CN105732508A - Continuous preparation method of N-methylimidazole - Google Patents
Continuous preparation method of N-methylimidazole Download PDFInfo
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- CN105732508A CN105732508A CN201610181460.8A CN201610181460A CN105732508A CN 105732508 A CN105732508 A CN 105732508A CN 201610181460 A CN201610181460 A CN 201610181460A CN 105732508 A CN105732508 A CN 105732508A
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- methylimidazole
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- ammonia
- aldehyde
- continuous preparation
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- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 122
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 61
- 150000001299 aldehydes Chemical class 0.000 claims abstract description 48
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000002808 molecular sieve Substances 0.000 claims abstract description 18
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 30
- 230000006837 decompression Effects 0.000 claims description 24
- 238000007599 discharging Methods 0.000 claims description 12
- 150000002460 imidazoles Chemical class 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 5
- 238000009834 vaporization Methods 0.000 claims description 4
- 230000008016 vaporization Effects 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 229940015043 glyoxal Drugs 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 12
- 238000002156 mixing Methods 0.000 description 5
- 238000010189 synthetic method Methods 0.000 description 5
- 238000000605 extraction Methods 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- XARVANDLQOZMMJ-CHHVJCJISA-N 2-[(z)-[1-(2-amino-1,3-thiazol-4-yl)-2-oxo-2-(2-oxoethylamino)ethylidene]amino]oxy-2-methylpropanoic acid Chemical compound OC(=O)C(C)(C)O\N=C(/C(=O)NCC=O)C1=CSC(N)=N1 XARVANDLQOZMMJ-CHHVJCJISA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000002083 C09CA01 - Losartan Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- KJJZZJSZUJXYEA-UHFFFAOYSA-N losartan Chemical compound CCCCC1=NC(Cl)=C(CO)N1CC1=CC=C(C=2C(=CC=CC=2)C=2[N]N=NN=2)C=C1 KJJZZJSZUJXYEA-UHFFFAOYSA-N 0.000 description 1
- 229960004773 losartan Drugs 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 1
- DMDOTRUOIVBPSF-UHFFFAOYSA-N naphthalene;hydrochloride Chemical compound Cl.C1=CC=CC2=CC=CC=C21 DMDOTRUOIVBPSF-UHFFFAOYSA-N 0.000 description 1
- -1 nitre azoles Chemical class 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000006175 van Leusen reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
- C07D233/58—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring nitrogen atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a continuous preparation method of N-methylimidazole. The method comprises the following steps: by taking an Hbeta molecular sieve as a catalyst, carrying out a gas phase catalytic reaction on mixed ammonia and mixed aldehyde in a tubular reactor, and performing rectification separation on the obtained reaction product, thereby obtaining the N-methylimidazole. The preparation method of the N-methylimidazole can be continuously operate, the conversion rate of glyoxal can be over 97.07 percent, the purity of N-methylimidazole can be over 99.0 weight percent, and the recovered mixed ammonia and mixed aldehyde can be recycled.
Description
Technical field
The present invention relates to the preparation method of a kind of N-Methylimidazole., particularly to the continuous preparation method of a kind of N-Methylimidazole..
Background technology
N-Methylimidazole. is the important source material of synthesis medicine intermediate, is used for preparing Losartan, nitre azoles sweet smell ketone, 1-Methylimidazole .-5-
Formyl chloride hydrochlorate and hydrochloric acid naphthalene first imidazoles etc.；In pesticide field, it is widely used in synthesizing fungicide and Plant growth-promoting effect
Agent, such as: N-Methylimidazole. is as the ionic liquid of cation parent generation quaterisation synthesis imidazoles；In addition N-methyl
Imidazoles is also used for the firming agent of other resins such as epoxy resin, adhesive etc.；N-Methylimidazole. is in cast with fiberglass field also
There is the biggest application.
Preparation method research currently, with respect to N-Methylimidazole. focuses primarily upon 1,2-dicarbonyl compound synthetic method, Van
Leusen synthetic method, Phillips synthetic method, Wohl-Marckwald synthetic method, Witting synthetic method and N-methyl chemical combination
6 kinds of modes of one-tenth method.The application of aldehyde and the condensation reaction of ammonia is quite varied, but produces N-Methylimidazole. at present still with between traditional
Having a rest reactor and distillation is main, course of reaction is that multistep drips raw material, gap still reaction, and reaction time is up to 24-36 hour
Left and right, primary first-order equation Biformyl conversion ratio are only about 59%, and production process can produce more coke-like waste liquid and waste water.In a word,
Autoclave liquid phase reactor prepares N-Methylimidazole., and operation is many, cycle length, yield are low and energy consumption is big.
