CN1721415A - Process for preparing N-acetyl morpholine - Google Patents
Process for preparing N-acetyl morpholine Download PDFInfo
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- CN1721415A CN1721415A CN 200410069308 CN200410069308A CN1721415A CN 1721415 A CN1721415 A CN 1721415A CN 200410069308 CN200410069308 CN 200410069308 CN 200410069308 A CN200410069308 A CN 200410069308A CN 1721415 A CN1721415 A CN 1721415A
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- morpholine
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- aceticanhydride
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Abstract
The present invention is preparation process of N-acetyl morpholine as the main material for synthesizing farm germicide dimethomorph and fluoro morpholine, and features that the reaction is completed inside waterborne agent and has acetic anhydride and morpholine in the molar ratio of 1 to 1.8-2.5 as material and strong acid as catalyst to produce N-acetyl morpholine through reaction and rectification, with the waterborne agent amount being 10-50 wt% of the material, reaction time being 3-9 hr and catalyst amount being 1-7 wt% of material. The preparation process also includes heating reflux at boiling temperature, condensing reflux, separating water, deacidifying, dewatering, filtering and vacuum rectifying. The technological process has great production capacity, low cost, less environmental pollution, conversion rate up to 98 % and yield up to 95 %.
Description
Technical field:
The present invention relates to the main raw material of a kind of synthetic disinfectant use in agriculture dimethomorph, flumorph and the preparation method of Sweet natural gas and synthetic gas acid gas removal agent N-acetyl morphine.
Background technology
The N-acetyl morphine is very important medicine, pesticide intermediate, is the main raw material of synthetic disinfectant use in agriculture dimethomorph, flumorph.The mixture of N-acetyl morphine and N-N-formyl morpholine N-is good Sweet natural gas and the agent of synthetic gas acid gas removal, is used for the external Morphysorb novel process of exploitation in recent years.
The synthesis technique of N-acetyl morphine mainly contains acetate method (Fr1580614), acetyl chloride method (GB2223492), ketene, acetic ester and aceticanhydride (CN1403449) route.
Acetate route conversion rate of products and yield are low, are up to 85% in morpholine, and seriously corroded, production cost height and quality product are low.
It is acylating agent that the Acetyl Chloride 98Min. route adopts Acetyl Chloride 98Min., and under lower temperature, morpholine generation acylation reaction generates the N-acetyl morphine, and yield can reach more than 95%.But Acetyl Chloride 98Min. raw material costliness, building-up process produces hydrogenchloride, seriously corroded, needing to adopt pyridine or triethylamine is solvent and de-acidying agent, the three wastes are more, solvent recuperation complexity, production cost height.
The ketene route adopts ketene and morpholine to carry out addition reaction, synthetic N-acetyl morphine.Technology is simple, and the separation burden is little, and product yield and quality are all very high.But its shortcoming is also very obvious: ketene raw material sources difficulty, and severe toxicity is arranged, and high to the equipment seal request, only suitable operate continuously, periodical operation performance difficulty.
The acetic ester route adopts acetic ester to make acylating agent, must be under the catalytic effect of strong basicity could with morpholine generation acylation reaction.The acidylate ability of ester class too a little less than, need to select appropriate catalyst.This reaction simultaneously also is a reversible reaction, and how shifting out by product as soon as possible is a difficult problem.
It is raw material that the aceticanhydride route adopts aceticanhydride and morpholine, by twice acylation process, and synthetic N-acetyl morphine product:
The employing aceticanhydride is that the process characteristic of acylating agent is; because the first step reaction at first takes place; speed of reaction is very fast; there is a large amount of N-acetyl morphine rapidly in reaction system; temperature of reaction can be improved; can adopt high boiling solvent to dewater, separate simply relatively, the transformation efficiency of morpholine and aceticanhydride, product yield and quality are all than higher.This technology is simultaneously applicable to the acetic acid operational path.
