CN1151120C - Prepn process of ethylamine - Google Patents
Prepn process of ethylamine Download PDFInfo
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- CN1151120C CN1151120C CNB011262877A CN01126287A CN1151120C CN 1151120 C CN1151120 C CN 1151120C CN B011262877 A CNB011262877 A CN B011262877A CN 01126287 A CN01126287 A CN 01126287A CN 1151120 C CN1151120 C CN 1151120C
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- ethamine
- acetonitrile
- ethylamine
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Abstract
The present invention relates to a method for preparing ethylamine, which mainly solves the problems of long reaction time and low yield coefficient of ethylamine in the existing technologies. The present invention adopts a technical scheme in which solvent that is the mixture of 10 to 50% of low-grade fatty alcohol (by volume percent) and 50 to 90% of arene, and Raney nickel is taken as the main catalyst, wherein the reaction temperature interval is from 30 to 120 DEG C, the hydrogen partial pressure of a gauge pressure meter is from 1.0 to 5.0MPa, and the reaction time is from 0.5 to 2.0 hours, so that the defects are well solved. Therefore, the method can be used in the industrial production of ethylamine.
Description
Technical field
The present invention relates to a kind of method for preparing ethamine, particularly prepare the method for ethamine about hydrogenation of acetonitrile.
Background technology
Ethylamine compounds comprises ethamine (Ethanamine or Monoethylamine are called for short MEA), diethylamine (Diethylamine, vehicle economy A) and triethylamine (Triethylamine is called for short TEA).Ethylamine compounds is important organic intermediate, is widely used in fields such as agricultural chemicals, medicine, dyestuff, rubber, water treatment, tackiness agent and catalyzer.Ethamine is colourless highly volatile liquid, poisonous, inflammable, be corrosive, main raw material and reagent as rubber ingredients, extraction agent, emulsifying agent, condensing agent, medicine, also be used for the production of dyestuff, tensio-active agent, oxidation inhibitor, aircraft fuel and lubricant, most important purposes is synthetic triazine herbicide, wherein have " G-30027 " (Atrazine), " ametryn " (Ametryne), " bladex " (Cyanagine), " simajine " (Simazine).Diethylamine is colourless liquid, and is volatile, is corrosive.Main as producing weedicide (as thiobencarb etc.), N, N-diethylethanolamine (DAPE), rubber accelerator is (as diethyl curing carbaminate, be called for short ZDC), ethyl ziram (Ethyl Ziram), tetraethylthiuram disulfide (being called for short TETD), alcohol treatment agent ethyl thiuram (Ethylthiuram), beneficiation reagent, textile auxiliary agent, sterilant, stopping agent, stopper and antifreezing agent, medicine is (as PROCAINE HCL, PHARMA GRADE, chloroquine etc.), agricultural chemicals, all as intermediate, also can be used for synthetic ethylamino-ethanol in dyestuff and the organic synthesis as inhibiter and organic intermediate.Triethylamine is a colourless oil liquid, inflammable, main as organic solvent and organic synthesis intermediate, in synthetic resins is made as the catalyzer of phosgenation polycarbonate and the stopper of tetrafluoroethylene, also can be used for anti-setting agent, the medicine in refining microbiotic, tensio-active agent, the porcelain enamel industry, the chemical intermediate of ion exchange resin, triethylamine can be used as high energy fuels.
The industrialized preparing process of ethamine class mainly contains: ethanol faces hydrogen ammoniation process, ethene ammoniation process, acetaldehyde ammoniation process.It is the main method of producing ethamine at present both at home and abroad that ethanol faces the synthetic ethamine of hydrogen ammoniation process.
It is reported, by C
2～C
6The synthetic C of hydrogenation of nitriles
2～C
6Organic amine be considered to a most economical operational path, limited because of raw material sources, be difficult to form scale operation, this method is produced the industrial application of ethamine and is not appeared in the newspapers.Commercial product acetonitrile mainly comes from the by-product of producing vinyl cyanide, and along with vinyl cyanide output constantly increases, the increase of acetonitrile output is very fast, and the utilization of acetonitrile seems more and more important.Acetonitrile is made catalyzer with precious metal or Fe, Co, Ni etc. under certain temperature and pressure, gas phase or liquid phase (facing ammonia) hydrogenation makes ethylamine compounds.Can regulate proportion of products to satisfy market demand by changing material proportion and reaction conditions.
