CN103922957B - A kind of preparation method of continuous production DEF - Google Patents
A kind of preparation method of continuous production DEF Download PDFInfo
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- CN103922957B CN103922957B CN201410107373.9A CN201410107373A CN103922957B CN 103922957 B CN103922957 B CN 103922957B CN 201410107373 A CN201410107373 A CN 201410107373A CN 103922957 B CN103922957 B CN 103922957B
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- diethylamine
- methyl formate
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Abstract
The present invention relates to a kind of production method of DEF. A preparation method for continuous production DEF, in the reactor that is filled with heterogeneous catalysis, will be converted into DEF by amidation process after diethylamine and methyl formate mixing, then by the refining finished product DEF that obtains; Diethylamine and methyl formate mol ratio are 1.0 ~ 1.1:1.0, and liquid phase air speed is 1.0 ~ 20.0h-1, reaction temperature control is 10 ~ 80 DEG C, reaction pressure (gauge pressure) is normal pressure ~ 0.2MPa. Method yield of the present invention is high, and owing to not needing, higher methyl formate and diethylamine mol ratio and diethylamine conversion ratio are high, and therefore whole process supplies consumption is few. The present invention develops preparation method the production that makes DEF is tending towards to serialization, and this will make production efficiency raising, investment and the production cost of process significantly reduce.
Description
Technical field:
The present invention relates to a kind of production method of DEF.
Background technology:
N, N-DEF (DEF), English N by name, N-Diethylformamide, is abbreviated as DEF; MoleculeFormula is C5H11NO; Molecular weight is 101.15; Density 0.9049,177 ~ 178 DEG C of boiling points, for water white low-density highBoiling point polar organic solvent, with water and alcohol, ether, ketone, benzene etc. are miscible, have very strong dissolubility, can dissolve many organic polymersThing, as polyacrylonitrile, urethane prepolymer, PVC, vinylidene chloride-vinyl chloride copolymer, polyvinyl formal, poly-The high molecular polymers such as acid imide, therefore DEF can be used as industrial solvent replacement DMF (DMF), and poisonSide effect is less than DMF out and away. In addition DEF synthesizes field and also has potential using value at the synthetic field of fiber, medicine,
Liu Xingquan etc. disclose the synthetic method of a kind of DEF, taking diethylamine (DEA) and carbon monoxide as raw material, through liquidPhase carbonylation synthesizes DEF (DEF). Its optimum reaction condition is: CO dividing potential drop is less than 6.0MPa, and reaction temperature is 80DEG C to 90 DEG C, catalyst concn is not more than 0.05mol/L, and co-catalyst PO concentration is not more than 4.0mol/L, now selectively notBe less than 96%. (" applied chemistry ", 1996, (5) 1-4DOI:ISSN:1000-0518CN:22-1128/O6) the method needsUse dangerous carbon monoxide, and reactor pressure is higher, cost of investment is high, and the follow-up expoxy propane that relates in additionSeparation problem.
The patent No. is: the patent of invention of CN201210550639.8 discloses a kind of N, the preparation side of N-DEFMethod, particularly a kind ofly prepares highly purified N, the preparation method of N-DEF taking diethylamine and methyl formate as raw material.It uses batch reactor, and does not use catalyst accelerated reaction, therefore needs reaction time of growing and larger firstAcid methyl esters and diethylamine mol ratio, and diethylamine residue is more. These defects can cause needs to use larger reactor, andAnd easily catch fire and wait extreme danger, separating energy consumption and supplies consumption increase.
Summary of the invention:
In order to overcome existing N, not enough in the industrial process of N-DEF (DEF), improve securityCan, and reduce production costs, the invention provides a kind of N, the preparation method of N-DEF.
The present invention is taking methyl formate and diethylamine as raw material, and main reaction equation is as follows:
HCOOCH3+HN（CH2CH3）2——CH3OH+HCO-N（CH2CH3）2
Technical scheme provided by the invention is:
A preparation method for continuous production DEF, in the reactor that is filled with heterogeneous catalysis, willDiethylamine and methyl formate are converted into DEF by amidation process after mixing, then by the refining finished product diethyl that obtainsBase formamide; Diethylamine and methyl formate mol ratio are 1.0 ~ 1.1:1.0, and liquid phase air speed is 1.0 ~ 20.0h-1, reaction temperature controlBe made as 10 ~ 80 DEG C, reaction pressure (gauge pressure) is normal pressure ~ 0.2MPa. Described process is in diethylamine, the one way of DEFYield can reach more than 99%.
