulation is anti-
Should, product 2,6- dichlorobenzaldehyde rectification are collected after purification, wherein target product 2, and the yield of 6- dichlorobenzaldehydes is up to 20%
～35%.
Wherein described catalyst is cobalt, molybdenum, bromine one or more metal complex catalysts, and which mainly includes：Acetic acid
Cobalt, cobalt oxalate, cobalt carbonate, cobalt naphthenate, sodium molybdate, ammonium molybdate, sodium bromide, ammonium bromide etc., wherein with oil-soluble catalyst being
It is main, can fully dissolve in 2,6-DCT, the mol ratio of its consumption and substrate 2,6-DCT is in (0.005～0.15)
: 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%～50% with mass concentration, and preferred concentration is
10%～35%.Hydrogen peroxide is (1.0～7.0) with the preferred molar ratio of substrate 2,6- dichlorotoleune: 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 which passes through 100ml, almost molecular oxygen form now should be anti-in 100ml
Answer, participate in reaction again.
Wherein described carboxylic acid solvent includes：Formic acid, acetic acid, propanoic acid, butanoic acid, caproic acid, octanoic acid etc..Wherein solvent and 2,6-
The volume ratio of dichlorotoleune is in (1～8): 1.
Wherein described reaction temperature is 60～140 DEG C, and preferable reaction temperature is 90～125 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 after completion of the reaction with dichloromethane sodium,
Then extracted by organic solvent, separated obtains target product after purification.
In above-mentioned technical proposal, described response system includes the difference in functionalitys such as raw material storage tank, reaction zone, product collection 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 adopts a kind of mode of production of serialization, and the response time is short, and reaction condition is gentle, and process safety can
Control, production efficiency are high.
2nd, the present invention is capable of achieving the effective control to course of reaction, is made by the tubular reactor made using different structure
Product rests on one step of aldehyde alcohol.
3rd, by the utilization rate of its reaction rate and raw material is greatly improved to mass transfer in course of reaction, heat transfer intensification,
And effectively reduce the usage amount of oxidant and catalyst, and the use of promoter is avoided, there is production cost
Effect is saved.
4th, the present invention is easy to operate, applied widely, and production is flexible, can pass through the expanding production rule in parallel of reaction unit
Mould.
Description of the drawings
Fig. 1 is the process chart that 2,6- dichlorotoleune continuous oxidation of the present invention prepares 2,6- dichlorobenzaldehydes.
Fig. 2 is continuous flow tubular reactor installation drawing used in the present invention：1st, 2- head tanks, 3,4- raw material dosing 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-, it is flat that d- strengthens mixed type cake formula
Pipeline, the Heart Cell structures microchannel of e-Corning.
Specific embodiment
Cobalt acetate and sodium molybdate are dissolved in the 1# tanks equipped with 2,6-DCT and acetic acid, 5# preheatings are pumped into by 3#
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 and reacts temperature required, and product is cooled down using 0 DEG C by flowing out in 8# reactors, collects products therefrom.
The present invention is described in detail with reference to embodiment, but the following examples is only the present invention preferably embodiment,
Protection scope of the present invention is not limited thereto, technology model of any those familiar with the art in present disclosure
In enclosing, the guarantor in the present invention should be all covered in technology according to the present invention scheme and its inventive concept in addition equivalent substitute or change
Within the scope of shield.
Embodiment 1
(1) device：The connected mode of tubular reactor is determined with reference to Fig. 2, 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
For conduction oil.
(2) 4.04g cobalt acetates and 4.04g sodium molybdate are dissolved in into 200ml2,6- dichlorotoleune and 200ml acetic acid shapes respectively
Into mixed solution, now n (cobalt acetate)：N (2,6- dichlorotoleune)=0.01:1,4.04g sodium bromide is dissolved in into 15%H2O2Shape
Into H2O2- acetic acid solution, now n (sodium bromide)：N (2,6- dichlorotoleune)=0.01:1,2,6-DCT-acetic acid solution with
And H2O2The tubular type that-acetic acid solution is persistently exchanged heat by constant flow pump injection with the flow velocity of 5.33ml/min and 10.67ml/min respectively
In reactor, now n (H2O2)：N (2,6- dichlorotoleune)=3:1, using Fig. 2 micro passage reactions, controlling reaction temperature 60
DEG C, time of staying 60s.0 DEG C of cooling of outlet material, reactant liquor are quenched with dichloromethane.Analyze through GC, 2,6-DCT turns
Rate is 50.3%, and 2,6- dichlorobenzaldehyde yields are 27.1%.
Embodiment 2
(1) device：The connected mode of tubular reactor is determined with reference to Fig. 2, 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 are determined with reaction time according to flow velocity with volume, exchange heat and be situated between
Matter is conduction oil.
