CN107540556A - A kind of preparation method of m-xylene diamine - Google Patents
A kind of preparation method of m-xylene diamine Download PDFInfo
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- CN107540556A CN107540556A CN201610486452.4A CN201610486452A CN107540556A CN 107540556 A CN107540556 A CN 107540556A CN 201610486452 A CN201610486452 A CN 201610486452A CN 107540556 A CN107540556 A CN 107540556A
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- isophthalodinitrile
- xylene diamine
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Abstract
A kind of preparation method of m-xylene diamine, it is characterized in that：Using fixed bed reactors, the isophthalodinitrile solution for being dissolved in mixed solvent is pumped into the bed for having loaded Ni/MgAlO catalyst, temperature be 60~140 DEG C, pressure is 1.0~8.0MPa, isophthalodinitrile mass space velocity is 0.1~5h‑1, hydrogen and isophthalodinitrile mol ratio be 5~50: 1 under conditions of, isophthalodinitrile and hydrogen reaction generation m-xylene diamine.Under preferred reaction conditions, m-xylene diamine yield reaches as high as 100%, can be applied to industrialization continuous production.
Description
Technical field
The present invention relates to a kind of preparation method of m-xylene diamine, belong to technical field of catalytic hydrogenation.
Technical background
M-xylene diamine (MXDA) is a kind of epoxy curing agent of excellent performance, has low-temperature setting, heat resistance, resistance to
Water-based, the advantages that resistance to chemical corrosion is good, viscosity is low, easy to operate, apply also for polyurethane, polyamide, rubber chemicals, agriculture
The fields such as medicine, fibre trimmer, rust remover, chelating agent, lubricant, paper conversion auxiliary agent and electronic chemical product, it is that a kind of application is wide
Fine chemicals general and that there is high added value.
M-xylene diamine is typically produced using isophthalodinitrile catalytic hydrogenation process.Domestic industry production m-xylene diamine is still
On a batch wise manner based on still reaction, production scale is small, and catalyst granules is thin, easy efflorescence, inferior separating effect, exist production cost compared with
The high, problem such as security is poor, automaticity is low, and batch process still reaction typically uses magnetic force or mechanical agitation, is catalyzed
Agent surface is difficult to ensure that the hydrogen supply of abundance, causes imine intermediate in reaction solution excessive, generates excessive accessory substance.It is and main
International producer, as Mitsubishi gas uses trickle bed continuous production processes, German BASF also uses fixed-bed catalytic
Method.For intermittent reaction mainly using Raney's nickel or modified Raney's nickel, fixed-bed process then more uses loading type nickel-based catalyst.
The pilot process of isophthalodinitrile hydrogenation reaction can produce the very high imine intermediate of reactivity, easily with reaction
Intermediate product and target product further occur polycondensation reaction, generation secondary amine, tertiary amine and other high boiling polymeric by-products,
These accessory substances are adsorbed and are deposited on catalyst surface, often result in catalyst poisoning inactivation.Suppress the one of polycondensation side reaction
Individual important method is as inhibitor using excessive liquefied ammonia or ammonia or organic amine.For example, CN101774928 discloses one kind
The preparation method of m-xylene diamine, isophthalodinitrile is dissolved in amide solvent, using liquefied ammonia as by-product suppressor,
Hydrogenation reaction is carried out on the Co-Ni catalyst supported, m-xylene diamine yield reaches 99.96%.But use a large amount of liquefied ammonia
Recovery cost is high, and can produce a large amount of ammonia-contaminated gas and waste water, seriously polluted.CN101955432 is disclosed between a kind of stirred tank
The method that hydrogenation of having a rest prepares m-xylene diamine, using modified Raney's nickel catalyst, reaction uses aromatic hydrocarbons, low-carbon alcohols and fatty halogen
The secondary amine inhibitor such as ternary mixed solvent and triethylamine, diethylamine for derivative.CN102690205 discloses one kind and is facing ammonia
Under the conditions of isophthalodinitrile Hydrogenation for m-xylene diamine technique, using diatomite or activated carbon or aluminum oxide or silica etc.
Ni or Co catalyst supporting, with the addition of the auxiliary agents such as Re, Cu, Ru, Fe, can be complete by isophthalodinitrile in trickle bed reactor
Full conversion, m-xylene diamine selectivity is up to 98.6%.
Catalytic activity can also be improved by adding auxiliary agent in the catalyst and suppress side reaction, so as to improve isophthalic diformazan
Amine yield.CN102029160 discloses a kind of Raney nickel supported on alumina, wherein adding copper, cobalt, iron, zinc etc.
