CN1015712B - Prepn. of n-alkyl morpholine compounds - Google Patents
Prepn. of n-alkyl morpholine compoundsInfo
- Publication number
- CN1015712B CN1015712B CN 87105893 CN87105893A CN1015712B CN 1015712 B CN1015712 B CN 1015712B CN 87105893 CN87105893 CN 87105893 CN 87105893 A CN87105893 A CN 87105893A CN 1015712 B CN1015712 B CN 1015712B
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- catalyzer
- alkyl
- reaction
- compound
- mol
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention relates to a method for preparing morpholine compounds, which adopts dialkylene glycol, compounds containing hydroxy groups and ammonia as raw materials by a catalyst of hydrogen and ammonification, which is characterized in that AL-[2]O-[3] and three or more than three metal or oxides thereof or mixture thereof selected from Ni, Cu, Cr, Ti and Re can be used as a catalyst under the pressure of 5*10+[5] to 6*10+[6]Pa and in the temperature range of 160 to 300 DEG C. The liquid feeding volume airspeed is kept in 0.1 to 2.5 h +[-1], the molar ratio of hydrogen and dialkylene glycol is between 1-10 and 1, and the molar ratio of ammonia and dialkylene glycol is between 1.5-8 and 1. Raw materials are continuously added from the top of a fixed bed catalytic reactor, and morpholine compound products are prepared according to a trickle bed reactive mode.
Description
The present invention relates to morpholinium compound, particularly the improvement manufacture method of N-alkyl morpholine compound.
More particularly, the present invention is in the presence of a kind of new amination catalysis, is the method that raw material is made morpholinium compound with two alkylidene group glycol (DAG) and hydroxy-containing compounds.
In the past, wherein mainly be DEG, i.e. glycol ether by DAG() and aliphatic amide (RNH
2) reaction, perhaps morpholine (
, MOR) with Fatty Alcohol(C12-C14 and C12-C18) (ROH), aldehyde (RCHO), ketone (R
1COR
2) reaction, perhaps N-alkyl diethanolamine (
) dehydration reaction make the N-alkyl morpholine.When making morpholinium compound according to these class methods, desired raw material RNH
2,
Itself be exactly the aminating reaction synthetic product from alcohol, these class methods obviously are uneconomic.(English Patent GB1,409,978; GB1,494,886; The open DT2624016A1 of Deutsches Reichs-Patent application had once introduced these methods).
U.S. Pat P3, having proposed a kind of in 151, No. 113 specification sheetss is the method for raw material one-step synthesis morpholinium compound with DEG, Fatty Alcohol(C12-C14 and C12-C18) and ammonia directly.This method adopts the Ni-Cu-Cr catalyzer, in 150～400 ℃ of temperature ranges in autoclave inherence and 3.5 * 10
6～3.5 * 10
7Carry out liquid phase reaction under the Pa pressure.This method needs elevated pressures because of being liquid phase reaction, uses autoclave, can make operation inconvenience.In addition, because the catalyst system therefor performance is general, can not obtain the morpholinium compound product of high yield.
The purpose of this invention is to provide the particularly manufacture method of N-alkyl morpholine compound of a kind of morpholinium compound of one-step synthesis easily.
Further purpose of the present invention is the morpholinium compound product that will obtain high yield.
The said morpholinium compound of the present invention is meant a series products that meets following logical formula III:
In the formula, R
1, R
2, R
3Can be identical or different, each represents the alkyl of H or 1～4C atom.R
4Represent H or replacement or do not replace alkyl, aryl, cycloalkyl, acyl group and the saturated heterocyclic radical of 1～7C atom.
Task of the present invention is achieved through the following technical solutions.
In the presence of hydrogen and catalyzer, be that raw material is made morpholinium compound (III) with two alkylidene group glycol (DAG, I), hydroxy-containing compounds (II) and ammonia.Wherein (I) and (II) is respectively the compound with following general formula:
R in the formula
1, R
2, R
3And R
4The implication of representative is identical with the front.