A kind of manufacture method of ethamine class is disclosed among the clear 53-50109 of document Japanese Patent JP.Being raw material with the crude acetonitrile that contains prussic acid in the document, in the presence of organic solvent, is catalyzer with the skeleton nickel, in the hydrogen dividing potential drop is 0.5～10.0MPa, temperature is under 40～200 ℃ of conditions, carries out hydrogenation reaction and generates ethamine, and wherein organic solvent is ethanol or toluene.As calculated, its acetonitrile transformation efficiency is 100%, and the yield of ethamine is also lower, is up to 95.4%.In addition its reaction times longer, need reaction just can finish reaction in 3 hours, catalyst levels is bigger, is generally 12% of acetonitrile raw material weight, promptly its catalyst loading is lower.A kind of manufacture method of ethamine is disclosed among the clear 50-47909 of document Japanese Patent JP.Being raw material with pure acetonitrile in the document, in the presence of organic solvent, is catalyzer with the skeleton nickel that contains cobalt, is 4.0MPa in the hydrogen dividing potential drop, and temperature is to carry out hydrogenation reaction under 100 ℃ of conditions to generate ethamine, and wherein organic solvent is ethanol or toluene.Its reaction times is longer, needs 3 hours just can finish reaction, and the acetonitrile transformation efficiency is 100%, and the yield of ethamine is yet lower, is about 88%.
Summary of the invention
Technical problem to be solved by this invention is to overcome in the past to exist the reaction times longer in the document, and the defective that the yield of ethamine is lower provides a kind of new method for preparing ethamine.This method is used for the reaction that hydrogenation of acetonitrile prepares ethamine, has the reaction times weak point, the characteristics that the yield of ethamine is high.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method for preparing ethamine, skeleton nickel with tungstenic, molybdenum is a catalyzer, by count 10～50% the ethanol or the toluene of methyl alcohol and 50～90% or the mixture that dimethylbenzene is formed with volume percent is solvent, in temperature of reaction is 30～120 ℃, is under 1.0～5.0MPa condition in the gauge pressure reaction pressure, and acetonitrile and hydrogen react, reaction times is 0.5～2.0 hour, gets ethamine.
In the technique scheme, the temperature of reaction preferable range is 50～80 ℃, is 2.0～2.5MPa in gauge pressure reaction pressure preferable range, and the reaction times preferable range is 0.5～1.5 hour.
Employed method for preparing catalyst is as follows among the present invention:
At first nickel-aluminium alloy is reacted with the sodium hydroxide solution of required reacting weight earlier, water cleans to neutral, and tungsten and other promotor compositions of adding aequum then carry out modification, through wash, washing with alcohol 2～3 times and being kept in the ethanol.
Because nitrile shortening system amine, reaction experience hydrogenation generates the pilot process of imines.The reactive behavior of imines is very high, easily take place further to react with reaction intermediate and principal product, by condensation, ammonia is separated, the crosslinked reaction generation secondary amine that waits, by-product such as tertiary amine and high boiling material, influence reaction conversion ratio, selectivity and yield, therefore must improve the reactive behavior of catalyzer, strengthen catalyzer to the absorption of unsaturated intermediates such as imines or suppress its desorption, reduce the amount of free imines in the reaction process as far as possible, improve hydrogenation reaction speed, shorten the reaction times, reduce the possibility that side reaction takes place, thereby reach the purpose of acetonitrile high conversion and primary amine highly selective.From the hydrogenation of acetonitrile reaction mechanism, the interaction of intermediate product imines that desorption gets off on the catalyzer and false add hydrogen product can aggravate the formation of high boiling material.High boiling material is adsorbed on catalyst surface can further reduce absorption to imines etc., forms vicious cycle, causes the very fast inactivation of catalyzer, therefore must strengthen the adsorption strength of catalyst active center.On the other hand, because the skeletal nickel catalyst active centre is too much, the hydrogen supply amount is big, can cause the aggravation of product hydrogenolysis.The present invention is by introducing tungsten in skeleton nickel, strengthened the stability of catalyzer, introduce other promotor composition simultaneously, catalyzer and its main reaction are adapted, strengthened the absorption of catalyzer to unsaturated compounds such as imines, reduce the activity and the number of absorption hydrogen simultaneously, suppressed side reaction and deep hydrogenation, thereby improved catalyzer to the active of main reaction and improved reaction conversion ratio and yield.On the other hand, mixture by the pure and mild aromatic hydrocarbons of employing lower aliphatic among the present invention is a solvent, and proportioning conditioned reaction polarity of solvent by solvent, played the effect of priming reaction raw molecule, promptly increased the electron density of cyano group in the raw material, make that raw material is easier to be adsorbed by catalyzer, thereby can improve reactive behavior, raw material diluting effect and clean catalysis agent surface action have been played in the adding of additionally mixed thing solvent, the intermolecular condensation of product ethamine is weakened, reduce side reaction, improved reaction preference.Use method of the present invention, be used for hydrogenation of acetonitrile and prepare the ethamine reaction, 30～120 ℃ of temperature of reaction, reaction pressure 1.0～5.0MPa, when being solvent with the pure and mild aromatic hydrocarbons of lower aliphatic, reacted 30～120 minutes, its acetonitrile transformation efficiency reaches 100%, the ethamine yield can reach 99.0%, than the highest ethamine yield 95.4% of bibliographical information in the past, increased closely 3.6%, and the reaction times was by original 3～4 hours, shorten to 0.5～2.0 hour, obtained effect preferably.