Co-catalyst, isophthalodinitrile can be converted completely compared with temperate condition, the selectivity of m-xylene diamine reaches 98.8%.
CN103539676 discloses a kind of preparation method of m-xylene diamine, the concentration pore size distribution nickel catalyst supported using aluminum oxide
Agent, molybdenum component is with the addition of in catalyst to suppress the generation of macromolecular, extends the life-span.CN101062898 discloses one
Kind makees solvent with mixed xylenes and liquefied ammonia, uses Ni/MgO-SiO2Catalyst and secondary hydrogenation technique, make isophthalodinitrile complete
The full method for being converted into m-xylene diamine, m-xylene diamine total recovery 99.5%, MgO addition is catalyst gross mass
1%-2%, MgO introducing reduce the acidity of catalyst, it is suppressed that the generation of condensation polymer, extend catalyst life, improve
Hydrogenation yield, but the secondary hydrogenation technogenic influence economy of this technique.
In summary, life can not only be improved using supporting Raney nickel and fixed bed hydrogenation technique productions m-xylene diamine
Produce efficiency and target product yield, and safety and environmental protection.It is then to improve target product m-xylene diamine to receive to suppress polycondensation side reaction
The key of rate, this not only needs to develop high activity, high selectivity, the hydrogenation catalyst of long lifespan, it is also necessary to improves hydrogenation reaction
Technique.
The content of the invention
It is an object of the invention to provide a kind of method of isophthalodinitrile Hydrogenation m-xylene diamine, prior art is overcome
The defects of existing, m-xylene diamine yield is improved under relatively mild reaction condition.
Existing isophthalodinitrile hydrogenation technique is usually using Al2O3And SiO2As catalyst carrier, but they have necessarily
Acidity, readily facilitate condensation side reaction generation, cause the increase of accessory substance and the activity decrease of catalyst or even inactivation.With
Some prior arts introduce a small amount of alkaline components (such as MgO) and difference are modified to catalyst, and technical scheme is direct
Based on basic supports MgO, by introducing a small amount of Al2O3To improve carrier surface area, promote point of the active component on carrier
Dissipate, while the surface acidic-basic property of catalyst is adjusted, to adapt to the hydrogenation needs of isophthalodinitrile, obtain preferable target
Selectivity of product.
, can be under more gentle reaction condition by single hop hydrogenation technique, between making using technical scheme
Benzene dicarbonitrile 100% converts, and the yield of m-xylene diamine is up to 100%, can be applied to industrialization continuous production.
Technical scheme is as follows：
A kind of method of isophthalodinitrile Hydrogenation m-xylene diamine, it is characterized in that：Using fixed bed reactors, will dissolve
The bed for having loaded Ni/MgAlO catalyst is pumped into the isophthalodinitrile solution of mixed solvent, is 60~140 DEG C, presses in temperature
Power is 1.0~8.0MPa, isophthalodinitrile mass space velocity is 0.1~5h-1, hydrogen and isophthalodinitrile mol ratio be 5~50:
Under conditions of 1, isophthalodinitrile and hydrogen reaction generation m-xylene diamine.
The mixed solvent by one kind in DMF, DMA, tetrahydrofuran or its
Mixture, mixed with one kind in m-xylene diamine, piperidines, isopropylamine, butylamine, triethylamine, monoethanolamine, aniline or its mixture
With.The mass percentage concentration of isophthalodinitrile is 2~20%, preferably 3~15% in isophthalodinitrile solution.
The mass space velocity of the isophthalodinitrile solution is calculated as 0.1~5h with isophthalodinitrile-1, preferably 0.25~2h-1。
The mol ratio of the hydrogen and isophthalodinitrile is 5~50: 1, preferably 10~20: 1.
60~140 DEG C of the reaction temperature, preferably 90~110 DEG C.
The reaction pressure is 1.0~8.0MPa, preferably 3.0~5.0MPa.
The weight/mass percentage composition of metallic nickel is 50~80% in the Ni/MgAlO catalyst, preferably 60~70%, MgO's
Weight/mass percentage composition is 20~50%, preferably 30~40%, Al2O3Weight/mass percentage composition for 0.5~15%, preferably 1~
10%.
The Ni/MgAlO catalyst is prepared using coprecipitation.Catalyst is using preceding needing to be reduced with hydrogen.
Embodiment
Below by way of specific embodiment, present invention is described, but the scope of the present invention is not limited to the specific implementation
Example.
