CN105198754B - One kind prepares N, the method for the propane diamine of N dimethyl 1,3 - Google Patents
One kind prepares N, the method for the propane diamine of N dimethyl 1,3 Download PDFInfo
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Abstract
N is prepared the present invention relates to one kind, be added to acrylonitrile in synthesis reactor by the method for the propane diamine of N dimethyl 1,3, add dimethylamine, N, N dimethylaminopropionitriles is obtained by rectification under vacuum removal dimethylamine；Hydrogenation catalyst is added, to liquefied ammonia is passed through in autoclave, hydrogen is passed through, reacted, fore-running after sedimentation, rectifying obtains N, the propane diamine of N dimethyl 1,3.The invention provides a kind of method for preparing DMAPA, process is simple, it is ensured that the raising of selectivity, the yield of unit weight slag is greatly reduced, saved the processing cost of a large amount of dangerous wastes；The consumption of raw material propylene nitrile and dimethylamine is reduced, the consumption of raw materials cost of DMAPA synthesizers has been saved, that is, saves production cost, improve company interest.
Description
Technical field
The invention belongs to field of fine chemical, it is related to one kind to prepare N, N- dimethyl -1, the method for 3- propane diamine.
Background technology
Diamines is the important chemical substance of a class, is widely used as raw material, intermediate or product, and such as diamines is synthesis polyamides
Important feature unit during amine and in other polycondensation reactions.
N, N- dimethyl -1,3- propane diamine（DMAPA）It is a kind of important intermediate, for the industry system of such as lubricant
Standby, in addition, DMAPA is used as to prepare the raw material of coagulant, itself should have antiseptic property.
Patent CN102617356A is summarized the synthetic method of DMAPA, but is had with domestic production synthetic method
Institute is different.Main cause is domestic main for the purpose of producing DMAPA, and the synthetic method that the patent is provided is with effectively using phase
For the purpose of the nitrile raw material answered.
At present, the production technology of domestic main flow is acrylonitrile and dimethylamine synthesis N, N- dimethyl propionitrile, then by N, N- bis-
Methyl propionitrile is solvent, is also raw material, in the case where the temperature and appropriate liquefied ammonia examined are used as inhibitor, in Raney's nickel catalyst
The lower high-pressure hydrogenation of effect prepares thick propane diamine, and country's propionitrile prepares the selectivity of propane diamine in 95-96% at present, wherein there is 2-
3% heavy constituent impurity is produced so that domestic DMAPA devices produce the substantial amounts of heavy slag to need treatment every year, for professional production third
Be undoubtedly for the device of diamines one it is very worried and have the problem wasted raw material with production cost so that Some Enterprises must not
Secondary amine is not reclaimed, the ratio yet with secondary amine is very low, weight slag viscosity is larger, reclaim separating difficulty very big, it is necessary to volume
Outer increase Technical investment and set up rectifying device and reclaimed, greatly increase investment and the production operating cost of DMAPA devices.
The content of the invention
It is an object of the invention in order to solve existing DMAPA synthesizers produce every year substantial amounts of heavy slag need treatment,
Not only production and operation had been wasted raw material but also had increased to produce this defect and one kind is provided and is easy to large-scale industry to prepare, and had in preparation process
Effect ground improves the selectivity that propionitrile prepares DMAPA, reduces synthesis material, and especially the consumption of acrylonitrile, also greatly reduces
The content of secondary amine in product, it is to avoid contain excessive heavy slag in product, reduces DMAPA and the investment and production running into device
Preparation N, N- dimethyl -1 of cost, the method for 3- propane diamine.
To achieve these goals, the present invention uses following technical scheme：
One kind prepares N, and N- dimethyl -1, the method for 3- propane diamine the described method comprises the following steps：
a）Acrylonitrile is added in synthesis reactor, 120-140 DEG C of temperature, stirring, the condition of cooling water circulation cooling is controlled
Lower addition dimethylamine, N, N- dimethylaminopropionitriles are obtained by rectification under vacuum removal dimethylamine；
b）By step a）Obtained N, N- dimethylaminopropionitrile add autoclave, hydrogenation catalyst are added, to autoclave
Liquefied ammonia is inside passed through, 80-95 DEG C is warming up to, pressure is maintained at 2.5-3MPa, be passed through hydrogen, stir 80-95 DEG C of keeping temperature simultaneously,
Reaction, fore-running after sedimentation, rectifying obtains N, N- dimethyl -1,3- propane diamine, then basin packaging.In the technical program, system
Nitrile reactive chemistry equation：（CH3）2NH+CH2=CHCN→（CH3）2NCH2CH2CN
Hydrogenation reaction chemical equation：（CH3）2NCH2CH2CN+2H2→（CH3）2NCH2CH2CH2NH2
Side reaction： CH2=CHCN + 3H2 → CH3CH2CH2NH2。
Preferably, step a）In, acrylonitrile is 1 with the mol ratio of dimethylamine:1.