(2) 6.06g cobalt acetates and 6.06g sodium molybdate are dissolved in into 200ml2,6- dichlorotoleune and 200ml acetic acid shapes respectively
Into mixed solution, now n (cobalt acetate)：N (2,6- dichlorotoleune)=0.015:1,6.06g sodium bromide is dissolved in into 15%H2O2
Form H2O2- acetic acid solution, now n (sodium bromide)：N (2,6- dichlorotoleune)=0.015:1,2,6-DCT-acetic acid solution
With and H2O2The pipe that-acetic acid solution is persistently exchanged heat by constant flow pump injection with the flow velocity of 8.33ml/min and 16.67ml/min respectively
In formula reactor, now n (H2O2)：N (2,6- dichlorotoleune)=2:1, using Fig. 2 micro passage reactions, controlling reaction temperature 65
DEG C, time of staying 200s.0 DEG C of cooling of outlet material, reactant liquor are quenched with dichloromethane.Analyze through GC, 2,6-DCT
Conversion ratio is 56.0%, and 2,6- dichlorobenzaldehyde yields are 31.7%.
Embodiment 3
(1) device：The connected mode of tubular reactor is determined with reference to Fig. 2, conduit types are：(3a+3d) once-through type passage+
Strengthen mixed type cake formula narrow rectangular tube road, internal diameter of the pipeline is determined with reaction time according to flow velocity with volume, heat transferring medium
For conduction oil.
(2) 6.06g cobalt acetates and 6.06g sodium molybdate are dissolved in into 200ml2,6- dichlorotoleune and 200ml acetic acid shapes respectively
Into mixed solution, now n (cobalt acetate)：N (2,6- dichlorotoleune)=0.015:1,6.06g sodium bromide is dissolved in into 15%H2O2
Form H2O2- acetic acid solution, now n (sodium bromide)：N (2,6- dichlorotoleune)=0.015:1,2,6-DCT-acetic acid solution
With and H2O2The pipe that-acetic acid solution is persistently exchanged heat by constant flow pump injection with the flow velocity of 8.33ml/min and 16.67ml/min respectively
In formula reactor, now n (H2O2)：N (2,6- dichlorotoleune)=3:1, using Fig. 2 micro passage reactions, controlling reaction temperature
105 DEG C, time of staying 600s.0 DEG C of cooling of outlet material, reactant liquor are quenched with dichloromethane.Analyze through GC, 2,6- dichloromethanes
Benzene conversion ratio is 41.8%, and 2,6- dichlorobenzaldehyde yields are 22.2%.
Embodiment 4
(1) device：The connected mode of tubular reactor is determined with reference to Fig. 2, 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
For conduction oil.
(2) 6.06g cobalt acetates and 6.06g sodium molybdate are dissolved in into 200ml2,6- dichlorotoleune and 200ml acetic acid shapes respectively
Into mixed solution, now n (cobalt acetate)：N (2,6- dichlorotoleune)=0.015:1,6.06g sodium bromide is dissolved in into 25%H2O2
Form H2O2- acetic acid solution, now n (sodium bromide)：N (2,6- dichlorotoleune)=0.015:1,2,6-DCT-acetic acid solution
With and H2O2The pipe that-acetic acid solution is persistently exchanged heat by constant flow pump injection with the flow velocity of 5.33ml/min and 10.67ml/min respectively
In formula reactor, now n (H2O2)：N (2,6- dichlorotoleune)=2:1, using Fig. 2 micro passage reactions, controlling reaction temperature
105 DEG C, time of staying 600s.0 DEG C of cooling of outlet material, reactant liquor are quenched with dichloromethane.Analyze through GC, 2,6- dichloromethanes
Benzene conversion ratio is 51.5%, and 2,6- dichlorobenzaldehyde yields are 25.1%.
Embodiment 5
(1) device：The connected mode of tubular reactor is determined with reference to Fig. 2, 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 are determined with reaction time according to flow velocity with volume, exchange heat and be situated between
Matter is conduction oil.
(2) 6.06g cobalt acetates and 6.06g sodium molybdate are dissolved in into 200ml2,6- dichlorotoleune and 200ml acetic acid shapes respectively
Into mixed solution, now n (cobalt acetate)：N (2,6- dichlorotoleune)=0.015:1,6.06g sodium bromide is dissolved in into 25%H2O2
Form H2O2- acetic acid solution, now n (sodium bromide)：N (2,6- dichlorotoleune)=0.015:1,2,6-DCT-acetic acid solution
With and H2O2The pipe that-acetic acid solution is persistently exchanged heat by constant flow pump injection with the flow velocity of 8.33ml/min and 16.67ml/min respectively
In formula reactor, now n (H2O2)：N (2,6- dichlorotoleune)=2:1, using Fig. 2 micro passage reactions, controlling reaction temperature
105 DEG C, time of staying 600s.0 DEG C of cooling of outlet material, reactant liquor are quenched with dichloromethane.Analyze through GC, 2,6- dichloromethanes
Benzene conversion ratio is 50.7%, and 2,6- dichlorobenzaldehyde yields are 29.1%.
