CN106748684A - A kind of method of fluorobenzaldehyde between m-fluorotoluene continuous oxidation preparation - Google Patents
A kind of method of fluorobenzaldehyde between m-fluorotoluene continuous oxidation preparation Download PDFInfo
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- CN106748684A CN106748684A CN201610972046.9A CN201610972046A CN106748684A CN 106748684 A CN106748684 A CN 106748684A CN 201610972046 A CN201610972046 A CN 201610972046A CN 106748684 A CN106748684 A CN 106748684A
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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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- 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
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- C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
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Abstract
The method of fluorobenzaldehyde, belongs to organic synthesis technology field between a kind of m-fluorotoluene continuous oxidation preparation of the present invention.The method is that, with m-fluorotoluene compound as raw material, one or more metal ion complexs of cobalt, molybdenum, bromine are catalyst, and hydrogen peroxide is oxidant, and acetic acid is solvent, the technology of fluorobenzaldehyde between the continuous oxidation preparation by m-fluorotoluene in tubular reactor.This method mild condition, the reaction time is short, and raw material availability is high, is capable of achieving the effective control in course of reaction, and safety and stability, continuous operation, production efficiency is high.
Description
Technical field
The invention belongs to organic synthesis technology field, it is related to a kind of continuous by m-fluorotoluene under liquid-phase reaction condition
Oxidation prepare between fluorobenzaldehyde method, be more specifically, with m-fluorotoluene as substrate, hydrogen peroxide is oxidant, cobalt, molybdenum, bromine
One or more metal ion complexs are catalyst, and monocarboxylic acid is solvent, in the tubular reactor with different micro-structurals
In it is continuous prepare between fluorobenzaldehyde product.
Background technology
Between fluorobenzaldehyde be a kind of important organic synthesis intermediate, be colourless or lurid liquid, irritant gas
Taste, can be dissolved in many organic solvents such as ethanol, ether, dichloromethane, toluene.66-68 DEG C of boiling point, 56 DEG C of flash-point, phase
To density 1.17.Between fluorobenzaldehyde easily by the dioxygen oxidation in air into m-fluorobenzoic acid, therefore, answer closed storage.Between fluorine
Benzaldehyde can be widely used in the synthesis of the fine chemicals such as medicine, agricultural chemicals, plastic additive.
The document of fluorobenzaldehyde is little between report synthesis, mostly in reference to the process route for synthesizing other substituted aromatic aldehydes.Virtue
The preparation of aldehyde mainly includes following five kinds：Halogenation Hydrolyze method, direct chemical oxidization method, electrolytic oxidation, hydrogen peroxide are oxygen source pair
The oxidation of aromatic hydrocarbons, oxygen are oxidizing process of the oxygen source to aromatic hydrocarbons.
In by fluorobenzaldehyde between prepared by traditional m-fluorotoluene chlorinolysis, inevitably all contain chlorine,
And in the medicine and the industry such as spices between fluorobenzaldehyde can not contain chlorine, therefore, produced by m-fluorotoluene chlorinolysis
Between the range of application of fluorobenzaldehyde receive certain limitation, such as United States Patent (USP) of Patent No. US2816144 and US4229379
Fluorobenzaldehyde between being prepared by m-fluorotoluene chlorinolysis.This method is more disadvantageously produced in process of production
The substantial amounts of waste water of life, and these wastewater treatments are very difficult, and greatly threat is caused to environment.Fluorobenzaldehyde between traditional
The shortcomings of industrial process all has big seriously polluted, toxicity, high cost, therefore, it is possible to be directed to the deficiency of existing process, grinds
Study carefully and the new technology of fluorobenzaldehyde between a kind of environmentally friendly and process is simple preparation and be of great practical significance.
