CN1019934C - Synthesis of mocpholine and its derivatives - Google Patents
Synthesis of mocpholine and its derivatives Download PDFInfo
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- CN1019934C CN1019934C CN 89100687 CN89100687A CN1019934C CN 1019934 C CN1019934 C CN 1019934C CN 89100687 CN89100687 CN 89100687 CN 89100687 A CN89100687 A CN 89100687A CN 1019934 C CN1019934 C CN 1019934C
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- ammonia
- hydrogen
- glycol ether
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- morpholine
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Abstract
The present invention relates to a method for synthesizing morpholine and derivatives thereof by diglycol under the existence of hydrogen and an additional-dehydrogenation catalyst, which adopts two stages of cooling steam-liquid to separate and recover ammonia and hydrogen. The present invention particularly provides a use method of a CN88107491 patent application catalyst. Compared with the prior art, the present invention simplifies devices and operation processes and reduces device investment and energy consumption. The operation cost is also correspondingly reduced.
Description
The present invention relates to a kind of by glycol ether and ammonia at hydrogen with add-dehydrogenation catalyst in the presence of the method for synthesize morpholine and morpholine derivative.
By glycol ether and ammonia at hydrogen with add-dehydrogenation catalyst in the presence of in the process of synthesize morpholine and morpholine derivative; ammonia is excessive in reactor; and hydrogen plays guard catalyst, therefore must solve the separation of ammonia, hydrogen on technology, reclaims and recycle problem.The scheme that the clear 55-31781 of Japanese Patent JP proposes is, the resultant of reaction that reactor is derived is introduced flashing tower with the ammonia of surplus and the mixture of hydrogen under certain temperature, pressure condition, the mixed airflow that isolate product liquid and the mixed airflow that mainly contains ammonia, hydrogen, contains ammonia, hydrogen contacts with the raw material glycol ether is reverse in ammonia absorber, ammonia is absorbed, the diethylene glycol solution that contains ammonia is mixed enough ammonia again and is sent into reactor, thereby realizes recycling of ammonia and hydrogen.In above-mentioned technological process, need with a flashing tower and a stripping tower, production cost height not only, and operation is difficult for steadily, and the more important thing is with glycol ether and absorb ammonia, be difficult to accurately control the ratio of ammonia and glycol ether in the reaction mass, can not guarantee to be reflected under the top condition and carry out, cause vicious cycle.The scheme and the aforesaid method of U.S. Pat 4091218 are similar, also are based on glycol ether to absorb the method realization ammonia of ammonia and recycling of hydrogen, and have same defective.
The purpose of this invention is to provide a kind of easy technological process, have more simple equipment, can control the ratio of ammonia and glycol ether more exactly.Purpose of the present invention also comprises simultaneously provides the catalyzer that is suitable for Chinese patent application CN88107491 using method.
Technological process of the present invention does not need stripping tower or flashing tower, but with two sections refrigerated separation, reaches the purpose that recycles ammonia and hydrogen.
Technological process of the present invention mainly comprises:
At hydrogen and add-dehydrogenation catalyst exists and suitable temperature, pressure under, glycol ether and ammonia are reacted, generate morpholine or generate morpholine derivative simultaneously, as N-methylmorpholine, N-ethylmorpholine;
2. go out autoreactor, the mixture that contains the water composition of morpholine and derivative thereof and ammonia, hydrogen or the unreacted glycol ether and the generation of surplus, pressure is adjusted to enters first step water cooler in the 1.0-4.0MPa scope, first step cooler outlet temperature of charge is controlled between 100-140 ℃, this material is delivered to first step separating tank again and is carried out the vapour-liquid separation.The separating tank end opening is discharged the Generation Liquid that contains ammonia about 5%, enters the work in-process basin.Separating tank discharge ammonia suitable for reading, hydrogen mixed airflow along with adding-reactivity worth of dehydrogenation catalyst and reaction conditions different, also may contain the non-condensing gas of minute quantity in the mixed airflow.
3. from first step separating tank mixed airflow suitable for reading, by second-stage cooler, make temperature of charge reduce to 0-20 ℃ under the close pressure condition to enter second stage separating tank and separate separating with the first step, at this moment Jue Dabufen ammonia is liquefied.The liquefied ammonia of second stage separating tank end opening is delivered to anhydrous ammonia tank.The separating tank hydrogen of isolating suitable for reading in the second stage wherein approximately contains the 5%(body) ammonia, be sent to the hydrogen circulator, enter reactor after sending calorifier inlets and ammonia Hybrid Heating again.
4. according to the requirement of reaction pressure, the liquefied ammonia that will store narrow-necked earthen jar from liquefied ammonia is with the ammonia pump pressurization and deliver to hybrid heater and recycle.Simultaneously, according to the requirement of reaction pressure, hydrogen adds by recycle compressor
Press and deliver to hybrid heater and recycle as feed hydrogen.
