CN108794311A - A kind of method that ortho-chlorotolu'ene continuous oxidation prepares o-chlorobenzaldehyde - Google Patents
A kind of method that ortho-chlorotolu'ene continuous oxidation prepares o-chlorobenzaldehyde Download PDFInfo
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- CN108794311A CN108794311A CN201810780724.0A CN201810780724A CN108794311A CN 108794311 A CN108794311 A CN 108794311A CN 201810780724 A CN201810780724 A CN 201810780724A CN 108794311 A CN108794311 A CN 108794311A
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- IQBJZMIJKQKEBX-SCFJQAPRSA-N C/C(/C=C\C=C)=C\Cl Chemical compound C/C(/C=C\C=C)=C\Cl IQBJZMIJKQKEBX-SCFJQAPRSA-N 0.000 description 1
- FPYUJUBAXZAQNL-UHFFFAOYSA-N O=Cc(cccc1)c1Cl Chemical compound O=Cc(cccc1)c1Cl FPYUJUBAXZAQNL-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/28—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of CHx-moieties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0006—Controlling or regulating processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0006—Controlling or regulating processes
- B01J19/0013—Controlling the temperature of the process
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/24—Stationary reactors without moving elements inside
- B01J19/2415—Tubular reactors
Abstract
The invention discloses a kind of methods that ortho-chlorotolu'ene continuous oxidation prepares o-chlorobenzaldehyde, belong to organic synthesis technology field.This method be using ortho-chlorotolu'ene compound as raw material, cobalt, molybdenum, bromine one or more of metal ion complexes be catalyst, hydrogen peroxide is oxidant, and acetic acid is solvent, and oxidation ofochlorotoluene is continuously prepared to the technology of o-chlorobenzaldehyde in tubular reactor.This method mild condition, the reaction time is short, and raw material availability is high, it can be achieved that effective control in reaction process, safety and stability, continuous operation, production efficiency are high.
Description
Technical field
The invention belongs to organic synthesis technology fields, are related to a kind of continuous by ortho-chlorotolu'ene under liquid-phase reaction condition
The method that oxidation prepares o-chlorobenzaldehyde is more specifically using ortho-chlorotolu'ene as substrate, hydrogen peroxide is oxidant, cobalt, molybdenum, bromine
One or more of metal ion complexes are catalyst, and monocarboxylic acid is solvent, in the tubular reactor with different micro-structures
In continuously prepare o-chlorobenzaldehyde product.
Background technology
O-chlorobenzaldehyde, also known as 2- chlorobenzaldehydes, are the important source materials in fine chemistry industry, are in important in organic synthesis
Mesosome.It is widely used in the industries such as pesticide, medicine, dyestuff.For producing very big efficient of domestic demand amount on pesticide industry
Less toxic acaricide mite kills only；For producing o-chlorobenzaldehyde oxime, o-chlorobenzaldehyde oxime chlorine and chlorobenzene azoles mould in pharmaceuticals industry
Plain sodium；Adjacent benzaldehyde sodium sulfonate can be produced on dye industry, it is the raw material of food colour Blue VRS number, also serves as plating
Slot additive is to improve brightness.Currently, CIBA companies of Switzerland produce one kind for the clean high-grade optics in laundry with it
Brightening agent Tinopal.In addition, also serving as the intermediate etc. in tear-gas product.The market capacity of o-chlorobenzaldehyde 2000t/a with
On, as o-chlorobenzaldehyde downstream product is continually developed, application field is also constantly extending, both at home and abroad to its demand
It is increasing.From the point of view of current domestic and international market, supply falls short of demand for o-chlorobenzaldehyde product, and domestic production enterprise should combine a variety of elder generations
Into production technology, a kind of production technology of new o-chlorobenzaldehyde is researched and developed, while creating economic benefit, and can be reduced
Pollution, turns waste into wealth, is to kill two birds with one stone.
Current o-chlorobenzaldehyde is synthetically produced method mainly including following several：Ortho-chlorotolu'ene chlorinolysis, neighbour
Chlorotoluene direct oxidation method acyl chlorides reduction method, carboxylic acid reduction method etc., since selected reduction method technical difficulty is relatively high, production
Of high cost, using seldom report in industrial production, and chlorinolysis is most widely used.
