CN1315814C - Technique for producing N-formyl morpholine - Google Patents
Technique for producing N-formyl morpholine Download PDFInfo
- Publication number
- CN1315814C CN1315814C CNB2005100204832A CN200510020483A CN1315814C CN 1315814 C CN1315814 C CN 1315814C CN B2005100204832 A CNB2005100204832 A CN B2005100204832A CN 200510020483 A CN200510020483 A CN 200510020483A CN 1315814 C CN1315814 C CN 1315814C
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- CN
- China
- Prior art keywords
- morpholine
- tower
- formyl morpholine
- formyl
- under
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 238000000034 method Methods 0.000 title claims abstract description 25
- LCEDQNDDFOCWGG-UHFFFAOYSA-N morpholine-4-carbaldehyde Chemical compound O=CN1CCOCC1 LCEDQNDDFOCWGG-UHFFFAOYSA-N 0.000 title abstract 8
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims abstract description 50
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 150000002148 esters Chemical class 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 230000032683 aging Effects 0.000 claims abstract description 5
- 230000032050 esterification Effects 0.000 claims abstract description 5
- 238000005886 esterification reaction Methods 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims description 11
- 230000029087 digestion Effects 0.000 claims description 5
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 239000007789 gas Substances 0.000 abstract description 8
- 238000007670 refining Methods 0.000 abstract description 2
- 239000012295 chemical reaction liquid Substances 0.000 abstract 1
- 238000004821 distillation Methods 0.000 abstract 1
- 238000005292 vacuum distillation Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 13
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 235000019253 formic acid Nutrition 0.000 description 3
- 150000002780 morpholines Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- NMJJFJNHVMGPGM-UHFFFAOYSA-N butyl formate Chemical compound CCCCOC=O NMJJFJNHVMGPGM-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000007701 flash-distillation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention discloses a production process for N-formyl morpholine with an esterification method. Raw materials of morpholine and formic ester are continuously or indirectly conveyed into a reactor; under the condition of continuously stirring the raw materials, the reaction temperature is controlled between -20 DEG C and 60 DEG C; the raw materials are aged in an aging container for 10 to 35 hours; the aged reaction liquid can distill alcohol generated by the reaction in a dealcoholization tower; residues in the dealcoholization tower enter a light component removing tower; residual light components, such as alcohol, ester, morpholine, etc., are removed by operating the light component removing tower under the condition of low vacuum; stripping gases are led in the process of removing light components for gas stripping; after the contents of the light components achieve the requirements, the residues in the dealcoholization tower are conveyed into a product tower; the product of N-formyl morpholine is distilled by the product tower under the condition of high vacuum. The N-formyl morpholine with high purity is prepared in a high morpholine conversion rate by the refining mode of reaction and aging combination, vacuum distillation and stirring distillation.
Description
The invention belongs to organic chemical industry's synthesis technical field.
The N-N-formyl morpholine N-is a kind of fine solvent, can be used for the recovery of aromatic hydrocarbons, clean system; From C
4Isolate n-butene-1 in the gas, then hydration system butanone; Also can be used for the desulfurization of liquid state or gaseous state lower paraffin hydrocarbons.
The prior art situation
The main industrialized production method of N-N-formyl morpholine N-has formic acid method, chloride method at present.The formic acid method is by the reaction of formic acid and morpholine, generates N-N-formyl morpholine N-and water, the main drawback of this method be dewatering process complexity, product the free acid content height, cause seriously corroded.Chloride method is to generate N-N-formyl morpholine N-and hydrogenchloride by acyl chlorides and morpholine reaction, and the main drawback of this method is that the hydrogenchloride of reaction generation is serious to equipment corrosion.(1974 have reported the method that esterification process is produced the N-N-formyl morpholine N-to Deutsches Reichs-Patent Ger.offen 2445192, and the test conditions of this method is: the mol ratio of morpholine and methyl-formiate is 1: 1～1.1.75～85 ℃ of temperature of reaction.7～8 hours reaction times.Then, reactant is flash distillation in flasher, contains 1% N-N-formyl morpholine N-in the phlegma that flashes off.Like this, reactant and resultant are not acidic substance in the system, have solved the acid of product and to the etching problem of equipment.But it is lower that the main drawback of this method is a ultimate yield, and by product is many, is difficult to industrial applications; The purity of product is lower, is difficult to satisfy the high quality requirement of the continuous progress of chemical production technical to the N-N-formyl morpholine N-, is used for extracting and refining benzene when the N-N-formyl morpholine N-especially, and this benzene requires to use highly purified N-N-formyl morpholine N-when being used for synthesizing styrene.Its morpholine content≤0.1%, water-content≤0.2%, free acid content≤0.02%.