The present invention by above-mentioned steps and equipment realization response, separate and the recycling of ammonia and hydrogen.If there is non-condensability material to produce in the system, just can constantly descend along with passing density of hydrogen cycling time, reduce to 70% molecule when following, should emit certain impure hydrogen by the gas blow-off valve when density of hydrogen, and additional fresh hydrogen, to guarantee enough hydrogen dividing potential drops.Certainly for guaranteeing normally carrying out of reaction, must control proportioning raw materials exactly, additional fresh hydrogen often is necessary.
Ni-Cu-Zn-Al or Ni-Cu-Zn-Cr catalyzer that a preferred embodiment of the invention is to use CN88107491 to provide, when adopting above-mentioned catalyzer, suitable proportioning raw materials is, glycol ether: ammonia: hydrogen (molecular ratio)=1: (5-20): (3-8), during the suitable air speed LHSV=0.1-1.0 of charging glycol ether
-1, suitable reaction pressure is 1.0-4.0MPa, suitable temperature of reaction is 200-250 ℃.Preferred reaction conditions is glycol ether: ammonia: when hydrogen (molecular ratio)=1: 10: 5, the air speed LHSV=0.2-0.4 of charging glycol ether
-1, reaction pressure 1.8-2.2MPa and temperature of reaction 220-240 ℃.With this understanding, the per pass conversion of glycol ether can reach 99%, and the morpholine selectivity is more than 66%, and the selectivity of N-ethylmorpholine generates minor N-methylmorpholine simultaneously about 20%, and the overall selectivity of three kinds of products can reach 87-90%.When using Ni-Cu-Zn-Al or Ni-Cu-Zn-Cr catalyzer, reaction pressure is identical with separation system pressure, so the hydrogen recycle system does not need the compressor of high compression ratio yet, the effluent of reactor does not need step-down and directly enters first step water cooler.Ni-Cu-Zn-Al or Ni-Cu-Zn-Cr catalyzer have the alkylation performance of good organic aminated substance in addition, and methyl alcohol, ethanol and morpholine that reaction is produced react, and generate N-methylmorpholine, N-ethylmorpholine.
Based on above-mentioned basic skills, in conjunction with the accompanying drawings process of the present invention is further described.With the reaction raw materials glycol ether, liquefied ammonia and hydrogen are according to reacting desired ratio respectively through pipeline 1,2 and 3 send into hybrid heater 7 mixes, and be heated to temperature of reaction, the mixture of heating is introduced to be equipped with and is added-reactor 8 of dehydrogenation catalyst, reactor 8 effusive resultant of reaction enter water cooler 9 through interchanger 4 and heat exchange of charging glycol ether and step-down, water cooler 9 effusive materials are introduced vapour-liquid separator 10, the service temperature of vapour-liquid separator 10 is controlled between 100-140 ℃, working pressure is controlled between the 1.0-4.0MPa, vapour-liquid separator 10 isolated liquid streams are introduced work in-process basin 15, the isolated air-flow of vapour-liquid separator enters water cooler 11, the service temperature that enters vapour-liquid separator 12 after the steam flow cooling is between 0-20 ℃, and working pressure is between 1.0-4.0MPa.Vapour-liquid separator 12 isolated liquefied ammonia are introduced anhydrous ammonia tank 5, liquefied ammonia in the anhydrous ammonia tank 5 is delivered to hybrid heater 7 by ammonia pump 6, realize recycling of liquefied ammonia, vapour-liquid separator 12 separated hydrogen are sent into hybrid heater 7 by hydrogen recycle compressor pressurizes to reaction pressure, realize recycling of hydrogen.Valve 13 is hydrogen blow-off valves in the accompanying drawing.
Compared with prior art, process of the present invention is simple, does not need stripping tower or flashing tower, and facility investment is low.The present invention absorbs the ammonia recovery method of ammonia without the raw material glycol ether, thereby can join ammonia exactly, and then makes system operation easier steadily.Particularly when using Ni-Cu-Zn-Al or Ni-Cu-Zn-Cr catalyzer, reactor carries out under identical low pressure with separation system, and does not produce non-condensed gas, does not need frequent emission gases, hydrogen consumption reduces greatly, and production cost will further reduce.
Example one
On device, experimentize as accompanying drawing.
Pack in the reactor 8 0.47 meter
3The Ni-Cu-Zn-Al catalyzer, reaction pressure 1.96MPa, temperature of reaction 220-230 ℃, reactant molecule ratio, glycol ether: ammonia: hydrogen=1: 10: 5; Glycol ether air speed=0.2 o'clock
-1, get glycol ether transformation efficiency 98%, morpholine selectivity 66.8%, the overall selectivity 88% of morpholine and N-methylmorpholine, N-ethyl.
From the effusive resultant of reactor bottom through water cooler 9, be cooled to 120 ℃, not step-down enters vapour-liquid separator 10, isolated liquid stream contains 5% ammonia (molecule), and 44.9%(is heavy) morpholine, 2.6%(is heavy) N-methylmorpholine, 13.4%(is heavy) N-ethylmorpholine, 0.48(heavy) glycol ether, 8.5%(is heavy) the diglycol monotertiary morpholine, and 25%(is heavy) water.Ammonia 93.7%(is heavy in the isolated gas-liquid), hydrogen 6%(is heavy) and small amount of impurities, this air-flow is chilled to 10 ℃ (not step-down) through water cooler 11 and enters vapour-liquid separator 12, in vapour-liquid separator 12, isolate liquefied ammonia, the introducing anhydrous ammonia tank also recycles, ammonia recovery 97% contains ammonia 3-10%(body in the separated hydrogen).