The commercial synthesis method of current o-chlorobenzaldehyde has following several：
(1) chlorinolysis
In chemical method, most traditional technique of o-chlorobenzaldehyde synthesis, is exactly ortho-chlorotolu'ene chlorinolysis, it is
Adjacent chlorine benzyl dichloride is made in ortho-chlorotolu'ene pendant chlorine under the effect of the catalyst, is then hydrolyzed under hydrolyst effect,
Generate o-chlorobenzaldehyde.Catalyst used in catalyzing hydrolysis is generally transition metal salt M Xn such as：SnCl4, ZnCl2.With adjacent chlorine
Toluene is that the technological process of Material synthesis o-chlorobenzaldehyde is as follows：
This method is producing, and due to the difference of depth of chlorination, causes the result of chlorination also different, can often go out in chlorination
Now different degrees of by-product, such as adjacent chlorobenzyl chloride, three benzyl chloride of adjacent chlorine.Also, hydrolysis mostly uses greatly sulphuric acid catalysis, receives
Rate is only 80% or so, and generates a large amount of spent acid, seriously pollutes environment.
(2) chloride oxidation method
Chloride oxidation method is that ortho-chlorotolu'ene is carried out pendant chlorine, generates adjacent chlorobenzyl chloride compound, then oxidized dose of oxygen
Metaplasia is at corresponding benzaldehyde.Its reaction equation is as follows：
The oxidant of selection is different, and the oxidizing condition that oxidation reaction requires is also different.Usually make oxidant with methenamine,
It need to be heated to reflux in ethyl alcohol, hydrochloric acid system and obtain aldehyde.Also with HNO3For oxidant, adjacent chlorobenzyl chloride is first made to be oxidized to adjacent chlorine
Benzyl dichloride, then hydrolyze and can obtain aldehyde.But this method is in production, needs to consume a large amount of catalyst, and cause a large amount of waste water
Pollution so that the production cost increases, also pollutes environment.
(3) direct oxidation method
Direct oxidation method is that the methyl in ortho-chlorotolu'ene is direct oxidation into aldehyde radical.It is general different by the oxidant selected,
It is divided into manganese dioxide/sulfuric acid oxidation method, catalytic air or dioxygen oxidation method etc..Reaction equation is as follows：
Catalytic oxidation is using ortho-chlorotolu'ene as raw material, in catalyst bismuth oxide, molybdenum oxide, cobalt acetate and manganese acetate, vinegar
In the presence of sour cobalt and sodium bromide and cobalt acetate and lithium bromide etc., is reacted with air direct oxidation and generate aldehyde.Reaction conversion ratio
20%~50%, selectivity 70%, actual recovery 20%, product purity 99%.This method is simple for process, at low cost, product is pure
Degree is high.But due to being gas phase reaction, equipment requirement is very high, currently, this method is still in further research.
(4) Indirect Electrooxidation
Teng Yadi etc. uses Mn (III) for oxidation medium, and using ortho-chlorotolu'ene as raw material, benzene makees solvent, exists in the concentrated sulfuric acid
Under, using first butylammonium bromide as phase transfer catalyst, o-chlorobenzaldehyde, optimum reaction condition have been synthesized with Indirect Electrooxidation：
Sulfuric acid concentration 8.0mol/L, 63 DEG C of reaction temperature, ortho-chlorotolu'ene and [Mn3+] raw material proportioning be 5:4, reaction time 4h, highest are received
Rate is up to 55%.Li Zhuxia etc. is electrolysed MnSO using sulfuric acid as medium3To produce Mn3+, it is o-chlorobenzaldehyde by oxidation ofochlorotoluene,
By electrolytic oxidation orthogonal experiment and MnSO3 experiment of single factor, electrolysis optimum condition is obtained：Dense H2SO4For 6.8mol/L, temperature
It it is 80 DEG C, raw material is 1 with sulfuric acid proportioning:3, speed of agitator 500r/min.Under this optimal conditions, current efficiency reaches
84.30%, for the yield of o-chlorobenzaldehyde up to 90.63%, reaction rate is 6.183 × 10-3mol/(L·min).The process route
Simply, but production cost is expensive, is not suitable for large-scale promotion also at present.
Approach described above prepares o-chlorobenzaldehyde to oxidation ofochlorotoluene from different angles and optimizes and improve, but
There are still some problems needs to solve：It is still mainly produced using batch still batch first in large-scale production；Secondly above-mentioned
It is excessive that there are still catalyst amounts in method, and the waste water for hydrolyzing generation is excessive, and depth of chlorination is too deep, and side reaction increases, target production
Object selectivity, low yield the main reason for and utilize the continuous flow tubular reactor of specific structure progress ortho-chlorotolu'ene continuous oxygen
It is combined to o-chlorobenzaldehyde, it can many-sided many deficiencies for solving prior art technology.
Tubular reactor is the general designation of the mini-reactor with micro-structure, compared with conventional reactor, tubular reactor
With small, large specific surface area, easily amplify, process is continuous, and quick good mixing effect, heat-transfer effect is good, high temperature high voltage resistant etc.
