CN1049432C - Method for prepn. of morpholine compound - Google Patents
Method for prepn. of morpholine compound Download PDFInfo
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- CN1049432C CN1049432C CN96105036A CN96105036A CN1049432C CN 1049432 C CN1049432 C CN 1049432C CN 96105036 A CN96105036 A CN 96105036A CN 96105036 A CN96105036 A CN 96105036A CN 1049432 C CN1049432 C CN 1049432C
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- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Abstract
The present invention relates to a method for preparing morpholine compounds, which adopts high-boiling-point substances of byproducts in the process of preparing morpholine compounds as raw materials or the high-boiling-point substances and liquid ammonia as the raw materials. The high-boiling-point substances and the liquid ammonia are continuously added from the top of a fixed bed reactor by H2 and a catalyst, the reaction is carried out by a trickle bed mode, and morpholine compounds are obtained. The present invention has the advantage that the high-boiling-point substances of low additional value can be converted to morpholine compounds of high additional value, and the present invention provides a middle raw material for fine chemical industry products.
Description
The present invention relates to the preparation method of morpholinium compound, exactly is that the high boiling material for preparing by-product in the morpholinium compound process with two alkylidene group glycol aminations is the method for feedstock production morpholinium compound.
Making morpholinium compound by glycol ether and liquefied ammonia reaction is known technology morning, CN87105892 and CN 87105893 patents have been reported with above-mentioned raw materials respectively and have been made morpholinium compound, the method of N-alkyl morpholine compound when making N-alkyl morpholine compound, also need add oxy-compound.CN 87105833 discloses a kind of amination catalysis that is used to make morpholinium compound, and this catalyzer is by δ-or θ-or arbitrary proportion (Al of δ+θ)
2O
3Load Ni, Cu, Cr and Re active constituent are formed.The clear 59-5174 of Japanese Patent discloses a kind of manufacture method of N-alkyl morpholine compound, this method is to be raw material with N-alkyl diethanolamine, to be selected from silicon-dioxide, titanium dioxide, the metal oxide of one or more in the zirconium white etc. are that (content of metal oxide accounts for whole catalyzer 0.01～20wt%) and carries out the pouring of prepared in reaction N-alkyl in gas phase catalyzer.
Preparing in the process of morpholinium compound with two alkylidene group glycol aminations, high boiling point by-products produced generation about about 30 heavy % is arranged, mainly be the morpholinyl glycol ether, morpholinyl diglycolamine, two molecules of two morpholinyl glycol ethers and glycol ether and diglycolamine or three molecule condensess.
The purpose of this invention is to provide a kind of high boiling material (hereinafter to be referred as high boiling material) with by-product in the preparation morpholinium compound process is the method for feedstock production morpholinium compound.
The present invention is achieved through the following technical solutions: the high boiling material with by-product in the preparation morpholinium compound process is a raw material, or is raw material with this high boiling material and liquefied ammonia, at H
2Exist down with the amination reaction catalyzer, high boiling material and liquefied ammonia are added from the fixed-bed reactor top continuously, react, promptly get morpholinium compound by the trickle bed mode.
The structural formula of said high boiling material of the present invention (I) and morpholinium compound (II) is as follows:
Among general formula (I), (II): R
1, R
2, R
3Can be identical or different, be the alkyl of H or 1-4C atom; R
4And R
5Can be identical or different, they are to be selected from-OH-NH
2,-NHC
2H
4NH
2,-NHC
2H
4OH ,-OC
2H
4OH ,-OC
2H
4NH
2,
-OC
2H
4OC
2H
4OH ,-OC
2H
4OC
2H
4NH
2,-NHC
2H
4OC
2H
4OH ,-NHC
2H
4OC
2H
4NH
2In any one; R
6Be selected from H ,-CH
3,-C
2H
5,-C
2H
5NH
2In a kind of.
The reaction conditions that the present invention prepares morpholinium compound is: pressure 0.5～7.0MPa, 220～320 ℃ of temperature, high boiling material (I) liquid feeding air speed 0.1～1.0 hour
-1, NH
3With high boiling material (I) mol ratio be 0～30: 1, H
2O and high boiling material (I) mol ratio is 0～20: 1.