Embodiment 6
(1) device：The connected mode of tubular reactor is determined with reference to Fig. 2, conduit types are：(3a+3d) once-through type passage+
Strengthen mixed type cake formula narrow rectangular tube road, internal diameter of the pipeline is determined with reaction time according to flow velocity with volume, heat transferring medium
For conduction oil.
(2) 6.06g cobalt acetates and 6.06g sodium molybdate are dissolved in into 200ml2,6- dichlorotoleune and 200ml acetic acid shapes respectively
Into mixed solution, now n (cobalt acetate)：N (2,6- dichlorotoleune)=0.015:1,6.06g sodium bromide is dissolved in into 25%H2O2
Form H2O2- acetic acid solution, now n (sodium bromide)：N (2,6- dichlorotoleune)=0.015:1,2,6-DCT-acetic acid solution
With and H2O2The pipe that-acetic acid solution is persistently exchanged heat by constant flow pump injection with the flow velocity of 5.56ml/min and 11.11ml/min respectively
In formula reactor, now n (H2O2)：N (2,6- dichlorotoleune)=2:1, using Fig. 2 micro passage reactions, controlling reaction temperature
105 DEG C, time of staying 900s.0 DEG C of cooling of outlet material, reactant liquor are quenched with dichloromethane.Analyze through GC, 2,6- dichloromethanes
Benzene conversion ratio is 34.7%, and 2,6- dichlorobenzaldehyde yields are 25.0%.
Embodiment 7
(1) device：The connected mode of tubular reactor is determined with reference to Fig. 2, conduit types are：(3a+3e) once-through type passage+
Corningde Heart Cell structures, internal diameter of the pipeline determine with reaction time according to flow velocity that with volume heat transferring medium is
Conduction oil.
(2) 6.06g cobalt acetates and 6.06g sodium molybdate are dissolved in into 200ml2,6- dichlorotoleune and 200ml acetic acid shapes respectively
Into mixed solution, now n (cobalt acetate)：N (2,6- dichlorotoleune)=0.015:1,6.06g sodium bromide is dissolved in into 25%H2O2
Form H2O2- acetic acid solution, now n (sodium bromide)：N (2,6- dichlorotoleune)=0.015:1,2,6-DCT-acetic acid solution
With and H2O2The pipe that-acetic acid solution is persistently exchanged heat by constant flow pump injection with the flow velocity of 5.56ml/min and 11.11ml/min respectively
In formula reactor, now n (H2O2)：N (2,6- dichlorotoleune)=2:1, using Fig. 2 micro passage reactions, controlling reaction temperature 90
DEG C, time of staying 900s.0 DEG C of cooling of outlet material, reactant liquor are quenched with dichloromethane.Analyze through GC, 2,6-DCT
Conversion ratio is 50.8%, and 2,6- dichlorobenzaldehyde yields are 28.0%.
Embodiment 8
(1) device：The connected mode of tubular reactor is determined with reference to Fig. 2, conduit types are：(3a+3d) once-through type passage+
Strengthen mixed type cake formula narrow rectangular tube road, internal diameter of the pipeline is determined with reaction time according to flow velocity with volume, heat transferring medium
For conduction oil.
(2) 6.06g cobalt acetates and 6.06g sodium molybdate are dissolved in into 200ml2,6- dichlorotoleune and 200ml acetic acid shapes respectively
Into mixed solution, now n (cobalt acetate)：N (2,6- dichlorotoleune)=0.015:1,6.06g sodium bromide is dissolved in into 25%H2O2
Form H2O2- acetic acid solution, now n (sodium bromide)：N (2,6- dichlorotoleune)=0.015:1,2,6-DCT-acetic acid solution
With and H2O2The pipe that-acetic acid solution is persistently exchanged heat by constant flow pump injection with the flow velocity of 5.56ml/min and 11.11ml/min respectively
In formula reactor, now n (H2O2)：N (2,6- dichlorotoleune)=2:1, using Fig. 2 micro passage reactions, controlling reaction temperature
120 DEG C, time of staying 1200s.0 DEG C of cooling of outlet material, reactant liquor are quenched with dichloromethane.Analyze through GC, 2,6- dichloros
Toluene conversion is 37.9%, and 2,6- dichlorobenzaldehyde yields are 26.1%.
Embodiment 9
(1) device：The connected mode of tubular reactor is determined with reference to Fig. 2, 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 are determined with reaction time according to flow velocity with volume, exchange heat and be situated between
Matter is conduction oil.