Patent CA1403449A promptly adopts the aceticanhydride route.But only utilized the first step reaction, and adopted acetic acid as solvent.The transformation efficiency of morpholine surpasses 98%, and quality product is high than the Acetyl Chloride 98Min. route also.But the raw material availability of this synthetic method low excessively (utilization ratio of aceticanhydride only is 50%), the production intensity of reactor is little, and production cost is too high.
Summary of the invention
The present invention adopts batch reactive distillation technology, with aceticanhydride and morpholine is raw material, strong acid is catalyzer, in containing phenyl ring class, alicyclic ring class hydro carbons band aqua, carry out the method for the synthetic N-acetyl morphine of reactive distillation, to react with the product dehydration and carry out simultaneously, suppress the hydrolysis of product, promote the carrying out of reversible reaction, improve transformation efficiency.
Main processes of the present invention is as follows:
1. building-up reactions
Initial stage after the reaction beginning is carried out total reflux, begins azeotropic dehydration after 1～2 hour.Water and band aqua form azeotrope, enter overhead condenser, and condensing temperature is 65～105 ℃, and phegma enters water trap and carries out layering, the continuous extraction of water layer, and oil reservoir refluxes.Stopped reaction obtains reaction solution when no longer including water in the water trap and occur.
Process conditions: the mol ratio of morpholine and diacetyl oxide is 1.8-2.5: 1, and optimum proportion is 2.1: 1.Band aqua consumption is 10～50% of a raw material total amount, is preferably 15%.Reaction times is 3～9 hours, and the best is 6 hours, and catalyst levels is 1～7% (is benchmark with the raw material gross weight), and optimum amount is 3%.
Acylating agent can be diacetyl oxide or acetic acid.
Selectable band aqua has benzene,toluene,xylene or hexanaphthene.The strongly acidic catalyst that adopts can comprise sulfuric acid (93% or 98%, the industry first grade), tosic acid, large hole strong acid styrene system cation exchange resin's [sulfonic acid type, aperture=20～50nm, pore volume 0.30～0.48mL/g, exchange capacity=4.0～5.0 mmole/grams (butt)] (D072, D061, D001-CC, NKC-9 etc., Tianjin; Perhaps TS-98, Beijing) or SiO
2/ Al2O
3Be the beta molecular sieve of 20-50, wherein the performance of ion exchange resin or molecular sieve catalyst is more superior.
2. reaction solution is handled and wastewater treatment
(1) reaction solution
In reaction solution, add solid alkaline material and chemical dehydrator, under violent stirring, carry out depickling and dehydration, enter the product purification operation then after filtration.
Operational condition is as follows: the de-acidying agent consumption is 0.5～5% of a reaction solution gross weight, and the chemical dehydrator consumption is 3～10% of a reaction solution gross weight, and treatment temp is 30～45 ℃, and the best is 35 ℃, and the treatment time is 0.5～1.5 hour, and the best is 1 hour.De-acidying agent is sodium hydroxide, potassium hydroxide, yellow soda ash or salt of wormwood, and employing sodium hydroxide is de-acidying agent, and optimum amount is 1%; Chemical dehydrator is anhydrous sodium carbonate, anhydrous sodium sulphate or calcium chloride, and the employing anhydrous sodium sulphate is a dewatering agent, and optimum amount is 4%.
(2) wastewater treatment
This building-up process produces a small amount of waste water (about 80kg/t product).Wherein contain and be no more than 1% azeotropic dehydration solvent, morpholine and acetic acid.Total organic content is no more than 10g/L.Can directly deliver to sewage work and handle, also can concentrate the back is that 22 batch fractionating tower carries out rectifying recovery organism with a number of theoretical plate, and the organic content of its waste water is no more than 0.3%, and bottom product directly returns synthesis system and recycles.
3, product purification
Adopt batch fractionating tower to carry out the refining finished product of method of intermittent vacuum rectifying or the rectifying of double tower continous vacuum.Purification condition is as follows:
(1) batch fractionating: vacuum tightness 0.095MPa, the overhead collection temperature is 70～149 ℃ front-end volatiles, recycles, tower still temperature is at 145～165 ℃; The cut of gathering 150～155 ℃ of tower top temperatures is as product, and tower still temperature is 165～170 ℃.
