CN1467033A - Catalyst for preparing benzyl amine - Google Patents

Catalyst for preparing benzyl amine Download PDF

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CN1467033A
CN1467033A CNA02112437XA CN02112437A CN1467033A CN 1467033 A CN1467033 A CN 1467033A CN A02112437X A CNA02112437X A CN A02112437XA CN 02112437 A CN02112437 A CN 02112437A CN 1467033 A CN1467033 A CN 1467033A
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benzylamine
nickel
consumption
catalyzer
cyanobenzene
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CN1187120C (en
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刘仲能
侯闽渤
朱海燕
宗弘元
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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Abstract

A catalyst for preparing benzylamine by catalytic hydrogenation of phenylmethyl nitrile is composed of the primary catalyst which is skeleton Ni and the secondary catalyst chosen from RE, Cr or W or their mixture, Mo, Ti, Zr, P, Bi, Sn, B, Al, Ga and halogen. Its advatnage is high output rate of benzylamine.

Description

Be used to prepare the catalyzer of benzylamine
Technical field
The present invention relates to be used to prepare the catalyzer of benzylamine.
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.
Figure A0211243700041
Figure A0211243700042
(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.
Figure A0211243700043
(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.Being Primary Catalysts with cancellated skeleton nickel alloy in the document, is promotor with molybdenum, titanium, tantalum, ruthenium or aluminium, is 175～200 ℃ in temperature, and pressure is under 800～1400 P.S.I conditions, and cyanobenzene 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 to overcome in the past that to have cyanobenzene hydrogenation in the document be in the benzylamine process, and the problem that the benzylamine yield is not high provides a kind of new catalyzer that is used to prepare benzylamine.This catalyzer is used for the cyanobenzene catalytic hydrogenation 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 catalyzer that is used to prepare benzylamine, comprise 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%.
Technique scheme middle-weight rare earths 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 preferable range 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 scope 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.
Method for preparing catalyst of 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.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
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
[embodiment 6]
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%.

Claims (6)

1, a kind of catalyzer that is used to prepare benzylamine, comprise skeleton nickel, rare earth element, be selected from chromium or tungsten and miscellany thereof and be selected from least a promotor in molybdenum, titanium, zirconium, phosphorus, bismuth, tin, boron, aluminium, 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%, and the consumption that is selected from least a promotor in molybdenum, titanium, zirconium, phosphorus, bismuth, tin, boron, aluminium, gallium or the halogen is 0.005～0.5%.
2, according to the described catalyzer that is used to prepare benzylamine 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%.
According to the described catalyzer that is used to prepare benzylamine of claim 1, it is characterized in that 3, the consumption that is selected from chromium or tungsten and miscellany thereof is 0.05～0.5% in weight ratio with respect to nickel.
According to the described catalyzer that is used to prepare benzylamine of claim 3, it is characterized in that 4, the consumption that is selected from chromium or tungsten and miscellany thereof is 0.1～0.3% in weight ratio with respect to nickel.
5,, it is characterized in that halogen is selected from least a in fluorine, the chlorine or bromine according to the described catalyzer that is used to prepare benzylamine of claim 1.
According to the described catalyzer that is used to prepare benzylamine of claim 5, it is characterized in that 6, 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% in weight ratio with respect to nickel.
CNB02112437XA 2002-07-10 2002-07-10 Catalyst for preparing benzyl amine Expired - Lifetime CN1187120C (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102718673A (en) * 2011-12-16 2012-10-10 常江 Novel technology for synthesis of aminomethylbenzoic acid
CN104803856A (en) * 2015-03-31 2015-07-29 常州大学 Method for synthesizing benzylamine through continuous catalytic hydrogenation of cyanobenzene
CN109225261A (en) * 2018-10-22 2019-01-18 广西博测检测技术服务有限公司 A kind of preparation method and applications of Raney's nickel-iron catalyst are in the discoloration method of waste water from dyestuff

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102718673A (en) * 2011-12-16 2012-10-10 常江 Novel technology for synthesis of aminomethylbenzoic acid
CN102718673B (en) * 2011-12-16 2014-01-15 常江 Novel technology for synthesis of aminomethylbenzoic acid
CN104803856A (en) * 2015-03-31 2015-07-29 常州大学 Method for synthesizing benzylamine through continuous catalytic hydrogenation of cyanobenzene
CN109225261A (en) * 2018-10-22 2019-01-18 广西博测检测技术服务有限公司 A kind of preparation method and applications of Raney's nickel-iron catalyst are in the discoloration method of waste water from dyestuff
CN109225261B (en) * 2018-10-22 2021-09-14 广西博测检测技术服务有限公司 Preparation method of Raney nickel-iron catalyst and application of Raney nickel-iron catalyst in decolorizing method of dye wastewater

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