CN101062896A - Method for manufacturing trimethylamine - Google Patents
Method for manufacturing trimethylamine Download PDFInfo
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- CN101062896A CN101062896A CN 200610074993 CN200610074993A CN101062896A CN 101062896 A CN101062896 A CN 101062896A CN 200610074993 CN200610074993 CN 200610074993 CN 200610074993 A CN200610074993 A CN 200610074993A CN 101062896 A CN101062896 A CN 101062896A
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- trimethylamine
- methylamine
- dimethylamine
- ammonia
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Abstract
The invention discloses a preparing method of insufficient section trimethylamine in methylamine manufacture time, which is characterized by the following: separating and purifying methylamine from the getting mixture; separating out of ammonia and trimethylamine; proceeding gas phase reaction with dimethylamine or dimethylamine with not less than 50 mole % and single aminomethane mixture and ammonia.
Description
Technical field
The present invention relates to make the method for Trimethylamine 99.Trimethylamine 99 is used to feed, field of electronic materials etc., is especially increasing in its demand of field of electronic materials in recent years.
Background technology
Usually have in the presence of the solid acid catalyst of dehydration and ammonification at aluminum oxide, sial etc., react with high temperature (about 400 ℃) in gas phase, can produce methylamine by making methyl alcohol and ammonia.Usually, in this reaction, generate the mixture of single methylamine, dimethylamine, Trimethylamine 99.These methylamines demand except dimethylamine seldom just is recycled to the reaction system after resultant of reaction is isolated dimethylamine and utilizes.
And, adopt distillation when separating the purification methylamine mixture usually.But Trimethylamine 99 so want to separate Trimethylamine 99, just needs very miscellaneous distillation procedure and large-scale plant owing to form complicated azeotropic system with ammonia, single methylamine, dimethylamine, and is very big thereby the consumes energy cost of methylamine manufacturing process becomes.Reclaim technology about this, for example in " change manufacturing engineering figure complete or collected works " (clear and on April 25th, 53 chemical industry society of Co., Ltd. issue), detailed disclosing arranged.
For the minimizing that realizes the dimethylamine manufacturing cost and the miniaturization of device, do one's utmost to be suppressed at the by product Trimethylamine 99 that generates in the reaction, to promote that it is very important generating dimethylamine.But, the selection coefficient of three kinds of methylamines, by the thermodynamic(al)equilibrium decision, the production rate of Trimethylamine 99 is much higher than dimethylamine under common reaction conditions on non-crystalline solids acid catalysts such as described aluminum oxide or silicon-dioxide.For example, when the ratio of the ammonia of 400 ℃ of temperature of reaction, reactor inlet and methyl alcohol was 1: 1 (weight ratio), the balance of each amine that calculation of thermodynamics goes out generated than counting single methylamine with weight ratio: dimethylamine: Trimethylamine 99=0.284: 0.280: 0.436.
Disclosed non-crystalline solids acid catalyst,, suppressed to generate Trimethylamine 99, to promote to generate the method for dimethylamine by utilizing the shape selective of zeolite catalyst for the domination that is subjected to the thermodynamic(al)equilibrium relation.For example, the patent documentation 1 etc. that mordenite is used for catalyzer.In addition, in patent documentation 2, put down in writing Trimethylamine 99 has been carried out the method that disproportionation is made dimethylamine, in patent documentation 3, put down in writing single methylamine is carried out the method that disproportionation is made dimethylamine.
Be to study in methylamine is made in the past, suppress Trimethylamine 99, as mentioned above to generate the method for a large amount of dimethylamine.But the demand for Trimethylamine 99 is increasing in recent years, has the insufficient problem of Trimethylamine 99 growing amount in the manufacture method of using zeolite catalyst.When using zeolite catalyst, if though improve temperature of reaction then can increase the Trimethylamine 99 growing amount, catalyst life shortens.
But, can think the Requirement Increases of Trimethylamine 99, if use non-crystalline solids acid catalyst such as sial, the growing amount of Trimethylamine 99 will be superfluous, remaining Trimethylamine 99 need carry out recirculation, thereby causes energy cost very big.And will develop new catalyzer needs spended time, whenever changes in demand is just developed catalyzer and unrealistic.From this situation, waiting in expectation can be corresponding to the Trimethylamine 99 manufacture method of the economy of demand shift.
Patent documentation 1: the spy opens clear 56-46846 number
Patent documentation 2: the spy opens clear 57-169445 number
Patent documentation 3: the spy opens flat 11-228507 number
Summary of the invention
The invention provides a kind of zeolite catalyst that when making methylamine, passes through to use, can be when reducing the consumes energy cost, efficient produces the method for the Trimethylamine 99 of insufficient section well.