(2) 6.06g cobalt acetates and 6.06g sodium molybdate are dissolved in into 200ml2,6- dichlorotoleune and 200ml acetic acid shapes respectively
Into mixed solution, now n (cobalt acetate)：N (2,6- dichlorotoleune)=0.015:1,6.06g sodium bromide is dissolved in into 25%H2O2
Form H2O2- acetic acid solution, now n (sodium bromide)：N (2,6- dichlorotoleune)=0.015:1,2,6-DCT-acetic acid solution
With and H2O2The pipe that-acetic acid solution is persistently exchanged heat by constant flow pump injection with the flow velocity of 5.56ml/min and 11.11ml/min respectively
In formula reactor, now n (H2O2)：N (2,6- dichlorotoleune)=2:1, using Fig. 2 micro passage reactions, controlling reaction temperature
140 DEG C, time of staying 1800s.0 DEG C of cooling of outlet material, reactant liquor are quenched with dichloromethane.Analyze through GC, 2,6- dichloros
Toluene conversion is 40.1%, and 2,6- dichlorobenzaldehyde yields are 27.2%.
Claims (6)
1. a kind of method that 2,6-DCT continuous oxidation prepares 2,6- dichlorobenzaldehydes, it is characterised in that as steps described below
Carry out：
（1）Under room temperature, by substrate 2,6-DCT and part carboxylic acid solvent with volume ratio 1:1 is uniformly mixed, will oxidation
Agent and part carboxylic acid solvent are with volume ratio 1:1 mix homogeneously, then pours metal complex mixing into 2,6-DCT-carboxylic acid
Solution, sodium salt is poured in hydrogen peroxide-carboxylic acid solution；By the required response time, the not cocurrent flow of two kinds of materials is calculated
Speed, continuously squeezes in tubular reactor Jing dosing pump respectively and is reacted into reaction zone after preheated mixing, 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 carry out the time of staying 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 2,6-DCT circular response, product 2,6- dichloro-benzenes
Formaldehyde rectification is collected after purification.
2. the method that a kind of 2,6-DCT continuous oxidation according to claims 1 prepares 2,6- dichlorobenzaldehydes,
It is characterized in that described catalyst is cobalt, molybdenum, sodium one or more metal complex catalysts, which 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 dissolve in 2,6-DCT, its consumption is existed with the mol ratio of substrate 2,6-DCT（0.005~0.15）: 1,
Wherein preferred molar ratio is（0.01~0.08）∶1.
3. the method that a kind of 2,6-DCT continuous oxidation according to claims 1 prepares 2,6- dichlorobenzaldehydes,
It is characterized in that described oxidant is hydrogen peroxide, its solution concentration is calculated as 5% ~ 50% with mass concentration, preferred concentration is 15% ~
30%, hydrogen peroxide with the preferred molar ratio of substrate 2,6-DCT is（1.0~7.0）∶1.
4. the method that a kind of 2,6-DCT continuous oxidation according to claims 1 prepares 2,6- dichlorobenzaldehydes,
It is characterized in that described carboxylic acid solvent includes：Formic acid, acetic acid, propanoic acid, butanoic acid, caproic acid, octanoic acid；Wherein solvent and 2,6- dichloros
The volume ratio of toluene exists（1~8）∶1.
5. the method that a kind of 2,6-DCT continuous oxidation according to claims 1 prepares 2,6- dichlorobenzaldehydes,
It is characterized in that：Reaction temperature is 60 ~ 140 DEG C, and preferable reaction temperature is 95 ~ 125 DEG C, reaction time 60s ~ 1800s.
6. the method that a kind of 2,6-DCT continuous oxidation according to claims 1 prepares 2,6- dichlorobenzaldehydes,
It is characterized in that：Total overall reaction process is carried out continuously in the tubular reactor of ad hoc structure, and the response system includes raw material
The difference in functionality such as storage tank, reaction zone, product collection 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
Narrow rectangular tube road structure, cardioid channel design.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610972021.9A CN106588602A (en) | 2016-11-07 | 2016-11-07 | Method for preparing 2,6-dichlorobenzaldehyde through continuous oxidization of 2,6-dichlorotoluene |
Applications Claiming Priority (1)
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| CN109336732A (en) * | 2018-09-13 | 2019-02-15 | 南京工业大学 | A method of producing 2,6- dichloro benzal chloride by-product 2,6- dichlorotoleune simultaneously |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109336732A (en) * | 2018-09-13 | 2019-02-15 | 南京工业大学 | A method of producing 2,6- dichloro benzal chloride by-product 2,6- dichlorotoleune simultaneously |
| CN109336732B (en) * | 2018-09-13 | 2021-03-30 | 南京工业大学 | Method for producing 2, 6-dichlorobenzylidene dichloride and co-producing 2, 6-dichlorotoluene |
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