Summary of the invention
It is an object of the invention to overcome the deficiency of traditional method, it is provided that the continuous preparation method of a kind of new N-Methylimidazole., its
Preparation method with H beta-molecular sieve as catalyst, use tubular reactor with decompression side line rectifying column be combined serialization carry out mix ammonia and
The gas phase catalytic reaction of mixed aldehyde prepares N-Methylimidazole., and Biformyl conversion ratio reaches and can reach more than 97.07%, N-Methylimidazole. pure
Degree can reach more than 99.0%, and mixed ammonia and mixed aldehyde can be recycled.
Completing foregoing invention purpose, the present invention adopts the following technical scheme that
The continuous preparation method of a kind of N-Methylimidazole., it is characterised in that with H beta-molecular sieve as catalyst, at pipe reaction
In device, containing the mixed ammonia of ammonia Yu methylamine, and the mixed aldehyde containing formaldehyde with Biformyl carries out gas phase catalytic reaction, and gained reaction is produced
Thing is through rectification isolated N-Methylimidazole..
Comprising the concrete steps that of described method:
(1) in tubular reactor, add H beta-molecular sieve catalyst, be passed through continuously after raw material is mixed ammonia and the heating vaporization of mixed aldehyde
In tubular reactor, gas phase catalytic reaction generate mixed gas condensed after obtain the thick product of N-Methylimidazole.；
(2) the thick product of N-Methylimidazole. that step (1) obtains adds decompression side line rectifying column rectification and separates, and controls decompression side line
Rectification column pressure is 0.20MPa, and decompression side line rectifying column lateral line discharging is the N-Methylimidazole. of content >=99.0wt%, depressurised side
Line rectifying column tower top obtains the purity water at more than 99.0wt%, and discharging at the bottom of decompression side line rectifying tower is containing trace N-methyl miaow
The high boiling mixture of azoles；
(3) purity obtained on decompression side line rectifying tower top adds rectifying column at the water of more than 99.0wt%, separates through rectification,
Rectifying column tower top obtains the aqueous solution of mixed ammonia and mixed aldehyde and uses as feedstock circulation, and discharging at the bottom of rectifying tower is water.
In described method, in mixed ammonia, ammonia is 0.5-0.6:1 with the mass ratio of methylamine, formaldehyde and the quality of Biformyl in mixed aldehyde
Ratio is 0.5-0.7:1, and mixed ammonia is 0.8-1:1 with the mass ratio of mixed aldehyde.
Preferred: in described method, when the mass ratio of mixed ammonia and mixed aldehyde is 0.89:1, ammonia and the mass ratio of methylamine in mixed ammonia
For 0.53:1；In mixed aldehyde, formaldehyde is 0.62:1 with the mass ratio of Biformyl.
In described method, the pressure of gas phase catalytic reaction is 0.15-0.35Mpa, and reaction temperature is 110-130 DEG C, and air speed is
1.01-1.25。
In described method, the pressure of decompression side line rectifying column is 0.020MPa, and tower top temperature (DEG C) is 81.3-82.7 DEG C, side
Line temperature (DEG C) is 121.3-122.7 DEG C, and column bottom temperature (DEG C) is 166.4-169.2 DEG C, and reflux ratio is 1-2.
In described method, the pressure of rectifying column is 0.1013MPa, and tower top temperature (DEG C) is 71.5-72.6 DEG C, column bottom temperature (DEG C)
For 102.1-104.7 DEG C, reflux ratio is 2.
Decompression side line rectifying tower top obtains purity and reclaims through rectification at the water of more than 99.0wt%, rectifying column tower top obtain mixed ammonia with
The water solution cycle of mixed aldehyde >=52.1wt% uses, the water obtained at the bottom of rectifying tower, its purity >=99.92wt%.
Preferably, the mesh number of described H beta-molecular sieve is 60-80 mesh.
