CN1482121A - Process for preparing N-formyl morpholine - Google Patents
Process for preparing N-formyl morpholine Download PDFInfo
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- CN1482121A CN1482121A CNA031451713A CN03145171A CN1482121A CN 1482121 A CN1482121 A CN 1482121A CN A031451713 A CNA031451713 A CN A031451713A CN 03145171 A CN03145171 A CN 03145171A CN 1482121 A CN1482121 A CN 1482121A
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Abstract
The present invention is the production process of N-formyl morpholine. Morpholine and formic acid entering the decompressing reaction distilling tower from two different material feeding ports, one upper and one lower, are reacted and the rectified product, N-formyl morpholine, is exhausted while water is exhausted from the tower top. The product is led into a refining tower for further decompression distillation and high purity N-formyl morpholine is obtained from the tower top while the residue produced in the reaction is left in the tower.
Description
Technical field: the production method that the present invention relates to a kind of N-N-formyl morpholine N-.
Background technology: N-N-formyl morpholine N-morpholine can be carried dense solvent as aromatic hydrocarbons extracting and butylene industrial, also can be used as the sorbent material of selexol process.At present, the N-N-formyl morpholine N-adopts the method for morpholine and formic acid or methyl-formiate reaction to synthesize more, as application number is: 00125399.9 and application number be as described in 01131970.4 the patent application.In the preparation process of N-N-formyl morpholine N-, have following problem to be difficult to solve:
(1) the initial reaction stage thermal discharge is very big, and temperature of reaction system is difficult to control, causes side reaction many, and yield is low;
(2) reaction late phase reaction speed is slower, and transformation efficiency is low, and significant loss is big;
(3) reactant formic acid and product water boiling point are approaching, are difficult to separate, reclaim;
(4) N-N-formyl morpholine N-boiling point is 244 ℃, adopts the method for air distillation, and tower still temperature is very high, causes product to decompose.
For solving as above problem, the method for existing N-N-formyl morpholine N-preparation adopts the method that adds the band aqua in reaction system more, and the band aqua can be aromatic hydrocarbon solvent oil, fats solvent wet goods (as No. 00125399.9 application); Or hexanaphthene, benzene, toluene etc. (as 011 No. 31970.4 applications).Add the band aqua initial reaction speed and temperature of reaction are controlled, reduce side reaction.Reaction finishes the back and isolates unreacted morpholine, formic acid and product water with the method for underpressure distillation, and the N-N-formyl morpholine N-is purified.Yet there are the following problems to add the method for being with aqua in reaction system:
(1) behind the adding band aqua, increases the amount that needs isolated compound in the system of reaction back, increased energy consumption.The consumption of band aqua is generally raw material total amount about 50%, and reaction finishes back band aqua and must all steam, and makes one times of energy consumption increase nearly;
(2) can only adopt intermittently or the operating procedure of semi-batch;
(3) reaction product N-N-formyl morpholine N-can not be separated from reaction system, be caused reaction late phase reaction speed to reduce, need to prolong the reaction times or add catalyzer to improve reaction conversion ratio;
(4) reaction heat is not fully utilized.
Summary of the invention: task of the present invention is exactly to solve the above-mentioned difficulties that the N-N-formyl morpholine N-runs in synthetic.