Feature can have the mixing of reaction mass and mass transfer, diabatic process using the continuous flow tubular reactor of specific structure
Effect control.Enhance its mass-and heat-transfer effect by the contact area that can be effectively increased between reactant to the design of pipeline configuration and size
Fruit improves the utilization rate of oxidant, reduces the usage amount of oxidant and avoids the use of co-catalyst, solves simultaneously
" temperature runaway " phenomenon generated by hot-spot in reaction process.Pass through length to tubular reactor and reaction time
Control, can further be such that the distribution of raw material and product more optimizes controllably；Flow velocity by adjusting raw material pump can realize substrate neighbour
Chlorine ortho-chlorotolu'ene react greatly reducing back-mixing into tubular reactor in proportion with oxidant, further reduces secondary anti-
The generation answered, the stability of oxidant and the selectivity of target product also greatly improve；By the way that pressure is arranged in tubular reactor
Power safety valve can give off the excessive oxidant in reactor in time, ensure that the safety of reaction carries out, level of significance is down to most
It is low.The method that the present invention prepares o-chlorobenzaldehyde using the tubular reactor progress ortho-chlorotolu'ene continuous oxidation of specific structure is opposite
There is unrivaled advantage in conventional batch production method, and quantity-produced improvement can be industrialized for it and provide one
Important approach.
Invention content
The present invention provides one kind in tubular reactor by ortho-chlorotolu'ene continuous oxidation system for the deficiency present on
The method of standby o-chlorobenzaldehyde.This method reaction time is short, and production efficiency is high, and mass transfer, heat transfer are optimized significantly, reaction process
It is more stably and controllable.Further object of the present invention is that process through the invention realizes the continuous oxygen of ortho-chlorotolu'ene
That changes is stably and controllable, reduces the generation of by-product.Reaction mass is improved by the reinforcing of mass-and heat-transfer process and process optimization
Effective rate of utilization further decreases the usage amount of oxidant and catalyst and avoids making for co-catalyst during the reaction
With to which effectively save production cost improves existing industrialized preparing process in turn.
To achieve the above object, the technical solution adopted by the present invention is：
A method of ortho-chlorotolu'ene continuous oxidation is prepared by o-chlorobenzaldehyde using the tubular reactor of special construction, is pressed
It is carried out according to following step：
(1) first at room temperature, by substrate ortho-chlorotolu'ene and carboxylic acid solvent with volume ratio 1:1 is uniformly mixed, by oxygen
Agent and part carboxylic acid solvent are with volume ratio 1:1 is uniformly mixed, and then mixes metal complex catalyst and pours into ortho-chlorotolu'ene-
Carboxylic acid solution pours into sodium salt in oxidant-carboxylic acid solution；By the required reaction time, two kinds of materials are calculated not
Same flow velocity is continuously squeezed into tubular reactor through metering pump reacted into reaction zone after preheated mixing respectively, reaction temperature
Degree is controlled by outer loop heat-exchange system；
(2) molar ratio that reaction mass is controlled by the method for adjusting flow velocity and weight calculation, by changing tubular reactor
0.5~15mm of internal diameter of the pipeline, 25~750ml of volume carry out 60~1800s of residence time of control material hybrid reaction；It is reacting
Cheng Hou, product exit into collecting tank, product rectification separation, unreacted ortho-chlorotolu'ene circular response, production from reactor end
Object o-chlorobenzaldehyde rectifying is collected after purification, and wherein the yield of target product o-chlorobenzaldehyde is up to 35%~45%.
The wherein described metal complex catalyst is cobalt, molybdenum, bromine one or more metal complex catalyst, main
Including：Cobalt acetate, cobalt oxalate, cobalt carbonate, cobalt naphthenate, sodium molybdate, ammonium molybdate, sodium bromide, ammonium bromide etc., wherein with oil-soluble
It based on catalyst, can fully be dissolved in ortho-chlorotolu'ene, the molar ratio of dosage and substrate ortho-chlorotolu'ene is in (0.005~0.15)
: 1, wherein preferred molar ratio is (0.01~0.12): 1.
Wherein the oxidant is hydrogen peroxide, and solution concentration is calculated as 5%~50% with mass concentration, and preferred concentration is
10%~35%.The preferred molar ratio of hydrogen peroxide and substrate ortho-chlorotolu'ene is (1.0~8.0): 1.
The wherein hydrogen peroxide, in tubular reactor, when hydrogen peroxide is by 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 at this time should be anti-in 100ml
It answers the hydrogen peroxide for additionally supplementing isoconcentration at volume to enter, participates in reaction again.