Preferably, the mol ratio of hydrogenation catalyst and N, N- dimethyl propionitrile is 10:1.
Preferably, cut during fore-running by temperature more than 134 DEG C sends into rectifying.
Preferably, the preparation method of hydrogenation catalyst is as follows：Weigh by weight 65-70 parts of Ni, 55-60 part of Al with
10-12 parts of auxiliary additive, cools down after being melted at 3200-3300 DEG C, crushed 300-400 mesh sieves and obtains alloy powder, will
Alloy powder is activated in alkali lye, applies the magnetic field of 1.5-1.8T while activation in outside, and it is 10.2- to be washed out to pH value
11.3, products therefrom is hydrogenation catalyst.
In the technical program, the high catalytic activity of Raney's nickel comes from nickel catalytic property in itself and its porous knot
Structure, and loose structure is to be derived from the aluminium removed with strong caustic in nickel alumin(i)um alloy, this process is referred to as leaching, letter
Leach reaction after change is as follows：
2Al + 2NaOH + 6H2O → 2Na[Al(OH)4] + 3H2
The activity of catalyst is brought due to Leach reaction, while the hydrogen storage for producing has been entered in catalyst, therefore also referred to as
For activation.The surface area of finished product generally passes through gas（Such as hydrogen）Adsorption experiment measure.Experiment finds almost all of
Contact area all has nickel.The average nickel contact area of commercialized Raney's nickel is 100 ㎡/g.
Preferably, the auxiliary additive is Graphene, nano titanium oxide, lanthana or nano silicon.
In the technical program, the presence of auxiliary additive is in order to improve activity to Raney's nickel, due to Raney's nickel activity height and surface
The quantity in activated centre is relevant, and superficial density big person's catalysis activity in activated centre is high, and auxiliary additive selection specific surface area is big
Material so that Active sites quantity increases, so as to improve the catalysis activity of Raney's nickel, and increases in preparation process
Magnetic field so that the sequence in activated centre is more smooth, so as to further increase its catalysis activity.
Preferably, the alkali lye is the sodium hydroxide solution of mass fraction 38-40%.
Preferably, before alloy powder activation with the dimethyl formamide solution of mass concentration 30-50% and acid solution according to
1g：40-50mL：The solid-liquid ratio mixing of 15-20mL, stirs mixing 60-75min at 95-100 DEG C of temperature of control, filtering is used respectively
Water and absolute ethanol washing, are vacuum dried 15-20min and obtain primary modified alloy powder at 160-180 DEG C；By primary modified alloy
Powder is with chemical shearing liquid according to 1g：The solid-liquid ratio mixing of 45-55mL, is heated to 280-320 DEG C, and hydro-thermal reaction 2-3h is cooled down,
Washing, obtains secondary modified alloy powder；The perchloric acid of secondary modified alloy powder and mass concentration 50-60% is according to 1g：35-
The solid-liquid ratio of 45mL is well mixed, and is heated to 180-220 DEG C and is kept for 10 hours, and cooling, filtering, washing must change after vacuum drying
Property alloy powder.It is in the technical program, alloy powder is molten with the dimethyl formamide solution of mass concentration 30-50% and acid
Liquid mixes, while it is aided with stirring, to expand the contact surface of alloy powder and liquid so that alloy powder is uniformly dispersed, and quality is dense
The dimethyl formamide solution of 30-50% and the specific solvent combined system of acid solution are spent, enables to the alloy powder can be in system
Middle dispersion evenly, is prevented effectively from alloy powder reunion.