At present, m-fluorotoluene fluorobenzaldehyde between direct oxidation generation under gas phase or liquid-phase condition is relatively inexpensive and ring
The method of guarantor, early in the United States Patent (USP) of the Patent No. US1321959 of 1919, discloses a kind of m-fluorotoluene gas phase oxygen
The method for changing fluorobenzaldehyde between system, the reaction temperature of the method is 500 ~ 700 DEG C, but do not provide in that patent conversion ratio and
The related data of selectivity, it was reported that in above-mentioned course of reaction, has substantial amounts of carbon dioxide to produce, and illustrates there is excessive oxygen
The problem of change.M-fluorotoluene is primarily present that reaction temperature is high by the method for vapor phase method direct oxidation, and m-fluorotoluene is easily excessive
The defect of oxidation, declines more obvious in the selectivity for improving conversion ratio time fluorobenzaldehyde.
In the United States Patent (USP) of the Patent No. US3387036 of nineteen sixty-eight, between disclosing a kind of m-fluorotoluene liquid phase preparation
The method of fluorobenzaldehyde and phenmethylol, the reaction is carried out at being 170 ~ 220 DEG C in temperature, and m-fluorotoluene turns in the method
Rate at most only 10%, and the selectivity of a fluorobenzaldehyde is not also high.In U.S. of the Patent No. US6495726 of 2002
In state's patent and in the United States Patent (USP) of the Patent No. US6743952 of 2004, report in organic acid medium,
At a temperature of 60-130 DEG C, the method for carrying out liquid phase catalytic oxidation m-fluorotoluene as major catalyst with cobalt salt, in m-fluorotoluene
In the case that conversion ratio is 15-25%, the selectivity of a fluorobenzaldehyde is 40-50%.In the Patent No. CN1663941 of 2005
Chinese patent in, the method for disclosing fluorobenzaldehyde between a kind of m-fluorotoluene liquid phase oxidation system, the temperature of the reaction is 90-
160 DEG C, when the conversion ratio of m-fluorotoluene is 10%, the selectivity of a fluorobenzaldehyde is up to 62%.In the Patent No. of 2009
In the Chinese patent of CN101607867, the method for employing multi-stage oxidizing reactor and gas-liquid separator series connection, m-fluorotoluene turns
Rate has reached more than 95%, and the overall selectivity of a fluorobenzaldehyde and phenmethylol reaches more than 50%, but single-stage reactor conversion
Rate is low, high energy consumption.In sum, to there is high cost, high energy consumption, complex process, a fluorobenzaldehyde selectively low for existing technology
Deng shortcomings.
Fluorobenzaldehyde is optimized and improved approach described above is prepared m-fluorotoluene oxidation from different angles, but
Still suffering from some problems needs to solve：First, ripe industrialized production is remained based on chlorinated hydrolysis, and what chlorination was obtained
Between the use scope of fluorobenzaldehyde be greatly reduced in diameter；Secondly, hydrolysis causes substantial amounts of spent acid and waste water to produce, and environment is made
Into king-sized pollution；Finally, the reaction process of its interval, the time is long, and consumption is big, and conversion ratio is not very high yet.And it is sharp
Fluorobenzaldehyde between the continuous oxidation synthesis of m-fluorotoluene is carried out with the continuous flow tubular reactor of ad hoc structure, many-sided can be solved
Many deficiencies of existing process technology.
Tubular reactor is the general designation of the mini-reactor with micro-structural, compared with conventional reactor, tubular reactor
Big, the small volume with specific surface area, process is continuous, easily amplifies, 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.The contact area that can be effectively increased between reactant by the design to pipeline configuration and size strengthens its mass-and heat-transfer effect
Really, accelerate reaction rate and shorten the reaction time, and improve the utilization rate of oxidant, reduce the usage amount of oxidant and avoid
The use of co-catalyst, while " temperature runaway " phenomenon produced by hot-spot in solving course of reaction.By to tubular type
The control of the length and reaction time of reactor, can further make raw material and product distribution more optimize it is controllable；Pass through
The flow velocity of regulation raw material pump can realize that substrate m-fluorotoluene is reacted into tubular reactor in proportion with oxidant and subtract significantly
Back-mixing is lacked, has further reduced the generation of side reaction, the stability of oxidant and the selectivity of target product have also been greatly improved；
By setting pressure safety valve in tubular reactor, the excessive oxidant in reactor can be in time given off, it is ensured that reaction
Safety carry out, level of significance is minimized.The present invention carries out the continuous oxygen of m-fluorotoluene using the tubular reactor of ad hoc structure
The method for changing fluorobenzaldehyde between preparing has unrivaled advantage relative to conventional batch production method, and can be its work
Industry quantity-produced is improved and provides an important approach.