Wherein the carboxylic acid solvent includes：Formic acid, acetic acid, propionic acid, butyric acid, caproic acid, octanoic acid etc..Wherein solvent and adjacent chlorine
The volume ratio of toluene is in (1~5): 1.
Wherein the reaction temperature is 60~130 DEG C, and preferable reaction temperature is 90~125 DEG C, and reaction time is
60s~1800s.
In further technical solution, the oxidant for having neither part nor lot in reaction is first quenched with dichloromethane sodium after completion of the reaction,
Then it is extracted by organic solvent, distillation obtains target product after isolating and purifying.
In above-mentioned technical proposal, the reaction system includes the different function such as raw material storage tank, reaction zone, collection of products area
Region.Tubular reactor channel design includes：Pipe once-through type channel design, cake formula pulse diameter varied narrow rectangular tube road knot
Structure, rectangle cake formula pulse diameter varied narrow rectangular tube road structure, enhancing mixed type cake formula narrow rectangular tube road structure and Corning
Heart Cell channel designs.
The present invention has the following advantages：
1, the present invention uses a kind of mode of production of serialization, and the reaction time is short, and reaction condition is mild, and process safety can
Control, production efficiency are high.
2, the tubular reactor made by using different structure of the present invention is, it can be achieved that effective control to reaction process, makes
Reaction product rests on one step of aldehyde alcohol.
3, by the way that its reaction rate and the utilization rate of raw material greatly improved to mass transfer, heat transfer intensification in reaction process,
And the usage amount of oxidant and catalyst is effectively reduced, and the use of co-catalyst is avoided, so that production cost is had
Effect is saved.
4, 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.
Description of the drawings
Fig. 1 is the process flow chart that ortho-chlorotolu'ene continuous oxidation of the present invention prepares o-chlorobenzaldehyde.
Fig. 2 is continuous flow tubular reactor installation drawing used in the present invention：1,2- head tanks, 3,4- raw material metering pumps,
The preheating zones 5-, 6,7- reaction zones, collecting region is quenched in 8- products.
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 rectangles c- cake formula pulse diameter varied narrow rectangular tube road, it is flat that d- enhances mixed type cake formula
Pipeline, e-Corning Heart Cell structures microchannel.
Specific implementation mode
As shown in Fig. 2, being dissolved in cobalt acetate and sodium molybdate in the 1# tanks equipped with ortho-chlorotolu'ene and acetic acid, it is pumped by 3#
In the pre- thermal reactors of 5#, 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 passed through
4# is pumped into the pre- thermal reactors of 6#, and pre- thermal reactor is heated to 50 DEG C, and then by two strands of preheating materials, it is anti-to be delivered to 7#, 8#
It answers in device, temperature of reactor is set in reaction required temperature, and product, using 0 DEG C of cooling, collects institute by being flowed out in 8# reactors
Obtain product.
With reference to embodiment, the present invention will be described in detail, but the following examples are only the preferable embodiment of the present invention,
Scope of protection of the present invention is not limited thereto, technology model of any one skilled in the art in present disclosure
In enclosing, it is subject to equivalent substitute or change according to the technical scheme of the invention and its inventive conception, should all covers the guarantor in the present invention
Within the scope of shield.
Embodiment 1
(1) device：Determine that the connection type of tubular reactor, conduit types are with reference to Fig. 2：(3a+3b) once-through type channel+
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) respectively by 3.03g cobalt acetates and 3.03g sodium molybdates be dissolved in 200ml ortho-chlorotolu'enes and 200ml acetic acid formed it is mixed
Solution is closed, at this time n (cobalt acetate)：N (ortho-chlorotolu'ene)=0.0075:1,3.03g sodium bromides are dissolved in 5%H2O2Form H2O2-
Acetic acid solution, at this time n (sodium bromide)：N (ortho-chlorotolu'ene)=0.0075:1, ortho-chlorotolu'ene-acetic acid solution with and H2O2Acetic acid is molten
Liquid is injected by constant flow pump in the tubular reactor persistently to exchange heat with the flow velocity of 8.33ml/min and 16.67ml/min respectively, this
When n (H2O2)：N (ortho-chlorotolu'ene)=2:1, using Fig. 2 micro passage reactions, 60 DEG C of controlling reaction temperature, residence time 60s.Go out
Mouth 0 DEG C of cooling of material, reaction solution are quenched with dichloromethane.It is analyzed by GC, ortho-chlorotolu'ene conversion ratio is 65.3%, adjacent chlorobenzene first
Aldehyde yield is 37.1%.