(2) continuous processing: take off 74～76 ℃ of the tower top temperatures of front-end volatiles tower, tower still temperature is 145～147 ℃, vacuum tightness 0.095MPa, reflux ratio 3.0～3.5, theoretical plate number 31 (rectifying section/stripping section=17/14); 150～152 ℃ of the tower top temperatures of product tower, tower still temperature is 165～167 ℃, vacuum tightness 0.095MPa, reflux ratio 1.0～1.5, theoretical plate number 19 (rectifying section/stripping section=8/11).
4, the reactive distillation synthesis technique of N-acetyl morphine
Adopt batch reactive distillation technology, device comprises equipment (seeing accompanying drawing for details, batch technology) such as stirred autoclave (being rectifying still simultaneously), fixed-bed reactor, batch fractionating tower, condenser, quantizer.In reactor, add a kind of of above-mentioned catalyzer, add fixed-bed reactor (filling strongly acidic ion-exchange resin catalyst) in rectifier bottoms simultaneously, disposable the feeding intake of wherein a kind of raw material, another raw material adopts the continuous charging mode, keep reaction system to be in boiling state, steam enters rectifying tower through fixed-bed reactor and carries out azeotropic dehydration, and the cat head gas phase enters quantizer after condensation, oil phase refluxes, the water extraction.Liquid phase is returned reactor through fixed-bed reactor at the bottom of the tower.Stopped reaction when no longer including water in the water trap and occur.
The advance of this technology is: one, Zhuan Zhi throughput is big, and cost is low, and three-waste pollution is few, contains morpholine and acetic acid in the waste water hardly, does not need special processing (COD is about 1100mg/L) directly to deliver to sewage disposal unit and handles.Two, adopt reactive distillation process, will react with the product dehydration and carry out simultaneously, suppressed the hydrolysis of product, promote reversible reaction to carry out, improve transformation efficiency, and rationally utilize reaction heat to positive dirction.Three, adopt strong acid catalyst, shorten the reaction times greatly, improve transformation efficiency.The transformation efficiency of the morpholine of this technology building-up process can reach 98%, and the transformation efficiency of aceticanhydride can reach 99%, and yield is not less than 95%.The transformation efficiency of the morpholine of patent CA1403449 is about 98%, and yield 95%, the transformation efficiency of aceticanhydride are 50%.
Description of drawings
Fig. 1 .N-acetyl morphine batch reactive distillation process schematic representation (throughput is 300t/a)
Wherein:
(1) (inside reactor has double-deck heating coil, heating-surface area 6.5m to stirred-tank reactor (batch fractionating still)
2, the outside is a cooling jacket, reactor useful volume 1.5m
3, propeller agitator).
(2) fixed-bed reactor (φ 500 * 1500, and the catalyst bed layer height is 700mm).
