CN85100307A - Process of producing dipropylamine by hydrogenation of acrylonitrile - Google Patents
Process of producing dipropylamine by hydrogenation of acrylonitrile Download PDFInfo
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- CN85100307A CN85100307A CN85100307.9A CN85100307A CN85100307A CN 85100307 A CN85100307 A CN 85100307A CN 85100307 A CN85100307 A CN 85100307A CN 85100307 A CN85100307 A CN 85100307A
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- hydrogenation
- amine
- vinyl cyanide
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Abstract
Existing vinyl cyanide synthesizes high yield dipropyl amine method, or adopts precious metal catalyst, or adopts a large amount of solvents and high-nickel catalyst multistage hydrogenation process.
The present invention then neither uses precious metal catalyst, does not also use solvent, and adopts two step of vinyl cyanide hydrogenated by-product circulation technology.Be vinyl cyanide with the synthetic propionitrile of nickel hydrogenation of skeleton, synthetic one, two with the low levels cu-ni catalytic hydrogenation again, tripropyl amine, by product one, tripropyl amine are recycled into the propionitrile hydrogenation reactor, and process obtains the single product dipropyl amine.Process is carried out under normal pressure-6kg/cm2 gauge pressure, normal temperature-200 ℃ temperature continuously.Obtain the dipropyl amine of purity＞98% with general rectificating method, meet the requirement of aspects such as novel weiyao proglumide of preparation and high-efficient herbicide trifluralin, have distinct economic.
Description
The invention belongs to the processing method of hydrogenation of acrylonitrile synthesis of alkyl amine.Specifically be meant the processing method of vinyl cyanide synthetic dipropyl amine of two step hydrogenation by product circulations on the ambrose alloy series catalysts.
Mostly the scale operation dialkylamine is to be realized by the ammonification hydrogenation method of the aminolysis of alcohol and aldehyde
(1)These method two alkylamine selectivity are not high, all obtain mixed amine, and water generation reaction and product azeotropic separate relatively difficulty.Especially Chun ammonia is separated needs High Temperature High Pressure.
Developing afterwards with the vinyl cyanide is the research of the synthetic dipropyl amine of raw material
(2)Though overcome unfavorable factor pure, that the aldehyde method generates water, but mostly still mixed amine, as example: document Akad Nauk.G ruz, SSR(1976.83(2) 373-6) in the vinyl cyanide of narration in the method for the synthetic dipropyl amine of Cu-Ni series catalysts previous step hydrogenation, have to mixed amine.Practice shows, this method exists acrylonitrile polymerization, bed overheated, and catalyzer is because of shortcomings such as cokings very fast inactivation.The synthetic dipropyl amine of vinyl cyanide one step hydrogenation of same Belg.860740 report though obtain the dipropyl amine of higher yields, needs to use noble metal Rh to make catalyzer.The Hung.Teljes.Hu21826 of one nine eight two chronology synthesizes dipropyl amine technology by the hydrogenation of vinyl cyanide multistage, and the dipropyl amine selectivity reaches 92%.Use in the first step hydrogenation of acrylonitrile system propionitrile and contain 15%Nis.30%Ni-carrier, catalyzer; The second step propionitrile hydrogenation system dipropyl amine divides two sections again, epimere 30-50%Ni carried catalyst, hypomere 5-20%Ni carried catalyst.This process catalyst content is higher, and need to introduce a large amount of carbon six alkane and make solvent (for two times of vinyl cyanide consumption).Increased solvent recuperation.
The objective of the invention is to adopt low levels non-precious metal catalyzer, do not use solvent and under low pressure carry out the hydrogenation of acrylonitrile reaction, obtain the single product dipropyl amine.
According to method of the present invention, hydrogenation of acrylonitrile system dipropyl amine, undertaken by following reaction:
Evidence: above-mentioned reaction is strong exothermal reaction.(1) is the easiest carries out in reaction.Reaction (2), (3), (4), generate one, two, the distribution of tripropyl amine in product, depend primarily on the factors such as kind, content and carrier of catalyzer, also be subjected to the influence of reaction process condition.When using the ambrose alloy series catalysts, can obtain mixing propylamine based on dipropyl amine.When by product one, tripropyl amine again during return course, can suppress to generate one, the reaction of tripropyl amine.
