CN107935970A - A kind of preparation method of 3 methylamine tetrahydrofuran of high-purity low water content - Google Patents
A kind of preparation method of 3 methylamine tetrahydrofuran of high-purity low water content Download PDFInfo
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- CN107935970A CN107935970A CN201711445216.9A CN201711445216A CN107935970A CN 107935970 A CN107935970 A CN 107935970A CN 201711445216 A CN201711445216 A CN 201711445216A CN 107935970 A CN107935970 A CN 107935970A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D307/10—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/14—Radicals substituted by nitrogen atoms not forming part of a nitro radical
Abstract
The invention discloses a kind of preparation method of 3 methylamine tetrahydrofuran of high-purity low water content, it includes the following steps：1）Imine intermediate is made in liquefied ammonia and the reaction of 3 formaldehyde tetrahydrofurans in the presence of absolute methanol；2）In the presence of catalyst, imine intermediate is reacted with hydrogen, cool down after reaction, reacting liquid filtering is transferred in distillation still after removing catalyst, is distilled to recover ammonia and methanol, reheats distillation, temperature in the kettle is 75 80 DEG C, kettle top temperature is 65 75 DEG C, collects cut, is 3 methylamine tetrahydrofurans.3 obtained methylamine tetrahydrofurans have the purity of higher and lower water content compared with the prior art, intermediate best in quality is provided further to synthesize other chemical products using 3 methylamine tetrahydrofurans, the raw material of the present invention also recycles, not only reduce production cost, and energy conservation and environmental protection, meet the theory of Green Chemistry instantly.
Description
Technical field
The invention belongs to technical field of organic synthesis, is related to a kind of preparation of high-purity low water content 3- methylamine tetrahydrofurans
Method.
Background technology
3- methylamine tetrahydrofurans are to synthesize third generation nicotinic insecticide dinotefuran and the important centre of other newtype drugs
Body, dinotefuran are developed by Mitsui company, and in 2002, in Japan, registration listed first, obtained agricultures in multiple countries
Medicine is registered.Since structure is special, compared with traditional nicotinic insecticide, the performance of dinotefuran is more excellent, has the interior of brilliance
Osmosis is inhaled, and is to show very high insecticidal activity in very low dosage.Therefore, dinotefuran grows animals and plants safety, residual effect,
Desinsection wide spectrum, suitable for rice, vegetables, fruit tree and flowers prevention Orthoptera, Hymenoptera, Diptera, beetle mesh, Semiptera and squama
The pests such as wing mesh.
Dinotefuran has very wide insecticidal spectrum, fool proof to crop, people and animals and environment, then is equipped with the use of various uses
Method, makes the pesticide be expected to the large-scale pesticide that becomes international, at present the sharp increase of domestic and international market demand, and 3- methylamines four
Key intermediate of the hydrogen furans as synthesis dinotefuran, dinotefuran expense per ton are 0.63 ton.At present, 3- methylamines tetrahydrofuran
Annual only medical market demand is just at 500 tons or so at home, and overseas market demand is more than 1700 tons, it is contemplated that aggregate demand
About 2200 tons or so of domestic market is measured, and is increased every year with the speed of 20-25%, about 3800 tons or so of overseas market demand,
But 3- methylamine tetrahydrofuran generally existing purity prepared by the prior art is low, high-water content problem, this is carries out in next step
Synthesis cause obstruction, it can be seen that, there is an urgent need for work out a kind of system of high-purity low water content 3- methylamine tetrahydrofurans at present
Preparation Method.
To solve this problem, people have also carried out exploratory development in long-term production and living.For example, Chinese invention is special
Profit application discloses a kind of preparation method [application number of 3- methylamines tetrahydrofuran：201510447636.5], which includes：
(1) ring-closure reaction：Isosorbide-5-Nitrae-butylene glycol is used as raw material, 2,5- dihydro furans are made in dehydration condensation under the catalytic action of solid acid
Mutter；(2) aldehyde reaction：2,5-dihydrofuran obtained by step (1) generates under the catalytic action of cobalt acetate with water gas reaction
3- tetrahydrofuran formaldehyde；(3) hydrogenation：3- tetrahydrofurans formaldehyde obtained by step (2) under the catalytic action of 5%Pd/C,
Target product 3- methylamine tetrahydrofurans are made with ammonia, hydrogen reaction.