Embodiment 1
Weigh 29.7g Ni (NO3)2·6H2O、19.1g Mg(NO3)2·6H2O and 7.4g Al (NO3)3·9H2O is dissolved in
Water, 100ml solution is made；Separately take 24.1g Na2CO3Water is dissolved in, 100ml solution is made.It is under agitation that above-mentioned two parts of solution is same
When be added drop-wise in 200ml distilled water, generate green precipitate, by the precipitation with distillation water washing after, add 200ml n-butanols, water
Bath is evaporated, then is dried in 393K baking ovens, and then tabletting, broken, sieve take 20-40 mesh, and the catalyst precursor particles are being flowed
723K reductase 12s h in hydrogen, hydrogen GSVH=1000h-1, then use at room temperature and contain 0.5%O2/N2Gaseous mixture is passivated, i.e.,
Obtain catalyst A.
Embodiment 2
Weigh 29.7g Ni (NO3)2·6H2O、22.3g Mg(NO3)2·6H2O and 3.7g Al (NO3)3·9H2O is dissolved in
Water, 100ml solution is made；Separately take 23.8g Na2CO3Water is dissolved in, 100ml solution is made.It is under agitation that above-mentioned two parts of solution is same
When be added drop-wise in 200ml distilled water, generate green precipitate, by the precipitation with distillation water washing after, add 200ml n-butanols, water
Bath is evaporated, then is dried in 393K baking ovens, and then tabletting, broken, sieve take 20-40 mesh, and the catalyst precursor particles are being flowed
723K reductase 12s h in hydrogen, hydrogen GSVH=1000h-1, 0.5%O is then used at room temperature2/N2Gaseous mixture is passivated, and is produced
Catalyst B.
Embodiment 3
Weigh 29.7g Ni (NO3)2·6H2O、23.9g Mg(NO3)2·6H2O and 1.8gAl (NO3)3·9H2O is dissolved in water,
100ml solution is made；Separately take 23.6g Na2CO3Water is dissolved in, 100ml solution is made.Under agitation by above-mentioned two parts of solution simultaneously
It is added drop-wise in 200ml distilled water, generates green precipitate, by the precipitation with after distillation water washing, adds 200ml n-butanols, water-bath
It is evaporated, then is dried in 393K baking ovens, then tabletting, broken, sieve takes 20-40 mesh, by the catalyst precursor particles in flowing hydrogen
723K reductase 12s h in gas, hydrogen GSVH=1000h-1, 0.5%O is then used at room temperature2/N2Gaseous mixture is passivated, and is produced and is urged
Agent C.
Embodiment 4
The hydrogenation evaluation response of isophthalodinitrile is carried out in fixed bed reactors, 3ml catalyst A is filled in a diameter of
In the middle part of 10mm fixed bed reaction pipe, filled up and down with the quartz sand of mesh number same with catalyst granules, using high pressure micro
Isophthalodinitrile solution, the solution quality percentage composition be by pump：Triethylamine -83%N, the N- diformazan of 12% isophthalodinitrile -5%
Base formamide, is pumped into reactor, passes through beds, 80 DEG C, Hydrogen Vapor Pressure 3MPa of reaction temperature, isophthalic after being mixed with hydrogen
The mass space velocity 0.25h of dimethoxy nitrile-1, the mol ratio 20: 1 of hydrogen and isophthalodinitrile.Reaction mixture uses gas-chromatography after collecting
Analysis.The conversion ratio of isophthalodinitrile is 100%, and the selectivity of m-xylene diamine is 97.8%.
Embodiment 5
According to the operation of embodiment 4, using catalyst B, isophthalodinitrile solution quality percentage composition used is：10%
Piperidines-the 70%N of isophthalodinitrile -20%, dinethylformamide, 100 DEG C, Hydrogen Vapor Pressure 4MPa of reaction temperature, isophthalic diformazan
The mass space velocity 0.5h of nitrile-1, the mol ratio 15: 1 of hydrogen and isophthalodinitrile, the conversion ratio of isophthalodinitrile is 100%, isophthalic
The selectivity of dimethylamine is 100%.
Embodiment 6
According to the operation of embodiment 4, using catalyst C, the percentage composition of isophthalodinitrile solution quality is 8% isophthalic diformazan
The isopropylamine of nitrile -10% -82%N, N- dimethyl acetamide, 120 DEG C, Hydrogen Vapor Pressure 6MPa of reaction temperature, the matter of isophthalodinitrile
Measure air speed 0.5h-1, the mol ratio 20: 1 of hydrogen and isophthalodinitrile, the conversion ratio of isophthalodinitrile is 100%, m-xylene diamine
Selectivity be 99.5%.
