CN85100326A - N-alkylamines preparation method - Google Patents
N-alkylamines preparation method Download PDFInfo
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- CN85100326A CN85100326A CN 85100326 CN85100326A CN85100326A CN 85100326 A CN85100326 A CN 85100326A CN 85100326 CN85100326 CN 85100326 CN 85100326 A CN85100326 A CN 85100326A CN 85100326 A CN85100326 A CN 85100326A
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- alkylamines
- catalyzer
- productive rate
- amine
- raw material
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Abstract
A kind of N-alkylamines synthetic method is that raw material, Fatty Alcohol(C12-C14 and C12-C18) are alkylating agent with amine, uses Cu-Zn-Al
2O
3The fixed-bed reactor of catalyzer, synthetic under low pressure, general temperature of reaction, it is low to have overcome autoclave formula rhythmic reaction production efficiency, and shortcomings such as aftertreatment complexity, acid consumpting alkali and etching apparatus and are used Co, Ni, Cu/Al
2O
3Or the synthetic method of Cu/ silicate catalyst compares, and has the product yield height, reaction pressure is low and uses same device can synthesize the characteristics of three class N-alkylamines.
Description
The present invention relates to the synthetic of N-alkylamines.
The preparation method of general N-alkyl benzene amine adopts the high pressure tank reactor more, also useful fixed-bed reactor, the Deutsches Reichs-Patent 2646379 relevant with invention.A kind of method that discloses is: at Co, Ni, Cu/Al
2O
3On the catalyzer, be raw material with 1.25: 1 aniline and propyl carbinol mixture, 200 ℃, 204 normal atmosphere carry out the dewatering alkylation reaction under the nitrogen gas stream, and N-butylaniline productive rate 97.5%(is heavy) (being equivalent to mol productive rate 60.8%); European patent application 6590, another kind of method has been proposed: on the Cu/ silicate catalyst, be raw material with 1: 1 aniline and carbinol mixture, 250 ℃ of 42 seconds duration of contact, the transformation efficiency of aniline is 85%, and the weight yield of methylphenylamine is that 97.7%(is equivalent to mol productive rate 84.99).
The preparation method of general N-alkyl aliphatic cyclic amine has: the full Su Mendelei of the Ba Shijiya republic also council of husband Chemical Society publishes petroleum chemistry partial report 1976, the 35-8(Soviet Union) (Dokl, Neftekhim, Sekts-Baskk, Res-P Pravl 1976,35-8) with hexahydroaniline: monochloroethane=2.5: 1 aqueous solution is raw material, in autoclave, 95～100 ℃, reacted 2 hours, N-ethyl cyclohexylamine weight yield is that 92.6%(is equivalent to mol productive rate 72.2%).
The preparation method of general N-alkyl heterocycle amine has United States Patent (USP) 3087928, and with morpholine: methyl alcohol=1: 1～10 mixed solutions are raw material, uses Ni, Cu, Cr mixed catalyst, in autoclave, and hydrogen pressure 29 kilograms per centimeter
2, 220 ℃ were reacted 2 hours, and the weight yield of N-methylmorpholine is that 51%(is equivalent to mol productive rate 43.9%).
Other prepares the method for N-alkylamines, uses Raney Ni, Na, NiSO
4, CoSO
4, MnO
4, H
2SO
4.HCl, H
2SO
4Fat, H
3PO
4, PoCl
3, the alkali metal compound catalyzer reacts in autoclave, its complicated operation, and a large amount of soda acids of pin consumption, and have problems such as etching apparatus, contaminate environment.Though existing report Co, Ni, Cu/Al
2O
3With the continuous process of solid catalysts such as Cu/ silicate, but activity that these catalyzer showed and selectivity still can not be satisfactory.
The objective of the invention is to obtain a kind of preparation method of N-alkylamines.Its core missions are sought a kind of cheapness, and are used for the catalyzer that hydramine dewatering alkylation reaction process has high reactivity, highly selective, and phase proper technical conditions with it, overcome the shortcoming in the prior art.
The inventive method is to be Al surplus Cu10～50%, Zn70～10% containing
2O
3Cu-Zn-Al
2O
3Carry out the dewatering alkylation reaction of aromatic amine or aliphatic cyclic amine or heterocyclic amine and Fatty Alcohol(C12-C14 and C12-C18) on the catalyzer, make N-alkyl aromatic amine or N-alkyl aliphatic cyclic amine or N-alkyl heterocycle amine product.
The raw material that is suitable for present method can be an aromatic amine, perhaps aliphatic cyclic amine, and perhaps heterocyclic amine, alkylating agent is a lower aliphatic alcohols.
Present method adopts fixed-bed reactor, low pressure, general temperature, air speed and proportioning raw materials, i.e. 1～10 kilograms per centimeter
2, 150～300 ℃, 0.1～50 o'clock
-1With react under the condition of 1: 1～20 raw materials and alkylating agent.
Realize that present method step is as follows:
(1) according to aforementioned ratio mixing raw material and alkylating agent, if more macromolecular raw material, heat makes it to become the mixed solution of raw material and alkylating agent a little.
(2) mixed solution is by being pumped into a well heater, and heating is vaporized, and reaches temperature of reaction.
(3) feeding of raw material steam is filled with Cu-Zn-Al
2O
3The fixed-bed reactor of catalyzer.
(4) separate after the reaction product condensation.