The feature of the inventive method is 5 * 10
5～6 * 10
6Under the pressure of Pa, in 160～300 ℃ of temperature ranges, with Al
2O
3And the metal more than three kinds or three kinds selected from Ni, Cu, Cr, Ti and Re or its oxide compound or their mixture be catalyzer, and keeping the liquid feeding volume space velocity is 0.1～2.5 hour
-1The mole ratio of hydroxy-containing compounds and two alkylidene group glycol is 0～2: 1, the mole ratio of hydrogen and two alkylidene group glycol is 1～10: between 1, the mole ratio of ammonia and two alkylidene group glycol is 1.5～8: between 1, above-mentioned raw materials is added from the fixed bed catalytic reactor top continuously, make the morpholinium compound product according to the trickle bed reactive mode.
Said catalyzer is a kind of amination catalysis in the inventive method, can be the composite oxides of Ni, the Cu, Cr, Ti and the Al that are made by the precipitator method, wherein Al
2O
3Weight percent in catalyzer is 63～32, and all the other components are 37～68.Be respectively according to grammeatom ratio: Ni: Cu=1 with Ni: 1～2, Ni: Cr=1: 0.1～0.5, Ni: Ti=1: 1～2.
In the inventive method, more preferred catalyzer is with δ-Al
2O
3Or θ-Al
2O
3Or both are with Ni, Cu, Cr and/or the Re isoreactivity component of the mixture load of arbitrary proportion; Said Al
2O
3The specific surface area of carrier is 50～200m
2/ g, pore volume are 0.2～1.0ml/g, are 80～170m as adopting specific surface area
2/ g, pore volume are the Al of 0.3～0.5ml/g
2O
3Better effects if then.Said Al
2O
3Weight ratio in catalyzer is 65～90%, and all the other are 10～35% for active ingredient (in oxide compound).Each active component content is respectively according to the grammeatom ratio to Ni: Ni: Cu=1: 0.2～0.8; Ni: Cr=1: 0～0.5; Ni: Re=1: 0.001～0.01 or Ni: Re=1: 0.001～0.005.
Above-mentioned catalyzer and carrier thereof all can be prepared according to the disclosed method of CN87105833 patent application.
When using method of the present invention and making morpholinium compound, except that catalyzer, other processing condition also are crucial.
Suitable pressure helps keeping NH
3Certain solubleness is arranged in the liquid phase of DAG, can make the morpholinium compound of generation escape into gas phase simultaneously from the catalyst surface liquid film.Hypotony is not enough to keep balance.Hypertonia then increases the difficulty of operation.The pressure range of the inventive method should maintain 5 * 10
5～6 * 10
6Between the Pa, preferably 1.5～4.5 * 10
6Between the Pa.
H
2Existence, to the reduction degree that keeps catalyzer with to suppress the dehydrogenation by product favourable.In the inventive method, H
2With the mole ratio of DAG be 1～10: 1, preferably 3～6: 1.
Higher ammonia helps obtaining high DAG transformation efficiency and high morpholinium compound selectivity with the ratio of two alkylidene group glycol.NH
3And the mole ratio of DAG can be 1.5～8: between 1, and preferably 2～5: 1.Such ammonia ratio makes easily control of reaction, can avoid since ammonia than excessive and difficulty on the increase equipment with bring operational trouble.
The air speed of liquid feeding not only influences the selectivity of transformation efficiency and the morpholinium compound of DAG, also influences the morpholinium compound growing amount of unit time, per volume of catalyst.In the inventive method, the liquid feeding volume space velocity can be at 0.1～2.5 hour
-1Between, preferably at 0.3～1.5 hour
-1Scope in.
Temperature of reaction depends on activity of such catalysts state in initial reaction stage and the long-term operation process, and with air speed synergy is arranged.The temperature of reaction of the inventive method is between 160～300 ℃.Under optimum reaction condition, more suitable with 200～260 ℃.
Method of the present invention, because catalyst system therefor has good activity and selectivity, excellent mechanical intensity and stability are used for amination reaction, compared with the prior art, make the selectivity of conversion of raw material and generation morpholinium compound all obtain bigger raising.Simultaneously because the catalyst system therefor excellent property, make the reaction can be, thereby can and avoid high ammonia without high-tension apparatus than the trouble of bringing to operation at lower pressure and less ammonia than carrying out under the condition, reduce production costs.
Method of the present invention is most appropriate to produce N-alkyl morpholine compound, also can be used for producing respectively or simultaneously morpholine, N-alkyl morpholine, aliphatic amide and saturated N-heterogeneous ring compound.
Further specify characteristics of the present invention by the following examples.