The patent application provides a kind of synthetic method of 3- methylamines tetrahydrofuran, but product made from the synthetic method is pure
Degree still has much room for improvement, and the conversion ratio reacted is relatively low, higher which results in production cost.
The content of the invention
For the above-mentioned problems in the prior art, it is an object of the invention to provide a kind of high-purity low water content 3-
The preparation method of methylamine tetrahydrofuran.
The preparation method of a kind of high-purity low water content 3- methylamine tetrahydrofurans, it is characterised in that including following step
Suddenly：
Step 1：Absolute methanol is added into reaction kettle, liquefied ammonia and 3- formaldehyde tetrahydrochysene furans are sequentially added under stirring cooling
Mutter, stirred under nitrogen atmosphere reaction, is made imine intermediate；
Step 2：Obtained imine intermediate in catalyst and step 1 is added into reaction kettle, is stirred under nitrogen protection
Heating is mixed, is passed through hydrogen, continues temperature reaction to reaction and terminates；
Step 3：Cooling, reacting liquid filtering are transferred in distillation still after removing catalyst, are distilled to recover ammonia and first
Alcohol；
Step 4：After treating ammonia and Methanol Recovery, it is -0.095MPa to -0.075MPa to be decompressed to vacuum in kettle
Between, heating distillation, temperature in the kettle is 70-75 DEG C at this time, and kettle top temperature is 40-50 DEG C, and gained cut is transferred to another distillation
In kettle, n-hexane is added, is uniformly mixed, temperature rising reflux dehydration, sampling monitoring, after moisture content change is gentle, recycling
N-hexane, then it is -0.1MPa to -0.09MPa to be decompressed to vacuum in kettle, heating distillation, temperature in the kettle is 75-80 DEG C at this time,
Kettle top temperature is 65-75 DEG C, collects cut, is 3- methylamine tetrahydrofurans.
The preparation method of the high-purity low water content 3- methylamine tetrahydrofurans, it is characterised in that the slave nothing in step 1
Water methanol adds the whole process control temperature of reaction system completed to reaction and is no more than 0 DEG C.
The preparation method of the high-purity low water content 3- methylamine tetrahydrofurans, it is characterised in that the slave nothing in step 1
It is -10 DEG C -0 DEG C that water methanol, which adds the whole process completed to reaction and controls temperature of reaction system,.
The preparation method of the high-purity low water content 3- methylamine tetrahydrofurans, it is characterised in that the catalysis in step 2
Agent is palladium carbon or Raney Ni.
The preparation method of the high-purity low water content 3- methylamine tetrahydrofurans, it is characterised in that hydrogen is passed through in step 2
Temperature during gas is 35-40 DEG C, and Hydrogen Vapor Pressure is 1.0-2.0MPa in reaction kettle, and it is 65-75 to be passed through the reaction temperature after hydrogen
DEG C, reaction time 3-5h.
The preparation method of the high-purity low water content 3- methylamine tetrahydrofurans, it is characterised in that 3- formaldehyde tetrahydrochysene furans
Mutter, the mass ratio of liquefied ammonia and catalyst is 1:1.2-1.5:0.03-0.1.
The preparation method of the high-purity low water content 3- methylamine tetrahydrofurans, it is characterised in that 3- methylamine tetrahydrofurans
GC purity be more than 99.0%, water content be less than 0.2%.
