CN1345723A - Process for preparing N-formyl morpholine - Google Patents
Process for preparing N-formyl morpholine Download PDFInfo
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- CN1345723A CN1345723A CN 00125399 CN00125399A CN1345723A CN 1345723 A CN1345723 A CN 1345723A CN 00125399 CN00125399 CN 00125399 CN 00125399 A CN00125399 A CN 00125399A CN 1345723 A CN1345723 A CN 1345723A
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- morpholine
- preparation
- reaction
- solvent oil
- formyl morpholine
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- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Abstract
The preparation method of N-formylmorpholine is characterized by making morpholine and formic acid as raw material according to the mole ratio of 1: (0.8-1.2) produce reaction at 50-140 deg.C in the presence of water-carrying agent which can be any one kin dof aromatics solent oil, aliphatic solvent oil, mixture of them or ester solvent oil and whose added amount is 5.0-50.0% of total weight of raw material. Said invention possesses the advantages of low reaction temp., stable and easy to control reaction condition, less by-product, high yield and high-purity.
Description
The present invention relates to the production method of N-N-formyl morpholine N-, particularly the method for synthetic N-N-formyl morpholine N-under the condition that the band aqua exists.
The N-N-formyl morpholine N-is a kind of good extraction solvent in the arene extracting process, and it is much better than triglycol commonly used in the industry, Tetraglycol 99, tetramethylene sulfone etc. to the dissolving power of aromatic hydrocarbons and the performance index of selectivity ratios equal solvent.
At present, N-N-formyl morpholine N-synthetic mainly is to be that raw material reacts at a certain temperature with morpholine and formic acid or methyl-formiate, and thick product then separates with the method for rectification under vacuum usually purifies.This type of existing industrial process, because of the too fast temperature of reaction of exothermic heat of reaction usually is difficult to control, in causing producing side reaction many, reaction preference is low, yield is not high, energy consumption is big during the product rectifying separation, the production cost height.
The preparation method who the purpose of this invention is to provide a kind of N-N-formyl morpholine N-, this method temperature of reaction is lower than prior art temperature of reaction, and stablizes easy to controlly, and byproduct of reaction is few, the yield height.Reaction back product separation is simple and convenient, and energy consumption has effectively overcome far below common process
The problem that prior art exists.
The present invention is achieved by the following technical solutions.
N-N-formyl morpholine N-preparation method provided by the invention, with morpholine and formic acid is raw material, the mol ratio that morpholine and formic acid feed intake is a morpholine: formic acid=1: (0.8～1.2), temperature of reaction is 50～140 ℃, reaction pressure is a normal pressure, be reflected under the existence of band aqua and carry out, the band aqua is an aromatic hydrocarbon solvent oil, the fats solvent oil, any in the mixture of aromatic hydrocarbons and fats solvent oil or the esters solvent oil, the add-on of band aqua is weight percentage=5.0～50.0% of band aqua in the raw material total amount, and the reaction times that the present invention recommends is 4～14 hours.
After reaction finished, reaction mass under reduced pressure carried out rectifying separation, and rectifying pressure is 0.06～0.099Mpa, heated to 140 ℃ and steamed band aqua and excess raw material, continued to heat to 140～200 ℃, steamed the N-N-formyl morpholine N-, and condensation gets product.
Above-mentioned aromatic hydrocarbon solvent oil can be any or two or more mixture in benzene,toluene,xylene, ethylbenzene or the trimethylbenzene, preferably toluene; The fats solvent oil can be C
4～C
8Sherwood oil or C
8～C
12Solvent oil, C preferably
6～C
7Sherwood oil or solvent oil; Esters solvent oil can be any or two or more mixture in methyl-formiate, ethyl formate, butyl formate, methyl acetate, ethyl acetate or the butylacetate, preferably butylacetate.
In the above-mentioned reaction conditions, the mol ratio that morpholine and formic acid feed intake is preferably morpholine: formic acid=1: (1.01～1.08); The add-on of band aqua is preferably weight percentage=9.0～10.0% of band aqua in the raw material total amount; Temperature of reaction is preferably 75～85 ℃; Reaction times is preferably 6～10 hours.
Usually moderately make raw material drop into excessive the carrying out that helps driving a reaction, in this reaction, contriver's suggestion makes morpholine excessive a little comparatively suitable, raises because of the excessive meeting of formic acid makes the acid number of product N-N-formyl morpholine N-, strengthen the difficulty that product is purified, and corrosive equipment.