According to above-mentioned test-results, the present invention has adopted the synthetic dipropyl amine of vinyl cyanide two step hydrogenation by product circulation technology methods.The characteristics of this method are to react continuously to carry out.Its exemplary flow is seen Figure of description.
Its process is: technical pure hydrogen metering back and vinyl cyanide are by nitrile, hydrogen mole ratio 1: 1-5 mixes, and is entered by the bottom then and gives hydrogenation reactor I (skeletal nickel catalyst of interior dress certain volume), at liquid air speed 0.2-1h
-1, under the gauge pressure of normal temperature-100 ℃, normal pressure-6kg/(cm), carry out the liquid phase hydrogenation reaction and generate propionitrile, hydrogen after measure on propionitrile and another road then, press nitrile, hydrogen mole ratio 1: 4-10 mixing, incoming stockly give hot device II, be heated to 140-170 ℃, enter hydrogen reaction device III (nickel of interior dress certain volume, copper-carclazyte (or rAl
2O
3) catalyzer), at gas space velocity 400-800h
-1, temperature 140-200 ℃ and normal pressure-6kg/(cm)
2Carry out the vapour phase hydrogenation reaction under the gauge pressure, generate one, two, (wherein a propylamine accounts for 5-10% to the tripropyl amine mixture, dipropyl amine accounts for 50-60%, tripropyl amine accounts for 25-30%), product mixtures is through the cooler condenser IV, and water is cooled to liquid, enter the gas-liquid separator V then, isolated gaseous mixture enters ammonia absorption tower VI, and water absorbs ammonia and becomes ammoniacal liquor, discharges at the bottom of tower.The most of retrieval system of the exess of H2 gas recycles, and small part is from cat head emptying.The liquid mixing propylamine with the into separation of general atmospheric distillation tower VII, obtains purity＞98% dipropyl amine.Simultaneously, the propionitrile with isolated one, tripropyl amine and the first step hydrogenation generate is mixed into second by nitrile, a propylamine, tripropyl amine, hydrogen mole ratio 3: 0.5-1: 0.5-1: 15-18 and goes on foot the hydrogenation reactor III.Finally can get dipropyl amine yield 94-100%.
By the inventive method, it is the particle that nickel, 1: 1 alumel of aluminium weight ratio is broken into φ 3 * 3-5 * 5 that vinyl cyanide gives the suitable catalyzer of hydrogenant, uses caustic soda unfolded skeleton nickel again.And the suitable catalyzer of the synthetic dipropyl amine of propionitrile hydrogenation is nickeliferous 5-15%, cupric 1-5%, boracic 1-3%, is loaded in atlapulgite (or r-Al
2O
3) on nickel, the copper-carried catalyst of φ 3 * 3-φ 5 * 5.
The advantage of the inventive method is to adopt vinyl cyanide two step hydrogenations, uses lower concentration non-precious metal catalyzer in the reaction of second step, and process has solved the problem of removing a large amount of reaction heat with general method without solvent; Adopt by product one, tripropyl amine round-robin method, improved the selectivity of dipropyl amine, obtain single dipropyl amine product.The purity of this method gained meets the requirement of aspects such as novel weiyao proglumide of preparation and high-efficient herbicide trifluralin greater than 98% dipropyl amine.
Demonstrate method of the present invention below.
