A kind of method of continuous production Trifluoroacetic Acid Ethyl Ester
Technical field
The present invention relates to a kind of preparation methods of Trifluoroacetic Acid Ethyl Ester, prepare trifluoroacetic acid more particularly, to a kind of serialization
The method of ethyl ester.
Background technique
Trifluoroacetic Acid Ethyl Ester is a kind of important Organic Chemicals, is mainly used to synthesize trifluoroacetic ethyl acetoacetate, three
The organofluorine compounds such as acetyl fluoride acetone, 2- thioyl trifluoroacetone, it can also be used to prepare pesticide, medicine, dyestuff, liquid crystal
With industrial chemical etc..At present in the world more commonly used Trifluoroacetic Acid Ethyl Ester industrially prepared route mainly include the following types:
(1) P69 pages of the phase of " Wenzhou normal academy's report " 1996 the 6th discloses a kind of preparation method of Trifluoroacetic Acid Ethyl Ester,
Using trifluoroacetic acid and dehydrated alcohol as primary raw material, catalyst is made with the concentrated sulfuric acid, is heated to reflux, crude product is obtained;Chinese patent
CN102276463 is disclosed, and using trifluoroacetic acid and dehydrated alcohol as primary raw material, makees catalyst preparation crude product with the concentrated sulfuric acid,
Sulfur trioxide is added inside rectifying Liquid Residue, dilute sulfuric acid is made to become the concentrated sulfuric acid, thus realize recycling, save the cost, but this
Method concentrated sulfuric acid usage amount is bigger, and equipment corrosion is more serious;
(2) P4 pages of the phase of volume 48 the 4th of " Zhejiang chemical industry " discloses a kind of preparation method of Trifluoroacetic Acid Ethyl Ester, with trifluoro second
Acid and dehydrated alcohol are that primary raw material is heated to reflux with solid super strong acid as catalyst, obtain crude product;" Hebei chemical industry " the 35th
Roll up the 6th P24 pages of the phase disclose a kind of preparation method of Trifluoroacetic Acid Ethyl Ester, using trifluoroacetic acid and dehydrated alcohol as primary raw material,
Make catalyst with p-methyl benzenesulfonic acid, be heated to reflux, obtains crude product;CN101397249 discloses a kind of system of Trifluoroacetic Acid Ethyl Ester
Preparation Method makees catalyst using trifluoroacetic acid and dehydrated alcohol as primary raw material with storng-acid cation exchange resin, is being lower than 50
DEG C and normal pressure under dehydrated alcohol be added dropwise and kept for a period of time make fully reacting.Catalyst is filtered out, solid particle is being filled with
Dry in the drying tower of silica gel to remove surplus moisture, air-distillation, the fraction for collecting 58~64 DEG C is finished product.Production process is complete close
It is carried out under envelope state, catalyst recycling, tails can be recycled after harvest product.
Although it is catalyst that these methods, which relatively use the concentrated sulfuric acid, technique is more preferable, and yield is higher, and equipment corrosion is not serious,
It is that catalyst price is high, there are problems that catalyst treatment, need filtration drying etc..
(3) patent EP1070702 discloses a kind of preparation method of Trifluoroacetic Acid Ethyl Ester, with trifluoro-acetyl chloride and anhydrous second
Alcohol is primary raw material, and Trifluoroacetic Acid Ethyl Ester is solvent, to prepare Trifluoroacetic Acid Ethyl Ester;Patent US4916256 discloses one kind three
The preparation method of ethyl fluoroacetate becomes ethyl alcohol and trifluoro-acetyl chloride using trifluoro-acetyl chloride and dehydrated alcohol as primary raw material
Gas reaction, to prepare Trifluoroacetic Acid Ethyl Ester;Patent EP1070702 discloses a kind of preparation method of Trifluoroacetic Acid Ethyl Ester, with
Trifluoro-acetyl chloride and dehydrated alcohol are primary raw material, and the acid solution of salt is catalyst, and to prepare Trifluoroacetic Acid Ethyl Ester, reaction is produced
Object is layered to obtain crude product;These complex technical process, ethyl alcohol are not easy fully reacting, and post-processing is complicated, is unable to continuous production.