Embodiment 2
(1) device：Determine that the connection type of tubular reactor, conduit types are with reference to Fig. 2：(3a+3c) once-through type channel+
Rectangle cake formula pulse diameter varied narrow rectangular tube road, internal diameter of the pipeline determine that heat exchange is situated between with volume according to flow velocity and reaction time
Matter is conduction oil.
(2) respectively by 6.06g cobalt acetates and 6.06g sodium molybdates be dissolved in 200ml ortho-chlorotolu'enes and 200ml acetic acid formed it is mixed
Solution is closed, at this time n (cobalt acetate)：N (ortho-chlorotolu'ene)=0.015:1,6.06g sodium bromides are dissolved in 15%H2O2Form H2O2-
Acetic acid solution, at this time n (sodium bromide)：N (ortho-chlorotolu'ene)=0.015:1, ortho-chlorotolu'ene-acetic acid solution with and H2O2Acetic acid solution
It is injected in the tubular reactor persistently to exchange heat by constant flow pump with the flow velocity of 8.33ml/min and 16.67ml/min respectively, at this time n
(H2O2)：N (ortho-chlorotolu'ene)=2:1, using Fig. 2 micro passage reactions, 90 DEG C of controlling reaction temperature, residence time 200s.Outlet
0 DEG C of cooling of material, reaction solution are quenched with dichloromethane.It is analyzed by GC, ortho-chlorotolu'ene conversion ratio is 63.0%, o-chlorobenzaldehyde
Yield is 41.7%.
Embodiment 3
(1) device：Determine that the connection type of tubular reactor, conduit types are with reference to Fig. 2：(3a+3d) once-through type channel+
Enhance mixed type cake formula narrow rectangular tube road, internal diameter of the pipeline is determined with volume according to flow velocity and reaction time, heat transferring medium
For conduction oil.
(2) respectively by 6.06g cobalt acetates and 6.06g sodium molybdates be dissolved in 200ml ortho-chlorotolu'enes and 200ml acetic acid formed it is mixed
Solution is closed, at this time n (cobalt acetate)：N (ortho-chlorotolu'ene)=0.015:1,6.06g sodium bromides are dissolved in 15%H2O2Form H2O2-
Acetic acid solution, at this time n (sodium bromide)：N (ortho-chlorotolu'ene)=0.015:1, ortho-chlorotolu'ene-acetic acid solution with and H2O2Acetic acid solution
It is injected in the tubular reactor persistently to exchange heat by constant flow pump with the flow velocity of 8.33ml/min and 16.67ml/min respectively, at this time n
(H2O2)：N (ortho-chlorotolu'ene)=2:1, using Fig. 2 micro passage reactions, 105 DEG C of controlling reaction temperature, residence time 600s.Go out
Mouth 0 DEG C of cooling of material, reaction solution are quenched with dichloromethane.It is analyzed by GC, ortho-chlorotolu'ene conversion ratio is 60.8%, adjacent chlorobenzene first
Aldehyde yield is 35.2%.
Embodiment 4
(1) device：Determine that the connection type of tubular reactor, conduit types are with reference to Fig. 2：(3a+3b) once-through type channel+
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) respectively by 6.06g cobalt acetates and 6.06g sodium molybdates be dissolved in 200ml ortho-chlorotolu'enes and 200ml acetic acid formed it is mixed
Solution is closed, at this time n (cobalt acetate)：N (ortho-chlorotolu'ene)=0.015:1,6.06g sodium bromides are dissolved in 25%H2O2Form H2O2-
Acetic acid solution, at this time n (sodium bromide)：N (ortho-chlorotolu'ene)=0.015:1, ortho-chlorotolu'ene-acetic acid solution with and H2O2Acetic acid solution
It is injected in the tubular reactor persistently to exchange heat by constant flow pump with the flow velocity of 8.33ml/min and 16.67ml/min respectively, at this time n
(H2O2)：N (ortho-chlorotolu'ene)=2:1, using Fig. 2 micro passage reactions, 115 DEG C of controlling reaction temperature, residence time 600s.Go out
Mouth 0 DEG C of cooling of material, reaction solution are quenched with dichloromethane.It is analyzed by GC, ortho-chlorotolu'ene conversion ratio is 71.5%, adjacent chlorobenzene first
Aldehyde yield is 42.1%.
Embodiment 5
(1) device：Determine that the connection type of tubular reactor, conduit types are with reference to Fig. 2：(3a+3c) once-through type channel+
Rectangle cake formula pulse diameter varied narrow rectangular tube road, internal diameter of the pipeline determine that heat exchange is situated between with volume according to flow velocity and reaction time
Matter is conduction oil.