Embodiment 1
From specific surface 149m
2/ g, φ 1.2mm cloverleaf pattern strip δ-Al of pore volume 0.44ml/g
2O
3Set out, according to the catalyst A of the described method preparation of number of patent application CN87105833, its chemical constitution is Al
2O
3: NiO=5.6: 1, the metal grammeatom ratio of active ingredient is:
Ni∶Cu＝1∶0.35
Ni∶Cr＝1∶0.30
Ni∶Re＝1∶0.0044
The materialization data of carrier and catalyzer are shown in table 1.
Table 1
The specific surface area pore volume pore distribution (vol%) of name heap
Claim (g/ml) (m
2/ g) (ml/g) 30-40
40-50
50-100
100-200
Carrier 0.8 149 0.44 15.7 49.5 34.7 0.1
Catalyzer 1.0 130 0.31 35.1 44.6 20.1 0.2
Embodiment 2
With granularity is the catalyst A 4.5ml(4.5g of φ 1.2 * 1-2mm), the internal diameter 8mm that packs into, length 350mm is in the tubular reactor of being made by stainless steel, at 360 ℃, with pressure 3-5 * 10
5Pa, flow velocity regulate hydrogen pressure to 2.9 * 10 after being the hydrogen stream reduction 3hr of 83ml/min
6Pa according to the listed condition of table 2, enters DEG+EtOH and liquefied ammonia with pump from reactor head.Test-results is shown in Table 2.The DEG converted product mainly is N-ethylmorpholine (N-EtMOR), a small amount of MOR, and minute quantity DGA does not find that heavy product generates.Ethanol (EtOH) converted product also is mainly N-EtMOR, surpasses the stoichiometry part and then is converted into ethamine (EtNH basically
2).
Table 2
Reaction volume air speed H
2: DEG NH
3: DEG EtOH: DEG DEG changes selectivity
(2), A%
Temperature (DEG+EtOH,
(℃) hour
-1) (mol) (mol) (mol) change rate (A%)
(1)EtMOR MOR
210????0.49????9.2∶1????2.8∶1????1.5∶1????93.13????74.72????25.28
220????0.31????11.6∶1????4.5∶1????1.5∶1????100????88.06????11.94
220????0.60????7.5∶1????2.2∶1????1.5∶1????98.65????91.97????8.03
230????0.59????7.6∶1????2.4∶1????1.5∶1????100????94.73????5.27
230????0.51????8.1∶1????2.5∶1????1.2∶1????100????91.38????6.05
230????0.56????7.4∶1????2.3∶1????1.2∶1????100????93.17????6.83
230????0.39????10.6∶1????2.3∶1????1.2∶1????100????90.68????8.00
230????0.36????11.5∶1????2.5∶1????1.2∶1????100????96.70????2.59
230????0.57????6.8∶1????2.1∶1????1.0∶1????100????93.32????6.68
(1) based on the gas-chromatography calculated by peak area, down together.(2) with respect to the DEG that has transformed.
Embodiment 3
Except with DEG and methyl alcohol (CH
3OH, mixture MeOH) (the mol ratio is 1: 1) replace DEG and alcoholic acid mixture as reaction feed, and 230 ℃ of temperature of reaction, volume space velocity SV(DEG+MeOH)=0.58hr
-1, H
2: DEG=9.4: 1, NH
3: DEG=1.9: outside 1, all the other are identical with embodiment 2.Product based on chromatographic peak area distributes as shown in table 3.
Table 3
Small molecules
Title MeOH+CH
3NH
2The heavy product of DEG MeMOR MOR DGA
Impurity
A%????20.62????0.55????0.92????52.06????18.61????6.69????0.55
Calculation result based on the DEG converted product is:
DEG transformation efficiency: 99.08%
N-MeMOR selectivity: 66.82%
MOR selectivity: 23.88%
DGA selectivity: 8.59%
DEG utilization ratio: 99.29%
Embodiment 4
Except the mixture that replaces DEG and MeOH with the mixture (molecular ratio is 1: 1) of DEG and propyl carbinol (n-BuOH) as the reaction feed, all the other are identical with embodiment 3.Products distribution based on the GC calculated by peak area is as shown in table 4.
