CN1467197A - Method for preparing benzyl amine by catalytic hydrogenation - Google Patents
Method for preparing benzyl amine by catalytic hydrogenation Download PDFInfo
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- CN1467197A CN1467197A CNA021124388A CN02112438A CN1467197A CN 1467197 A CN1467197 A CN 1467197A CN A021124388 A CNA021124388 A CN A021124388A CN 02112438 A CN02112438 A CN 02112438A CN 1467197 A CN1467197 A CN 1467197A
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Abstract
A catalytic hydrogenation process for preparing benzylamine features that under the action of main catalyst of sleleton nickel, the phenylmethyl nitrile takes part in reaction at 15-100 deg.C under 2-12 MPa in the solvent of C1-4 low-grade emtrol or C6-C10 arylhydrocarbone and their mixture. Said main catalyst carriers also RE and at least one cocatalyst chosen from Cr, W and their mixture, Mo, Ti, Zr, P, Bi, Sn, B, Al, Ga and halogen. Its advantage is high output rate.
Description
Technical field
The present invention relates to the method for preparing benzyl amine by catalytic hydrogenation.
Background technology
Benzylamine (Benzylamine), molecular formula C
6H
5CH
2NH
2, molecular weight 107.16,184.5 ℃ of boiling points, n
D 201.5401,390 ℃ of spontaneous ignition temperatures, 65 ℃ of flash-points, relative density 0.9826.Benzylamine is colourless, the oily liquids of ammonia flavor slightly, is alkalescence, easily absorbs CO in the air
2Form white crystals, can dissolve each other, form azeotrope, skin and mucous membrane are had stronger pungency with aniline, phenol, m-methyl phenol with water, pure and mild ether, poisonous.
Benzylamine has stronger alkalescence, can generate adduct with effects such as phenol, p-methyl phenol, formic acid.Benzylamine is important Organic Chemicals and fine-chemical intermediate, at medicine, agricultural chemicals, tensio-active agent, inhibiter, dyestuff, explosive, chemical reagent, CO
2Aspects such as absorption agent all are widely used.Particularly in the medicine industry, benzylamine is the key compound of synthetic drugs active ingredient, can be used for synthetic antimicrobial Trimpex Trimethyl phosphate, broad-spectrum antibiotics oxyammonia benzylpenicillin, oxyammonia benzyl cephamycin, trifluperidol etc.; External application sulfonamide mafenide, Ambamide kill scabies germ killing drugs acryloyl benzylamine (crotamiton), antifungal drug trinitrogenazole alcohol benzyl amine derivative; Cardiovascular agent nicardipine, Phenoxybenzamine, bretylium; The antiemetic trimethobenzamide, haemostatic medicament para-amino-methyl-benzoic acid (carbaryl acid), amine methyl cyclohexane yl carboxylic acid (tranamic acid); Intend suprarenal gland class medicine phentolamine (Regnine) and antitumor drug etc., be widely used in the treatment of various diseases.In the pesticide industry, benzylamine is used for the active penetration enhancers of synthetic cell, new and effective low toxopyrimidine bigcatkin willow benzylamine class weedicide, novel pesticide alanycarb intermediate N, two (N-benzyl-Beta-alanine) diethyl esters of N-two sulphur etc.In the tensio-active agent industry, benzylamine is used for the synthesizing cationic tensio-active agent such as chlorine (bromine) is changed C
12～18The alkyl benzyl dimethyl ammonium, be widely used in all trades and professions such as oil field, water treatment, cleaning supplies, lubricating oil, inhibiter, biocide and personal hygiene article, also can be used as the phase-transfer catalyst of organic synthesis etc., as bromination dodecylbenzyl Dimethyl Ammonium (bromogeramine), be surfactivity sterilizing agent of many uses, excellent property.In the coatings industry, benzyl amine derivative is good epoxy curing agent component.In the dyestuffs industries, benzylamine can be used for composite reactive dyestuff gumbix, phenoxybenzamine base ether etc.Benzylamine also can be used as the qualitative reagent of metallic compound, is used for synthesizing new explosive CL-20, benzylamine-BO
3Can be used as the polymeric amide catalyzer.
The benzylamine production method mainly contains: benzyl chloride additive process, benzyl chloride ammonolysis process, phenyl aldehyde face hydrogen ammoniation process, cyanobenzene shortening method.