In the existing technique for preparing Trifluoroacetic Acid Ethyl Ester: preparing Trifluoroacetic Acid Ethyl Ester with ethanol synthesis with trifluoroacetic acid is
Prevailing technology needs to use the concentrated sulfuric acid, storng-acid cation exchange resin, to toluene although simple process is easily operated
The acidic materials such as sulphur are as catalyst, and there is only catalyst price height, the big and intractable problem of dead catalyst amount, Er Qieyi
So that equipment seriously corroded, the high requirements on the equipment;It is prepared in Trifluoroacetic Acid Ethyl Ester technique with trifluoro-acetyl chloride and ethanol synthesis, though
Acidic catalyst is not used so, and quantity of three wastes can be reduced, but be reacted again after needing to convert ethyl alcohol to gas, energy consumption of reaction
It is higher, while ethyl alcohol cannot react completely, since ethyl alcohol and Trifluoroacetic Acid Ethyl Ester will form azeotropic mixture, product not easy purification, also
It needs to remove ethyl alcohol and dry process by washing, regenerates a large amount of waste water, form new environmental issue, and cannot
Carry out continuous production.
Therefore, it is necessary to which the preparation process to Trifluoroacetic Acid Ethyl Ester is improved further.
Summary of the invention
The purpose of the present invention is to provide a kind of trifluoro-acetyl chlorides and ethanol synthesis serialization to prepare Trifluoroacetic Acid Ethyl Ester
Method enables ethyl alcohol in reaction process fully reacting, to reduce purifying products problem, and enables technique continuous production.
Synthesis route of the invention are as follows:
The invention provides the following technical scheme:
A kind of method that trifluoro-acetyl chloride prepares Trifluoroacetic Acid Ethyl Ester with ethanol synthesis serialization, the method is in microchannel
It is carried out in reactor, comprising the following steps:
(1) raw material 1 is made to enter warm-up block 3, preheating temperature is 0~100 DEG C, and the raw material 1 includes dehydrated alcohol;
(2) raw material 1 and raw material 2 after step (1) preheats is made to enter microchannel reaction module 4, the raw material 2 includes three
Fluoracyl chloride, raw material 2 are mixed and are reacted in the microchannel reaction module with raw material 1, mole of the raw material 2 and raw material 1
Proportion be 1.5:1~1.0:1,1 flow of raw material be 0.1~10g/min, reaction temperature be 0~100 DEG C, reaction pressure be 0~
1.0MPa;
(3) reaction module 9 exit in step (2) microchannel obtains compound after quenching module 10 to get to product three
Ethyl fluoroacetate.
Trifluoro-acetyl chloride provided by the invention and ethanol synthesis serialization prepare Trifluoroacetic Acid Ethyl Ester, will be micro- logical before preparation
Reactor each module in road is assembled to obtain micro passage reaction.As an example, one piece can be preheated according to shown in attached drawing 3
3, six pieces of microchannel reaction modules 4~9 of module and one piece of quenching module 10 carry out tandem installation, in which: with 3 phase of warm-up block
1 even is liquid phase pump, the feed inlet as raw material 1;1 to be connected with microchannel reaction module 4 is gas mass flow meter, as
2 feed inlet of raw material.
After micro passage reaction connects, conduction oil can be used and conduct heat.Connect in trifluoro-acetyl chloride and ethanol synthesis
During continuousization prepares Trifluoroacetic Acid Ethyl Ester, it can according to need and increase or decrease microchannel reaction module, can according to need
2 pieces or 2 pieces of selection or more microchannel reaction module participates in reaction.
Trifluoro-acetyl chloride provided by the invention and ethanol synthesis serialization are prepared in Trifluoroacetic Acid Ethyl Ester method, as preferred
Mode, the mass tranfer coefficient of the micro passage reaction is 1~30Ka, exchange capability of heat 1700KW/m2K or more.
Trifluoro-acetyl chloride provided by the invention and ethanol synthesis serialization are prepared in Trifluoroacetic Acid Ethyl Ester method, as preferred
Mode, the micro passage reaction is that healthy and free from worry G2 microreactor, microwell array decline channel reactor, finned microchannel plate
Answer device, capillary microchannels reactor or multiply parallel type microreactor.