The result that the inventor furthers investigate in order to solve above-mentioned problem, discovery separates purification ammonia and Trimethylamine 99 from methylamine mixture after, make dimethylamine or contain and carry out gas-phase reaction more than or equal to the dimethylamine of 50 moles of % dimethylamine and the mixture and the ammonia of single methylamine, just can efficient obtain the necessary amount of Trimethylamine 99 well, so that finished the present invention.
Promptly, the present invention relates to the manufacture method of Trimethylamine 99, it is characterized in that, by methyl alcohol and ammonia, methyl alcohol and methylamine mixture and ammonia or methylamine mixture and ammonia, use zeolite catalyst and make in the method for methylamine, comprise from the reaction mixture that obtains and to separate purification methylamine class, isolate ammonia and Trimethylamine 99 after, with dimethylamine or contain dimethylamine and the mixture of single methylamine and the operation that ammonia carries out gas-phase reaction more than or equal to 50 moles of % dimethylamine.
When making Trimethylamine 99,, can reduce recirculation flow, thereby can efficient produce Trimethylamine 99 well by making as the dimethylamine of raw material and the dimethylamine content in single methylamine mixture more than or equal to 50 moles of %.And, can increase and decrease Trimethylamine 99 output easily and effectively corresponding to demand shift, realize the high methylamine manufacturing of economy.
Embodiment
Of the present invention it is characterized in that, in the method for making methylamine, after separating purification ammonia and Trimethylamine 99 the reaction mixture that obtains from adopting zeolite catalyst, with dimethylamine or contain, carry out gas-phase reaction with ammonia and make Trimethylamine 99 more than or equal to the dimethylamine of 50 moles of % dimethylamine and the mixture of single methylamine.
The zeolite catalyst that uses in the present invention is preferably to generating the zeolite of the reaction and display shape selective of methylamine, for example mordenite, clinoptilolite, levyne, zeolite A, FU-1, ZSM-5, ZSM-11, ZSM-21, montmorillonite etc. from ammonia and methyl alcohol.Especially preferred mordenite.
Use zeolite catalyst to make the reaction of methylamine mixture,, preferably carry out 250～330 ℃ scope 230～350 ℃ of temperature.Can be normal pressure～5MPaG at pressure, preferably in the scope of 0.5～3MPaG, N/C (the nitrogen-atoms number in the reaction system and the ratio of carbonatoms) 1～2.5 scope and implement.
As the method for from the reaction mixture that obtains, separating the methylamine class, adopt distillation usually.Enumerate concrete example, at first remove ammonia from cat head, remove Trimethylamine 99 by the water filling distillation from the cat head distillation, dewater at the 3rd tower at second tower at first tower, remove single methylamine and remove dimethylamine from the cat head distillation at the 4th tower, thereby can obtain each methylamine from the tower bottom distillation.
Employed catalyzer in the reaction of making Trimethylamine 99, solid acid catalysts such as preferred silicon-dioxide, aluminum oxide, sial.
Make in the reaction of Trimethylamine 99, contain more than or equal to 50 moles of % dimethylamine in the mixture as the dimethylamine of raw material and single methylamine, preferably contain more than or equal to 80 moles of %.Most preferably has only dimethylamine.If dimethylamine is lower than 50 moles of %, then the recirculation flow of mixture increases, and needs to increase the flow that spends single methylamine of energy cost because of distillation most, therefore influences efficient.
Employed ammonia in the reaction of manufacturing Trimethylamine 99 can be raw material ammonia, also can be that unreacted ammonia is used in recirculation.
Use solid acid catalyst to make the reaction of Trimethylamine 99,, preferably carry out 360～420 ℃ scope 350～450 ℃ of temperature.Can be normal pressure～5MPaG at pressure, preferably in the scope of 0.5～3MPaG, N/C (the nitrogen-atoms number in the reaction system and the ratio of carbonatoms) 0.7～2.5 scope and implement.If N/C is too small, then cause the problem such as generation increase, catalyst life shortening of impurity; If excessive, then aspect balance, be unfavorable for generating Trimethylamine 99, the required recirculation flow of Trimethylamine 99 that obtains necessary amount increases.
Dimethylamine or contain more than or equal to the such methylamine class that is obtained by the recirculation reaction of the mixture of the dimethylamine of 50 moles of % dimethylamine and single methylamine can separate to purify and is each methylamine by above-mentioned distillating method.
Embodiment
Below, further specifically describe the present invention according to embodiment, but the present invention is not limited to following embodiment.
Embodiment 1
Adopt mordenite catalyst to carry out the methylamine building-up reactions, separate the resulting methylamine class of purifying.In order to obtain the Trimethylamine 99 of insufficient section, recirculation dimethylamine 8.6kmol/hr (192.6Nm3/hr) by mixing with ammonia 5.1kmol/hr (114.2Nm3/hr), makes N/C become 0.8, under 370 ℃, the condition of 1.8MPa, adopt silica-alumina catalyst to carry out the Trimethylamine 99 building-up reactions.Separate the resulting methylamine class of purifying, obtain single methylamine 1.5kmol/hr, dimethylamine 1.8kmol/hr, Trimethylamine 99 4.1kmol/hr (241kg/hr).