The present invention is further elaborated below by embodiment.
Embodiment
[embodiment 1]
In 300 milliliters of reactors, with the modified raney ni is catalyzer, comprise tungsten and molybdenum in the catalyzer, wherein with atomic ratio measuring with respect to Ni, Ni: W: Mo is 100: 1: 2, acetonitrile and hydrogen are 55 ℃ of temperature of reaction, and reaction pressure is counted 2.5MPa with gauge pressure, are solvent with methyl alcohol and toluene, methyl alcohol wherein: toluene (volume/volume)=1: 2.5, solvent: acetonitrile (w/w) is 4: 1, and catalyzer/acetonitrile is 3.5% (weight), and other adds 0.2 gram sodium hydroxide is reaction promoter, low whipping speed is under 500 rev/mins, reacted 120 minutes, the acetonitrile transformation efficiency is 100%, and the ethamine yield is 98.0% (weight).
[embodiment 2]
According to each operation steps and the condition of embodiment 1, just temperature of reaction is 50 ℃ in the reaction conditions, and reaction pressure is counted 2.0MPa with gauge pressure, and its reaction result is 100% for the acetonitrile transformation efficiency, and the ethamine yield is 97.9%.
[embodiment 3]
According to each operation steps and the condition of embodiment 1, just temperature of reaction is 75 ℃ in the reaction conditions, and reaction pressure is counted 2.0MPa with gauge pressure, and its reaction result is 100% for the acetonitrile transformation efficiency, and the ethamine yield is 97.8%.
[embodiment 4]
Each operation steps and condition according to embodiment 1, just reaction solvent adopts the mixture of ethanol and dimethylbenzene, wherein ethanol: dimethylbenzene (volume/volume)=1: 1, and the reaction times is 90 minutes, its reaction result is 100% for the acetonitrile transformation efficiency, and the ethamine yield is 99.0%.
[embodiment 5]
Each operation steps and condition according to embodiment 1, just reaction solvent adopts the mixture of ethanol and toluene, wherein ethanol: toluene (volume/volume)=15: 85, and the reaction times is 45 minutes, its reaction result is 100% for the acetonitrile transformation efficiency, and the ethamine yield is 97.7%.
[comparative example 1]
According to each operation steps and the condition of embodiment 1, just changing solvent is single component ethanol, and its reaction result is 99.2% for the acetonitrile transformation efficiency, and the ethamine yield is 94.6%.
[comparative example 2]
According to each operation steps and the condition of embodiment 1, just changing solvent is single component toluene, and its reaction result is 97.4% for the acetonitrile transformation efficiency, and the ethamine yield is 83.6%.
Claims (4)
1, a kind of method for preparing ethamine, skeleton nickel with tungstenic, molybdenum is a catalyzer, by count 10～50% the ethanol or the toluene of methyl alcohol and 50～90% or the mixture that dimethylbenzene is formed with volume percent is solvent, in temperature of reaction is 30～120 ℃, in the gauge pressure reaction pressure is under 1.0～5.0MPa condition, acetonitrile and hydrogen react, and the reaction times is 0.5～2.0 hour, get ethamine.
2,, it is characterized in that temperature of reaction is 50～80 ℃ according to the described method for preparing ethamine of claim 1.
3,, it is characterized in that in the gauge pressure reaction pressure be 2.0～2.5MPa according to the described method for preparing ethamine of claim 1.
4,, it is characterized in that the reaction times is 0.5～1.5 hour according to the described method for preparing ethamine of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011262877A CN1151120C (en) | 2001-07-20 | 2001-07-20 | Prepn process of ethylamine |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011262877A CN1151120C (en) | 2001-07-20 | 2001-07-20 | Prepn process of ethylamine |
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| CN1398847A CN1398847A (en) | 2003-02-26 |
| CN1151120C true CN1151120C (en) | 2004-05-26 |
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| CNB011262877A Expired - Fee Related CN1151120C (en) | 2001-07-20 | 2001-07-20 | Prepn process of ethylamine |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7196223B2 (en) * | 2005-05-03 | 2007-03-27 | Solutia, Inc. | Higher alcohols for solvents in amine production |
| CN108658787B (en) * | 2018-07-04 | 2019-11-05 | 浙江建业化工股份有限公司 | The preparation method of ethamine |
| CN114436827B (en) * | 2020-11-02 | 2024-07-02 | 中国石油化工股份有限公司 | Method for co-producing ethylamine and sec-butylamine |
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