The said amination reaction catalyzer of the present invention is according to CN 87105833, CN87105892 and CN 87105893 described method preparations.This catalyzer is made up of alumina supporter and two or more metal or its oxide compound that be selected among Ni, Cu, Cr, Ti and the Re, preferably by δ-or θ-or (Al of δ+θ) of arbitrary proportion
2O
3Load Ni, Cu, Cr and Re active constituent are formed, wherein Al
2O
3Account for the heavy % of 65-95, the atomic ratio of all the other each active constituents is Ni: Cu=1: 0.2～0.8, and Ni: Cr=1: 0.0～0.5, Ni: Re=1: 0.001～0.01, this catalyzer can recycle after regeneration, and its renovation process is referring to CN 96105035.7 described methods.The runtime of catalyzer is very big to activity of such catalysts influence, typically refers to the catalyzer that used 0～4000 hour, preferably uses 0～2000 hour catalyzer.Catalyzer reduces before use according to a conventional method.
The said raw material high boiling material of the present invention (I) can be the simplification compound, also can be the mixture that several compounds are formed by different ratios.
In the method for the invention, H
2Existence can keep the reduction degree of catalyzer, to reacting favourable, H
2With the ratio of raw material can be in the scope of a broad, H
2Flow is little to the reaction influence.
Higher NH
3With the ratio of high boiling material (I), can obtain the morpholinium compound (II) of high yield, NH
3: high boiling material (mol ratio) is 0～30: 1, preferably 5～20: 1.
Temperature of reaction is very big to the activity of such catalysts influence, and temperature of reaction is 220～320 ℃ in the inventive method, preferably 250～300 ℃.
Suitable pressure can keep NH
3In high boiling material (I), certain solubleness is arranged, help the generation of morpholinium compound, hypotony, be not enough to keep balance, hypertonia then increases equipment and operational difficulty, pressure range of the present invention maintains between 0.5～7.0MPa, preferably 2.0～5.5MMPa.
Adding an amount of water is favourable to reaction, among the present invention, and H
2O: high boiling material (mol ratio) is 0～20: 1, preferably 3～15: 1.
The liquid feeding air speed not only influences the transformation efficiency of high boiling material (I) and the selectivity of morpholinium compound, also influences the unit time, the growing amount of the morpholinium compound of per volume of catalyst (II).In the inventive method, high boiling material (I) liquid feeding air speed was controlled at 0.1～1.0 hour
-1, preferably 0.2～0.6 hour
-1
Morpholinium compound preparation method's of the present invention major advantage is: the high boiling material of by-product in the preparation morpholinium compound process can be changed into the morpholinium compound with high attached value.At present, in the technology of preparation morpholinium compound, there is about high boiling material of about 30% to generate.These high boiling material, so far also do not find suitable purposes, after the present invention converted it into morpholinium compound, its economic benefit can significantly improve, because morpholinium compound is not only synthetic rubber promotor, agricultural chemicals, the intermediate raw material that fine chemical products such as pharmaceutical industry are important also can be used as dyestuff, resin, the fine solvent of wax can also be used as emulsifying agent, has very high economic worth.
The following examples will the invention will be further described.
Example 1
Raw materials used A and raw material B are the high boiling material for preparing by-product in the morpholine process according to CN 87105892 described methods in the example of the present invention, and its component and content see Table 1.
This example catalyst system therefor Cat-0 is according to CN 87105833 described method preparations, Cat-1, Cat-2, Cat-3 are respectively that this catalyzer uses 2000～4000 hours inactivations after the outer regenerated catalyzer (its renovation process is seen the described method of CN96105035.7) of reactor.
With 60ml (66 gram) the catalyzer internal diameter 22mm that packs into, in the stainless steel fixed-bed reactor of length 720mm, at 360 ℃, with pressure 0.3～0.5MPa, the hydrogen stream reduction of flow velocity 1000ml/min 4 hours, then, at pressure 5.0MPa, 280 ℃ of temperature, water: high boiling material (mol ratio)=10, NH
3: high boiling material (mol ratio)=10, high boiling material liquid feeding air speed (LHSV)=0.38 hour
-1, H
2: under the reaction conditions of high boiling material (mol ratio)=20, with volume pump from incoming stock A of reactor head and liquid NH
3, reaction solution material composition is analyzed with gas chromatograph, and test-results sees Table 2.