First nm inorganic compound particle is uniformly dispersed, so beneficial to follow-up shearing, by finely dispersed nano inorganic
Compound particle and the specific chemical shearing liquid hydro-thermal reaction of the present invention, can effectively cut off alloy powder, obtain length more uniform
（Length is about in 100-150nm）The homogeneous alloy powder of left and right.
Then by homogeneous alloy powder in perchloric acid hydro-thermal reaction, perchloric acid molecule being capable of intercalation, swelling alloyed powder
End, makes alloy powder be separated from each other and its surface high reaction activity is exposed, so as to realize selectively functionalized.
Preferably, acid solution is the concentrated sulfuric acid of concentrated nitric acid and the mass concentration 98% of mass concentration 70% according to 2.5-3.2:
The mixture of 1 volume ratio.
Preferably, chemical shearing liquid is the sodium molybdate solution and concentration 0.6-0.8moL/L of concentration 0.9-1.2moL/L
Silicomolybdic acid solution is according to 1:The mixture of 1 volume ratio.
Beneficial effects of the present invention：
1）The invention provides a kind of method for preparing DMAPA, process is simple, it is ensured that the raising of selectivity, subtract significantly
Lack the yield of unit weight slag, save the processing cost of a large amount of dangerous wastes；
2）The method of the present invention reduces the consumption of raw material propylene nitrile and dimethylamine, has saved the original of DMAPA synthesizers
Material consuming cost, that is, save production cost, improves company interest；
3）The method of the present invention is easy to large-scale industry to prepare, and propionitrile preparation DMAPA is effectively improved in preparation process
Selectivity, reduce the content that synthesis material also greatly reduces secondary amine in product, it is to avoid in product contain excessive heavy slag,
Reduce DMAPA and the investment into device and production operating cost.
Brief description of the drawings
Fig. 1 is that one kind of the present invention prepares N, N- dimethyl -1, the process chart of the method for 3- propane diamine.
Specific embodiment
Explanation is further described to technical scheme below by specific embodiment.
If without specified otherwise, the raw material employed in embodiments of the invention is raw material commonly used in the art, implements
Method employed in example, is the conventional method of this area.
Embodiment 1
Reference picture 1, one kind prepares N, and N- dimethyl -1, the method for 3- propane diamine the described method comprises the following steps：
a）Acrylonitrile is added in synthesis reactor, 120 DEG C of temperature is controlled, added under conditions of stirring, cooling water circulation cooling
Enter dimethylamine, dimethylamine is removed by rectification under vacuum, pressure 0.03MPa is obtained N, N- dimethylaminopropionitriles；Acrylonitrile and two
The mol ratio of methylamine is 1:1；
b）By step a）Obtained N, N- dimethylaminopropionitrile add autoclave, hydrogenation catalyst are added, to autoclave
Liquefied ammonia is inside passed through, 80 DEG C are warming up to, pressure is maintained at 2.5MPa, be passed through hydrogen, stirring 80 DEG C of keeping temperature, reaction simultaneously is sunk
Fore-running after drop, rectifying obtains N, N- dimethyl -1,3- propane diamine, then basin packaging；Hydrogenation catalyst and N, N- dimethyl propylene
The mol ratio of nitrile is 10:1；Cut feeding rectifying during fore-running by temperature more than 134 DEG C takes reaction solution detection in autoclave,
DMAPA contents 99.4%, propionitrile residual volume 0.01%, light component impurity content 0.15%, heavy constituent impurity content 0.61%, wherein secondary
Amine 0.37%.
The preparation method of hydrogenation catalyst is as follows：65 parts of Ni, 55 parts of Al and 10 part of auxiliary additives are weighed by weight
Nano silicon, cools down after being melted at 3200 DEG C, crushed 300 mesh sieves and obtains alloy powder, by alloy powder in alkali lye
Middle activation, applies the magnetic field of 1.5T in outside while activation, it is 10.2 to be washed out to pH value, and products therefrom is hydrogenation and urges
Agent.The alkali lye is the sodium hydroxide solution of mass fraction 38%.