Embodiment 2
Adopt mordenite catalyst to carry out the methylamine building-up reactions, separate the resulting methylamine class of purifying.In order to obtain the Trimethylamine 99 of insufficient section, recirculation dimethylamine 9.2kmol/hr (206.1Nm3/hr) and single methylamine 1.1kmol/hr (24.6Nm3/hr) (dimethylamine 89mol%), by mixing with ammonia 14.1kmol/hr (315.8Nm3/hr), make N/C become 1.25, under 370 ℃, the condition of 1.8MPa, adopt silica-alumina catalyst to carry out the Trimethylamine 99 building-up reactions.Separate the resulting methylamine class of purifying, obtain single methylamine 2.6kmol/hr, dimethylamine 2.3kmol/hr, Trimethylamine 99 4.1kmol/hr (240kg/hr).
Comparative example 1
Adopt mordenite catalyst to carry out the methylamine building-up reactions, separate the resulting methylamine class of purifying.In order to obtain the Trimethylamine 99 of insufficient section, recirculation dimethylamine 2.4kmol/hr (53.8Nm3/hr) and single methylamine 14.7kmol/hr (329.3Nm3/hr) (dimethylamine 14mol%), by mixing with ammonia 7.3kmol/hr (163.5Nm3/hr), make N/C become 1.25, under 370 ℃, the condition of 1.8MPa, adopt silica-alumina catalyst to carry out the Trimethylamine 99 building-up reactions.Separate the resulting methylamine class of purifying, obtain single methylamine 2.6kmol/hr, dimethylamine 2.3kmol/hr, Trimethylamine 99 4.1kmol/hr (240kg/hr).
Comparative example 2
Adopt mordenite catalyst to carry out the methylamine building-up reactions, separate the resulting methylamine class of purifying.In order to obtain the Trimethylamine 99 of insufficient section, recirculation dimethylamine 4.0kmol/hr (89.6Nm3/hr) and single methylamine 18.6kmol/hr (416.6Nm3/hr) (dimethylamine 18mol%), by mixing with ammonia 57.1kmol/hr (1279.0Nm3/hr), make N/C become 3.0, under 370 ℃, the condition of 1.8MPa, adopt silica-alumina catalyst to carry out the Trimethylamine 99 building-up reactions.Separate the resulting methylamine class of purifying, obtain single methylamine 6.8kmol/hr, dimethylamine 3.8kmol/hr, Trimethylamine 99 4.1kmol/hr (240kg/hr).
Claims (2)
1. the manufacture method of Trimethylamine 99, it is characterized in that, by methyl alcohol and ammonia, methyl alcohol and methylamine mixture and ammonia or methylamine mixture and ammonia, use zeolite catalyst and make in the method for methylamine, comprise and from the reaction mixture that obtains, separate purification methylamine class, after isolating ammonia and Trimethylamine 99, make dimethylamine or contain dimethylamine and the mixture of single methylamine and the operation that ammonia carries out gas-phase reaction more than or equal to 50 moles of % dimethylamine.
2. the manufacture method of the described Trimethylamine 99 of claim 1 is characterized in that, carries out gas-phase reaction in the presence of silicon-dioxide, aluminum oxide and/or silica-alumina catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200610074993 CN101062896A (en) | 2006-04-25 | 2006-04-25 | Method for manufacturing trimethylamine |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200610074993 CN101062896A (en) | 2006-04-25 | 2006-04-25 | Method for manufacturing trimethylamine |
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| CN101062896A true CN101062896A (en) | 2007-10-31 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104141148A (en) * | 2014-08-04 | 2014-11-12 | 太原理工大学 | Method for electrochemically synthesizing trimethylamine |
| CN114768276A (en) * | 2022-05-23 | 2022-07-22 | 宁波美成生物科技有限公司 | Dimethylamine purification system and method |
| CN115636751A (en) * | 2022-06-14 | 2023-01-24 | 山东一飞药业股份有限公司 | Production process of trimethylamine hydrochloride |
-
2006
- 2006-04-25 CN CN 200610074993 patent/CN101062896A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104141148A (en) * | 2014-08-04 | 2014-11-12 | 太原理工大学 | Method for electrochemically synthesizing trimethylamine |
| CN114768276A (en) * | 2022-05-23 | 2022-07-22 | 宁波美成生物科技有限公司 | Dimethylamine purification system and method |
| CN114768276B (en) * | 2022-05-23 | 2024-03-29 | 宁波美成生物科技有限公司 | Dimethylamine purification system and method |
| CN115636751A (en) * | 2022-06-14 | 2023-01-24 | 山东一飞药业股份有限公司 | Production process of trimethylamine hydrochloride |
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