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 m-fluorotoluene continuous oxidation system
The method of fluorobenzaldehyde between standby.This method reaction time is short, and production efficiency is high, and mass transfer, heat transfer are optimized significantly, course of reaction
More stablize controllable.Further object of the present invention is, by process of the invention, realizes the continuous oxygen of m-fluorotoluene
That changes stablizes controllable, reduces the generation of accessory substance.Reaction mass is improved by the reinforcing of mass-and heat-transfer process and process optimization
Effective rate of utilization, further reduces the usage amount of oxidant and catalyst and avoids making for co-catalyst during the course of the reaction
With 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：
A kind of tubular reactor of use special construction by m-fluorotoluene continuous oxidation prepare between fluorobenzaldehyde method, under
Stating step is carried out：
(1) first at room temperature, by substrate m-fluorotoluene and part 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 well mixed, and it is molten that metal complex mixing then is poured into m-fluorotoluene-carboxylic acid
Liquid, sodium salt is poured into hydrogen peroxide-carboxylic acid solution；By the required reaction time, the different in flow rate of two kinds of materials is calculated,
Continuously squeezed into tubular reactor through measuring pump respectively and reacted into reaction zone after preheated mixing, reaction temperature is by outside
Circulating heat exchange system is controlled；
(2) mol ratio of reaction mass is controlled by adjusting the method for 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 60 ~ 1800s of residence time of control material hybrid reaction；After completion of the reaction, produce
Thing exits into collecting tank from reactor end, and product rectification is separated, unreacted m-fluorotoluene circular response, fluorobenzene between product
Formaldehyde rectification is collected after purification, and the yield of fluorobenzaldehyde is up to 20% ~ 60% wherein between target product.
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 m-fluorotoluene, its consumption exists with the mol ratio of substrate m-fluorotoluene（0.003~0.30）: 1, wherein excellent
The mol ratio is selected to be（0.01~0.15）∶1.
Wherein described oxidant is hydrogen peroxide, and its solution concentration is calculated as 5% ~ 80% with mass concentration, and preferred concentration is 15%
~65%.Hydrogen peroxide is with the preferred molar ratio of substrate m-fluorotoluene（1.0~10.0）∶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 a fluorine
The volume ratio of toluene exists（1~12）∶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 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 is controllable, raw
Produce efficiency 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 ketone 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 of fluorobenzaldehyde between prepared by m-fluorotoluene continuous oxidation of the present invention.
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-
Cake formula pulse diameter varied narrow rectangular tube road, the oblique side cake formula pulse diameter varied narrow rectangular tube roads of c-, d- enhancing mixed type cake formulas
Flat tube road, the Heart Cell structures microchannel of e-Corning.
Specific embodiment
Cobalt acetate and sodium molybdate are dissolved in the 1# tanks equipped with m-fluorotoluene and acetic acid, the pre- thermal responses of 5# are pumped into by 3#
In device, pre- thermal reactor is heated to 50 DEG C；Sodium bromide is dissolved in the 2# tanks equipped with hydrogen peroxide and acetic acid, 6# is pumped into by 4#
In pre- thermal reactor, pre- thermal reactor is heated to 50 DEG C, then by two strands of preheating materials, is delivered in 7#, 8# reactor, reaction
Device temperature 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 determines that heat transferring medium is to lead with volume according to flow velocity and reaction time
Deep fat.
（2）6.06g cobalt acetates and 6.06g sodium molybdates are dissolved in 200ml m-fluorotoluenes respectively and 200ml acetic acid forms mixed
Solution is closed, now n（Cobalt acetate）：n（M-fluorotoluene）=0.015:1,6.06g sodium bromides are dissolved in 25%H2O2Form H2O2- second
Acid solution, now n（Sodium bromide）：n（M-fluorotoluene）=0.015:1, m-fluorotoluene-acetic acid solution with and H2O2- acetic acid solution point
Do not injected in the tubular reactor of lasting heat exchange by constant flow pump with the flow velocity of 8.33ml/min and 16.67ml/min, now n
（H2O2）：n（M-fluorotoluene）=2:1, using Fig. 2 micro passage reactions, 60 DEG C of controlling reaction temperature, residence time 60s.Outlet thing
0 DEG C of cooling of material, reaction solution is quenched with dichloromethane.Analyzed by GC, m-fluorotoluene conversion ratio is 35.3%, and a fluorobenzaldehyde is received
Rate is 21.1%.