Reactive chemistry equation by morpholine and formic acid prepared in reaction N-N-formyl morpholine N-is seen formula (1) and formula (2):
Formula (1)
Formula (2)
From formula (1) as can be seen, reaction process will produce a large amount of water, add in the reaction band aqua its mainly act on be in the reaction process by the backflow of band aqua, take the water that most of reaction is produced out of, promote the carrying out of main reaction.In addition, the band aqua of backflow can make temperature of reaction more stably controlled, has effectively suppressed the generation of side reaction, thereby has improved the selectivity of main reaction, and the product that obtains has higher purity.
For carrying out fully of promoting to react, in reaction process, should constantly isolate most of water that reaction generates.Therefore the used reactor of contriver's proposal reactions is preferably with a water diversion system, its effect is in reaction process, band aqua and water azeotropic are to water trap, after the condensation layering, the water of lower floor is discharged system, the band aqua on upper strata then is back in the reactor, and the band aqua of backflow can be again and the water azeotropic.
Compared with prior art, its advantage of N-N-formyl morpholine N-preparation method provided by the invention is that temperature of reaction is low, and stable reaction is easy to control, and byproduct of reaction is few, the yield height.Reaction back product separation is simple and convenient, and energy consumption is far below common process, and its more outstanding advantage is to obtain highly purified N-N-formyl morpholine N-product.
Below will the invention will be further described by embodiment, among the embodiment:
Embodiment 1～7:
Morpholine after the metering and the adding of band aqua are had in the reactor of a water diversion system, add the formic acid that measured under the room temperature, heat, under normal pressure, react to required temperature.Constantly isolate most of water that reaction generates in the reaction from water trap, reaction proceeds to and no longer includes water sepn and go out.Reaction mass under reduced pressure carries out rectifying separation, and rectifying pressure is 0.06～0.099Mpa, heats to 140 ℃ and steams band aqua and excess raw material, continues to heat to 140～200 ℃, steams the N-N-formyl morpholine N-, and condensation gets product.
The concrete reaction conditions of each embodiment sees Table 1, and reaction result sees Table 2.Table 1.
| Raw material feed ratio (morpholine: formic acid) | The band aqua | Band aqua consumption (%) | Temperature of reaction (℃) | Reaction times (hour) | |
| Embodiment 1 | ????1∶0.8 | Toluene | ????5 | ??75～130 | ????6.0 |
| Embodiment 2 | ????1∶0.8 | Benzene/C 4～C 8Solvent oil | ????40 | ??55～90 | ????11.0 |
| Embodiment 3 | ????1∶0.9 | ?C 5～C 7Solvent oil | ????15 | ??55～90 | ????10.0 |
| Embodiment 4 | ????1∶0.96 | ?C 5～C 7Sherwood oil | ????10 | ??50～90 | ????12.0 |
| Embodiment 5 | ????1∶0.95 | Benzene/methylbenzene | ????20 | ??80～95 | ????7.0 |
| Embodiment 6 | ????1∶0.96 | Methyl-formiate | ????25 | ??80～100 | ????6.0 |
| Embodiment 7 | ????1∶0.96 | Butylacetate | ????30 | ??90～140 | ????4.5 |
| Embodiment 8 | ????1∶1.1 | Ethyl acetate and butyl acetate | ????20 | ??80～130 | ????9.0 |
| Embodiment 9 | ????1∶1.2 | Benzene | ????50 | ??70～110 | ????10.0 |
Table 2.
| Formic acid transformation efficiency (%) | Yield (%) | Product purity (%) | |
| Embodiment 1 | ????99.5 | ????98.2 | ????99.0 |
| Embodiment 2 | ????99.8 | ????98.0 | ????99.2 |
| Embodiment 3 | ????99.6 | ????98.0 | ????99.1 |
| Embodiment 4 | ????99.8 | ????99.0 | ????99.3 |
| Embodiment 5 | ????99.5 | ????97.5 | ????98.5 |
| Embodiment 6 | ????96.5 | ????98.5 | ????98.5 |
| Embodiment 7 | ????99.0 | ????9?7.0 | ????99.0 |
| Embodiment 8 | ????89.1 | ????97.5 | ????98.8 |
| Embodiment 9 | ????81.7 | ????98.0 | ????99.2 |
Claims (10)
1, a kind of preparation method of N-N-formyl morpholine N-, with morpholine and formic acid is raw material, the mol ratio that morpholine and formic acid feed intake is a morpholine: formic acid=1: 0.8～1: 1.2, temperature of reaction is 50～140 ℃, reaction pressure is a normal pressure, it is characterized in that being reflected under the existence of band aqua and carry out, the band aqua is any in the mixture of aromatic hydrocarbon solvent oil, fats solvent oil, aromatic hydrocarbons and fats solvent oil or the esters solvent oil, and the add-on of band aqua is weight percentage=5.0～50.0% of band aqua in the raw material total amount.