Concrete, the chemical composition of described heterogeneous catalysis is aluminium oxide, zinc oxide, calcium oxide, manganese oxide, oxidationOne or more mixtures in magnesium, barium monoxide, silica, zirconia, titanium oxide.
Preferably, the chemical composition of described heterogeneous catalysis is aluminium oxide, zinc oxide, calcium oxide, magnesia, oxidationOne or more mixtures in zirconium.
Preferably, described heterogeneous catalysis is the one in spherical, strip, Raschig ring shape, maximum length sizeBe less than 5mm.
Preferably, described heterogeneous catalysis is that particulate is suspended in reactor, be atomicly of a size of 0.1 ~0.5mm。
Concrete, described reaction condition is that diethylamine and methyl formate mol ratio are 1.0 ~ 1.10:1.0, liquid phase air speedBe 5.0 ~ 10.0h-1, reaction temperature control is 40 ~ 60 DEG C, reaction pressure (gauge pressure) is normal pressure ~ 0.1MPa. In diethylamine, twoThe once through yield of ethyl-formamide can reach more than 99.5%.
Preferably, it is characterized in that, described diethylamine water content is in 1wt%.
Preferably, it is characterized in that, the methanol content in methyl formate is 0wt% ~ 20wt%.
Preferably, described reactor is the tubular reactor of sealing
Gained DEF of the present invention is thick product, can be high-purity by thick product purification by traditional rectificating methodProduct, concrete method is known as the professionals. Lift a concrete scheme as follows:
First by thick product introduction the first atmospheric distillation tower, 10 ~ 30 DEG C of tower top temperature controls, tower reactor temperature control 60 ~ 90DEG C, overhead product is byproduct methyl alcohol and unreacted methyl formate, diethylamine, tower reactor is the thick DEF with certain colourity, thenBottom product is entered to the second atmospheric distillation tower, control 170 ~ 180 DEG C of tower reactor temperature, collect the colourless limpid product of tower top, DEF is pureDegree is more than 99.8%.
With respect to existing DEF production technology, method of the present invention has the following advantages:
1) method yield of the present invention is high, owing to not needing higher methyl formate and diethylamine mol ratio and diethylAmine conversion ratio is high, and therefore whole process supplies consumption is few.
2) method equipment size of the present invention is little, and industry is amplified simple, and the relative prior art investment of cost is less.
3) method Environmental Safety of the present invention.
4) the present invention develops preparation method the production that makes DEF is tending towards to serialization, and this will make the production of processEfficiency raising, investment and production cost significantly reduce.
Detailed description of the invention
Following examples are to more detailed the describing for example of the present invention, but the present invention is not limited to these embodiment.
Embodiment 1
A preparation method for continuous production DEF is anti-in the tubular type of sealing that is filled with heterogeneous catalysisAnswer in device, will diethylamine and methyl formate be converted into DEF by amidation process after mixing, by refiningTo finished product DEF.
Reaction condition is: diethylamine and methyl formate mol ratio are 1.0 ~ 1.1:1.0, and liquid phase air speed is 15.0h-1, reactionTemperature control is 80 DEG C, and reaction pressure (gauge pressure) is normal pressure ~ 0.2MPa. The chemical composition of described heterogeneous catalysis is: oxygenChange aluminium, magnesia and zirconic mixture.
Described heterogeneous catalysis is strip, and maximum length is of a size of 2mm.
Described diethylamine water content 0.2wt%.
Methanol content in methyl formate is 0.1wt%.
Measure exported product, diethylamine conversion ratio is that 99.3%, DEF selectively approaches 100%.
Embodiment 2
A preparation method for continuous production DEF is anti-in the tubular type of sealing that is filled with heterogeneous catalysisAnswer in device, will diethylamine and methyl formate be converted into DEF by amidation process after mixing, by refiningTo finished product DEF.
Reaction condition is: diethylamine and methyl formate mol ratio are 1.0 ~ 1.1:1.0, and liquid phase air speed is 10.0h-1, reactionTemperature control is 60 DEG C, and reaction pressure (gauge pressure) is normal pressure ~ 0.2MPa. The chemical composition of described heterogeneous catalysis is: oxygenChange the mixture of titanium, calcium oxide.
Described heterogeneous catalysis is spherical, and maximum length is of a size of 3mm.
Described diethylamine water content is 0.1wt%.
Methanol content in methyl formate is 0.05wt%.
Measure exported product, diethylamine conversion ratio is that 99.5%, DEF selectively approaches 100%.
Embodiment 3
A preparation method for continuous production DEF is anti-in the tubular type of sealing that is filled with heterogeneous catalysisAnswer in device, will diethylamine and methyl formate be converted into DEF by amidation process after mixing, by refiningTo finished product DEF.