The reaction equation of the present invention is as follows：
By using above-mentioned technology, compared with prior art, the advantage of the invention is that：
1) the 3- methylamines tetrahydrofuran obtained by the present invention has the purity of higher and lower water content compared with the prior art,
Intermediate best in quality is provided further to synthesize other chemical products using 3- methylamines tetrahydrofuran；
2) the recyclable recycling of reagent such as the ammonia of the invention utilized, methanol, catalyst, not only reduces and is produced into
Sheet, and energy conservation and environmental protection, meet the theory of Green Chemistry instantly；
3) present invention adds normal hexane after the completion of reaction, for removing water, greatly reduces the moisture in product, ties
Normal hexane recycles after beam, reduces cost；
4) present invention uses liquefied ammonia as amination reagent, middle compared with the prior art to be made using hydroxylamine compound or ammonium hydroxide
There is the amination rate of higher for amination reagent, reduce the generation of accessory substance, so as to improve the conversion ratio and product of reaction
Purity.
Brief description of the drawings
Fig. 1 is the product gas chromatogram that application examples 1 is produced；
Fig. 2 is the product gas chromatogram that application examples 2 is produced；
Fig. 3 is the product gas chromatogram that application examples 3 is produced；
Embodiment
Reagent used, unless otherwise specified, can be commercially available from routine biochemistry reagent shop in following embodiments.
Embodiment 1
As shown in Figure 1, the present embodiment provides a kind of preparation method of high-purity low water content 3- methylamine tetrahydrofurans, specifically
Say, comprise the following steps：
Step 1：Absolute methanol is added into reaction kettle, stirring cooling, it is 1.2 parts to sequentially add mass fraction
Liquefied ammonia and the 3- formaldehyde tetrahydrofurans that mass fraction is 1 part, stir reaction under conditions of nitrogen protection, imine intermediate are made,
The whole process control temperature of reaction system completed to reaction is added from absolute methanol and is no more than 0 DEG C；
Step 2：Mass fraction is added to reaction kettle for obtained imine intermediate in 0.1 part of palladium carbon and step 1
In, nitrogen protection, stirring is warming up to 35 DEG C, is passed through hydrogen so that the Hydrogen Vapor Pressure in kettle is 1.0MPa, is continuously heating to 65 DEG C
React 3h；
Step 3：Cooling, reacting liquid filtering are transferred in distillation still after removing palladium carbon, are distilled to recover ammonia and methanol；
Step 4：After treating ammonia and Methanol Recovery, it is -0.095MPa to be decompressed to vacuum in kettle, heating distillation, this
When temperature in the kettle be 75 DEG C, kettle top temperature is 50 DEG C, and gained cut is transferred in another distillation still, adds n-hexane, and stirring is mixed
Close uniformly, temperature rising reflux dehydration, sampling monitoring, after moisture content change tends towards stability, recycles n-hexane, then be decompressed in kettle
Vacuum is -0.1MPa, heating distillation, and temperature in the kettle is 80 DEG C at this time, and kettle top temperature is 75 DEG C, collects cut, is 3- first
Amine tetrahydrofuran, its gas chromatogram are as shown in Figure 1.
The reaction equation of the present invention is as follows：
React starting material 3- formaldehyde tetrahydrofurans and aminating reaction occurs with ammonia in absolute methanol solution, generate imines
Intermediate, the system temperature of whole process are maintained at less than 0 DEG C, to avoid the excessively violent of generation is reacted, after the completion of reaction, then
Catalyst, such as palladium carbon or Raney Ni are added, hydrogen is passed through and is reduced, obtain 3- methylamine tetrahydrofuran crude products, be filtered to remove
Catalyst is distilled to recover ammonia and methanol recycling so as to fulfill ammonia and methanol to realize recycling for catalyst,
N-hexane, n-hexane meeting azeotrope with water in distillation process are added, therefore can be taken away during n-hexane is distilled off
Water is difficult to separated accessory substance with some, so as to play raising product purity, reduces the effect of product water content, dehydration
In, often it is separated by 0.5-1h and takes a sample, detect water content, when adjacent detection data difference twice is less than 0.01%, that is, sentences
Determine moisture content change to tend towards stability.