2, the preparation method of N-N-formyl morpholine N-according to claim 1 is characterized in that the reaction times is 4～14 hours.
3, the preparation method of N-N-formyl morpholine N-according to claim 1, it is characterized in that reaction mass under reduced pressure carries out rectifying separation, rectifying pressure is 0.06～0.099MPa, heat to 140 ℃ and steam band aqua and excess raw material, continuing to heat to 140～200 ℃ steams the N-N-formyl morpholine N-, and condensation gets product.
4, the preparation method of N-N-formyl morpholine N-according to claim 1 is characterized in that described aromatic hydrocarbon solvent oil is any or two or more mixture in benzene,toluene,xylene, ethylbenzene or the trimethylbenzene.
5, the preparation method of N-N-formyl morpholine N-according to claim 1 is characterized in that described fats solvent oil is C
4～C
8Sherwood oil or C
8～C
12Solvent oil.
6, the preparation method of N-N-formyl morpholine N-according to claim 1 is characterized in that described esters solvent oil is any or two or more mixture in methyl-formiate, ethyl formate, butyl formate, methyl acetate, ethyl acetate or the butylacetate.
7, the preparation method of N-N-formyl morpholine N-according to claim 1 is characterized in that the mol ratio that described morpholine and formic acid feed intake is a morpholine: formic acid=1: 0.85～1: 0.97.
8, the preparation method of N-N-formyl morpholine N-according to claim 1 is characterized in that the add-on of described band aqua is weight percentage=9.0～10.0% of band aqua in the raw material total amount.
9, the preparation method of N-N-formyl morpholine N-according to claim 1 is characterized in that described temperature of reaction is 75～85 ℃.
10, the preparation method of N-N-formyl morpholine N-according to claim 2 is characterized in that the described reaction times is 6～10 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00125399 CN1112361C (en) | 2000-09-26 | 2000-09-26 | Process for preparing N-formyl morpholine |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00125399 CN1112361C (en) | 2000-09-26 | 2000-09-26 | Process for preparing N-formyl morpholine |
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| Publication Number | Publication Date |
|---|---|
| CN1345723A true CN1345723A (en) | 2002-04-24 |
| CN1112361C CN1112361C (en) | 2003-06-25 |
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|---|---|---|---|
| CN 00125399 Expired - Fee Related CN1112361C (en) | 2000-09-26 | 2000-09-26 | Process for preparing N-formyl morpholine |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1328266C (en) * | 2003-07-01 | 2007-07-25 | 烟台大学 | Process for preparing N-formyl morpholine |
| CN101062922B (en) * | 2006-04-28 | 2010-05-12 | 烟台大学 | Method for preparing N-formyl morpholine |
| CN101062923B (en) * | 2006-04-28 | 2010-06-09 | 烟台大学 | Synthesizing N-formyl morpholine by two-step process |
| CN102503759A (en) * | 2011-10-27 | 2012-06-20 | 天津大学 | Method and device for simultaneously recycling methylbenzene and dimethyl formamide in industrial waste gas by using solvent |
| CN104262293A (en) * | 2014-09-18 | 2015-01-07 | 四川之江高新材料股份有限公司 | Preparation method of low-acidity N-formylmorpholine |
-
2000
- 2000-09-26 CN CN 00125399 patent/CN1112361C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1328266C (en) * | 2003-07-01 | 2007-07-25 | 烟台大学 | Process for preparing N-formyl morpholine |
| CN101062922B (en) * | 2006-04-28 | 2010-05-12 | 烟台大学 | Method for preparing N-formyl morpholine |
| CN101062923B (en) * | 2006-04-28 | 2010-06-09 | 烟台大学 | Synthesizing N-formyl morpholine by two-step process |
| CN102503759A (en) * | 2011-10-27 | 2012-06-20 | 天津大学 | Method and device for simultaneously recycling methylbenzene and dimethyl formamide in industrial waste gas by using solvent |
| CN102503759B (en) * | 2011-10-27 | 2013-10-09 | 天津大学 | Method and device for simultaneously recycling methylbenzene and dimethyl formamide in industrial waste gas by using solvent |
| CN104262293A (en) * | 2014-09-18 | 2015-01-07 | 四川之江高新材料股份有限公司 | Preparation method of low-acidity N-formylmorpholine |
| CN104262293B (en) * | 2014-09-18 | 2016-04-13 | 四川之江高新材料股份有限公司 | The preparation method of Low acid N-N-formyl morpholine N- |
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| Publication number | Publication date |
|---|---|
| CN1112361C (en) | 2003-06-25 |
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