(2) respectively by 6.06g cobalt acetates and 6.06g sodium molybdates be dissolved in 200ml ortho-chlorotolu'enes and 200ml acetic acid formed it is mixed
Solution is closed, at this time n (cobalt acetate)：N (ortho-chlorotolu'ene)=0.015:1,6.06g sodium bromides are dissolved in 25%H2O2Form H2O2-
Acetic acid solution, at this time n (sodium bromide)：N (ortho-chlorotolu'ene)=0.015:1, ortho-chlorotolu'ene-acetic acid solution with and H2O2Acetic acid solution
It is injected in the tubular reactor persistently to exchange heat by constant flow pump with the flow velocity of 8.33ml/min and 16.67ml/min respectively, at this time n
(H2O2)：N (ortho-chlorotolu'ene)=2:1, using Fig. 2 micro passage reactions, 115 DEG C of controlling reaction temperature, residence time 600s.Go out
Mouth 0 DEG C of cooling of material, reaction solution are quenched with dichloromethane.It is analyzed by GC, ortho-chlorotolu'ene conversion ratio is 53.7%, adjacent chlorobenzene first
Aldehyde yield is 35.1%.
Embodiment 6
(1) device：Determine that the connection type of tubular reactor, conduit types are with reference to Fig. 2：(3a+3d) once-through type channel+
Enhance mixed type cake formula narrow rectangular tube road, internal diameter of the pipeline is determined with volume according to flow velocity and reaction time, heat transferring medium
For conduction oil.
(2) respectively by 6.06g cobalt acetates and 6.06g sodium molybdates be dissolved in 200ml ortho-chlorotolu'enes and 200ml acetic acid formed it is mixed
Solution is closed, at this time n (cobalt acetate)：N (ortho-chlorotolu'ene)=0.015:1,6.06g sodium bromides are dissolved in 25%H2O2Form H2O2-
Acetic acid solution, at this time n (sodium bromide)：N (ortho-chlorotolu'ene)=0.015:1, ortho-chlorotolu'ene-acetic acid solution with and H2O2Acetic acid solution
It is injected in the tubular reactor persistently to exchange heat by constant flow pump with the flow velocity of 5.56ml/min and 11.11ml/min respectively, at this time n
(H2O2)：N (ortho-chlorotolu'ene)=2:1, using Fig. 2 micro passage reactions, 115 DEG C of controlling reaction temperature, residence time 900s.Go out
Mouth 0 DEG C of cooling of material, reaction solution are quenched with dichloromethane.It is analyzed by GC, ortho-chlorotolu'ene conversion ratio is 54.7%, adjacent chlorobenzene first
Aldehyde yield is 35.0%.
Embodiment 7
(1) device：Determine that the connection type of tubular reactor, conduit types are with reference to Fig. 2：(3a+3e) once-through type channel+
Corning Heart Cell structures, internal diameter of the pipeline determine that heat transferring medium is to lead with volume according to flow velocity and reaction time
Deep fat.
(2) respectively by 6.06g cobalt acetates and 6.06g sodium molybdates be dissolved in 200ml ortho-chlorotolu'enes and 200ml acetic acid formed it is mixed
Solution is closed, at this time n (cobalt acetate)：N (ortho-chlorotolu'ene)=0.015:1,6.06g sodium bromides are dissolved in 25%H2O2Form H2O2-
Acetic acid solution, at this time n (sodium bromide)：N (ortho-chlorotolu'ene)=0.015:1, ortho-chlorotolu'ene-acetic acid solution with and H2O2Acetic acid solution
It is injected in the tubular reactor persistently to exchange heat by constant flow pump with the flow velocity of 5.56ml/min and 11.11ml/min respectively, at this time n
(H2O2)：N (ortho-chlorotolu'ene)=2:1, using Fig. 2 micro passage reactions, 90 DEG C of controlling reaction temperature, residence time 900s.Outlet
0 DEG C of cooling of material, reaction solution are quenched with dichloromethane.It is analyzed by GC, ortho-chlorotolu'ene conversion ratio is 52.8%, o-chlorobenzaldehyde
Yield is 39.0%.
Embodiment 8
(1) device：Determine that the connection type of tubular reactor, conduit types are with reference to Fig. 2：(3a+3d) once-through type channel+
Enhance mixed type cake formula narrow rectangular tube road, internal diameter of the pipeline is determined with volume according to flow velocity and reaction time, heat transferring medium
For conduction oil.