Alloy powder activates the dimethyl formamide solution and acid solution of preceding and mass concentration 30% according to 1g：40mL：15mL
Solid-liquid ratio mixing, control 95 DEG C of temperature at stir mixing 60min, filtering, respectively with water and absolute ethanol washing, at 160 DEG C
Vacuum drying 15min obtains primary modified alloy powder；By primary modified alloy powder and chemical shearing liquid according to 1g：The material of 45mL
Liquor ratio mixes, and is heated to 280 DEG C, and hydro-thermal reaction 2h, cooling, washing obtains secondary modified alloy powder；Secondary modified alloy powder
With the perchloric acid of mass concentration 50% according to 1g：The solid-liquid ratio of 35mL is well mixed, and is heated to 180 DEG C and is kept for 10 hours, cooling,
Filtering, washing obtains modified alloy powder after vacuum drying.
Acid solution is the concentrated nitric acid of mass concentration 70% and the concentrated sulfuric acid of mass concentration 98% according to 2.5:1 volume ratio it is mixed
Compound.Chemical shearing liquid is the sodium molybdate solution of concentration 0.9moL/L and the silicomolybdic acid solution of concentration 0.6moL/L according to 1:1
The mixture of volume ratio.
Embodiment 2
Reference picture 1, one kind prepares N, and N- dimethyl -1, the method for 3- propane diamine the described method comprises the following steps：
a）Acrylonitrile is added in synthesis reactor, 130 DEG C of temperature is controlled, added under conditions of stirring, cooling water circulation cooling
Enter dimethylamine, dimethylamine is removed by rectification under vacuum, pressure is 0.04MPa, N, N- dimethylaminopropionitriles is obtained；Acrylonitrile with
The mol ratio of dimethylamine is 1:1；
b）By step a）Obtained N, N- dimethylaminopropionitrile add autoclave, hydrogenation catalyst are added, to autoclave
Liquefied ammonia is inside passed through, 90 DEG C are warming up to, pressure is maintained at 2.8MPa, be passed through hydrogen, stirring 90 DEG C of keeping temperature, reaction simultaneously is sunk
Fore-running after drop, rectifying obtains N, N- dimethyl -1,3- propane diamine, then basin packaging；Hydrogenation catalyst and N, N- dimethyl propylene
The mol ratio of nitrile is 10:1；Cut during fore-running by temperature more than 134 DEG C sends into rectifying.Reaction solution detection in autoclave is taken,
DMAPA contents 99.2%, propionitrile residual volume 0.01%, light component impurity content 0.08%, heavy constituent impurity content 0.51%, wherein secondary
Amine 0.16%.
The preparation method of hydrogenation catalyst is as follows：68 parts of Ni, 58 parts of Al and 11 part of auxiliary additives are weighed by weight
Graphene, is cooled down after being melted at 3250 DEG C, crushed 350 mesh sieves and obtains alloy powder, and alloy powder is activated in alkali lye,
Apply the magnetic field of 1.7T while activation in outside, it is 10.8 to be washed out to pH value, and products therefrom is hydrogenation catalyst.
The alkali lye is the sodium hydroxide solution of mass fraction 39%.
Alloy powder activates the dimethyl formamide solution and acid solution of preceding and mass concentration 45% according to 1g：45mL：18mL
Solid-liquid ratio mixing, control 98 DEG C of temperature at stir mixing 70min, filtering, respectively with water and absolute ethanol washing, at 180 DEG C
Vacuum drying 18min obtains primary modified alloy powder；By primary modified alloy powder and chemical shearing liquid according to 1g：The material of 50mL
Liquor ratio mixes, and is heated to 300 DEG C, and hydro-thermal reaction 2.5h, cooling, washing obtains secondary modified alloy powder；Secondary modified alloy powder
The perchloric acid of end and mass concentration 55% is according to 1g：The solid-liquid ratio of 40mL is well mixed, and is heated to 200 DEG C and is kept for 10 hours, cold
But, filter, washing obtains modified alloy powder after vacuum drying.
Acid solution is the concentrated nitric acid of mass concentration 70% and the concentrated sulfuric acid of mass concentration 98% according to 3:The mixing of 1 volume ratio
Thing.Chemical shearing liquid is the sodium molybdate solution of concentration 1moL/L and the silicomolybdic acid solution of concentration 0.7moL/L according to 1:1 volume
The mixture of ratio.