Embodiment 2
（1）Device：Reference picture 2 determines the connected mode of tubular reactor, and conduit types are：（3a+3c）Once-through type passage+tiltedly square
Cake formula pulse diameter varied narrow rectangular tube road, internal diameter of the pipeline determines that heat transferring medium is with volume according to flow velocity and reaction time
Conduction oil.
（2）12.12g cobalt acetates and 12.12g sodium molybdates are dissolved in 200ml m-fluorotoluenes respectively and 200ml acetic acid is formed
Mixed solution, now n（Cobalt acetate）：n（M-fluorotoluene）=0.03:1,12.12g sodium bromides are dissolved in 25%H2O2Form H2O2-
Acetic acid solution, now n（Sodium bromide）：n（M-fluorotoluene）=0.03:1, m-fluorotoluene-acetic acid solution with and H2O2- acetic acid solution point
Do not injected in the tubular reactor of lasting heat exchange by constant flow pump with the flow velocity of 8.33ml/min and 16.67ml/min, now n
（H2O2）：n（M-fluorotoluene）=2:1, using Fig. 2 micro passage reactions, 105 DEG C of controlling reaction temperature, residence time 600s.Outlet
0 DEG C of cooling of material, reaction solution is quenched with dichloromethane.Analyzed by GC, m-fluorotoluene conversion ratio is 75.8%, a fluorobenzaldehyde
Yield is 45.3%.
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 determines that heat transferring medium is to lead with volume according to flow velocity and reaction time
Deep fat.
（2）6.06g cobalt acetates and 6.06g sodium molybdates are dissolved in 200ml m-fluorotoluenes respectively and 200ml acetic acid forms mixed
Solution is closed, now n（Cobalt acetate）：n（M-fluorotoluene）=0.015:1,6.06g sodium bromides are dissolved in 30%H2O2Form H2O2- second
Acid solution, now n（Sodium bromide）：n（M-fluorotoluene）=0.015:1, m-fluorotoluene-acetic acid solution with and H2O2- acetic acid solution point
Do not injected in the tubular reactor of lasting heat exchange by constant flow pump with the flow velocity of 8.33ml/min and 16.67ml/min, now n
（H2O2）：n（M-fluorotoluene）=2:1, using Fig. 2 micro passage reactions, 105 DEG C of controlling reaction temperature, residence time 600s.Outlet
0 DEG C of cooling of material, reaction solution is quenched with dichloromethane.Analyzed by GC, m-fluorotoluene conversion ratio is 76.8%, a fluorobenzaldehyde
Yield is 39.1%.
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 determines that heat transferring medium is to lead with volume according to flow velocity and reaction time
Deep fat.
（2）6.06g cobalt acetates and 6.06g sodium molybdates are dissolved in 200ml m-fluorotoluenes respectively and 200ml acetic acid forms mixed
Solution is closed, now n（Cobalt acetate）：n（M-fluorotoluene）=0.015:1,6.06g sodium bromides are dissolved in 25%H2O2Form H2O2- second
Acid solution, now n（Sodium bromide）：n（M-fluorotoluene）=0.015:1, m-fluorotoluene-acetic acid solution with and H2O2- acetic acid solution point
Do not injected in the tubular reactor of lasting heat exchange by constant flow pump with the flow velocity of 8.33ml/min and 16.67ml/min, now n
（H2O2）：n（M-fluorotoluene）=3:1, using Fig. 2 micro passage reactions, 105 DEG C of controlling reaction temperature, residence time 600s.Outlet
0 DEG C of cooling of material, reaction solution is quenched with dichloromethane.Analyzed by GC, m-fluorotoluene conversion ratio is 60.5%, a fluorobenzaldehyde
Yield is 38.1%.