Embodiment 2
As shown in Figure 1, the present embodiment provides a kind of preparation method of high-purity low water content 3- methylamine tetrahydrofurans, specifically
Say, comprise the following steps：
Step 1：Absolute methanol is added into reaction kettle, stirring cooling, it is 1.5 parts to sequentially add mass fraction
Liquefied ammonia and the 3- formaldehyde tetrahydrofurans that mass fraction is 1 part, stir reaction under conditions of nitrogen protection, imine intermediate are made,
The whole process control temperature of reaction system completed to reaction is added from absolute methanol and is no more than 0 DEG C；
Step 2：Mass fraction is added to reaction for obtained imine intermediate in 0.03 part of Raney Ni and step 1
In kettle, nitrogen protection, stirring is warming up to 40 DEG C, is passed through hydrogen so that the Hydrogen Vapor Pressure in kettle is 2.0MPa, is continuously heating to 75
DEG C reaction 5h；
Step 3：Cooling, reacting liquid filtering are transferred in distillation still after removing Raney Ni, are distilled to recover ammonia and first
Alcohol；
Step 4：After treating ammonia and Methanol Recovery, it is -0.095MPa to be decompressed to vacuum in kettle, heating distillation, this
When temperature in the kettle be 75 DEG C, kettle top temperature is 50 DEG C, and gained cut is transferred in another distillation still, adds n-hexane, and stirring is mixed
Close uniformly, temperature rising reflux dehydration, sampling monitoring, after moisture content change tends towards stability, recycles n-hexane, then be decompressed in kettle
Vacuum is -0.1MPa, heating distillation, and temperature in the kettle is 80 DEG C at this time, and kettle top temperature is 75 DEG C, collects cut, is 3- first
Amine tetrahydrofuran, its gas chromatogram are as shown in Figure 1.
Embodiment 3
As shown in Figure 1, the present embodiment provides a kind of preparation method of high-purity low water content 3- methylamine tetrahydrofurans, specifically
Say, comprise the following steps：
Step 1：Absolute methanol is added into reaction kettle, stirring cooling, it is 1.35 parts to sequentially add mass fraction
Liquefied ammonia and the 3- formaldehyde tetrahydrofurans that mass fraction is 1 part, stir reaction under conditions of nitrogen protection, imine intermediate are made,
The whole process control temperature of reaction system completed to reaction is added from absolute methanol and is no more than 0 DEG C；
Step 2：Mass fraction is added to reaction for obtained imine intermediate in 0.05 part of Raney Ni and step 1
In kettle, nitrogen protection, stirring is warming up to 38 DEG C, is passed through hydrogen so that the Hydrogen Vapor Pressure in kettle is 1.5MPa, is continuously heating to 70
DEG C reaction 4h；
Step 3：Cooling, reacting liquid filtering are transferred in distillation still after removing Raney Ni, are distilled to recover ammonia and first
Alcohol；
Step 4：After treating ammonia and Methanol Recovery, it is -0.095MPa to be decompressed to vacuum in kettle, heating distillation, this
When temperature in the kettle be 75 DEG C, kettle top temperature is 50 DEG C, and gained cut is transferred in another distillation still, adds n-hexane, and stirring is mixed
Close uniformly, temperature rising reflux dehydration, sampling monitoring, after moisture content change tends towards stability, recycles n-hexane, then be decompressed in kettle
Vacuum is -0.1MPa, heating distillation, and temperature in the kettle is 80 DEG C at this time, and kettle top temperature is 75 DEG C, collects cut, is 3- first
Amine tetrahydrofuran, its gas chromatogram are as shown in Figure 1.