Embodiment 3
Reference picture 1, one kind prepares N, and N- dimethyl -1, the method for 3- propane diamine the described method comprises the following steps：
a）Acrylonitrile is added in synthesis reactor, 140 DEG C of temperature is controlled, added under conditions of stirring, cooling water circulation cooling
Enter dimethylamine, dimethylamine is removed by rectification under vacuum, pressure 0.05MPa is obtained N, N- dimethylaminopropionitriles；Acrylonitrile and two
The mol ratio of methylamine is 1:1；
b）By step a）Obtained N, N- dimethylaminopropionitrile add autoclave, hydrogenation catalyst are added, to autoclave
Liquefied ammonia is inside passed through, 95 DEG C are warming up to, pressure is maintained at 3MPa, be passed through hydrogen, stirring 95 DEG C of keeping temperature, reaction simultaneously is settled
Fore-running afterwards, rectifying obtains N, N- dimethyl -1,3- propane diamine, then basin packaging；Hydrogenation catalyst and N, N- dimethyl propionitrile
Mol ratio be 10:1；Cut during fore-running by temperature more than 134 DEG C sends into rectifying.Take reaction solution detection, DMAPA in autoclave
Content 98.9%, propionitrile residual volume 0.01%, light component impurity content 0.12%, wherein heavy constituent impurity content 0.87%, secondary amine
0.23%。
The preparation method of hydrogenation catalyst is as follows：70 parts of Ni, 60 parts of Al and 12 part of auxiliary additives are weighed by weight
Nano titanium oxide, cools down after being melted at 3300 DEG C, crushed 400 mesh sieves and obtains alloy powder, by alloy powder in alkali lye
Middle activation, applies the magnetic field of 1.8T in outside while activation, it is 11.3 to be washed out to pH value, and products therefrom is hydrogenation and urges
Agent.The alkali lye is the sodium hydroxide solution of mass fraction 40%.
Alloy powder activates the dimethyl formamide solution and acid solution of preceding and mass concentration 50% according to 1g：50mL：20mL
Solid-liquid ratio mixing, control 100 DEG C of temperature at stir mixing 75min, filtering, respectively with water and absolute ethanol washing, 180 DEG C
Lower vacuum drying 20min obtains primary modified alloy powder；By primary modified alloy powder and chemical shearing liquid according to 1g：55mL's
Solid-liquid ratio mixes, and is heated to 320 DEG C, and hydro-thermal reaction 3h, cooling, washing obtains secondary modified alloy powder；Secondary modified alloy powder
The perchloric acid of end and mass concentration 60% is according to 1g：The solid-liquid ratio of 45mL is well mixed, and is heated to 220 DEG C and is kept for 10 hours, cold
But, filter, washing obtains modified alloy powder after vacuum drying.
Acid solution is the concentrated nitric acid of mass concentration 70% and the concentrated sulfuric acid of mass concentration 98% according to 3.2:1 volume ratio it is mixed
Compound.Chemical shearing liquid is the sodium molybdate solution of concentration 1.2moL/L and the silicomolybdic acid solution of concentration 0.8moL/L according to 1:1
The mixture of volume ratio.
Claims (4)
1. one kind prepares N, N- dimethyl -1, the method for 3- propane diamine, it is characterised in that the described method comprises the following steps：
a）Acrylonitrile is added in synthesis reactor, 120-140 DEG C of temperature is controlled, added under conditions of stirring, cooling water circulation cooling
Enter dimethylamine, N, N- dimethylaminopropionitriles is obtained by rectification under vacuum removal dimethylamine；
b）By step a）Obtained N, N- dimethylaminopropionitrile add autoclave, add hydrogenation catalyst, lead to in autoclave
Enter liquefied ammonia, be warming up to 80-95 DEG C, pressure is maintained at 2.5-3MPa, be passed through hydrogen, stir 80-95 DEG C of keeping temperature simultaneously, instead
Should, fore-running after sedimentation, rectifying obtains N, N- dimethyl -1,3- propane diamine, then basin packaging；Hydrogenation catalyst and N, N- diformazan
The mol ratio of base propionitrile is 10:1；
Wherein, the preparation method of hydrogenation catalyst is as follows：65-70 parts Ni, 55-60 part Al and 10-12 parts is weighed by weight