Beneficial effect: the preparation method of the N-Methylimidazole. of the present invention can continuous operation, Biformyl conversion ratio reaches and can reach
The purity of more than 97.07%, N-Methylimidazole. can reach more than 99.0%, and mixed ammonia and the mixed aldehyde of recovery can be recycled；Described side
Method technological process is simple, and compared with prior art, formaldehyde consumption reduces 27.0%, methylamine consumption reduces 21.0%, ammonia is used
Amount reduces 32.0%, and the waste water produced substantially reduces.
Describe the present invention below in conjunction with specific embodiment.Protection scope of the present invention with detailed description of the invention is not
Limit, but be defined in the claims.
Accompanying drawing explanation
Fig. 1 is the process chart of the continuous preparation method of a kind of N-Methylimidazole..
Fig. 2 is that gas phase catalytic reaction pressure is to Biformyl conversion ratio and the thick product purity of N-Methylimidazole. (disregarding water content)
Impact.
Fig. 3 is that gas phase catalytic reaction temperature is to Biformyl conversion ratio and the thick product purity of N-Methylimidazole. (disregarding water content)
Impact.
Fig. 4 is to mix ammonia with mixed aldehyde mass ratio to Biformyl conversion ratio and the thick product purity of N-Methylimidazole. (disregarding water content)
Impact.
Fig. 5 is formaldehyde with Biformyl mass ratio to Biformyl conversion ratio and the thick product purity of N-Methylimidazole. (disregarding water content)
Impact.
Fig. 6 is that air speed is on Biformyl conversion ratio and the impact of the thick product purity of N-Methylimidazole. (disregarding water content).
Detailed description of the invention
Below by specific embodiment, technical solutions according to the invention are further described in detail, but it is necessary to note that with
Lower embodiment is served only for the description to summary of the invention, is not intended that limiting the scope of the invention.
The continuous preparation method of a kind of N-Methylimidazole. of the present invention, process chart is as it is shown in figure 1,1 be wherein mixed
Ammonia storage tank, 2 be filter, 3 be pressure maintaining valve, 4 be mixed aldehyde storage tank, 5 be dosing pump, 6 be blender, 7 be preheater, 8
For preheater heating furnace, 9 tubular reactors, 10 tubular reactor heating furnaces, 11 be condenser, 12 be condenser, 13 be
Counterbalance valve, 14 catchers, 15 be collecting tank, 16 be H beta-molecular sieve, 17 be decompression side line rectifying column, 18 for rectifying column.
Tubular reactor 9 equipment such as grade and pipeline are respectively provided with as required stop valve V, threeway conversion valve S and temperature measurer T1 and
Measuring cell P1 etc..
The main streams related in technological process includes: 1. for mixing ammonia, 2. for mixing aldehyde, 3. for the gaseous mixture of mixed ammonia and mixed aldehyde
Body, 4. for catcher bottom discharge the thick product of N-Methylimidazole., 5. for decompression side line rectifying tower eject material, 6. for subtracting
Pressure side line rectifying column lateral line discharging, 7. for decompression side line rectifying tower at the bottom of discharging, 8. for rectifying tower eject material, 9. be rectification
Condensed fluid at the bottom of tower tower.
Embodiment 1:
First the H beta-molecular sieve adding 60-80 mesh, wherein H beta-molecular sieve it is surrounded by the tubular reactor of rustless steel chuck in outside
With tubular reactor pipe inner volume than for 0.52:1；Raw material mixing ammonia with mixed aldehyde is that 0.89:1 is squeezed into by dosing pump according to mass ratio
In blender, wherein mixing the mass ratio of ammonia and methylamine in ammonia is 0.53:1, and in mixed aldehyde, formaldehyde with the mass ratio of Biformyl is
0.62:1.0；Raw material mixes after ammonia device blended with mixed aldehyde mix, and enters pipe reaction after entering the heating vaporization of preheater heated stove
Device reacts, and enters catcher after the mixed gas condensed device condensation that reaction generates, and bottom catcher, extraction content is 87.96wt%
The thick product of N-Methylimidazole. (disregarding water content), yield is 97.07%；The N-Methylimidazole. of extraction bottom catcher is slightly produced
Product add decompression side line rectifying column, through rectification under vacuum separate, decompression side line rectifying column lateral line discharging be content be the N-of 99.06wt%
Methylimidazole., yield are 96.00%；Discharging at the bottom of decompression side line rectifying tower is the mixture containing N-Methylimidazole.；Decompression side line
The aqueous solution that rectifying column tower top obtains, separates through rectifying column rectification, and it is 52.1wt% with mixed aldehyde that rectifying column tower top obtains mixed ammonia
Aqueous solution, recycle, the water obtained at the bottom of rectifying tower, its purity is 99.92wt%.