(2) respectively by 6.06g cobalt acetates and 6.06g sodium molybdates be dissolved in 200ml ortho-chlorotolu'enes and 200ml acetic acid formed it is mixed
Solution is closed, at this time n (cobalt acetate)：N (ortho-chlorotolu'ene)=0.015:1,6.06g sodium bromides are dissolved in 25%H2O2Form H2O2-
Acetic acid solution, at this time n (sodium bromide)：N (ortho-chlorotolu'ene)=0.015:1, ortho-chlorotolu'ene-acetic acid solution with and H2O2Acetic acid solution
It is injected in the tubular reactor persistently to exchange heat by constant flow pump with the flow velocity of 5.56ml/min and 11.11ml/min respectively, at this time n
(H2O2)：N (ortho-chlorotolu'ene)=2:1, using Fig. 2 micro passage reactions, 100 DEG C of controlling reaction temperature, residence time 900s.Go out
Mouth 0 DEG C of cooling of material, reaction solution are quenched with dichloromethane.It is analyzed by GC, ortho-chlorotolu'ene conversion ratio is 47.9%, adjacent chlorobenzene first
Aldehyde yield is 36.1%.
Embodiment 9
(1) device：Determine that the connection type of tubular reactor, conduit types are with reference to Fig. 2：(3a+3c) once-through type channel+
Rectangle cake formula pulse diameter varied narrow rectangular tube road, internal diameter of the pipeline determine that heat exchange is situated between with volume according to flow velocity and reaction time
Matter is conduction oil.
(2) respectively by 6.06g cobalt acetates and 6.06g sodium molybdates be dissolved in 200ml ortho-chlorotolu'enes and 200ml acetic acid formed it is mixed
Solution is closed, at this time n (cobalt acetate)：N (ortho-chlorotolu'ene)=0.015:1,6.06g sodium bromides are dissolved in 50%H2O2Form H2O2-
Acetic acid solution, at this time n (sodium bromide)：N (ortho-chlorotolu'ene)=0.015:1, ortho-chlorotolu'ene-acetic acid solution with and H2O2Acetic acid solution
It is injected in the tubular reactor persistently to exchange heat by constant flow pump with the flow velocity of 5.56ml/min and 11.11ml/min respectively, at this time n
(H2O2)：N (ortho-chlorotolu'ene)=2:1, using Fig. 2 micro passage reactions, 130 DEG C of controlling reaction temperature, residence time 1800s.Go out
Mouth 0 DEG C of cooling of material, reaction solution are quenched with dichloromethane.It is analyzed by GC, ortho-chlorotolu'ene conversion ratio is 75.1%, adjacent chlorobenzene first
Aldehyde yield is 44.2%.
Claims (10)
1. a kind of method that ortho-chlorotolu'ene continuous oxidation is prepared o-chlorobenzaldehyde by tubular reactor using special construction, special
Sign is to carry out as steps described below：
(1) first at room temperature, by substrate ortho-chlorotolu'ene and carboxylic acid solvent with volume ratio 1:1 is uniformly mixed, by oxidant
With part carboxylic acid solvent with volume ratio 1:1 is uniformly mixed, and then mixes metal complex catalyst and pours into ortho-chlorotolu'ene-carboxylic acid
Solution pours into sodium salt in oxidant-carboxylic acid solution；By the required reaction time, the not cocurrent flow of two kinds of materials is calculated
Speed is continuously squeezed into tubular reactor through metering pump reacted into reaction zone after preheated mixing respectively, reaction temperature by
Outer loop heat-exchange system is controlled；
(2) molar ratio that 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 60~1800s of residence time of control material hybrid reaction；It is completed in reaction
Afterwards, product exits into collecting tank, product rectification separation, unreacted ortho-chlorotolu'ene circular response, product from reactor end
O-chlorobenzaldehyde rectifying is collected after purification.
2. a kind of tubular reactor using special construction according to claim 1 prepares ortho-chlorotolu'ene continuous oxidation adjacent
The method of chlorobenzaldehyde, it is characterised in that wherein the metal complex catalyst is cobalt, molybdenum, bromine one or more metal network
Mixture catalyst.
3. a kind of tubular reactor using special construction according to claim 2 prepares ortho-chlorotolu'ene continuous oxidation adjacent
The method of chlorobenzaldehyde, it is characterised in that wherein the metal complex catalyst is：Cobalt acetate, cobalt oxalate, cobalt carbonate, ring
Alkanoic acid cobalt, sodium molybdate, ammonium molybdate, sodium bromide, ammonium bromide.
4. a kind of tubular reactor using special construction according to claim 1 prepares ortho-chlorotolu'ene continuous oxidation adjacent
The method of chlorobenzaldehyde, it is characterised in that wherein mole of described metal complex catalyst its dosage and substrate ortho-chlorotolu'ene
Than in (0.005~0.15): 1.