Method of the present invention is carried out in the synthetic and N-N-formyl morpholine N-of N-N-formyl morpholine N-and the reactive distillation column (1 tower) that is incorporated in a decompression separating of unreacted raw material formic acid, morpholine and water byproduct with reference to the accompanying drawings.1 tower adopts decompression operation, working pressure-0.1～-0.07MPa (gauge pressure).Reaction raw materials formic acid and morpholine are from two different positions chargings of 1 tower bottom, and the formic acid charging is following, and the morpholine charging is last, and the tower section between two opening for feeds is a conversion zone.According to the distillation principle, reaction product N-N-formyl morpholine N-boiling point is higher, will be to the enrichment of tower still, and the water byproduct boiling point is lower, will be to the cat head enrichment.Morpholine is suitably excessive in the control tower, can make the formic acid total overall reaction, and rectifying section only need be considered separating of morpholine and water, designs suitable tower height, can not contained the N-N-formyl morpholine N-of reactant and not contained the water byproduct of reactant at cat head at the tower still.Adopt suitable working pressure tower still temperature can be controlled at 140～180 ℃.Adding an acidic catalyst such as sulfuric acid, phosphoric acid, hydrochloric acid can improve speed of response in raw material, reduce the conversion zone height.Perhaps solid acid catalyst is installed, also can be improved speed of response, reduce the conversion zone height at conversion zone.Product in the 1 Tata still is introduced N-N-formyl morpholine N-treating tower (2 tower) again, and further underpressure distillation obtains highly purified N-N-formyl morpholine N-at cat head, and the tower still is the residue that produces in the reaction process.2 towers are operation under reduced pressure also, working pressure-0.1～-0.07MPa (gauge pressure), tower still temperature is controlled to be 140～180 ℃.
Characteristics of the present invention are:
(1) react with being separated in the vacuum distillation tower and carry out, tower still temperature is low, and side reaction is few, the yield height;
(2) reaction heat can utilize, and has reduced energy consumption;
(3) do not add the band aqua after, need not steam the band aqua, also reduced energy consumption;
(4) formic acid and morpholine are from the different positions charging, and speed of response and temperature are easy to control;
(5) morpholine is excessive in the tower, and the formic acid total overall reaction has avoided formic acid and water to be difficult for the difficult problem of fractionation by distillation;
(6) adopt continuous production technology, less investment, output height, purity height, yield height.
Description of drawings: accompanying drawing is about schematic flow sheet of the present invention.
1 tower: reaction fractionating tower.
2 towers: N-N-formyl morpholine N-treating tower.
Embodiment: below be an example of this patent.
Used reaction fractionating tower (1 tower) is a packing tower: the material stainless steel, and tower diameter 50mm, conversion zone filler are the porcelain ring filler, other filler is the Stainless Steel Cloth filler; N-N-formyl morpholine N-treating tower (2 tower) also is a packing tower: the material stainless steel, and tower diameter 50mm, filler are the θ ring filler; The equal adiabatic heat-insulation of two towers; Morpholine is added by the last charging opening of 1 tower, and formic acid adds 25 ℃ of temperature by the following charging opening of 1 tower; Add a small amount of morpholine in the tower in advance, and morpholine/formic acid raw materials components mole ratio 1: 1 makes to keep morpholine excessive in the tower; 1 tower reflux ratio: 2.5～8; 1 tower working pressure :-0.1～-0.07MPa (gauge pressure); 1 Tata still temperature: 140～180 ℃; 2 tower reflux ratios: 1.0～2.0; 2 tower working pressures :-0.1～-0.07MPa (gauge pressure); 2 Tata still temperature: 140～180 ℃; 1 overhead water purity 99.5%; 2 cat head N-N-formyl morpholine N-purity 99.9%.
Claims (4)
1.N-the production method of N-formyl morpholine N-is characterized in that, described method may further comprise the steps:
1) morpholine, formic acid enter from upper and lower two different opening for feeds in the reactive distillation column of a decompression and carry out reactive distillation, and the material that is come out by the tower still is the N-N-formyl morpholine N-, and the material that is come out by cat head is a water.
2) material that comes out of Jian Ya reaction distillation Tata still is introduced N-N-formyl morpholine N-treating tower again, and further underpressure distillation obtains highly purified N-N-formyl morpholine N-at cat head, and the tower still is the residue that produces in the reaction process.
2. method according to claim 1 is characterized in that, described decompression reaction fractionating tower working pressure is-0.1～-0.07MPa (gauge pressure), tower still temperature is 140～180 ℃.
3. method according to claim 1 is characterized in that, adds sulfuric acid, phosphoric acid, hydrochloric acid catalyst in raw material.