Trifluoro-acetyl chloride provided by the invention and ethanol synthesis serialization are prepared in Trifluoroacetic Acid Ethyl Ester method, described micro- logical
Microchannel structure in the reaction module of road reactor includes once-through type channel design and enhancing mixed type channel design.Preferably
It is that the once-through type channel design is tubular structure, the enhancing mixed type channel design is T-type structure, spherical structure, spherical shape
Band baffle arrangement, drops structure or heart-shaped structure, and channel diameter is 0.5mm~10mm.
Trifluoro-acetyl chloride provided by the invention and ethanol synthesis serialization prepare Trifluoroacetic Acid Ethyl Ester method, the microchannel
The material of reaction module is selected from silicon carbide, breathes out C alloy or manganese Nai Er alloy.
Trifluoro-acetyl chloride provided by the invention and ethanol synthesis serialization are prepared in Trifluoroacetic Acid Ethyl Ester method, raw material 1 into
It before entering warm-up block 3, is preheated, preheating temperature is 0~100 DEG C.Preferably, the preheating temperature is 20~80
℃。
Trifluoro-acetyl chloride provided by the invention and ethanol synthesis serialization are prepared in Trifluoroacetic Acid Ethyl Ester method, raw material 1 with
The mol ratio satisfaction of raw material 2 goes on smoothly reaction.As a preferred mode, the raw material 2 and raw material 1 rub
Your proportion is 1.5:1~1.0:1.As further preferred mode, the mol ratio of the raw material 2 and raw material 1 be 1.2:1~
1.05:1。
Trifluoro-acetyl chloride provided by the invention and ethanol synthesis serialization are prepared in Trifluoroacetic Acid Ethyl Ester method, raw material 2
Flow enough goes on smoothly reaction.As a preferred mode, 1 flow of raw material is 0.1~10g/min.
Trifluoro-acetyl chloride provided by the invention and ethanol synthesis serialization are prepared in Trifluoroacetic Acid Ethyl Ester method, step (2)
Middle reaction temperature is 0~100 DEG C.As a preferred mode, the reaction temperature is 20~80 DEG C.
Trifluoro-acetyl chloride provided by the invention and ethanol synthesis serialization are prepared in Trifluoroacetic Acid Ethyl Ester method, step (2)
Middle reaction pressure is 0~1.0MPa.As a preferred mode, the reaction pressure is 0~0.5MPa.
Trifluoro-acetyl chloride provided by the invention and ethanol synthesis serialization prepare Trifluoroacetic Acid Ethyl Ester method, with the prior art
Compare, have that high conversion rate, the reaction time is short, reaction is safely controllable, product be easy purifying and can continuous chemical industry amplify
Characteristic advantage.
Detailed description of the invention
Fig. 1 is the typical structure unit figure of micro passage reaction module used in the present invention;
Fig. 2 is institute of the invention to module map for Corning micro passage reaction;
Fig. 3 is institute of the invention to micro channel reactor system device figure for Corning microchannel module, and in Fig. 3:
1 it is liquid phase pump (1 feed inlet of raw material), 2 be gas mass flow meter (2 feed inlet of raw material), 3 be warm-up block, 4~9 is micro- logical
Road reaction module, 10 are quenching module.
Specific embodiment
Next combined with specific embodiments below invention is further explained, but does not limit the invention to these tools
Body embodiment.One skilled in the art would recognize that present invention encompasses may include in Claims scope
All alternatives, improvement project and equivalent scheme.
Embodiment 1
Select 1 piece of corning straight channel module in attached drawing 2 (as premix warm-up block 3), corning " heart " micro- logical
6 pieces of road reaction module, 1 piece of corning straight channel module (as quenching module 10).It is formed according to reaction process shown in attached drawing 3
Continuous flow microchannel reaction system.Reacting replacing heat medium uses conduction oil.Heat transfer theory is forced according to micro passage reaction, is only existed
Two temperature measuring points are arranged in the reactor feed mouth and discharge port.Microchannel reaction system and connecting line are carried out respectively before reaction
Water removal is dried, and carries out 1.0MPa airtight test.By 1 liquid phase pump (such as diaphragm metering pump) in attached drawing 3, to microchannel
Feed ethanol is added in reaction system continuous-stable.By 2 gas mass flow meters in attached drawing 3, connect to microchannel reaction system
It is continuous to be quantitatively adding trifluoroacetyl chlorine body.