In table 1, the table 2, the dummy suffix notation meaning is as follows: MOR (morpholine), Et-MOR (ethyl morpholine), DEG (glycol ether), MDEG (morpholinyl glycol ether), BMDEG (two morpholinyl glycol ether).
As can be seen from Table 2: the runtime of catalyzer is very big to the activity of such catalysts influence, and the catalyzer that turned round 2000 hours is suitable with live catalyst after regenerating, but the catalyzer that turned round 4000 hours, after regeneration, activity descends to some extent.
Table 1
*Other: be meant contain glycol ether and (or) two molecule condensess of diglycolamine.
Table 2
Annotate: (1) other
*: be glycol ether and (or) diglycolamine two molecule condensess and a certain amount of small molecules organic amine and hydroxyethyl morpholine etc., down with.(2) Cat-O
* *Temperature of reaction be 265 ℃, the remaining reaction condition is identical.
| The catalyzer numbering | Catalyzer duration of service (h) | Product organic phase distribution m% | |||||
| MOR | EtMOR | DEG | MDEG | BMDEG | Other ** | ||
| Cat-0 *** | 0 | 35.5 | 21.6 | 0.7 | 1.2 | 33.5 | 7.5 |
| Cat-1 | 2000 | 37.7 | 16.5 | 1.1 | 2.3 | 36.9 | 5.5 |
| Cat-2 | 2500 | 32.8 | 20.5 | 1.2 | 1.8 | 35.7 | 8.0 |
| Cat-3 | 4000 | 20.1 | 5.6 | 2.0 | 3.4 | 59.8 | 9.1 |
Example 2
The reaction conditions of this example: use regenerated catalyst Cat-1 and raw material A, the regeneration condition of catalyzer is with example 1, H
2O: high boiling material (mol ratio)=4.3, pressure changes between 1.0～5.0MPa, and all the other conditions the results are shown in Table 3 with example 1.
As can be seen from Table 3: H
2Existence be favourable to reaction, suitable pressure can keep NH
3Certain solubleness is arranged in the raw material high boiling material, help the generation of morpholinium compound.
Table 3
| Pressure (MPa) | Product organic phase distribution (m%) | |||||
| MOR | Et-MOR | DEG | MDEG | BMDEG | Other ** | |
| 1.0 | 2.8 | 3.6 | 2.3 | 4.9 | 62.4 | 24.0 |
| 3.0 | 20.8 | 21.5 | 1.4 | 1.3 | 45.7 | 9.3 |
| 5.0 | 32.5 | 20.2 | 0.8 | 1.9 | 37.7 | 6.9 |
Example 3
The reaction conditions of this example: 270 ℃ of temperature, pressure 3.0MPa, water: high boiling material (mol ratio)=10, NH
3: high boiling material (mol ratio) is 0～20, and all the other conditions the results are shown in Table 4 with example 2.
As can be seen from Table 4: higher NH
3With the ratio of high boiling material, can obtain the morpholinium compound of higher yields.
Table 4
| NH 3: high boiling material (mol ratio) | Product organic phase distribution (m%) | |||||
| MOR | Et-MOR | DEG | MDEG | BMDEG | Other ** | |
| 0 | 7.0 | 29.8 | 0.7 | 1.3 | 43.8 | 17.4 |
| 10 | 29.5 | 19.3 | 0.9 | 1.7 | 41.0 | 7.6 |
| 20 | 36.0 | 8.8 | 1.8 | 2.6 | 43.3 | 7.5 |
Example 4
The reaction conditions of this example: pressure 3.0Mpa, water: high boiling material (mol ratio) is 4.3～10, other condition is identical with example 2, the results are shown in Table 5.
As can be seen from Table 5: adding an amount of water is favourable to the yield that improves morpholinium compound.
Table 5
| Water: high boiling material (mol ratio) | Product organic phase distribution (m%) | |||||
| MOR | Et-MOR | DEG | MDEG | BMDEG | Other ** | |
| 4.3 | 20.8 | 21.5 | 1.4 | 1.3 | 45.7 | 9.3 |
| 10 | 39.3 | 28.9 | 0.7 | 0 | 21.8 | 9.3 |
Example 5
The reaction conditions of this example: pressure 3.0MPa, NH
3: high boiling material (mol ratio)=0, temperature of reaction are between 260～300 ℃, and the remaining reaction condition is with example 2, and test-results sees Table 6.