Embodiment 4
As shown in Figure 1, the present embodiment provides a kind of preparation method of high-purity low water content 3- methylamine tetrahydrofurans, specifically
Say, comprise the following steps：
Step 1：Absolute methanol is added into reaction kettle, stirring cooling, it is 1.2 parts to sequentially add mass fraction
Liquefied ammonia and the 3- formaldehyde tetrahydrofurans that mass fraction is 1 part, stir reaction under conditions of nitrogen protection, imine intermediate are made,
The whole process control temperature of reaction system completed to reaction is added from absolute methanol and is no more than 0 DEG C；
Step 2：Mass fraction is added to reaction kettle for obtained imine intermediate in 0.1 part of palladium carbon and step 1
In, nitrogen protection, stirring is warming up to 35 DEG C, is passed through hydrogen so that the Hydrogen Vapor Pressure in kettle is 1.0MPa, is continuously heating to 65 DEG C
React 3h；
Step 3：Cooling, reacting liquid filtering are transferred in distillation still after removing palladium carbon, are distilled to recover ammonia and methanol；
Step 4：After treating ammonia and Methanol Recovery, it is -0.075MPa to be decompressed to vacuum in kettle, heating distillation, this
When temperature in the kettle be 70 DEG C, kettle top temperature is 40 DEG C, and gained cut is transferred in another distillation still, adds n-hexane, and stirring is mixed
Close uniformly, temperature rising reflux dehydration, sampling monitoring, after moisture content change tends towards stability, recycles n-hexane, then be decompressed in kettle
Vacuum is -0.09MPa, heating distillation, and temperature in the kettle is 75 DEG C at this time, and kettle top temperature is 65 DEG C, collects cut, is 3- first
Amine tetrahydrofuran.
Embodiment 5
As shown in Figure 1, the present embodiment provides a kind of preparation method of high-purity low water content 3- methylamine tetrahydrofurans, specifically
Say, comprise the following steps：
Step 1：Absolute methanol is added into reaction kettle, stirring cooling, it is 1.5 parts to sequentially add mass fraction
Liquefied ammonia and the 3- formaldehyde tetrahydrofurans that mass fraction is 1 part, stir reaction under conditions of nitrogen protection, imine intermediate are made,
The whole process control temperature of reaction system completed to reaction is added from absolute methanol and is no more than 0 DEG C；
Step 2：Mass fraction is added to reaction for obtained imine intermediate in 0.03 part of Raney Ni and step 1
In kettle, nitrogen protection, stirring is warming up to 40 DEG C, is passed through hydrogen so that the Hydrogen Vapor Pressure in kettle is 2.0MPa, is continuously heating to 75
DEG C reaction 5h；
Step 3：Cooling, reacting liquid filtering are transferred in distillation still after removing Raney Ni, are distilled to recover ammonia and first
Alcohol；
Step 4：After treating ammonia and Methanol Recovery, it is -0.075MPa to be decompressed to vacuum in kettle, heating distillation, this
When temperature in the kettle be 70 DEG C, kettle top temperature is 40 DEG C, and gained cut is transferred in another distillation still, adds n-hexane, and stirring is mixed
Close uniformly, temperature rising reflux dehydration, sampling monitoring, after moisture content change tends towards stability, recycles n-hexane, then be decompressed in kettle
Vacuum is -0.09MPa, heating distillation, and temperature in the kettle is 75 DEG C at this time, and kettle top temperature is 65 DEG C, collects cut, is 3- first
Amine tetrahydrofuran.
Embodiment 6
As shown in Figure 1, the present embodiment provides a kind of preparation method of high-purity low water content 3- methylamine tetrahydrofurans, specifically
Say, comprise the following steps：
Step 1：Absolute methanol is added into reaction kettle, stirring cooling, it is 1.35 parts to sequentially add mass fraction
Liquefied ammonia and the 3- formaldehyde tetrahydrofurans that mass fraction is 1 part, stir reaction under conditions of nitrogen protection, imine intermediate are made,
The whole process control temperature of reaction system completed to reaction is added from absolute methanol and is no more than 0 DEG C；
Step 2：Mass fraction is added to reaction for obtained imine intermediate in 0.05 part of Raney Ni and step 1
In kettle, nitrogen protection, stirring is warming up to 38 DEG C, is passed through hydrogen so that the Hydrogen Vapor Pressure in kettle is 1.5MPa, is continuously heating to 70
DEG C reaction 4h；
Step 3：Cooling, reacting liquid filtering are transferred in distillation still after removing Raney Ni, are distilled to recover ammonia and first
Alcohol；
Step 4：After treating ammonia and Methanol Recovery, it is -0.075MPa to be decompressed to vacuum in kettle, heating distillation, this
When temperature in the kettle be 70 DEG C, kettle top temperature is 40 DEG C, and gained cut is transferred in another distillation still, adds n-hexane, and stirring is mixed
Close uniformly, temperature rising reflux dehydration, sampling monitoring, after moisture content change tends towards stability, recycles n-hexane, then be decompressed in kettle
Vacuum is -0.09MPa, heating distillation, and temperature in the kettle is 75 DEG C at this time, and kettle top temperature is 65 DEG C, collects cut, is 3- first
Amine tetrahydrofuran.