(3) batch fractionating tower (φ 300 * 12500, and packed height 8m divides two sections fillings)
(4) reflux exchanger (I16B20-0.6/700-6)
(5) reflux condensation mode quantizer (vertical elipse head, Vg=0.2m
2)
(6) light constituent reclaims test tank (vertical elipse head, Vg=0.5m
2)
(7) ganging of products jar (vertical elipse head, Vg=0.8m
2)
(8) reflux pump (32GPB-16)
(9) vacuum buffer tank (vertical elipse head, Vg=0.5m
2)
(10) vacuum pump (W2 (V4) type)
Embodiment:
Embodiment 1
This embodiment is the specific embodiments of technical process of the present invention.With feedstock pump respectively with morpholine (after reclaiming liquid and recycling, the amount minimizing 4% of morpholine), aceticanhydride, toluene are (after recovery liquid recycles, the amount of toluene reduces 95%) squeeze in morpholine scale tank, aceticanhydride scale tank and the toluene scale tank (unlisted among the figure), molecular sieve catalyst (Powdered) is put into stirred-tank reactor (1), successively join morpholine and toluene in the reactor, start stirring, heat up.When temperature in the kettle reaches 110 ℃, beginning slowly adds aceticanhydride (it is principle that feed rate with the batch reactive distillation tower liquid flooding does not take place), stop heating simultaneously, this moment is because exothermic heat of reaction, system temperature is along with the carrying out of reaction constantly raises and the generating gasification phenomenon, after the aceticanhydride adding finishes, restart heating.The gas phase of reactor enters batch fractionating tower (3) bottom by the rising vapour pipe and carries out azeotropic dehydration, and the cat head gas phase enters backflow quantizer (5) after reflux exchanger (4) condensation, and upper oil phase refluxes through reflux pump (8), by liquid level control quantity of reflux.Initial reaction stage begins to adopt the total reflux mode, drops to 93 ℃ until tower top temperature, illustrates that water begins to generate.Water regularly extraction also collects, concentrates back unified processing backflow liquid phase to return tank reactor through fixed-bed reactor (2).When the water layer liquid level of return tank no longer changes, finish reaction in 15～20min.
After reaction finishes, stop heating earlier, the terminal valve of fixed-bed reactor is closed, open the valve of by-pass.Start vacuum pump (10), make system pass through vacuum buffer tank (9) vacuum tightness and slowly improve, finally remain on 0.095MPa, after trim the top of column stops, restarting heating.Gas phase enters return tank after rectifying tower, reflux exchanger condensation.A part refluxes, a part of extraction enters light constituent and reclaims test tank (6).The control reflux ratio between 4～10, tower top temperature 74～76 ℃ keep for some time after, the light component of extraction enters light constituent and reclaims test tank (6).Along with after light component major part such as morpholine and toluene is recovered, tower top temperature begins to rise, and stops the light component of extraction and keep total reflux when tower top temperature reaches 150 ℃.The still temperature is at 85～170 ℃.
Behind the total reflux certain hour, keep reflux ratio about 2.0, continuous extraction N-acetyl morphine product is also put in the ganging of products jar (7), till cat head does not have backflow.After product purification finishes, stop heating, and vacuum is laid down.Light components such as toluene in the recovery liquid scale tank and morpholine are put into the reactor internal recycle to be used.N-acetyl morphine product in the ganging of products groove is directly packed.
Embodiment 2
In the four-hole boiling flask of being furnished with agitator, thermometer, constant pressure funnel, reflux exchanger and water trap, add 174.2g morpholine, 98% vitriol oil 8.3g and toluene 41.5g, be heated to and occur refluxing, in violent stirring and reflux, reflux temperature is under 70～74 ℃ of conditions, slowly drip the 102.1g aceticanhydride, morpholine: aceticanhydride=2.1: 1, reinforced and the reflux time is 1.5 hours, condensing reflux divided water after 2 hours, stopped reaction when no longer including water in the water trap and occur, the reaction times is 5 hours.In the morpholine transformation efficiency is 95.1%, and yield is 91.4%.
Example 3
In the four-hole boiling flask of being furnished with agitator, thermometer, constant pressure funnel, reflux exchanger and water trap, add 174.2g morpholine, N-72 strong acid ion exchange resin 8.7g and toluene 43.7g, be heated to and occur refluxing, little boil or boiling temperature under reflux, with the slow 117.3g aceticanhydride that drips under the violent stirring condition, morpholine: aceticanhydride=1.8: 1, reinforced and the reflux time is 1.5 hours, condensing reflux divided water after 2 hours, stopped reaction when no longer including water in the water trap and occur, the reaction times is 5 hours.In the morpholine transformation efficiency is 98.3%, and yield is 95.4%.