Example one:
In two step of vinyl cyanide hydrogenation process flow process, the stainless steel single tube reactor of two φ 39 * 7 is used in series connection, in first reactor, the 410ml propionitrile of at first packing into, reinstall the 200ml raney nickel catalyst, when bed temperature was raised to 50 ℃, the mole ratio of vinyl cyanide and hydrogen was pressed 1: 3 proportioning, at room temperature the bottom from reactor feeds continuously, reaction pressure 5kg/(cm)
2, 70 ± 5 ℃ of temperature of reaction, reactant is derived continuously by reactor top, and the result is as follows through gas chromatographic analysis:
In second reactor, the 200ml copper nickel-clay catalyst of packing into, in the presence of hydrogen stream, heat-up rate with 30-50 ℃/h activates, when temperature is raised to 260 ℃, kept 11 hours, in 4 hours, reaction bed temperature reduced to 140 ℃ then after, first reactor gained propionitrile and hydrogen are entered reaction pressure 3kg/(cm by 1: 6 mole ratio (comprising two mol hydrogen of the first step hydrogenation surplus) continuously from second hydrogen-gasified reactor top)
2, 165 ± 5 ℃ of temperature of reaction, gas phase air speed 600h
-1, test-results is as follows:
Example two:
In vinyl cyanide two step hydrogenation by product round-robin flow processs, used reactor, catalyzer, temperature of reaction and pressure etc. are identical with example one, and material mol proportioning is a propionitrile: a propylamine: tripropyl amine: hydrogen=3: 1: 1: 18, and gas phase air speed 400h
-1, test-results is as follows:
Basically obtained the single product dipropyl amine.
Claims (5)
1, hydrogenation of acrylonitrile synthesis of alkyl amine processing method.It is characterized in that adopting vinyl cyanide two step hydrogenation by product circulation technology methods, can obtain the single product dipropyl amine.
2, by the described processing method of claim 1, it is characterized in that the first step be vinyl cyanide and hydrogen in fixed bed, use skeletal nickel catalyst, at normal temperature-100 ℃, normal pressure-6kg/(cm)
2Gauge pressure, nitrile, hydrogen mole ratio 1: 1-5, liquid air speed 0.2-1h
-1Condition under, carry out the propionitrile that liquid phase hydrogenation generates high yield.
3, by claim 1,2 described processing methodes, it is characterized in that second step was propionitrile and hydrogen, with containing 1-5% copper, 5-15% nickel, 1-3% boron, be stated from atlapulgite (or r-AI
2O
3) on catalyzer, at 140-200 ℃, normal pressure-6kg/(cm)
2Gauge pressure, nitrile hydrogen mole ratio 1: 4-10, gas space velocity 400-800h
-1Under the condition, carry out the mixing propylamine of gas phase hydrogenation generation based on dipropyl amine.
4, by claim 1,2,3 described processing methodes, it is characterized in that pair product one, tripropyl amine that process generates are returned the second step hydrogenation reactor, mole ratio at nitrile, a propylamine, tripropyl amine and hydrogen is 3: react under the condition of 0.5-1: 0.5-1: 15-18, can obtain yield 94-100% dipropyl amine.
5,, it is characterized in that reaction carries out continuously by claim 1,2,3,4 processing method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 85100307 CN1008815B (en) | 1985-04-01 | 1985-04-01 | Process of producing dipropylamine by hydrogenation of acrylonitrile |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 85100307 CN1008815B (en) | 1985-04-01 | 1985-04-01 | Process of producing dipropylamine by hydrogenation of acrylonitrile |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85100307A true CN85100307A (en) | 1986-08-06 |
| CN1008815B CN1008815B (en) | 1990-07-18 |
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ID=4791047
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 85100307 Expired CN1008815B (en) | 1985-04-01 | 1985-04-01 | Process of producing dipropylamine by hydrogenation of acrylonitrile |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1008815B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100584820C (en) * | 2007-06-06 | 2010-01-27 | 中国日用化学工业研究院 | Method for preparing 3-alkoxypropylamine |
| CN101735105A (en) * | 2009-12-17 | 2010-06-16 | 上海化学试剂研究所 | Preparation method of alpha-acetamido-phenylpropionitrile |
-
1985
- 1985-04-01 CN CN 85100307 patent/CN1008815B/en not_active Expired
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100584820C (en) * | 2007-06-06 | 2010-01-27 | 中国日用化学工业研究院 | Method for preparing 3-alkoxypropylamine |
| CN101735105A (en) * | 2009-12-17 | 2010-06-16 | 上海化学试剂研究所 | Preparation method of alpha-acetamido-phenylpropionitrile |
| CN101735105B (en) * | 2009-12-17 | 2013-11-20 | 上海化学试剂研究所 | Preparation method of alpha-acetamido-phenylpropionitrile |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1008815B (en) | 1990-07-18 |
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