Embodiment 7
As shown in Figure 1, the present embodiment provides a kind of preparation method of high-purity low water content 3- methylamine tetrahydrofurans, specifically
Say, comprise the following steps：
Step 1：Absolute methanol is added into reaction kettle, stirring cooling, it is 1.2 parts to sequentially add mass fraction
Liquefied ammonia and the 3- formaldehyde tetrahydrofurans that mass fraction is 1 part, stir reaction under conditions of nitrogen protection, imine intermediate are made,
The whole process control temperature of reaction system completed to reaction is added from absolute methanol and is no more than 0 DEG C；
Step 2：Mass fraction is added to reaction kettle for obtained imine intermediate in 0.1 part of palladium carbon and step 1
In, nitrogen protection, stirring is warming up to 35 DEG C, is passed through hydrogen so that the Hydrogen Vapor Pressure in kettle is 1.0MPa, is continuously heating to 65 DEG C
React 3h；
Step 3：Cooling, reacting liquid filtering are transferred in distillation still after removing palladium carbon, are distilled to recover ammonia and methanol；
Step 4：After treating ammonia and Methanol Recovery, it is -0.085MPa to be decompressed to vacuum in kettle, heating distillation, this
When temperature in the kettle be 73 DEG C, kettle top temperature is 45 DEG C, and gained cut is transferred in another distillation still, adds n-hexane, and stirring is mixed
Close uniformly, temperature rising reflux dehydration, sampling monitoring, after moisture content change tends towards stability, recycles n-hexane, then be decompressed in kettle
Vacuum is -0.095MPa, heating distillation, and temperature in the kettle is 77 DEG C at this time, and kettle top temperature is 70 DEG C, collects cut, is 3-
Methylamine tetrahydrofuran.
Embodiment 8
As shown in Figure 1, the present embodiment provides a kind of preparation method of high-purity low water content 3- methylamine tetrahydrofurans, specifically
Say, comprise the following steps：
Step 1：Absolute methanol is added into reaction kettle, stirring cooling, it is 1.5 parts to sequentially add mass fraction
Liquefied ammonia and the 3- formaldehyde tetrahydrofurans that mass fraction is 1 part, stir reaction under conditions of nitrogen protection, imine intermediate are made,
The whole process control temperature of reaction system completed to reaction is added from absolute methanol and is no more than 0 DEG C；
Step 2：Mass fraction is added to reaction for obtained imine intermediate in 0.03 part of Raney Ni and step 1
In kettle, nitrogen protection, stirring is warming up to 40 DEG C, is passed through hydrogen so that the Hydrogen Vapor Pressure in kettle is 2.0MPa, is continuously heating to 75
DEG C reaction 5h；
Step 3：Cooling, reacting liquid filtering are transferred in distillation still after removing Raney Ni, are distilled to recover ammonia and first
Alcohol；
Step 4：After treating ammonia and Methanol Recovery, it is -0.085MPa to be decompressed to vacuum in kettle, heating distillation, this
When temperature in the kettle be 73 DEG C, kettle top temperature is 45 DEG C, and gained cut is transferred in another distillation still, adds n-hexane, and stirring is mixed
Close uniformly, temperature rising reflux dehydration, sampling monitoring, after moisture content change tends towards stability, recycles n-hexane, then be decompressed in kettle
Vacuum is -0.095MPa, heating distillation, and temperature in the kettle is 77 DEG C at this time, and kettle top temperature is 70 DEG C, collects cut, is 3-
Methylamine tetrahydrofuran.