Table 4
Title n-BuNH
2The heavy product of n-BuOH MOR BuMOR DGA DEG
A%????17.99????1.84????15.03????49.88????7.06????2.16????6.02
Calculation result based on the DEG converted product is as follows:
DEG transformation efficiency: 97.31%
N-BuMOR selectivity: 63.96%
MOR selectivity: 19.27%
DGA selectivity: 9.05%
DEG utilization ratio: 92.28%
N-Butyl Amine 99 (n-BuNH based on residue n-BuOH
2) production rate is: 90.72%
Embodiment 5
Except the mixture with DEG and n-Heptyl alcohol (n-HeOH) replaces DEG and MeOH mixture as the reaction feed, all the other are identical with embodiment 3.Products distribution based on the GC calculated by peak area is as shown in table 5.
Table 5
Title n-HeNH
2The heavy product of MOR DGA HeMOR n-HeOH DEG
A%????4.99????12.67????2.08????55.38????15.94????0????8.01
Calculation result based on the DEG converted product is as follows:
DEG transformation efficiency: 100%
N-HeMOR selectivity: 70.87%
MOR selectivity: 16.21%
DGA selectivity: 2.66%
DEG utilization ratio: 89.74%
Claims (5)
1, a kind of is R with glycol ether (DEG), liquefied ammonia and general formula
4-OH (R
4Represent the alkyl of 1～7C atom) oxy-compound for the feedstock production general formula be
(R
4Represent the alkyl of 1-7C atom) the method for N-alkyl morpholine compound, it is characterized in that at H
2With with δ-Al
2O
3Be carrier, the catalyzer that load Ni, Cu, Cr and Re active ingredient are formed exists down, raw material is added continuously its reaction pressure 5 * 10 from the fixed bed catalytic reactor top
5～6 * 10
6Pa, 160～300 ℃ of temperature, liquid feeding air speed 0.1～2.5 hour
-1, R
4-OH: DEG (mol) is 1.0～1.5: 1, NH
3: DEG (mol) is 2～5: 1, H
2: DEG (mol) is 6.8～11.6: 1, carries out according to the trickle bed reactive mode.
2, according to the said method of claim 1, it is characterized in that the weight percent of wherein said support of the catalyst in catalyzer is 65～90, all the other are active ingredient; Each active ingredient of catalyzer is respectively with respect to the metal grammeatom ratio of Ni: Ni: Cu=1: 0.2～0.8, and Ni: Cr=1: 0.0～0.5, Ni: Re=1: 0.001～0.01.
3,, it is characterized in that wherein said δ-Al according to the said method of claim 1
2O
3The specific surface area of carrier is 50～200m
2/ g, pore volume are 0.2～1.0ml/g.
4, according to the said method of claim 1, wherein reaction pressure is 1.5～4.5 * 10
6Pa.
5, according to the said method of claim 1, wherein temperature of reaction is 200～260 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 87105893 CN1015712B (en) | 1987-08-31 | 1987-08-31 | Prepn. of n-alkyl morpholine compounds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 87105893 CN1015712B (en) | 1987-08-31 | 1987-08-31 | Prepn. of n-alkyl morpholine compounds |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1031699A CN1031699A (en) | 1989-03-15 |
| CN1015712B true CN1015712B (en) | 1992-03-04 |
Family
ID=4815482
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 87105893 Expired CN1015712B (en) | 1987-08-31 | 1987-08-31 | Prepn. of n-alkyl morpholine compounds |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1015712B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2146906C (en) * | 1993-12-22 | 1999-03-16 | Stephen Wayne King | Reductive amination catalysts |
| CN100371333C (en) * | 2006-04-26 | 2008-02-27 | 吉林化工学院 | Method for producing marpholine and monoethylamine using by-products N-ethylamine from morpholine prodn. installation as raw material |
| EP3083596A1 (en) | 2013-12-18 | 2016-10-26 | Basf Se | Azole compounds carrying an imine-derived substituent |
| CN111111670B (en) * | 2019-12-05 | 2022-11-29 | 华茂伟业绿色科技股份有限公司 | Supported catalyst and preparation method and application thereof |
| CN115710185B (en) * | 2021-08-23 | 2024-05-03 | 中国石油化工股份有限公司 | Method for producing methylamine using metal carbide catalyst |
-
1987
- 1987-08-31 CN CN 87105893 patent/CN1015712B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| CN1031699A (en) | 1989-03-15 |
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