55 DEG C of heat exchange temperature of setting, i.e. reaction temperature set reaction pressure 0MPa.Feed ethanol, charging rate are
0.67g/min, trifluoro-acetyl chloride gas feed speed are 2.12g/min, and residence time of reaction is 25s, trifluoro-acetyl chloride with
The mol ratio of ethyl alcohol is 1.1:1.Reaction raw materials enter " heart " microchannel reaction module after microchannel premixes warm-up block 3
4, trifluoroacetyl chlorine body is directly entered " heart " microchannel reaction module 4 by gas mass flow meter, micro- logical in " heart "
In road reaction module 4-9, trifluoro-acetyl chloride and ethanol synthesis.Crude reaction collects after quenching module 10 and obtains trifluoroacetic acid second
Ester crude product.
GC analysis is carried out to the mixed liquor of reaction, the results showed that, the residual quantity of ethyl alcohol is 0, and the conversion ratio of ethyl alcohol is
100%.
Embodiment 2
Using healthy and free from worry micro passage reaction similarly to Example 1, and according to same connection type and control method.This
Embodiment changes reaction condition.
60 DEG C of heat exchange temperature of setting, i.e. reaction temperature set reaction pressure 0MPa.Feed ethanol, charging rate are
0.88g/min, trifluoro-acetyl chloride gas feed speed are 2.66g/min, and residence time of reaction is 20s, trifluoro-acetyl chloride with
The mol ratio of ethyl alcohol is 1.05:1.Reaction raw materials enter " heart " microchannel plate Ying Mo after microchannel premixes warm-up block 3
Block 4, trifluoroacetyl chlorine body is directly entered " heart " microchannel reaction module 4 by gas mass flow meter, micro- in " heart "
In pathway reaction module 4-9, trifluoro-acetyl chloride and ethanol synthesis.Crude reaction collects after quenching module 10 and obtains trifluoroacetic acid
Ethyl ester.
GC analysis is carried out to reaction mixture, the results showed that, the residual quantity of ethyl alcohol is 0, and the conversion ratio of ethyl alcohol is 100%.
Embodiment 3
Using healthy and free from worry micro passage reaction similarly to Example 1, and according to same connection type and control method.This
Embodiment changes reaction condition.
65 DEG C of heat exchange temperature of setting, i.e. reaction temperature set reaction pressure 0MPa.Feed ethanol, charging rate are
1.68g/min, trifluoro-acetyl chloride gas feed speed are 5.31g/min, and residence time of reaction is 10s, trifluoro-acetyl chloride with
The mol ratio of ethyl alcohol is 1.1:1.Reaction raw materials enter " heart " microchannel reaction module after microchannel premixes warm-up block 3
4, trifluoroacetyl chlorine body is directly entered " heart " microchannel reaction module 4 by gas mass flow meter, micro- logical in " heart "
In road reaction module 4-9, trifluoro-acetyl chloride and ethanol synthesis.Crude reaction collects after quenching module 10 and obtains trifluoroacetic acid second
Ester crude product.
GC analysis is carried out to reaction mixture, the results showed that, the residual quantity of ethyl alcohol is 0, and the conversion ratio of ethyl alcohol is 100%.
Embodiment 4
Using healthy and free from worry micro passage reaction similarly to Example 1, and according to same connection type and control method.This
Embodiment changes reaction condition.
80 DEG C of heat exchange temperature of setting, i.e. reaction temperature set reaction pressure 0MPa.Feed ethanol, charging rate are
0.88g/min, trifluoro-acetyl chloride gas feed speed are 2.66g/min, and residence time of reaction is 20s, trifluoro-acetyl chloride with
The mol ratio of ethyl alcohol is 1.05:1.Reaction raw materials enter " heart " microchannel plate Ying Mo after microchannel premixes warm-up block 3
Block 4, trifluoroacetyl chlorine body is directly entered " heart " microchannel reaction module 4 by gas mass flow meter, micro- in " heart "
In pathway reaction module 4-9, trifluoro-acetyl chloride and ethanol synthesis.Crude reaction collects after quenching module 10 and obtains trifluoroacetic acid
Ethyl ester.
GC analysis is carried out to reaction mixture, the results showed that, the residual quantity of ethyl alcohol is 0, and the conversion ratio of ethyl alcohol is 100%.
Embodiment 5
Using healthy and free from worry micro passage reaction similarly to Example 1, and according to same connection type and control method.This
Embodiment changes reaction condition.