Embodiment 9
As shown in Figure 1, the present embodiment provides a kind of preparation method of high-purity low water content 3- methylamine tetrahydrofurans, specifically
Say, comprise the following steps：
Step 1：Absolute methanol is added into reaction kettle, stirring cooling, it is 1.35 parts to sequentially add mass fraction
Liquefied ammonia and the 3- formaldehyde tetrahydrofurans that mass fraction is 1 part, stir reaction under conditions of nitrogen protection, imine intermediate are made,
The whole process control temperature of reaction system completed to reaction is added from absolute methanol and is no more than 0 DEG C；
Step 2：Mass fraction is added to reaction for obtained imine intermediate in 0.05 part of Raney Ni and step 1
In kettle, nitrogen protection, stirring is warming up to 38 DEG C, is passed through hydrogen so that the Hydrogen Vapor Pressure in kettle is 1.5MPa, is continuously heating to 70
DEG C reaction 4h；
Step 3：Cooling, reacting liquid filtering are transferred in distillation still after removing Raney Ni, are distilled to recover ammonia and first
Alcohol；
Step 4：After treating ammonia and Methanol Recovery, it is -0.085MPa to be decompressed to vacuum in kettle, heating distillation, this
When temperature in the kettle be 73 DEG C, kettle top temperature is 45 DEG C, and gained cut is transferred in another distillation still, adds n-hexane, and stirring is mixed
Close uniformly, temperature rising reflux dehydration, sampling monitoring, after moisture content change tends towards stability, recycles n-hexane, then be decompressed in kettle
Vacuum is -0.095MPa, heating distillation, and temperature in the kettle is 77 DEG C at this time, and kettle top temperature is 70 DEG C, collects cut, is 3-
Methylamine tetrahydrofuran.
Application examples 1
3- formaldehyde tetrahydrofuran 170.0kg are taken, using the stainless steel kettle of 1000L as reaction vessel, according to described in embodiment 1
Method reacted, final products 3- methylamine tetrahydrofuran 151.3kg are collected to obtain, according to formula：
Yield=(amount of amount/raw material of reaction product material) × 100%
The rate of output can be calculated as 88.1%.
The results are shown in Figure 2 for the gas chromatographic detection of products obtained therefrom, and GC purity is 99.61%, and testing result is come to Shimadzu
The GC-2014C type gas chromatographs of company's production；The moisture of products obtained therefrom be 0.15%, testing result come to plum Teller-
The METTLER TOLEDO V20 Moisture Meters of benefit group production are held in the palm, the wherein moisture standards of product are less than or equal to 0.5%.
Application examples 2
3- formaldehyde tetrahydrofuran 170.0kg are taken, using the stainless steel kettle of 1000L as reaction vessel, according to described in embodiment 5
Method reacted, final products 3- methylamine tetrahydrofuran 147.6kg are collected to obtain, according to formula：
Yield=(amount of amount/raw material of reaction product material) × 100%
The rate of output can be calculated as 85.9%.
The results are shown in Figure 2 for the gas chromatographic detection of products obtained therefrom, and GC purity is 99.33%, and testing result is come to Shimadzu
The GC-2014C type gas chromatographs of company's production；The moisture of products obtained therefrom be 0.19%, testing result come to plum Teller-
The METTLER TOLEDO V20 Moisture Meters of benefit group production are held in the palm, the wherein moisture standards of product are less than or equal to 0.5%.
Application examples 3
3- formaldehyde tetrahydrofuran 170.0kg are taken, using the stainless steel kettle of 1000L as reaction vessel, according to described in embodiment 9
Method reacted, final products 3- methylamine tetrahydrofuran 151.9kg are collected to obtain, according to formula：
Yield=(amount of amount/raw material of reaction product material) × 100%
The rate of output can be calculated as 88.4%.