(1) benzyl chloride additive process
Benzyl chloride, urotropine and ethanol are added in the reactor, in 30～35 ℃ of reactions 4 hours, add hydrochloric acid then and be warming up to 45～50 ℃ of reactions 2 hours, be chilled to below 25 ℃, elimination ammonium chloride heats up filtrate again, steams aldehydo-ester, alcohol mixeding liquid; Rectification under vacuum adds the neutralization of industry alkali behind the evaporate to dryness, standing separation alkali lye, and after the air distillation, 100 ℃/80kpa benzylamine cut is collected in underpressure distillation again.
(2) benzyl chloride ammonolysis process
Benzyl chloride, ammoniacal liquor, bicarbonate of ammonia are added in the reactor, stirring is warming up to 30～35 ℃ of reactions 6 hours, leave standstill the 3 little time-divisions layer that deoils, then reaction solution is pressed into the ammonia excretion jar, heats up and remove ammonia, again in 100 ℃ of underpressure distillation, add the alkali neutralization when steaming again to 2 times of volumes adding benzyl chloride, standing separation alkali lye, 100 ℃/80kpa benzylamine cut is collected in the oil reservoir distillation.
(3) phenyl aldehyde faces the hydrogen ammoniation process
(weight in wet base 100%Ni) adds in the stainless steel autoclave, and 100 ℃, 15Mpa reacted 3～5 hours with phenyl aldehyde, methyl alcohol, liquefied ammonia, Glacial acetic acid and Raney Ni catalyzer.Hydrogen every supplement consumed at 10 minutes intermittences.Till no longer absorbing back 30 minutes to hydrogen.Catalyzer adopts press filtration to separate.Contain benzylamine in the filtrate, benzylalcohol, Schiff alkali (N-phenylbenzylamine), all the other are methyl alcohol, water generation reaction and ammonia, yield 93%.Underpressure distillation can obtain the benzylamine of technical grade purity.
(4) cyanobenzene shortening method
Cyanobenzene, solvent, (liquefied ammonia) and catalyzer are pressed feed ratio add in the stainless steel autoclave, at 50～100 ℃, 5.0～12.0Mpa reacted 2～6 hours, till no longer absorbing back 30 minutes to hydrogen.Catalyzer adopts press filtration to separate, and solvent and catalyst recirculation are used, and filtrate can obtain the benzylamine of technical grade purity through desolventizing, underpressure distillation, and total recovery is greater than 92%.
(1), (2) method is because loaded down with trivial details, equipment corrosion of technology and serious three wastes, low, the poor product quality (chloride) of yield abroad no longer adopt, and mainly adopts phenyl aldehyde to face cleaning procedure productions such as hydrogen ammoniation process.In recent years, more and more higher to the requirement of benzylamine quality owing to pharmacy, farmingization, tensio-active agent industrial expansion, the benzylamine that adopts traditional benzyl chloride explained hereafter can't satisfy the demands owing to environmental protection, quality aspect.It is higher that phenyl aldehyde faces hydrogen ammoniation process reaction pressure, and production cost is also high.At present, because the ammoxidation of aromatic hydrocarbon development of technology, the cyanobenzene production cost reduces significantly, makes that cyanobenzene shortening method produces that benzylamine possesses skills, cost, qualitative advantage.
A kind of production benzylamine and dibenzylamine method have been introduced in the document U.S. Pat 4163025.Being Primary Catalysts with the skeleton nickel in the document, is promotor with zirconium and platinum, is benzylamine with cyanobenzene hydrogenation, and its temperature of reaction is below 100 ℃, and reaction pressure is 165～215P.S.I, and the yield of benzylamine is up to 94.6%.
Introduced a kind of skeletal nickel catalyst of amination aromatic hydrocarbons in the document U.S. Pat 4503251.Be Primary Catalysts with cancellated skeleton nickel alloy in the document, with molybdenum, titanium, tantalum, ruthenium or aluminium is promotor, is 175～200 ℃ in temperature, and pressure is under 800～1400 P.S.I conditions, the cyanobenzene catalytic hydrogenation is that the highest yield of benzylamine is 66.9%, and is lower.
Summary of the invention
Technical problem to be solved by this invention is that to have cyanobenzene hydrogenation in the document be the not high problem of benzylamine yield in the benzylamine process in the past, and a kind of method of new preparing benzyl amine by catalytic hydrogenation is provided.This method is used for the cyanobenzene shortening and generates benzylamine, has the high characteristics of benzylamine yield.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method of preparing benzyl amine by catalytic hydrogenation is a raw material with the cyanobenzene, is 15～100 ℃ in temperature of reaction, in gauge pressure H-H reaction pressure is under 2.0～12.0MPa condition, with lower aliphatic alcohols or the C that contains 1～4 carbon atom
6～C
10Aromatic hydrocarbons and composition thereof be solvent, under catalyst action, react and generated benzylamine in 0.3～20 hour, cyanobenzene wherein: the volume ratio of solvent is 1: 1～10, used catalyzer comprises skeleton nickel, rare earth element, be selected from chromium or tungsten and miscellany thereof and be selected from molybdenum, titanium, zirconium, phosphorus, bismuth, tin, boron, aluminium, at least a promotor in gallium or the halogen, wherein in weight ratio with respect to nickel, the consumption of rare earth element is 0.005～0.2%, the consumption that is selected from chromium or tungsten and miscellany thereof is 0.01～1%, is selected from molybdenum, titanium, zirconium, phosphorus, bismuth, tin, boron, aluminium, the consumption of at least a promotor in gallium or the halogen is 0.005～0.5%.