Specifically, the method step of the present invention is as follows:
(1) adding the H beta-molecular sieve catalyst 16 of 60-80 mesh in tubular reactor 9, wherein H beta-molecular sieve is anti-with tubular type
Answer device 9 pipe inner volume than for 0.52:1；By mixed ammonia storage tank 1,1. and mixed aldehyde is 2. according to mass ratio with the mixed ammonia in mixed aldehyde storage tank 4
Being squeezed in blender 6 for 0.89:1 by dosing pump 5, the mass ratio wherein mixing ammonia 1. middle ammonia and methylamine is 0.53:1, mixed
Aldehyde 2. middle formaldehyde is 0.62:1.0 with the mass ratio of Biformyl；After raw material mixes ammonia 1. device 6 the most blended with mixed aldehyde mixes, enter
Enter tubular reactor 9 after entering the heating vaporization of preheater 7 preheated device heating furnace 8 to react, the mixed ammonia that reaction generates and mixed aldehyde
Entering catcher 14 after the condensation of mixed gas the most condensed device 11, bottom catcher 14, extraction content is the N-first of 87.96wt%
4., yield is 97.07% to the thick product of base imidazoles (disregarding the water yield)；
(2) 4. the thick product of N-Methylimidazole. of extraction bottom catcher 14 adds decompression side line rectifying column 17 rectification to separate,
Decompression side line rectifying column 17 lateral line discharging be content be 99.06wt% N-Methylimidazole. 6., yield be 96.00%, depressurised side
5. line rectifying column 17 tower top obtains water that purity is 99.35wt%, and discharging at the bottom of decompression side line rectifying column 17 tower is containing N-methyl
The mixture of imidazoles is 7.；
(3) 5. the water that purity is 99.35wt% that decompression side line rectifying column 17 tower top obtains is added rectifying column 18, through rectification
Separate, rectifying column 18 tower top obtain mixed ammonia and mixed aldehyde be the aqueous solution of 52.1wt% 8., recycle；Rectifying column 18 tower
The water that the end obtains, its purity be 99.92wt% 9..
The process conditions of said process: mixed ammonia and mixed aldehyde mass ratio, formaldehyde and Biformyl mass ratio, ammonia and methylamine mass ratio,
Preheater preheating temperature, tubular reactor temperature, tubular reactor pressure, air speed, each tower temperature, pressure control, reflux ratio,
Feed entrance point and the number of plates are shown in Table 1, shown in table 2, the results are shown in Table shown in 3.
Table 1 continuous pipe type gas phase catalysis prepares the operating condition of N-Methylimidazole.
Table 2 reduces pressure the operating condition of side line rectifying column and rectifying column
The continuous gas phase catalytic reaction of table 3 prepares the result of N-Methylimidazole.
The preparation method of the N-Methylimidazole. of the present invention can continuous operation, be easily achieved, Biformyl conversion ratio reaches and can reach
The purity of more than 97.07%, N-Methylimidazole. can reach more than 99.0%, and mixed ammonia and the mixed aldehyde of recovery can be recycled；Described side
Method technological process is simple, and compared with prior art, formaldehyde consumption reduces 27.0%, methylamine consumption reduces 21.0%, ammonia is used
Amount reduces 32.0%, and waste water substantially reduces.
Embodiment 2:
Change the pressure of tubular reactor, use the condition identical with step (1) in embodiment 1 to carry out gas phase catalytic reaction.Control
Making in tubular reactor, the H beta-molecular sieve amount of being filled with and tubular reactor pipe inner volume ratio is for 0.52:1, the quality of mixed ammonia/mixed aldehyde
Than during for 0.89:1, in mixed aldehyde, the mass ratio of formaldehyde/Biformyl is 0.62:1.0, the mass ratio of ammonia/methylamine in mixed ammonia
For 0.53:1, air speed is than for 1.11h-1Time, controlling reaction temperature is 125.1 DEG C, and pressure is to Biformyl conversion ratio and N-first
The impact of the thick product purity of base imidazoles (disregarding water content).As shown in Figure 2, pressure when 0.15-0.25MPa, conversion ratio with
And slightly product purity increases, when pressure continues to increase, conversion ratio and thick product purity have declined, mainly due to N-first
Base imidazoles generates derived product and polymerization further, reduces Biformyl conversion ratio and the thick product purity of N-Methylimidazole. (is disregarded
Water content).