4. method according to claim 1 is characterized in that, at the conversion zone of reaction fractionating tower solid acid catalyst is installed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031451713A CN1328266C (en) | 2003-07-01 | 2003-07-01 | Process for preparing N-formyl morpholine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031451713A CN1328266C (en) | 2003-07-01 | 2003-07-01 | Process for preparing N-formyl morpholine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1482121A true CN1482121A (en) | 2004-03-17 |
| CN1328266C CN1328266C (en) | 2007-07-25 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB031451713A Expired - Fee Related CN1328266C (en) | 2003-07-01 | 2003-07-01 | Process for preparing N-formyl morpholine |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1315814C (en) * | 2005-03-09 | 2007-05-16 | 西南化工研究设计院 | Technique for producing 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 |
| CN106565516A (en) * | 2016-11-14 | 2017-04-19 | 成都惠恩精细化工有限责任公司 | Long-chain alkyl formamide, preparation method thereof, and formylation rectification device |
| CN107406345A (en) * | 2015-03-25 | 2017-11-28 | 三菱化学株式会社 | The manufacture method of alpha olefin oligomer |
| CN109251137A (en) * | 2018-09-14 | 2019-01-22 | 新昌县泰如科技有限公司 | The synthetic method of one kind 2,4- dichloroacetophenone |
| CN109721480A (en) * | 2018-11-14 | 2019-05-07 | 新昌县泰如科技有限公司 | The synthetic method of one kind 2,4- dichloroacetophenone |
| CN109956849A (en) * | 2017-12-22 | 2019-07-02 | 湖南中创化工股份有限公司 | A kind of method preparing ethylene acetate and sec-butyl alcohol and catalyst system and device |
| CN112321537A (en) * | 2020-11-03 | 2021-02-05 | 西南化工研究设计院有限公司 | Method for synthesizing formylmorpholine through heterogeneous reaction |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3558619A (en) * | 1967-08-31 | 1971-01-26 | Basf Ag | Production of n-formylmorpholine or n-acetylmorpholine |
| CN1112361C (en) * | 2000-09-26 | 2003-06-25 | 上海爱德化工有限公司 | Process for preparing N-formyl morpholine |
| CN1132825C (en) * | 2001-10-18 | 2003-12-31 | 复旦大学 | Process for preparing N-formyl morpholine |
-
2003
- 2003-07-01 CN CNB031451713A patent/CN1328266C/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1315814C (en) * | 2005-03-09 | 2007-05-16 | 西南化工研究设计院 | Technique for producing 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 |
| CN107406345A (en) * | 2015-03-25 | 2017-11-28 | 三菱化学株式会社 | The manufacture method of alpha olefin oligomer |
| CN106565516A (en) * | 2016-11-14 | 2017-04-19 | 成都惠恩精细化工有限责任公司 | Long-chain alkyl formamide, preparation method thereof, and formylation rectification device |
| CN109956849A (en) * | 2017-12-22 | 2019-07-02 | 湖南中创化工股份有限公司 | A kind of method preparing ethylene acetate and sec-butyl alcohol and catalyst system and device |
| CN109956849B (en) * | 2017-12-22 | 2022-01-25 | 湖南中创化工股份有限公司 | Method for preparing ethylene glycol diacetate and sec-butyl alcohol, catalytic system and device |
| CN109251137A (en) * | 2018-09-14 | 2019-01-22 | 新昌县泰如科技有限公司 | The synthetic method of one kind 2,4- dichloroacetophenone |
| CN109721480A (en) * | 2018-11-14 | 2019-05-07 | 新昌县泰如科技有限公司 | The synthetic method of one kind 2,4- dichloroacetophenone |
| CN112321537A (en) * | 2020-11-03 | 2021-02-05 | 西南化工研究设计院有限公司 | Method for synthesizing formylmorpholine through heterogeneous reaction |
| CN112321537B (en) * | 2020-11-03 | 2022-08-09 | 西南化工研究设计院有限公司 | Method for synthesizing formylmorpholine through heterogeneous reaction |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1328266C (en) | 2007-07-25 |
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