The temperature of reaction preferable range is 50～80 ℃ in the technique scheme, and the reaction pressure preferable range is 4.0～6.0MPa, and the reaction times preferable range is 0.3～5 hour, and the solvent preferred version is an ethanol, cyanobenzene: the volume ratio preferable range of solvent is 1: 1～5.The rare earth element preferred version is to be selected from least a in lanthanum, cerium, praseodymium or the neodymium, and in the weight ratio with respect to nickel, its consumption is 0.005～0.08%.In the weight ratio with respect to nickel, the consumption preferable range that is selected from chromium or tungsten and miscellany thereof is 0.05～0.5%, and more preferably scheme is 0.1～0.3%.Halogen is selected from least a in fluorine, the chlorine or bromine.In the weight ratio with respect to nickel, the consumption preferable range that is selected from least a promotor in molybdenum, titanium, zirconium, phosphorus, bismuth, tin, boron, aluminium, gallium or the halogen is 0.01～0.15%.
The used raw material of catalyzer composition of the present invention is:
Boron: be selected from halogenation boron or hydroborates;
Phosphoric: be selected from phosphoric acid salt or phosphite;
Chromium element: be selected from chromic salt, oxide compound or nitrate;
W elements: be selected from tungstate, oxide compound or nitrate;
Molybdenum element: be selected from molybdate, oxide compound or nitrate;
Halogen element: be selected from simple substance or its salt;
Rare earth element: be selected from its oxide compound, nitrate or other soluble salt;
Other element: be selected from its metal, oxide compound, nitrate or other soluble salt.
The method for preparing catalyst that uses among the present invention is as follows:
At first nickel-aluminium alloy is reacted with the sodium hydroxide solution of required reacting weight earlier, water cleans to neutral, at least a promotor that adds chromium, tungsten, the rare earth element of aequum then and be selected from molybdenum, titanium, zirconium, phosphorus, bismuth, tin, boron, aluminium, gallium or the halogen carries out modification, through washing, washing with alcohol 2～3 times and being kept in the ethanol.
Because the skeletal nickel catalyst active centre is more, the hydrogen supply amount is big, can cause the product deep hydrogenation.The present invention is selected from boron, phosphorus, tin, rare earth element etc. by adding in skeleton nickel and has suppressed unnecessary active centre, and catalyzer and main reaction are adapted, and makes the cyanobenzene molecule not by the excessive hydrogenation deamination simultaneously.Add in the catalyzer chromium or tungsten help reacting in the absorption of imines on catalyzer, help reducing the amount of free imines, can improve reactive behavior simultaneously.Suitably improve the solvent usage quantity, help removing heat and improve product benzylamine selectivity.Use catalyzer of the present invention, be used for cyanobenzene hydrogenation preparing benzylamine, 15～100 ℃ of temperature of reaction, reaction pressure 2～12MPa, with ethanol is solvent, cyanobenzene: the solvent volume ratio is a hydrogenation reaction 0.5～20 hour under 1: 1～10 conditions, and the cyanobenzene transformation efficiency reaches as high as 100%.The benzylamine yield reaches as high as more than 98%, has obtained better technical effect.
The invention will be further elaborated below by embodiment.
Embodiment [embodiment 1]
In 500 milliliters of reactors, add benzene feedstock formonitrile HCN 50 grams, skeletal nickel catalyst 7 grams (weight in wet base) of modification, comprise boron, rare earth lanthanum and tungsten in the catalyzer, wherein in weight ratio with respect to Ni, Ni: B: La: W is 100: 0.02: 0.02: 0.15, cyanobenzene and hydrogen are 65 ℃ in temperature of reaction, in gauge pressure H-H reaction pressure is 5MPa, with ethanol is solvent, solvent: cyanobenzene (volume/volume) is 4: 1, reacts 50 minutes, the cyanobenzene transformation efficiency is 100%, and the yield of benzylamine is 98.1%.[embodiment 2～5]
According to each operation steps and the condition of embodiment 1, just change the composition of catalyzer, its reaction result is listed in table 1.[comparative example 1]
According to each operation steps of embodiment 1, just change the composition of catalyzer, its reaction result is listed in table 1.