Content of the present invention
In view of the above shortcoming of prior art, the objective of the invention is to study a kind of esterification process production technique of N-N-formyl morpholine N-, make it to overcome the above shortcoming of prior art, under higher morpholine transformation efficiency, make high purity N-N-formyl morpholine N-.The objective of the invention is to realize by following means.
The production technique of N-N-formyl morpholine N-, make the N-N-formyl morpholine N-with morpholine and manthanoate for the raw material esterification, the mol ratio of morpholine and methyl-formiate is 1: 1～1.1, raw material morpholine and manthanoate are sent in the reactor continuously or indirectly, under continuous condition of stirring, control reaction temperature is at-20 ℃ to 60 ℃; Put into digestion tank and carried out ageing 10～35 hours, preferably 10～25 hours; Steam the alcohol that reaction generates through aged reaction solution in dealcoholize column, the still liquid of dealcoholize column enters lightness-removing column, and lightness-removing column is operated under the rough vacuum situation, takes off light component such as remaining alcohols, ester class and morpholine; Feed stripping gas in taking off light process, carry out stripping, after the content of light component reached requirement, lightness-removing column still liquid was sent into the product tower; The product tower steams product N-N-formyl morpholine N-under the condition of high vacuum degree situation.
Adopt method as above, make the transformation efficiency of morpholine make high purity N-N-formyl morpholine N-more than 98%, and obtain industrialized application.
Description of drawings is as follows:
Fig. 1 is the schema of technology of the present invention.
Embodiment
Below in conjunction with accompanying drawing technology contents of the present invention is described in further detail.
As shown in Figure 1, raw material morpholine and manthanoate (can be methyl-formiate, ethyl formate, butyl formate etc.) are sent in the reactor continuously or indirectly, and under continuous condition of stirring, control reaction temperature is at-20 ℃ to 60 ℃, between preferably 10 ℃～30 ℃; Add restir for some time behind the material, put into digestion tank, allow it display 10～25 hours, the transformation efficiency of guaranteeing morpholine is greater than 98%, reaction solution steams the alcohol that reaction generates in dealcoholize column then, the still liquid of dealcoholize column enters lightness-removing column, and this tower is operated under the rough vacuum situation, takes off light component such as remaining alcohols, ester class and morpholine.For guaranteeing that light component thoroughly displaces, in the tower still, feed gases such as nitrogen, air, carry out stripping, after the content of light component reaches requirement, lightness-removing column still liquid is sent into the product tower, and this tower steams product N-N-formyl morpholine N-under the condition of high vacuum degree situation, and the raffinate of still liquid is made fuel treatment.
Embodiment 1:
348 gram morpholines (in pure morpholine) add in the reactor 1, then under stirring state, slowly add 264 gram methyl-formiates, control reaction temperature is at 10～30 ℃, add methyl-formiate after, keep said temperature to continue to stir, question response transformation efficiency (in morpholine) reaches after about 80%, and reaction mass is put into digestion tank 2, and ageing is after 24 hours, aged substance is sent into dealcoholize column 3, and the control tower top temperature reclaims methyl alcohol for 65～120 ℃ under normal pressure.
Still liquid enters lightness-removing column 4, under absolute pressure 100～150mmHg, and 90～100 ℃ of control tower top temperatures.And in the tower still, feed nitrogen, and light component is driven out of as far as possible, after the light component of still liquid is qualified, still liquid is sent into product tower 5, under absolute pressure 20～50mmHg, under 130～150 ℃ of the temperature, steam product, N-N-formyl morpholine N-content 〉=99%; Moisture content≤0.2%; Morpholine≤0.1%; Free acid≤0.02%.
Embodiment 2:
348 gram morpholines (in pure morpholine) add in the reactors, under stirring state, slowly add 325.6 gram ethyl formates then, under the test conditions identical with example 1, and the product that equally can the production equal in quality requires.
Embodiment 3:
348 gram morpholines (in pure morpholine) add in the reactor, under stirring state, slowly add 264 gram methyl-formiates then, and control reaction temperature is at 50～60 ℃.Under the identical condition of other condition and example 1, occur some impurity in the bearing reaction thing, for example, the retention value that gas-chromatography occurred is 1 ' 02 ", 2 ' 45 ", 3 ' 30 " impurity peaks.And reaction mass is yellow, and color raises with temperature of reaction and deepens.Though can make qualified product, increase the isolating workload in back.So the temperature of reaction control reaction temperature can keep higher speed of reaction and can reduce foreign matter content in the product in the time of 10～30 ℃.