Embodiment 7
According to the operation of embodiment 4, using catalyst A, the percentage composition of isophthalodinitrile solution quality is 8% isophthalic diformazan
M-xylene diamine-the 90%N of nitrile -2%, dinethylformamide, 90 DEG C, Hydrogen Vapor Pressure 3MPa of reaction temperature, isophthalodinitrile
Mass space velocity 0.25h-1, the mol ratio 15: 1 of hydrogen and isophthalodinitrile, the conversion ratio of isophthalodinitrile is 100%, isophthalic two
The selectivity of methylamine is 99.0%.
Embodiment 8
According to the operation of embodiment 4, using catalyst B, the percentage composition of isophthalodinitrile solution quality is 12% isophthalic two
The tetrahydrofuran of the monoethanolamine of formonitrile HCN -6% -82%, 120 DEG C, Hydrogen Vapor Pressure 6MPa of reaction temperature, the mass space velocity of isophthalodinitrile
0.25h-1, the mol ratio 20: 1 of hydrogen and isophthalodinitrile, the conversion ratio of isophthalodinitrile is 100%, the choosing of m-xylene diamine
Selecting property is 99.3%.
Claims (3)
1. a kind of method of isophthalodinitrile Hydrogenation m-xylene diamine, it is characterized in that：Using fixed bed reactors, will be dissolved in
The isophthalodinitrile solution of mixed solvent is pumped into reactor, by having loaded the catalyst of Ni/MgAlO catalyst together with hydrogen
Bed, temperature be 60~140 DEG C, pressure is 1.0~8.0MPa, isophthalodinitrile mass space velocity is 0.1~5h-1, hydrogen with
Under conditions of the mol ratio of isophthalodinitrile is 5~50: 1, isophthalodinitrile is set to react generation m-xylene diamine with hydrogen.
2. according to the method for claim 1, it is characterised in that：The matter of isophthalodinitrile in described isophthalodinitrile solution
It is 2~20%, preferably 3~15% to measure percentage concentration；Described mixed solvent is by DMF, N, N- dimethyl second
One kind or its mixture in acid amides, tetrahydrofuran, with m-xylene diamine, piperidines, isopropylamine, butylamine, triethylamine, monoethanolamine,
One kind or its mixture mixing composition in aniline.
3. method according to claim 1, it is characterised in that：The quality percentage of metallic nickel contains in the Ni/MgAlO catalyst
Measure as 50~80%, preferably 60~70%, MgO weight/mass percentage composition is 20~50%, preferably 30~40%, Al2O3Quality
Percentage composition is 0.5~15%, preferably 1~10%.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108273507A (en) * | 2018-01-26 | 2018-07-13 | 中南民族大学 | A kind of method of catalytic hydrogenating reduction nitrile compounds |
| CN109456200A (en) * | 2018-11-23 | 2019-03-12 | 万华化学集团股份有限公司 | A kind of preparation method of m-xylene diamine |
| CN110152642A (en) * | 2019-05-24 | 2019-08-23 | 常州大学 | A kind of catalyst being used to prepare m-xylene diamine and application |
| CN112934250A (en) * | 2019-12-11 | 2021-06-11 | 中国科学院大连化学物理研究所 | Nitrile hydrogenation catalyst, preparation and application |
| CN113402396A (en) * | 2020-03-16 | 2021-09-17 | 中国石油化工股份有限公司 | Production method for m-xylylenediamine and co-production of 1, 3-diamine methylcyclohexane |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108273507A (en) * | 2018-01-26 | 2018-07-13 | 中南民族大学 | A kind of method of catalytic hydrogenating reduction nitrile compounds |
| CN108273507B (en) * | 2018-01-26 | 2020-12-01 | 中南民族大学 | Method for reducing nitrile compound by catalytic hydrogenation |
| CN109456200A (en) * | 2018-11-23 | 2019-03-12 | 万华化学集团股份有限公司 | A kind of preparation method of m-xylene diamine |
| CN109456200B (en) * | 2018-11-23 | 2021-07-23 | 万华化学集团股份有限公司 | Preparation method of m-xylylenediamine |
| CN110152642A (en) * | 2019-05-24 | 2019-08-23 | 常州大学 | A kind of catalyst being used to prepare m-xylene diamine and application |
| CN112934250A (en) * | 2019-12-11 | 2021-06-11 | 中国科学院大连化学物理研究所 | Nitrile hydrogenation catalyst, preparation and application |
| CN112934250B (en) * | 2019-12-11 | 2023-06-09 | 中国科学院大连化学物理研究所 | Nitrile hydrogenation catalyst, preparation and application |
| CN113402396A (en) * | 2020-03-16 | 2021-09-17 | 中国石油化工股份有限公司 | Production method for m-xylylenediamine and co-production of 1, 3-diamine methylcyclohexane |
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