Table 1
[embodiment 6]
| Sequence number | Skeletal nickel catalyst is formed (weight ratio meter) | Temperature of reaction ℃ | Reaction pressure MPa | Cyanobenzene transformation efficiency % | Benzylamine yield % |
| Embodiment 1 | ?Ni 100B 0.02La 0.02W 0.15 | ????65 | ????5 | ????100 | ??98.1 |
| Embodiment 2 | ?Ni 100B 0.01Ce 0.03W 0.3Sn 0.01 | ????65 | ????5 | ????99.8 | ??98.3 |
| Embodiment 3 | ?Ni 100P 0.01Ce 0.01Cr 0.04Mo 0.06W 0.05 | ????65 | ????5 | ????100 | ??98.6 |
| Embodiment 4 | ?Ni 100B 0.02La 0.01Mo 0.06W 0.10Ti 0.02 | ????65 | ????5 | ????99.9 | ??98.7 |
| Embodiment 5 | ?Ni 100B 0.05La 0.04Mo 0.06W 0.2Zr 0.03Sn 0.01 | ????65 | ????5 | ????100 | ??98.9 |
| Comparative example 1 | ?Ni 100Zr 0.3 | ????65 | ????5 | ????100 | ??93.8 |
According to each operation steps and the condition of embodiment 1, just in the reaction conditions, temperature of reaction is 70 ℃, in gauge pressure H-H reaction pressure is 5MPa, ethanol: cyanobenzene (volume/volume) is 5: 1, and its reaction result is 100% for the cyanobenzene transformation efficiency, and the benzylamine yield is 98.2%.[embodiment 7]
According to each operation steps and the condition of embodiment 1, just in the reaction conditions, temperature of reaction is 50 ℃, ethanol: cyanobenzene (volume/volume) is 7: 1, reaction times is 60 minutes, and its reaction result is 99.7% for the cyanobenzene transformation efficiency, and the benzylamine yield is 97.6%.[embodiment 8]
Each step according to embodiment 1, just in the reaction conditions, temperature of reaction is 80 ℃, solvent adopts methyl alcohol: toluene (volume/volume) is 50: 50 solvent, solvent: cyanobenzene (volume/volume) is 2: 1, is 6.0MPa in the gauge pressure reaction pressure, and the reaction times is 240 minutes, its reaction result is 100% for the cyanobenzene transformation efficiency, and the benzylamine yield is 96.8%.[embodiment 9]
According to each step of embodiment 1, just in the reaction conditions, temperature of reaction is 70 ℃, in gauge pressure H-H reaction pressure is 6MPa, and the reaction times is 30 minutes, ethanol: cyanobenzene (volume/volume) is 5: 1, its reaction result is 100% for the cyanobenzene transformation efficiency, and the benzylamine yield is 97.9%.
Claims (9)
1, a kind of method of preparing benzyl amine by catalytic hydrogenation is a raw material with the cyanobenzene, is 15～100 ℃ in temperature of reaction, is under 2.0～12.0MPa condition in gauge pressure H-H reaction pressure, with lower aliphatic alcohols or the C that contains 1～4 carbon atom
6～C
10Aromatic hydrocarbons and composition thereof be solvent, under catalyst action, react and generated benzylamine in 0.3～20 hour, cyanobenzene wherein: the volume ratio of solvent is 1: 1～10, used catalyzer comprises skeleton nickel, rare earth element, be selected from chromium or tungsten and miscellany thereof and be selected from molybdenum, titanium, zirconium, phosphorus, bismuth, tin, boron, aluminium, at least a promotor in gallium or the halogen, wherein in weight ratio with respect to nickel, the consumption of rare earth element is 0.005～0.2%, the consumption that is selected from chromium or tungsten and miscellany thereof is 0.01～1%, is selected from molybdenum, titanium, zirconium, phosphorus, bismuth, tin, boron, aluminium, the consumption of at least a promotor in gallium or the halogen is 0.005～0.5%.
2, according to the method for the described preparing benzyl amine by catalytic hydrogenation of claim 1, it is characterized in that temperature of reaction is 50～80 ℃, reaction pressure is 4.0～6.0MPa, the reaction times is 0.3～5 hour.
3,, it is characterized in that solvent is an ethanol according to the method for the described preparing benzyl amine by catalytic hydrogenation of claim 1.