Embodiment 3:
Change the pressure of tubular reactor, use the condition identical with step (1) in embodiment 1 to carry out gas phase catalytic reaction.?
In tubular reactor, the H beta-molecular sieve amount of being filled with and tubular reactor pipe inner volume ratio is for 0.52:1, and the mass ratio of mixed ammonia/mixed aldehyde is
During 0.89:1, in mixed aldehyde, the mass ratio of formaldehyde/Biformyl is 0.62:1.0, and in mixed ammonia, the mass ratio of ammonia/methylamine is 0.53:
1, air speed is than for 1.11h-1Time, control reactor pressure is 0.25MPa, and temperature Biformyl conversion ratio and N-Methylimidazole. are thick
The impact of product purity (disregarding water content) as shown in Figure 3, temperature when 110.0-120.1, conversion ratio and thick product purity
Increase, when temperature continues to increase, and conversion ratio and thick product purity have declined, generate mainly due to N-Methylimidazole. derivative
Product and further polymerization, reduce Biformyl conversion ratio and the thick product purity of N-Methylimidazole. (disregarding water content).
Embodiment 4:
Change the mass ratio of mixed ammonia and mixed aldehyde, use the condition identical with step (1) in embodiment 1 to carry out gas phase catalytic reaction.
In tubular reactor, the H beta-molecular sieve amount of being filled with and tubular reactor pipe inner volume are than for 0.52:1, formaldehyde and second in mixed aldehyde
The mass ratio of dialdehyde is 0.62:1.0, and in mixed ammonia, ammonia is 0.53:1 with the mass ratio of methylamine, and air speed ratio is for 1.11h-1Time,
Control reactor pressure is 0.25MPa, temperature is 120.1 DEG C, and mixed ammonia and mixed aldehyde mass ratio are to Biformyl conversion ratio and N-first
The impact of the thick product purity of base imidazoles (disregarding water content) as shown in Figure 4, mixes ammonia with mixed aldehyde when 0.80-0.9:1, conversion ratio
Increase with thick product purity, when ratio continues to increase, and conversion ratio and thick product purity have declined, main excess aldehyde and N-
Methylimidazole. reacts generation derived product and polymerization further, reduces Biformyl conversion ratio and the thick product purity of N-Methylimidazole.
(disregarding water content).
Embodiment 5:
Change the mass ratio of formaldehyde and Biformyl, use the condition identical with step (1) in embodiment 1 to carry out gas phase catalytic reaction.
In tubular reactor, the H beta-molecular sieve amount of being filled with and tubular reactor pipe inner volume ratio for 0.52:1, the quality of mixed ammonia and mixed aldehyde
Than being 0.89:1, in mixed ammonia, ammonia is 0.53:1 with the mass ratio of methylamine, and air speed ratio is for 1.11h-1Time, control reactor pressure
Power is 0.25MPa, temperature is 120.1 DEG C, and formaldehyde and the mass ratio of Biformyl are thick to Biformyl conversion ratio and N-Methylimidazole.
The impact of product purity (disregarding water content) as shown in Figure 5, when the mass ratio of formaldehyde and Biformyl is 0.50-0.62:1, turns
Rate and thick product purity increase, when ratio continues to increase, and conversion ratio and thick product purity have declined, and main excess second
Dialdehyde reacts generation derived product further and is polymerized with N-Methylimidazole., reduces Biformyl conversion ratio and N-Methylimidazole. is thick
Product purity (disregards water content).