Example 4
In the four-hole boiling flask of being furnished with agitator, thermometer, constant pressure funnel, reflux exchanger and water trap, add 187.31g morpholine, β-molecular sieve 8.67g and toluene 43.39g, be heated to and occur refluxing, little boil or boiling temperature under reflux, with the slow 102g aceticanhydride that drips under the violent stirring condition, morpholine: aceticanhydride=2.15: 1, the reinforced and reflux time is 1.5 hours, condensing reflux divided water after 2 hours, stopped reaction when no longer including water in the water trap and occur, the reaction times is 5 hours.In the morpholine transformation efficiency is 87.5%, and yield is 86.1%.
Example 5
In the four-hole boiling flask of being furnished with agitator, thermometer, constant pressure funnel, reflux exchanger and water trap, add 174.24g morpholine, large hole strong acid styrene system cation exchange resin 8.3g and toluene 41.45g, be heated to and occur refluxing, little boil or boiling temperature under reflux, with the slow 102g aceticanhydride that drips under the violent stirring condition, morpholine: aceticanhydride=2.3: 1, reinforced and the reflux time is 1.5 hours, condensing reflux divided water after 2 hours, stopped reaction when no longer including water in the water trap and occur, the reaction times is 3 hours.In the morpholine transformation efficiency is 83.4%, and yield is 82.7%.
Example 6
To being furnished with agitator, thermometer, constant pressure funnel, add the 174.24g morpholine in the four-hole boiling flask of reflux exchanger and water trap, large hole strong acid styrene system cation exchange resin 13.81g and toluene 41.45g, connect water of condensation, open the magnetic agitation electric mantle and be heated to the appearance backflow, little boil or boiling temperature under reflux, with the slow 102g aceticanhydride that drips under the violent stirring condition, morpholine: aceticanhydride=2.4: 1, reinforced and the reflux time is 1.5 hours, condensing reflux divided water after 2 hours, stopped reaction when no longer including water in the water trap and occur, the reaction times is 5 hours.In the morpholine transformation efficiency is 95.8%, and yield is 93.8%.
Example 7
In the four-hole boiling flask of being furnished with agitator, thermometer, constant pressure funnel, reflux exchanger and water trap, add 174.24g morpholine, 8.4g tosic acid and toluene 41.45g, connect water of condensation, open the magnetic agitation electric mantle and be heated to the appearance backflow, reflux under boiling temperature, with the slow 102g aceticanhydride that drips under the violent stirring condition, morpholine: aceticanhydride=2: 1, the reinforced time is 1.5 hours, condensing reflux divided water after 2 hours, stopped reaction when no longer including water in the water trap and occur, the reaction times is 6 hours.In the morpholine transformation efficiency is 94.1%, and yield is 90.1%.
Example 8
In the four-hole boiling flask of being furnished with heat collecting type magnetic stirring apparatus, thermometer, constant pressure funnel, resin filling glass reaction column, glass rectifying tower, reflux exchanger and water trap, add 174.2g morpholine, β-molecular sieve 8.3g and toluene 41.5g, be heated to and occur refluxing, reflux under boiling temperature, with the slow 102.1g aceticanhydride that drips under the violent stirring condition, morpholine: aceticanhydride=1.9: 1, reinforced and the reflux time is 1.5 hours, condensing reflux divided water after 2 hours, stopped reaction when no longer including water in the water trap and occur, the reaction times is 5 hours.In the morpholine transformation efficiency is 98.4%, and yield is 95.2%.
Claims (10)
1. the preparation method of an acetyl morphine, it is characterized in that: be reflected to contain in the phenyl ring class band aqua and carry out, with aceticanhydride and morpholine is raw material, add strongly acidic catalyst, reactive distillation synthesis of acetyl morpholine, the mol ratio of morpholine and aceticanhydride is 1.8-2.5: 1, band aqua consumption is 10～50% of a raw material gross weight, and the reaction times is 3～9 hours, and catalyst levels is 1～7% of a raw material gross weight, reflux is reacted under 70～185 ℃ of temperature, initial stage after the reaction beginning is carried out total reflux, begins azeotropic dehydration after 1～2 hour, and water and band aqua form azeotrope, enter overhead condenser, condensing temperature is 65～105 ℃, and phegma enters water trap and carries out layering, the continuous extraction of water layer, oil reservoir refluxes, and stopped reaction obtains reaction solution when no longer including water in the water trap and occur; Add 0.5～5% de-acidying agent of reaction solution gross weight and 3～10% chemical dehydrator, stirred 0.5～1.5 hour down, carry out depickling and dehydration at 30～45 ℃; Reaction solution after the dehydration depickling enters rectifying still after filtration and carries out rectification under vacuum, vacuum tightness 0.095MPa, and the overhead collection temperature is 70～149 ℃ front-end volatiles, recycles, tower still temperature is at 145～165 ℃; The cut of gathering 150～155 ℃ of tower top temperatures is as product, and tower still temperature is 165～170 ℃.