Embodiment 5
（1）Device：Reference picture 2 determines the connected mode of tubular reactor, and conduit types are：（3a+3c）Once-through type passage+tiltedly square
Cake formula pulse diameter varied narrow rectangular tube road, 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 200ml m-fluorotoluenes respectively and 200ml acetic acid forms mixed
Solution is closed, now n（Cobalt acetate）：n（M-fluorotoluene）=0.015:1,6.06g sodium bromides are dissolved in 25%H2O2Form H2O2- second
Acid solution, now n（Sodium bromide）：n（M-fluorotoluene）=0.015:1, m-fluorotoluene-acetic acid solution with and H2O2- acetic acid solution point
Do not injected in the tubular reactor of lasting heat exchange by constant flow pump with the flow velocity of 8.33ml/min and 16.67ml/min, now n
（H2O2）：n（M-fluorotoluene）=3:1, using Fig. 2 micro passage reactions, 105 DEG C of controlling reaction temperature, residence time 600s.Outlet
0 DEG C of cooling of material, reaction solution is quenched with dichloromethane.Analyzed by GC, m-fluorotoluene conversion ratio is 54.1%, a fluorobenzaldehyde
Yield is 28.1%.
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 determines that heat transferring medium is to lead with volume according to flow velocity and reaction time
Deep fat.
（2）6.06g cobalt acetates and 6.06g sodium molybdates are dissolved in 200ml m-fluorotoluenes respectively and 200ml acetic acid forms mixed
Solution is closed, now n（Cobalt acetate）：n（M-fluorotoluene）=0.015:1,6.06g sodium bromides are dissolved in 25%H2O2Form H2O2- second
Acid solution, now n（Sodium bromide）：n（M-fluorotoluene）=0.015:1, m-fluorotoluene-acetic acid solution with and H2O2- acetic acid solution point
Do not injected in the tubular reactor of lasting heat exchange by constant flow pump with the flow velocity of 5.56ml/min and 11.11ml/min, now n
（H2O2）：n（M-fluorotoluene）=2:1, using Fig. 2 micro passage reactions, 105 DEG C of controlling reaction temperature, residence time 900s.Outlet
0 DEG C of cooling of material, reaction solution is quenched with dichloromethane.Analyzed by GC, m-fluorotoluene conversion ratio is 55.7%, a fluorobenzaldehyde
Yield is 30.2%.
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 200ml m-fluorotoluenes respectively and 200ml acetic acid forms mixed
Solution is closed, now n（Cobalt acetate）：n（M-fluorotoluene）=0.015:1,6.06g sodium bromides are dissolved in 35%H2O2Form H2O2- second
Acid solution, now n（Sodium bromide）：n（M-fluorotoluene）=0.015:1, m-fluorotoluene-acetic acid solution with and H2O2- acetic acid solution point
Do not injected in the tubular reactor of lasting heat exchange by constant flow pump with the flow velocity of 5.56ml/min and 11.11ml/min, now n
（H2O2）：n（M-fluorotoluene）=2:1, using Fig. 2 micro passage reactions, 120 DEG C of controlling reaction temperature, residence time 900s.Outlet
0 DEG C of cooling of material, reaction solution is quenched with dichloromethane.Analyzed by GC, m-fluorotoluene conversion ratio is 69.8%, a fluorobenzaldehyde
Yield is 45.0%.
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 determines that heat transferring medium is to lead with volume according to flow velocity and reaction time
Deep fat.
（2）6.06g cobalt acetates and 6.06g sodium molybdates are dissolved in 200ml m-fluorotoluenes respectively and 200ml acetic acid forms mixed
Solution is closed, now n（Cobalt acetate）：n（M-fluorotoluene）=0.015:1,6.06g sodium bromides are dissolved in 35%H2O2Form H2O2- second
Acid solution, now n（Sodium bromide）：n（M-fluorotoluene）=0.015:1, m-fluorotoluene-acetic acid solution with and H2O2- acetic acid solution point
Do not injected in the tubular reactor of lasting heat exchange by constant flow pump with the flow velocity of 5.56ml/min and 11.11ml/min, now n
（H2O2）：n（M-fluorotoluene）=2:1, using Fig. 2 micro passage reactions, 140 DEG C of controlling reaction temperature, residence time 1800s.Go out
0 DEG C of cooling of mouth material, reaction solution is quenched with dichloromethane.Analyzed by GC, m-fluorotoluene conversion ratio is 77.9%, a fluorobenzene first
Aldehyde yield is 56.1%.