Table 6
| Temperature of reaction (℃) | Product organic phase distribution (m%) | |||||
| MOR | Et-MOR | DEG | MDEG | BMDEG | Other ** | |
| 260 | 6.2 | 21.6 | 1.2 | 2.3 | 49.4 | 19.3 |
| 270 | 16.6 | 25.9 | 0.7 | 1.6 | 44.4 | 10.8 |
| 290 | 8.3 | 36.3 | 1.1 | 1.8 | 35.2 | 17.3 |
| 300 | 7.9 | 42.4 | 0.8 | 1.2 | 25.3 | 22.4 |
Example 6
The reaction conditions of this example: pressure 5.0MPa, water: high boiling material (mol ratio)=10, temperature of reaction are 270～280 ℃, and all the other conditions are with example 2, and test-results sees Table 7.By table 6, table 7 as can be seen: temperature of reaction is very big to the activity of such catalysts influence.
Table 7
| Temperature of reaction (℃) | Product organic phase distribution (m%) | |||||
| MOR | Et-MOR | DEG | MDEG | BMDEG | Other ** | |
| 270 | 32.5 | 20.2 | 0.8 | 1.9 | 37.7 | 6.9 |
| 280 | 38.9 | 28.9 | 0.3 | 1.2 | 24.8 | 5.9 |
Example 7
The reaction conditions of this example: pressure 5.0MPa, water: high boiling material (mol ratio)=10, all the other conditions are with example 2, and the test-results of different material sees Table 8.
Table 8
| The raw material numbering | Product organic phase distribution (m%) | |||||
| MOR | Et-MOR | DEG | MDEG | BMDEG | Other ** | |
| Raw material A | 37.7 | 16.5 | 1.1 | 2.3 | 36.9 | 5.5 |
| Raw material B | 42.5 | 19.8 | 0.8 | 3.6 | 24.8 | 8.5 |
Example 8
The live catalyst Cat-0 that use makes according to CN 87105833 described methods is a raw material (seeing example 1) with 50m% raw material A solution relatively and be that raw material carries out the effect that amination reaction prepares morpholinium compound with the glycol ether of 90m%.The results are shown in Table 9.
Example 9
Use regenerated catalyst, be raw material (seeing example 7) relatively and be that raw material carries out the effect that amination reaction prepares morpholinium compound, the results are shown in Table 10 with the glycol ether of 90m% with 50m% raw material B solution.
By table 9, table 10 as can be seen: according to the method for the invention, being the morpholinium compound that raw material (as raw material A and raw material B) also can obtain higher yields with the high boiling material of preparation morpholinium compound attached product, and is that the raw material result is suitable with the glycol ether.
Table 9
| Example number | Example 1 | Example 8 | |
| Reaction conditions | Pressure (MPa) | 5.0 | 3.0 |
| Temperature (℃) | 26.5 | 225 | |
| LHSV(h -1) | 0.38 | 0.30 | |
| H 2/ raw material (molar) | 20 | 8 | |
| NH 3/ raw material (molar) | 10 | 14 | |
| Reaction raw materials | 50m% raw material A solution | The 90m% diethylene glycol solution | |
| Product is formed m% | MOR | 35.5 | 433 |
| Et-MOR | 21.6 | 9.6 | |
| DEG | 0.7 | 12.0 | |
| MDEG | 1.2 | 3.3 | |
| BMDEG | 33.5 | 27.8 | |
| Other ** | 7.5 | 4.0 | |
Annotate: " raw material " of indication is meant high boiling material or glycol ether in the table, down together.