2. the preparation method of acetyl morphine according to claim 1, it is characterized in that: the mol ratio of morpholine and aceticanhydride is 2.1: 1.
3. the preparation method of acetyl morphine according to claim 1 is characterized in that: band aqua consumption is 15% of a raw material gross weight.
4. the preparation method of acetyl morphine according to claim 1, it is characterized in that: the reaction times is 5 hours.
5. the preparation method of acetyl morphine according to claim 1 is characterized in that: the band aqua is benzene,toluene,xylene or hexanaphthene;
6. the preparation method of acetyl morphine according to claim 1, it is characterized in that: strongly acidic catalyst is 93% or 98% sulfuric acid, phosphoric acid, tosic acid, large hole strong acid styrene system cation exchange resin's [sulfonic acid type, aperture=20～50nm, pore volume 0.30～0.48mL/g, exchange capacity=4.0～5.0 mmole/grams (butt)] or SiO
2/ Al
2O
3Beta molecular sieve for 20-50.
The preparation method of 7 acetyl morphine according to claim 1 is characterized in that: de-acidying agent is sodium hydroxide, potassium hydroxide, yellow soda ash or salt of wormwood; Chemical dehydrator is anhydrous sodium carbonate, anhydrous sodium sulphate or calcium chloride.
8. the preparation method of acetyl morphine according to claim 7, it is characterized in that: the de-acidying agent sodium hydroxide concentration is 1% of a reaction solution gross weight; Chemical dehydrator anhydrous sodium sulphate consumption is 4% of a reaction solution gross weight.
9. the preparation method of acetyl morphine according to claim 1, it is characterized in that: catalyst consumption is 3% of a reaction solution gross weight.
10. the preparation method of acetyl morphine according to claim 1, the aceticanhydride raw material can be replaced by acetic acid.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410069308 CN1283632C (en) | 2004-07-16 | 2004-07-16 | Process for preparing N-acetyl morpholine |
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|---|---|---|---|
| CN 200410069308 CN1283632C (en) | 2004-07-16 | 2004-07-16 | Process for preparing N-acetyl morpholine |
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| CN1721415A true CN1721415A (en) | 2006-01-18 |
| CN1283632C CN1283632C (en) | 2006-11-08 |
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|---|---|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102295623A (en) * | 2011-05-26 | 2011-12-28 | 山东汇海医药化工有限公司 | Method for preparing N-acetylmorpholine by using ketene |
| CN103641797A (en) * | 2013-09-11 | 2014-03-19 | 西南化工研究设计院有限公司 | Preparation method for N-acetyl morpholine |
-
2004
- 2004-07-16 CN CN 200410069308 patent/CN1283632C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102295623A (en) * | 2011-05-26 | 2011-12-28 | 山东汇海医药化工有限公司 | Method for preparing N-acetylmorpholine by using ketene |
| CN102295623B (en) * | 2011-05-26 | 2013-05-22 | 山东汇海医药化工有限公司 | Method for preparing N-acetylmorpholine by using ketene |
| CN103641797A (en) * | 2013-09-11 | 2014-03-19 | 西南化工研究设计院有限公司 | Preparation method for N-acetyl morpholine |
| 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 |
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| CN1283632C (en) | 2006-11-08 |
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