Example two
On device, experimentize as accompanying drawing.
Pack 0.78 meter in the reactor into
3The Ni-Cu-Zn-Cr catalyzer, 230-240 ℃ of reaction pressure 1.96MPa temperature of reaction, the charging molecular ratio is glycol ether: ammonia: hydrogen=1: 12: 8, during glycol ether air speed LHSV=0.25
-1, glycol ether transformation efficiency 99%, morpholine selectivity 64%, overall selectivity 87% separation system with instead
Answer under the identical pressure of device and operate, resultant of reaction is chilled to 140 ℃ through water cooler 9 and enters first separator, isolated product liquid is formed, morpholine 47%(is heavy), N-methylmorpholine 2.7%(is heavy), N-ethylmorpholine 14%(is heavy), glycol ether 0.15%(is heavy), diglycol monotertiary morpholine 9.05%(is heavy), water 25.7%(is heavy), ammonia 1%(is heavy), gaseous product is formed: ammonia 95%(is heavy), hydrogen 4.7%(is heavy) and small amount of impurities, this gas is chilled to 10 ℃ through water cooler 11, enters separator 12, and ammonia recovery 98%(is heavy), contain ammonia 5%(molecule in the separated hydrogen), enter recycle compressor 14 and recycle.
Example three
Device, catalyzer is with example 1, reaction pressure 1.5MPa, and temperature of reaction 210-220 ℃, the charging molecular ratio, glycol ether: ammonia: hydrogen=1: 12: 5, during glycol ether air speed LHSV=0.3
-1Glycol ether transformation efficiency 96%, morpholine selectivity 62.5%(is heavy), overall selectivity 82%(is heavy), resultant of reaction is chilled to 110 ℃ through water cooler 9, enters separator 10, product liquid is formed: morpholine 44%(is heavy), N-methylmorpholine 1.3%(is heavy), N-ethylmorpholine 11%(is heavy), glycol ether 3.56%, morpholinyl glycol ether 11%, it is heavy that water 23%, ammonia 6%, separator 10 isolated gases contain ammonia 92.5%(), hydrogeneous 7.1%(is heavy), this gas is chilled to 10 ℃ through water cooler 11 and enters separator 12, and ammonia recovery 96% contains ammonia 6%(molecule in the hydrogen).
Claims (9)
1, a kind of method by glycol ether and the ammonia mixture of synthesize morpholine and morpholine derivative in the presence of hydrogen and dehydrogenation catalyst, it is characterized in that reactor is under 1.0-4.0MPa pressure and 200-250 ℃ of temperature, reaction feed glycol ether: ammonia: hydrogen (molecular ratio)=1: 5-20: 3-8, with two sections refrigerated separation, recovery ammonia and hydrogen, and recycle.
2, method according to claim 1 is characterized in that first section refrigerated separation operate under 1.0-4.0MPa pressure, first step cooler outlet temperature of charge is 100-140 ℃.
3, method according to claim 2 is characterized in that first section refrigerated separation operate under 1.8-2.2MPa pressure.
4, method according to claim 1 is characterized in that second section refrigerated separation operate under 1.0-4.0MPa pressure, second-stage cooler outlet material temperature is 0-20 ℃.
5, method according to claim 4 is characterized in that second section refrigerated separation operate under 1.8-2.2MPa pressure.
6, method according to claim 1 is characterized in that using Ni-Cu-Zn-Al or Ni-Cu-Zn-Cr dehydrogenation catalyst.
7, method according to claim 1 is characterized in that reactor operates under 1.8-2.2MPa pressure and 220-240 ℃ of temperature.
8, method according to claim 1 is characterized in that the reaction feed glycol ether: ammonia: hydrogen (molecular ratio)=1: 10: 5.
9, method according to claim 1 is when the air speed LHSV that it is characterized in that the charging glycol ether is 0.1-1.0
-1
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89100687 CN1019934C (en) | 1989-02-14 | 1989-02-14 | Synthesis of mocpholine and its derivatives |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89100687 CN1019934C (en) | 1989-02-14 | 1989-02-14 | Synthesis of mocpholine and its derivatives |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1044939A CN1044939A (en) | 1990-08-29 |
| CN1019934C true CN1019934C (en) | 1993-02-24 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 89100687 Expired - Fee Related CN1019934C (en) | 1989-02-14 | 1989-02-14 | Synthesis of mocpholine and its derivatives |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116178306A (en) * | 2021-11-29 | 2023-05-30 | 安徽昊源化工集团有限公司 | Morpholine synthesis process |
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- 1989-02-14 CN CN 89100687 patent/CN1019934C/en not_active Expired - Fee Related
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| CN1044939A (en) | 1990-08-29 |
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