Embodiment 6
Changing air speed in tubular reactor, in tubular reactor, the H beta-molecular sieve amount of being filled with tubular reactor pipe inner volume ratio is
0.52:1, mixed ammonia is 0.89:1 with the mass ratio of mixed aldehyde, and in mixed aldehyde, formaldehyde is 0.62:1 with the mass ratio of Biformyl, in mixed ammonia
Ammonia is 0.5:0.95 with the mass ratio of methylamine, control reactor pressure is 0.25MPa, temperature is 120.1 DEG C, air speed pair
As shown in Figure 6, air speed exists in the impact of Biformyl conversion ratio and the thick product purity of N-Methylimidazole. (disregarding water content)
0.9-1.11h-1Time, conversion ratio and thick product purity are held essentially constant, when air speed continues to increase, and conversion ratio and thick product purity
Decline, do not obtained effecting reaction mainly due to raw material, reduced Biformyl conversion ratio and the thick product of N-Methylimidazole. is pure
Degree (disregarding water content).
Claims (8)
1. the continuous preparation method of a N-Methylimidazole., it is characterised in that with H beta-molecular sieve as catalyst, anti-in tubular type
Answering in device, containing the mixed ammonia of ammonia Yu methylamine, and the mixed aldehyde containing formaldehyde with Biformyl carries out gas phase catalytic reaction, and gained reacts
Product is through rectification isolated N-Methylimidazole..
The continuous preparation method of a kind of N-Methylimidazole. the most according to claim 1, it is characterised in that described method
Step be:
(1) in tubular reactor, add H beta-molecular sieve catalyst, be passed through continuously after raw material is mixed ammonia and the heating vaporization of mixed aldehyde
In tubular reactor, gas phase catalytic reaction generate mixed gas condensed after obtain the thick product of N-Methylimidazole.；
(2) the thick product of N-Methylimidazole. that step (1) obtains adds decompression side line rectifying column rectification and separates, side line rectification of reducing pressure
Column overhead obtains the purity water at more than 99.0wt%, and decompression side line rectifying column lateral line discharging is the N-methyl of content >=99.0wt%
Imidazoles, discharging at the bottom of decompression side line rectifying tower is the mixture containing N-Methylimidazole.；
(3) purity obtained on decompression side line rectifying tower top adds rectifying column at the water of more than 99.0wt%, separates through rectification,
Rectifying column tower top obtains the aqueous solution of mixed ammonia and mixed aldehyde and uses as feedstock circulation, and discharging at the bottom of rectifying tower is water.
The continuous preparation method of a kind of N-Methylimidazole. the most according to claim 1 and 2, it is characterised in that described
In method, in mixed ammonia, ammonia is 0.5-0.6:1 with the mass ratio of methylamine, and in mixed aldehyde, formaldehyde with the mass ratio of Biformyl is
0.5-0.7:1, mixed ammonia is 0.8-1:1 with the mass ratio of mixed aldehyde.
The continuous preparation method of a kind of N-Methylimidazole. the most according to claim 1 and 2, it is characterised in that described
In method, the pressure of gas phase catalytic reaction is 0.15-0.35Mpa, and reaction temperature is 110-130 DEG C, and air speed is 1.01-1.25.
The continuous preparation method of a kind of N-Methylimidazole. the most according to claim 2, it is characterised in that described method
In, the pressure of decompression side line rectifying column is 0.020MPa, and tower top temperature (DEG C) is 81.3-82.7 DEG C, side stream temperature (DEG C)
For 121.3-122.7 DEG C, column bottom temperature (DEG C) is 166.4-169.2 DEG C, and reflux ratio is 1-2.
The continuous preparation method of a kind of N-Methylimidazole. the most according to claim 2, it is characterised in that described method
In, the pressure of rectifying column is 0.1013MPa, and tower top temperature (DEG C) is 71.5-72.6 DEG C, and column bottom temperature (DEG C) is
102.1-104.7 DEG C, reflux ratio is 2.
The continuous preparation method of a kind of N-Methylimidazole. the most according to claim 2, it is characterised in that described method
In, in mixed ammonia that rectifying column tower top obtains and the aqueous solution of mixed aldehyde, mixed ammonia and the content >=52.1wt% of mixed aldehyde, obtain at the bottom of rectifying tower
Water, its purity >=99.92wt%.
The continuous preparation method of a kind of N-Methylimidazole. the most according to claim 2, it is characterised in that described method
In, the mesh number of H beta-molecular sieve is 60-80 mesh.
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| CN107311932A (en) * | 2017-07-01 | 2017-11-03 | 中国科学院兰州化学物理研究所 | A kind of method for catalyzing and synthesizing 1 methylimidazole |
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