Auxiliary additive, cools down after being melted at 3200-3300 DEG C, crushed 300-400 mesh sieves and obtains alloy powder, by alloy powder
Activated in alkali lye, apply the magnetic field of 1.5-1.8T while activation in outside, it is 10.2-11.3, institute to be washed out to pH value
Obtain product and be hydrogenation catalyst；The auxiliary additive is Graphene or nano silicon；
Alloy powder activates the dimethyl formamide solution and acid solution of preceding and mass concentration 30-50% according to 1g：40-50mL：
The solid-liquid ratio mixing of 15-20mL, stirs mixing 60-75min, filtering, respectively with water and anhydrous second at 95-100 DEG C of temperature of control
Alcohol is washed, and 15-20min is vacuum dried at 160-180 DEG C and obtains primary modified alloy powder；By primary modified alloy powder and chemistry
Shearing liquid is according to 1g：The solid-liquid ratio mixing of 45-55mL, is heated to 280-320 DEG C, and hydro-thermal reaction 2-3h, cooling, washing obtains secondary
Level modified alloy powder；The perchloric acid of secondary modified alloy powder and mass concentration 50-60% is according to 1g：The solid-liquid ratio of 35-45mL
It is well mixed, is heated to 180-220 DEG C and is kept for 10 hours, cooling, filtering, washing obtains modified alloy powder after vacuum drying；Acid
Solution is the concentrated nitric acid of mass concentration 70% and the concentrated sulfuric acid of mass concentration 98% according to 2.5-3.2:The mixture of 1 volume ratio；
Chemical shearing liquid is the sodium molybdate solution of concentration 0.9-1.2moL/L and the silicomolybdic acid solution of concentration 0.6-0.8moL/L according to 1:1
Volume ratio mixture.
2. one kind according to claim 1 prepares N, N- dimethyl -1, the method for 3- propane diamine, it is characterised in that step
a）In, acrylonitrile is 1 with the mol ratio of dimethylamine:1.
3. one kind according to claim 1 prepares N, N- dimethyl -1, the method for 3- propane diamine, it is characterised in that fore-running
When by temperature more than 134 DEG C cut send into rectifying.
4. one kind according to claim 1 prepares N, N- dimethyl -1, the method for 3- propane diamine, it is characterised in that described
Alkali lye is the sodium hydroxide solution of mass fraction 38-40%.
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| CN110252322A (en) * | 2019-07-05 | 2019-09-20 | 安徽天择化工有限公司 | A kind of quaternary Raney nickel, preparation method and its application |
| CN113200870A (en) * | 2021-05-07 | 2021-08-03 | 大连理工大学 | Process for continuously preparing N, N-dimethyl-1, 3-propane diamine by using micro-mixing and fixed bed reactor |
| CN113501761B (en) * | 2021-07-16 | 2023-08-11 | 万华化学集团股份有限公司 | Method for continuously producing N, N-diethyl-1, 3-propanediamine by one-step method |
| CN116199588A (en) * | 2023-01-10 | 2023-06-02 | 大连理工大学 | Method for preparing N- (2-hydroxyethyl) -1, 3-propanediamine in semi-continuous mode by combining Y-type micro-mixing reactor and high-pressure reaction kettle |
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| US2877113A (en) * | 1955-07-23 | 1959-03-10 | Siemens Planiawerke Ag | Method of producing sintered nickelaluminum articles |
| US5869653A (en) * | 1997-10-30 | 1999-02-09 | Air Products And Chemicals, Inc. | Hydrogenation of nitriles to produce amines |
| US8710269B2 (en) * | 2010-07-29 | 2014-04-29 | Basf Se | DMAPN having a low DGN content and a process for preparing DMAPA having a low DGN content |
| CN104084219B (en) * | 2014-07-08 | 2016-02-24 | 赛鼎工程有限公司 | A kind of preparation method and application being applicable to fixed bed methanation Raney's nickel catalyst |
| CN104492449A (en) * | 2014-12-08 | 2015-04-08 | 九江天赐高新材料有限公司 | Preparation method of hydrogenation catalyst and method for synthesizing DMAPA (dimethyl amionopropylamine) by applying catalyst |
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Denomination of invention: A method for preparing N, n-dimethyl-1,3-propanediamine Effective date of registration: 20201223 Granted publication date: 20170623 Pledgee: Zhejiang Jiangshan rural commercial bank Limited by Share Ltd. Pledgor: ZHEJIANG HILL CHEMICAL Co.,Ltd. Registration number: Y2020330001267 |
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