Table 10
| Example number | Example 7 | Example 9 | |
| Reaction conditions | Pressure (MPa) | 5.0 | 3.0 |
| Temperature (℃) | 280 | 230 | |
| LHSV(h -1) | 0.38 | 0.30 | |
| H 2/ raw material (molar) | 20 | 8 | |
| NH 3/ raw material (molar) | 10 | 14 | |
| Reaction raw materials | 50m% raw material B solution | The 90m% diethylene glycol solution | |
| Amination catalysis | The catalyzer that makes by CN 87105833 uses 2000 hours regenerated catalyzer outside device later on | The catalyzer that makes by CN 87105833 uses 4000 hours regenerated catalyzer outside device later on | |
| Product is formed m% | MOR | 42.5 | 42.8 |
| Et-MOR | 19.8 | 8.4 | |
| DEG | 0.8 | 12.6 | |
| MDEG | 3.6 | 4.9 | |
| BMDEG | 24.8 | 26.9 | |
| Other ** | 8.5 | 4.4 | |
Claims (7)
1. method for preparing morpholinium compound in the presence of hydrogen and amination catalysis is characterized in that the high boiling material (I) with by-product in the preparation morpholinium compound process is a raw material, or is raw material with this high boiling material (I) and liquefied ammonia, at H
3Exist down with catalyzer, high boiling material (I) and liquefied ammonia are added from the fixed-bed reactor top continuously.React, promptly get morpholinium compound (II) by the trickle bed mode, reaction conditions: pressure 0.5～7.0MPa, 220～320 ℃ of temperature, high boiling material (I) liquid feeding air speed 0.1～1.0 hour
-1, NH
3With high boiling material (I) mol ratio be 0～30: 1, H
2O and high boiling material (I) mol ratio is 0～20: 1, and the catalyzer of reaction inactivation can recycle after regeneration, and the structural formula of said high boiling material (I) and morpholinium compound (II) is as follows:
Among general formula (I), (II): R
1, R
2, R
3Can be identical or different, be the alkyl of H or 1-4 C atom; R
4And R
5Can be identical or different, they are to be selected from-NH
2,-NHC
2H
4NH
2,-NHC
2H
4OH ,-OC
2H
4OH ,-OC
2H
4NH
2,
-OC
2H
4OC
2H
4OH ,-OC
2H
4OC
2H
4NH
2,-NHC
2H
4OC
2H
4OH ,-NHC
2H
4OC
2H
4NH
2In any one; R
6Be selected from H ,-CH
3,-C
2H
5,-C
2H
5NH
2In a kind of.
2. according to the said preparation method of claim 1, it is characterized in that said amination reaction catalyzer is by δ-or θ-or arbitrary proportion (Al of δ+θ)
2O
3Load Ni, Cu, Cr and Re active constituent are formed, wherein Al
2O
3Account for the heavy % of 65-95, the atomic ratio of all the other each active constituents is Ni: Cu=1: 0.2～0.8, and Ni: Cr=1: 0.0～0.5, Ni: Re=1: 0.001～0.01.
3. according to the said preparation method of claim 1, it is characterized in that reaction pressure is 2.0～5.5MPa.
4. according to the said preparation method of claim 1, it is characterized in that temperature of reaction is 250～300 ℃.
5. according to the said preparation method of claim 1, it is characterized in that NH
3With the mol ratio of high boiling material be 5～20: 1.
6. according to the said preparation method of claim 1, it is characterized in that H
2The mol ratio of O and high boiling material is 3～15: 1.
7. according to the said preparation method of claim 1, the liquid feeding air speed that it is characterized in that high boiling material (I) is 0.2～0.6 hour
-1
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96105036A CN1049432C (en) | 1996-05-20 | 1996-05-20 | Method for prepn. of morpholine compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96105036A CN1049432C (en) | 1996-05-20 | 1996-05-20 | Method for prepn. of morpholine compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1165820A CN1165820A (en) | 1997-11-26 |
| CN1049432C true CN1049432C (en) | 2000-02-16 |
Family
ID=5118687
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96105036A Expired - Lifetime CN1049432C (en) | 1996-05-20 | 1996-05-20 | Method for prepn. of morpholine compound |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1049432C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103214433A (en) * | 2013-04-11 | 2013-07-24 | 安徽昊源化工集团有限公司 | Raw liquid ammonia for producing morpholine |
| CN110627743B (en) * | 2019-09-20 | 2023-06-02 | 四川鸿鹏新材料有限公司 | Method for preparing morpholine and monoethylamine by using N-ethylmorpholine |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1041583A (en) * | 1988-10-04 | 1990-04-25 | 美国辉瑞有限公司 | Muscarmic receptor antagonists |
-
1996
- 1996-05-20 CN CN96105036A patent/CN1049432C/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1041583A (en) * | 1988-10-04 | 1990-04-25 | 美国辉瑞有限公司 | Muscarmic receptor antagonists |
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| Publication number | Publication date |
|---|---|
| CN1165820A (en) | 1997-11-26 |
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