4, according to the method for the described preparing benzyl amine by catalytic hydrogenation of claim 1, it is characterized in that cyanobenzene: the volume ratio of solvent is 1: 1～5.
5, according to the method for the described preparing benzyl amine by catalytic hydrogenation of claim 1, it is characterized in that rare earth element is selected from least a in lanthanum, cerium, praseodymium or the neodymium, in the weight ratio with respect to nickel, its consumption is 0.005～0.08%.
6,, it is characterized in that in weight ratio the consumption that is selected from chromium or tungsten and miscellany thereof is 0.05～0.5% with respect to nickel according to the method for the described preparing benzyl amine by catalytic hydrogenation of claim 1.
7,, it is characterized in that in weight ratio the consumption that is selected from chromium or tungsten and miscellany thereof is 0.1～0.3% with respect to nickel according to the method for the described preparing benzyl amine by catalytic hydrogenation of claim 6.
8,, it is characterized in that halogen is selected from least a in fluorine, the chlorine or bromine according to the method for the described preparing benzyl amine by catalytic hydrogenation of claim 1.
9, according to the method for the described preparing benzyl amine by catalytic hydrogenation of claim 1, it is characterized in that in weight ratio the consumption that is selected from least a promotor in molybdenum, titanium, zirconium, phosphorus, bismuth, tin, boron, aluminium, gallium or the halogen is 0.01～0.15% with respect to nickel.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1948266B (en) * | 2006-11-10 | 2010-05-12 | 清华大学 | Method of preparing N-mono substituted benzylamine by catalytic hydrogenation reduction amination |
| CN102267915A (en) * | 2011-06-16 | 2011-12-07 | 浙江大学 | Method for reducing aromatic nitriles |
| CN104151168A (en) * | 2014-08-08 | 2014-11-19 | 一帆生物科技集团有限公司 | Synthetic method of p-tert-butylbenzylamine |
| CN104602522A (en) * | 2012-09-03 | 2015-05-06 | 帝斯曼知识产权资产管理有限公司 | Novel compositions comprising p-hydroxybenzylamine |
| CN104602521A (en) * | 2012-09-03 | 2015-05-06 | 帝斯曼知识产权资产管理有限公司 | Novel compositions comprising p-hydroxybenzylamine |
| CN104803856A (en) * | 2015-03-31 | 2015-07-29 | 常州大学 | Method for synthesizing benzylamine through continuous catalytic hydrogenation of cyanobenzene |
| CN107056622A (en) * | 2017-01-10 | 2017-08-18 | 湖南大学 | A kind of method that antimony organic catalytic hydrogenation imines prepares benzylamine compound |
-
2002
- 2002-07-10 CN CN 02112438 patent/CN1218929C/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1948266B (en) * | 2006-11-10 | 2010-05-12 | 清华大学 | Method of preparing N-mono substituted benzylamine by catalytic hydrogenation reduction amination |
| CN102267915A (en) * | 2011-06-16 | 2011-12-07 | 浙江大学 | Method for reducing aromatic nitriles |
| CN102267915B (en) * | 2011-06-16 | 2013-11-20 | 浙江大学 | Method for reducing aromatic nitriles |
| CN104602522A (en) * | 2012-09-03 | 2015-05-06 | 帝斯曼知识产权资产管理有限公司 | Novel compositions comprising p-hydroxybenzylamine |
| CN104602521A (en) * | 2012-09-03 | 2015-05-06 | 帝斯曼知识产权资产管理有限公司 | Novel compositions comprising p-hydroxybenzylamine |
| CN104602522B (en) * | 2012-09-03 | 2017-04-19 | 帝斯曼知识产权资产管理有限公司 | Compositions comprising p-hydroxybenzylamine |
| CN104602521B (en) * | 2012-09-03 | 2018-01-12 | 帝斯曼知识产权资产管理有限公司 | Composition comprising gumbix |
| CN104151168A (en) * | 2014-08-08 | 2014-11-19 | 一帆生物科技集团有限公司 | Synthetic method of p-tert-butylbenzylamine |
| CN104151168B (en) * | 2014-08-08 | 2016-06-22 | 一帆生物科技集团有限公司 | A kind of synthetic method to tert-butyl benzyl amine |
| CN104803856A (en) * | 2015-03-31 | 2015-07-29 | 常州大学 | Method for synthesizing benzylamine through continuous catalytic hydrogenation of cyanobenzene |
| CN107056622A (en) * | 2017-01-10 | 2017-08-18 | 湖南大学 | A kind of method that antimony organic catalytic hydrogenation imines prepares benzylamine compound |
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