5. a kind of tubular reactor using special construction according to claim 4 prepares ortho-chlorotolu'ene continuous oxidation adjacent
The method of chlorobenzaldehyde, it is characterised in that wherein mole of described metal complex catalyst its dosage and substrate ortho-chlorotolu'ene
Than for (0.01~0.12): 1.
6. a kind of tubular reactor using special construction according to claim 1 prepares ortho-chlorotolu'ene continuous oxidation adjacent
The method of chlorobenzaldehyde, it is characterised in that wherein the oxidant is hydrogen peroxide, and solution concentration is calculated as 5% with mass concentration
~50%, the preferred molar ratio of hydrogen peroxide and substrate ortho-chlorotolu'ene is (1.0~8.0): 1.
7. a kind of tubular reactor using special construction according to claim 1 prepares ortho-chlorotolu'ene continuous oxidation adjacent
The method of chlorobenzaldehyde, it is characterised in that wherein the oxidant is hydrogen peroxide, and solution concentration is calculated as with mass concentration
10%~35%.
8. a kind of tubular reactor using special construction according to claim 1 prepares ortho-chlorotolu'ene continuous oxidation adjacent
The method of chlorobenzaldehyde, it is characterised in that the wherein hydrogen peroxide, in tubular reactor, when hydrogen peroxide passes through reactor body
When product 50ml, the beginning of hydrogen peroxide is decomposed rapidly, and a large amount of molecular oxygens are discharged, when it passes through 100ml, almost molecular oxygen shape
Formula, the hydrogen peroxide that should additionally supplement isoconcentration at 100ml reaction volumes at this time enter, and participate in reaction again.
9. a kind of tubular reactor using special construction according to claim 1 prepares ortho-chlorotolu'ene continuous oxidation adjacent
The method of chlorobenzaldehyde, it is characterised in that wherein the carboxylic acid solvent is：Formic acid, acetic acid, propionic acid, butyric acid, caproic acid, octanoic acid；
Wherein the volume ratio of solvent and ortho-chlorotolu'ene is in (1~5): 1.
10. a kind of tubular reactor using special construction according to claim 1 prepares ortho-chlorotolu'ene continuous oxidation
The method of o-chlorobenzaldehyde, it is characterised in that the wherein described reaction temperature is 60~130 DEG C, preferable reaction temperature is 90~
125 DEG C, reaction time is 60s~1800s.
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| CN111704534A (en) * | 2020-06-15 | 2020-09-25 | 杭州迈科瑞科技有限公司 | Process for continuously and industrially producing terephthalaldehyde by using microchannel reactor |
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| CN104447250A (en) * | 2014-12-24 | 2015-03-25 | 常熟市新华化工有限公司 | Method for synthesizing p-chlorobenzaldehyde from p-chlorotoluene |
| CN106588603A (en) * | 2016-11-07 | 2017-04-26 | 常州大学 | Method for preparing o-fluorobenzaldehyde through continuous oxidation of o-fluorotobuene |
| CN106588604A (en) * | 2016-11-07 | 2017-04-26 | 常州大学 | Method for preparing chlorobenzaldehyde through continuous oxidization of m-chlorobenzene |
| CN106748685A (en) * | 2016-11-07 | 2017-05-31 | 常州大学 | A kind of method that parachlorotoluene continuous oxidation prepares 4-chloro-benzaldehyde |
| CN106977381A (en) * | 2017-06-07 | 2017-07-25 | 南京信息职业技术学院 | The synthesis technique of o-chlorobenzaldehyde |
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| CN104447250A (en) * | 2014-12-24 | 2015-03-25 | 常熟市新华化工有限公司 | Method for synthesizing p-chlorobenzaldehyde from p-chlorotoluene |
| CN106588603A (en) * | 2016-11-07 | 2017-04-26 | 常州大学 | Method for preparing o-fluorobenzaldehyde through continuous oxidation of o-fluorotobuene |
| CN106588604A (en) * | 2016-11-07 | 2017-04-26 | 常州大学 | Method for preparing chlorobenzaldehyde through continuous oxidization of m-chlorobenzene |
| CN106748685A (en) * | 2016-11-07 | 2017-05-31 | 常州大学 | A kind of method that parachlorotoluene continuous oxidation prepares 4-chloro-benzaldehyde |
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| CN111704534A (en) * | 2020-06-15 | 2020-09-25 | 杭州迈科瑞科技有限公司 | Process for continuously and industrially producing terephthalaldehyde by using microchannel reactor |
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