The results are shown in Figure 2 for the gas chromatographic detection of products obtained therefrom, and GC purity is 99.74%, and testing result is come to Shimadzu
The GC-2014C type gas chromatographs of company's production；The moisture of products obtained therefrom be 0.13%, testing result come to plum Teller-
The METTLER TOLEDO V20 Moisture Meters of benefit group production are held in the palm, the wherein moisture standards of product are less than or equal to 0.5%.
Specific embodiment described herein is only to spirit explanation for example of the invention.Technology belonging to the present invention is led
The technical staff in domain can do various modifications or additions to described specific embodiment or replace in a similar way
Generation, but without departing from spirit of the invention or beyond the scope of the appended claims.
Claims (7)
1. a kind of preparation method of high-purity low water content 3- methylamine tetrahydrofurans, it is characterised in that comprise the following steps：
Step 1：Absolute methanol is added into reaction kettle, liquefied ammonia and 3- formaldehyde tetrahydrofurans, nitrogen are sequentially added under stirring cooling
Reaction is stirred under gas shielded, imine intermediate is made；
Step 2：Obtained imine intermediate in catalyst and step 1 is added into reaction kettle, stirred under nitrogen atmosphere liter
Temperature, is passed through hydrogen, continues temperature reaction to reaction and terminates；
Step 3：Cooling, reacting liquid filtering are transferred in distillation still after removing catalyst, are distilled to recover ammonia and methanol；
Step 4：After treating ammonia and Methanol Recovery, vacuum is decompressed in kettle between -0.095MPa to -0.075MPa,
Heating distillation, temperature in the kettle is 70-75 DEG C at this time, and kettle top temperature is 40-50 DEG C, and gained cut is transferred in another distillation still,
Add n-hexane, be uniformly mixed, temperature rising reflux dehydration, sampling monitoring, after moisture content change is gentle, recycling just oneself
Alkane, then it is -0.1MPa to -0.09MPa to be decompressed to vacuum in kettle, heating distillation, temperature in the kettle is 75-80 DEG C at this time, kettle top
Temperature is 65-75 DEG C, collects cut, is 3- methylamine tetrahydrofurans.
2. the preparation method of high-purity low water content 3- methylamine tetrahydrofurans as claimed in claim 1, it is characterised in that step
Slave absolute methanol in one adds the whole process control temperature of reaction system completed to reaction and is no more than 0 DEG C.
3. the preparation method of high-purity low water content 3- methylamine tetrahydrofurans as claimed in claim 1, it is characterised in that step
It is -10 DEG C -0 DEG C that slave absolute methanol in one, which adds the whole process completed to reaction and controls temperature of reaction system,.
4. the preparation method of high-purity low water content 3- methylamine tetrahydrofurans as claimed in claim 1, it is characterised in that step
Catalyst in two is palladium carbon or Raney Ni.
5. the preparation method of high-purity low water content 3- methylamine tetrahydrofurans as claimed in claim 1, it is characterised in that step
Temperature when hydrogen is passed through in two is 35-40 DEG C, and Hydrogen Vapor Pressure is 1.0-2.0MPa in reaction kettle, is passed through the reaction temperature after hydrogen
Spend for 65-75 DEG C, reaction time 3-5h.
6. the preparation method of high-purity low water content 3- methylamine tetrahydrofurans as claimed in claim 1, it is characterised in that 3- first
The mass ratio of aldehyde tetrahydrofuran, liquefied ammonia and catalyst is 1:1.2-1.5:0.03-0.1.
7. the preparation method of high-purity low water content 3- methylamine tetrahydrofurans as claimed in claim 1, it is characterised in that 3- first
The GC purity of amine tetrahydrofuran is more than 99.0%, and water content is less than 0.2%.
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| CN109507963A (en) * | 2018-11-16 | 2019-03-22 | 浙江工业大学 | A kind of tetrahydrofuran -3- Formaldehyde Production control system and method based on DCS control |
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