Reaction condition is: diethylamine and methyl formate mol ratio are 1.0 ~ 1.1:1.0, and liquid phase air speed is 5.0h-1, reaction temperatureIt is 50 DEG C that degree is controlled, and reaction pressure (gauge pressure) is normal pressure ~ 0.2MPa. The chemical composition of described heterogeneous catalysis is: oxidationAluminium, magnesia and zirconic mixture.
Described heterogeneous catalysis is spherical, and maximum length is of a size of 1.5mm.
Described diethylamine water content is 0.4wt%.
Methanol content in methyl formate is 0.08wt%.
Measure exported product, diethylamine conversion ratio is that 99.5%, DEF selectively approaches 100%.
Embodiment 4
A preparation method for continuous production DEF is anti-in the tubular type of sealing that is filled with heterogeneous catalysisAnswer in device, will diethylamine and methyl formate be converted into DEF by amidation process after mixing, by refiningTo finished product DEF.
Reaction condition is: diethylamine and methyl formate mol ratio are 1.0 ~ 1.1:1.0, and liquid phase air speed is 8.0.0h-1, reactionTemperature control is 42 DEG C, and reaction pressure (gauge pressure) is normal pressure ~ 0.1MPa. The chemical composition of described heterogeneous catalysis is: oxygenChange aluminium, magnesia and zirconic mixture.
Described heterogeneous catalysis is Raschig ring shape, and maximum length is of a size of 4mm.
Described diethylamine water content is 0.05wt%.
Methanol content in methyl formate is 0.02wt%.
Measure exported product, diethylamine conversion ratio is that 99.7%, DEF selectively approaches 100%.
Embodiment 5
A preparation method for continuous production DEF is anti-in the tubular type of sealing that is filled with heterogeneous catalysisAnswer in device, will diethylamine and methyl formate be converted into DEF by amidation process after mixing, by refiningTo finished product DEF.
Reaction condition is: diethylamine and methyl formate mol ratio are 1.0 ~ 1.1:1.0, and liquid phase air speed is 3.0.0h-1, reactionTemperature control is 20 DEG C, and reaction pressure (gauge pressure) is normal pressure ~ 0.1MPa. The chemical composition of described heterogeneous catalysis is: oxygenChange magnesium and zirconic mixture.
Described heterogeneous catalysis is Raschig ring shape, and maximum length is of a size of 4mm.
Described diethylamine water content is 0.04wt%.
Methanol content in methyl formate is 2wt%.
Measure exported product, diethylamine conversion ratio is that 99.6%, DEF selectively approaches 100%.
Embodiment 6
A preparation method for continuous production DEF is anti-in the tubular type of sealing that is filled with heterogeneous catalysisAnswer in device, will diethylamine and methyl formate be converted into DEF by amidation process after mixing, by refiningTo finished product DEF.
Reaction condition is: diethylamine and methyl formate mol ratio are 1.0 ~ 1.1:1.0, and liquid phase air speed is 10.0.0h-1, anti-Answering temperature control is 55 DEG C, and reaction pressure (gauge pressure) is normal pressure ~ 0.1MPa. The chemical composition of described heterogeneous catalysis is:The mixture of aluminium oxide, zinc oxide, calcium oxide, manganese oxide, magnesia, barium monoxide, silica, zirconia and titanium oxide.
Described heterogeneous catalysis is that particulate is suspended in reactor, the atomic 0.1 ~ 0.5mm that is of a size of.
Described diethylamine water content is 0.07wt%.
Methanol content in methyl formate is 3wt%.
Measure exported product, diethylamine conversion ratio is that 99.8%, DEF selectively approaches 100%.
Embodiment 7
A preparation method for continuous production DEF is anti-in the tubular type of sealing that is filled with heterogeneous catalysisAnswer in device, will diethylamine and methyl formate be converted into DEF by amidation process after mixing, by refiningTo finished product DEF.
Reaction condition is: diethylamine and methyl formate mol ratio are 1.0 ~ 1.1:1.0, and liquid phase air speed is 13.0.0h-1, anti-Answering temperature control is 65 DEG C, and reaction pressure (gauge pressure) is normal pressure ~ 0.1MPa. The chemical composition of described heterogeneous catalysis is:The mixture of manganese oxide, magnesia, barium monoxide, silica, zirconia and titanium oxide.
Described heterogeneous catalysis is that particulate is suspended in reactor, the atomic 0.1 ~ 0.5mm that is of a size of.
Described diethylamine water content is 0.06wt%.
Methanol content in methyl formate is 5wt%.
Measure exported product, diethylamine conversion ratio is that 99.5%, DEF selectively approaches 100%.