In reality was implemented, reaction can be carried out in tank reactor, also can carry out in tower reactor, can attended operation, and also can intermittent operation.The structural shape of tower can be a packing tower, also can be tray column.
Described stripping gas is rare gas element, air, carbon dioxide, one or more of synthetic gas.
Claims (4)
1, the production technique of N-N-formyl morpholine N-, make the N-N-formyl morpholine N-with morpholine and manthanoate for the raw material esterification, the mol ratio of morpholine and manthanoate is 1: 1～1.1 to it is characterized in that, raw material morpholine and manthanoate are sent in the reactor continuously or indirectly, under continuous condition of stirring, control reaction temperature is at-20 ℃ to 60 ℃; Put into digestion tank and carried out ageing 10～35 hours; Steam the alcohol that reaction generates through aged reaction solution in dealcoholize column, the still liquid of dealcoholize column enters lightness-removing column, and lightness-removing column is operated under the rough vacuum situation, takes off light component such as remaining alcohols, ester class and morpholine; Feed stripping gas in taking off light process, carry out stripping, after the content of light component reached requirement, lightness-removing column still liquid was sent into the product tower; The product tower steams product N-N-formyl morpholine N-under the condition of high vacuum degree situation.
2, the production technique of N-N-formyl morpholine N-according to claim 1 is characterized in that, control reaction temperature is between 10 ℃～30 ℃.
3, the production technique of N-N-formyl morpholine N-according to claim 1 is characterized in that, digestion time is 10～25 hours.
4, the production technique of N-N-formyl morpholine N-according to claim 1 is characterized in that, manthanoate is that molecular formula is the ester class of HCOOR, and wherein R is methyl, ethyl, butyl.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100204832A CN1315814C (en) | 2005-03-09 | 2005-03-09 | Technique for producing N-formyl morpholine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100204832A CN1315814C (en) | 2005-03-09 | 2005-03-09 | Technique for producing N-formyl morpholine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1687042A CN1687042A (en) | 2005-10-26 |
| CN1315814C true CN1315814C (en) | 2007-05-16 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100204832A Expired - Fee Related CN1315814C (en) | 2005-03-09 | 2005-03-09 | Technique for producing N-formyl morpholine |
Country Status (1)
| Country | Link |
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| CN (1) | CN1315814C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103641797B (en) * | 2013-09-11 | 2015-07-08 | 西南化工研究设计院有限公司 | Preparation method for N-acetyl morpholine |
| 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 |
Citations (4)
| 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 |
| DE2445192A1 (en) * | 1974-09-21 | 1976-04-01 | Basf Ag | Highly pure N-formyl morpholine prepn - from methyl formate and morpholine in quantitative yields |
| CN1356324A (en) * | 2001-10-18 | 2002-07-03 | 复旦大学 | Process for preparing N-formyl morpholine |
| CN1482121A (en) * | 2003-07-01 | 2004-03-17 | 烟台大学 | Process for preparing N-formyl morpholine |
-
2005
- 2005-03-09 CN CNB2005100204832A patent/CN1315814C/en not_active Expired - Fee Related
Patent Citations (4)
| 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 |
| DE2445192A1 (en) * | 1974-09-21 | 1976-04-01 | Basf Ag | Highly pure N-formyl morpholine prepn - from methyl formate and morpholine in quantitative yields |
| CN1356324A (en) * | 2001-10-18 | 2002-07-03 | 复旦大学 | Process for preparing N-formyl morpholine |
| CN1482121A (en) * | 2003-07-01 | 2004-03-17 | 烟台大学 | Process for preparing N-formyl morpholine |
Non-Patent Citations (4)
| Title |
|---|
| N-甲酰吗啉的合成研究 宋岩等，吉林化工学院学报，第18卷第4期 2001 * |
| N-甲酰吗啉的合成研究 宋岩等，吉林化工学院学报，第18卷第4期 2001;芳烃萃取剂N-甲酰吗啉的合成 邹东雷等，精细化工中间体，第33卷第4期 2003;甲酸甲酯下游化学品研究动态 王洪记，中氮肥，第2卷 2000 * |
| 甲酸甲酯下游化学品研究动态 王洪记，中氮肥，第2卷 2000 * |
| 芳烃萃取剂N-甲酰吗啉的合成 邹东雷等，精细化工中间体，第33卷第4期 2003 * |
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| Publication number | Publication date |
|---|---|
| CN1687042A (en) | 2005-10-26 |
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