Claims (6)
1. a kind of method of fluorobenzaldehyde between prepared by m-fluorotoluene continuous oxidation, it is characterised in that carry out as steps described below：
（1）At room temperature, by substrate m-fluorotoluene and part carboxylic acid solvent with volume ratio 1:1 is uniformly mixed, by oxidant and
Part carboxylic acid solvent is with volume ratio 1:1 is well mixed, and then mixes metal complex and pours into m-fluorotoluene-carboxylic acid solution, will
Sodium salt is poured into hydrogen peroxide-carboxylic acid solution；By the required reaction time, two kinds of different in flow rate, difference of material are calculated
Continuously squeezed into tubular reactor through measuring pump and reacted into reaction zone after preheated mixing, reaction temperature is 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 m-fluorotoluene circular response, fluorobenzaldehyde rectifying between product
Collect after purification.
2. the method for fluorobenzaldehyde between prepared by a kind of m-fluorotoluene continuous oxidation according to claim 1, it is characterised in that
Described catalyst is cobalt, molybdenum, sodium one or more metal complex catalysts, and it mainly includes：Cobalt acetate, cobalt oxalate, carbon
Sour cobalt, cobalt naphthenate, sodium molybdate, ammonium molybdate, sodium bromide, ammonium bromide etc., wherein based on oil-soluble catalyst, can be in a fluorine first
Fully dissolved in benzene, its consumption exists with the mol ratio of substrate m-fluorotoluene（0.003~0.30）: 1, wherein preferred molar ratio is
（0.01~0.15）∶1.
3. the method for fluorobenzaldehyde between prepared by a kind of m-fluorotoluene continuous oxidation according to claim 1, it is characterised in that
Described oxidant is hydrogen peroxide, and its solution concentration is calculated as 5% ~ 80% with mass concentration, and preferred concentration is 15% ~ 65%, hydrogen peroxide
Preferred molar ratio with substrate m-fluorotoluene is（1.0~10.0）∶1.
4. the method for fluorobenzaldehyde between prepared by a kind of m-fluorotoluene continuous oxidation according to claim 1, it is characterised in that
Described carboxylic acid solvent includes：Formic acid, acetic acid, propionic acid, butyric acid, caproic acid, octanoic acid;Wherein solvent exists with the volume ratio of m-fluorotoluene
（1~12）∶1.
5. the method for fluorobenzaldehyde between prepared by a kind of m-fluorotoluene continuous oxidation according to claim 1, it is characterised in that：
Reaction temperature is 60 ~ 140 DEG C, and preferable reaction temperature is 90 ~ 125 DEG C, reaction time 60s ~ 1800s.
6. the method for fluorobenzaldehyde between prepared by a kind of m-fluorotoluene continuous oxidation according to claim 1, it is characterised in that
Total overall reaction process is carried out continuously in the tubular reactor of ad hoc structure, the reaction system include raw material storage tank, reaction zone,
The difference in functionality such as 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 impulse type diameter varied narrow rectangular tube road structure, enhancing mixed type cake formula narrow rectangular tube road
Structure, cardioid channel design.
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| US5473101A (en) * | 1991-06-21 | 1995-12-05 | Solvay Interox Limited | Oxidation of alkylaromatics |
| WO1995020560A1 (en) * | 1994-01-27 | 1995-08-03 | Dsm N.V. | Process for the manufacture of benzaldehyde |
| CN1166480A (en) * | 1996-05-17 | 1997-12-03 | 东丽株式会社 | Method for preparing aromatic carboxylic acids, aromatic aldehydes, and aromatic alcohols |
| CN1827575A (en) * | 2005-04-06 | 2006-09-06 | 四川大学 | Process for one step preparation of benzaldehyde by selective oxidation of toluene |
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