The Cu-Zn-Al that present method is used
2O
3Catalyzer is cheap, this chemical reaction process had good activity and selectivity, surprisingly this catalyzer is used for aniline and methyl alcohol, aniline and alcoholic acid dewatering alkylation reaction process, aniline transforms and originally approaches 100%, and can use the same method, promptly same catalyzer, device and close processing condition prepare N-alkyl aromatic amine, N-alkyl aliphatic cyclic amine and N-alkyl heterocycle amine three series products.
Another characteristics of present method are that process and equipment are simple, and reaction pressure is low, and product is easily separated, and can not cause equipment corrosion and significantly environmental pollution.
Example 1,
Aniline: methyl alcohol (molecular ratio) 1: 2.24
Pressure 1 kilograms per centimeter
2
250 ℃ of temperature
Air speed (LHSv) 0.4 o'clock
-1
Aniline one way molecule transformation efficiency reaches 99%, methylphenylamine molecule productive rate 94.9%.
Example 2,
Aniline: ethanol (molecular ratio) 1: 1.55
Pressure 1 kilograms per centimeter
2
253 ℃ of temperature
During liquid hour air speed 5
-1
The one way molecule transformation efficiency of aniline and the molecule productive rate of N-ethylaniline are 100%.
Example 3,
Hexahydroaniline: methyl alcohol (body) 1: 1
Pressure 1 kilograms per centimeter
2
270 ℃ of temperature
During liquid hour air speed 2
-1
The one way molecule transformation efficiency 76.4% of hexahydroaniline, N-methylcyclohexylamine molecule productive rate 53.9%, N, N-dimethylcyclohexylamine molecule productive rate 22.7%.
Example 4,
Morpholine: ethanol (body) 1: 1
Pressure 1 kilograms per centimeter
2
264 ℃ of temperature
During liquid hour air speed 5
-1
The one way molecule transformation efficiency 87.6% of morpholine, the molecule productive rate 75.6% of N-ethylmorpholine.
Example 5,
To amino=aniline: Virahol (molecule) 1: 16
Pressure 1 kilograms per centimeter
2
224 ℃ of temperature
During liquid hour air speed 30
-1
Isopropylamine base=aniline molecule productive rate 56.25%.
Revisal 85100326
After the preceding revisal of the capable revisal of file name page or leaf
Specification sheets 17 N-butylaniline productive rate aniline transformation efficiencys 64.5%, N-
97.5%(is heavy) (phase butylaniline productive rate 62.8%
When in the mol productive rate
60.8%）
1 10 85% 86%
The productive rate of the heavy methylphenylamine of 1 10 methylphenylamines
The volume production rate is 97.7% 84%.
(be equivalent to mol
Productive rate 84.99).
1 17 hexahydroaniline weight yield are 92.6% for the hexahydroaniline productive rate.
92.6%(is equivalent to gram
Molecule productive rate 72.2%)
The productive rate of the weight yield methylmorpholine of 1 21 methylmorpholines is 51%
For being equivalent to gram, divides 51%(
Sub-productive rate 43.9%).
1 54 alkali metal compound catalyzer, the iodine metal compound as catalyst,
28 general temperature, general temperature,
Claims (3)
1, the preparation method of N-alkylamines is to be raw material with aromatic amine or cycloaliphatic amines or heterocyclic amine, and Fatty Alcohol(C12-C14 and C12-C18) is an alkylating agent, adopts fixed-bed reactor, and feature of the present invention is at Cu-Zn-Al
2O
3On the catalyzer, carry out the dewatering alkylation reaction under 150～300 ℃ the processing condition.
2, in accordance with the method for claim 1, it is characterized in that said catalyzer contains Cu10～50%, Zn70～10%, surplus is Al
2O
3
3,, it is characterized in that dewatering alkylation is reflected at 1～10 kilograms per centimeter according to claim 1 and 2 described methods
2Carry out under the pressure.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN85100326A CN85100326B (en) | 1985-04-01 | 1985-04-01 | Preparation of n-alkylamines |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN85100326A CN85100326B (en) | 1985-04-01 | 1985-04-01 | Preparation of n-alkylamines |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85100326A true CN85100326A (en) | 1986-09-17 |
| CN85100326B CN85100326B (en) | 1987-12-02 |
Family
ID=4791065
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN85100326A Expired CN85100326B (en) | 1985-04-01 | 1985-04-01 | Preparation of n-alkylamines |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN85100326B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102408352A (en) * | 2011-10-31 | 2012-04-11 | 江苏长青农化股份有限公司 | New synthesis technology of pretilachlor |
-
1985
- 1985-04-01 CN CN85100326A patent/CN85100326B/en not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102408352A (en) * | 2011-10-31 | 2012-04-11 | 江苏长青农化股份有限公司 | New synthesis technology of pretilachlor |
| CN102408352B (en) * | 2011-10-31 | 2014-04-09 | 江苏长青农化股份有限公司 | New synthesis technology of pretilachlor |
Also Published As
| Publication number | Publication date |
|---|---|
| CN85100326B (en) | 1987-12-02 |
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| SE01 | Entry into force of request for substantive examination | ||
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| C06 | Publication | ||
| C13 | Decision | ||
| GR02 | Examined patent application | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CI01 | Correction of invention patent gazette |
Correction item: Agency|Agent Correct: Fushun Patent Center|Li Wei False: Agency without agency|Agent Number: 52 Page: 51 Volume: 3 |
|
| ERR | Gazette correction |
Free format text: CORRECT FROM: NONE AGENCY TO: THE PATENT AGENCY OF FU-SHUN CITY(21102); FROM: AGENT TO: LI WEI |
|
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| C17 | Cessation of patent right | ||
| CX01 | Expiry of patent term |