50 DEG C of heat exchange temperature of setting, i.e. reaction temperature set reaction pressure 0MPa.Feed ethanol, charging rate are
0.56g/min, trifluoro-acetyl chloride gas feed speed are 1.77g/min, and residence time of reaction is 30s, trifluoro-acetyl chloride with
The mol ratio of ethyl alcohol is 1.1:1.Reaction raw materials enter " heart " microchannel reaction module after microchannel premixes warm-up block 3
4, trifluoroacetyl chlorine body is directly entered " heart " microchannel reaction module 4 by gas mass flow meter, micro- logical in " heart "
In road reaction module 4-9, trifluoro-acetyl chloride and ethanol synthesis.Crude reaction collects after quenching module 10 and obtains trifluoroacetic acid second
Ester crude product.
GC analysis is carried out to reaction mixture, the results showed that, the residual quantity of ethyl alcohol is 0, and the conversion ratio of ethyl alcohol is 100%.
Embodiment 6
Using healthy and free from worry micro passage reaction similarly to Example 1, and according to same connection type and control method.This
Embodiment changes reaction condition.
30 DEG C of heat exchange temperature of setting, i.e. reaction temperature set reaction pressure 0.1MPa.Feed ethanol, charging rate are
0.26g/min, trifluoro-acetyl chloride gas feed speed are 0.89g/min, and residence time of reaction is 30s, trifluoro-acetyl chloride with
The mol ratio of ethyl alcohol is 1.2:1.Reaction raw materials enter " heart " microchannel reaction module after microchannel premixes warm-up block 3
4, trifluoroacetyl chlorine body is directly entered " heart " microchannel reaction module 4 by gas mass flow meter, micro- logical in " heart "
In road reaction module 4-9, trifluoro-acetyl chloride and ethanol synthesis.Crude reaction collects after quenching module 10 and obtains trifluoroacetic acid second
Ester crude product.
GC analysis is carried out to reaction mixture, the results showed that, the residual quantity of ethyl alcohol is 0, and the conversion ratio of ethyl alcohol is 100%.
Embodiment 7
Using healthy and free from worry micro passage reaction similarly to Example 1, and according to same connection type and control method.This
Embodiment changes reaction condition.
40 DEG C of heat exchange temperature of setting, i.e. reaction temperature set reaction pressure 0.1MPa.Feed ethanol, charging rate are
0.32g/min, trifluoro-acetyl chloride gas feed speed are 1.06g/min, and residence time of reaction is 25s, trifluoro-acetyl chloride with
The mol ratio of ethyl alcohol is 1.15:1.Reaction raw materials enter " heart " microchannel plate Ying Mo after microchannel premixes warm-up block 3
Block 4, trifluoroacetyl chlorine body is directly entered " heart " microchannel reaction module 4 by gas mass flow meter, micro- in " heart "
In pathway reaction module 4-9, trifluoro-acetyl chloride and ethanol synthesis.Crude reaction collects after quenching module 10 and obtains trifluoroacetic acid
Ethyl ester.
GC analysis is carried out to reaction mixture, the results showed that, the residual quantity of ethyl alcohol is 0, and the conversion ratio of ethyl alcohol is 100%.
Embodiment 8
Using healthy and free from worry micro passage reaction similarly to Example 1, and according to same connection type and control method.This
Embodiment changes reaction condition.
70 DEG C of heat exchange temperature of setting, i.e. reaction temperature set reaction pressure 0.1MPa.Feed ethanol, charging rate are
0.59g/min, trifluoro-acetyl chloride gas feed speed are 1.77g/min, and residence time of reaction is 15s, trifluoro-acetyl chloride with
The mol ratio of ethyl alcohol is 1.05:1.Reaction raw materials enter " heart " microchannel plate Ying Mo after microchannel premixes warm-up block 3
Block 4, trifluoroacetyl chlorine body is directly entered " heart " microchannel reaction module 4 by gas mass flow meter, micro- in " heart "
In pathway reaction module 4-9, trifluoro-acetyl chloride and ethanol synthesis.Crude reaction collects after quenching module 10 and obtains trifluoroacetic acid
Ethyl ester.
GC analysis is carried out to reaction mixture, the results showed that, the residual quantity of ethyl alcohol is 0, and the conversion ratio of ethyl alcohol is 100%.