Finally should be noted that: above embodiment is only in order to illustrate that technical scheme of the present invention is not intended to limit; To the greatest extentPipe has been described in detail the present invention with reference to preferred embodiment, and those of ordinary skill in the field are to be understood that: stillCan modify or part technical characterictic is equal to replacement the specific embodiment of the present invention; And do not depart from thisThe spirit of bright technical scheme, it all should be encompassed in the middle of the technical scheme scope of request protection of the present invention.
Claims (9)
1. a preparation method who produces continuously DEF, is characterized in that: be filled with the anti-of heterogeneous catalysisAnswer in device, will diethylamine and methyl formate be converted into DEF by amidation process after mixing, then by refiningTo finished product DEF; Diethylamine and methyl formate mol ratio are 1.0 ~ 1.1:1.0, and liquid phase air speed is 1.0 ~ 20.0h-1，Reaction temperature control is 10 ~ 80 DEG C, and reaction pressure is counted normal pressure ~ 0.2MPa with gauge pressure.
2. the preparation method of a kind of continuous production DEF according to claim 1, is characterized in that, describedThe chemical composition of heterogeneous catalysis is aluminium oxide, zinc oxide, calcium oxide, manganese oxide, magnesia, barium monoxide, silica, oxygenChange one or more mixtures in zirconium, titanium oxide.
3. the production method of a kind of continuous production DEF according to claim 1, is characterized in that, describedThe chemical composition of heterogeneous catalysis is one or more mixing in aluminium oxide, zinc oxide, calcium oxide, magnesia, zirconiaThing.
4. according to the production method of a kind of continuous production DEF described in claim 1 or 2 or 3, it is characterized in that,Described heterogeneous catalysis is the one in spherical, strip, Raschig ring shape, and maximum length size is less than 5mm.
5. according to the production method of a kind of continuous production DEF described in claim 1 or 2 or 3, it is characterized in that,Described heterogeneous catalysis is that particulate is suspended in reactor, the atomic 0.1 ~ 0.5mm that is of a size of.
6. the production method of a kind of continuous production DEF according to claim 1, is characterized in that, describedReaction condition is that diethylamine and methyl formate mol ratio are 1.0 ~ 1.10:1.0, and liquid phase air speed is 5.0 ~ 10.0h-1, reaction temperatureControl is 40 ~ 60 DEG C, and reaction pressure is counted normal pressure ~ 0.1MPa with gauge pressure.
7. according to the production method of a kind of continuous production DEF described in claim 1 or 2 or 3 or 6, its feature existsIn, described diethylamine water content is in 1wt%.
8. according to the production method of a kind of continuous production DEF described in claim 1 or 2 or 3 or 6, its feature existsIn, the methanol content in methyl formate is 0wt% ~ 20wt%.
9. according to the production method of a kind of continuous production DEF described in claim 1 or 2 or 3 or 6, its feature existsIn, described reactor is the tubular reactor of sealing.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104262189A (en) * | 2014-10-11 | 2015-01-07 | 昊华(成都)科技有限公司 | Method for liquid-phase preparation of high-purity N, N-diethylformamide |
| CN107286041A (en) * | 2016-04-01 | 2017-10-24 | 成都川科化工有限公司 | A kind of preparation method of N, N- diethylformamide |
| CN106563438B (en) * | 2016-10-12 | 2020-01-03 | 中海油天津化工研究设计院有限公司 | Catalyst for synthesizing amide and method for synthesizing N, N-dimethylpropionamide |
| CN111253263B (en) * | 2020-02-17 | 2022-07-05 | 北京弗莱明科技有限公司 | Preparation method of chloroquine key intermediate 2-amino-5-diethylaminopentane |
| CN111253277A (en) * | 2020-03-31 | 2020-06-09 | 迈奇化学股份有限公司 | Production method of N, N-diethyl acetamide |
| CN115385813A (en) * | 2022-08-25 | 2022-11-25 | 宿迁新亚科技有限公司 | Production process for preparing dibutyl formamide |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101072748A (en) * | 2004-12-06 | 2007-11-14 | 巴斯福股份公司 | Method for the production of n,n-dimethylacetamide (DMAC) |
| CN103012183A (en) * | 2012-12-18 | 2013-04-03 | 王传良 | Preparation method of N,-N-diethyl-formamide |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101072748A (en) * | 2004-12-06 | 2007-11-14 | 巴斯福股份公司 | Method for the production of n,n-dimethylacetamide (DMAC) |
| CN103012183A (en) * | 2012-12-18 | 2013-04-03 | 王传良 | Preparation method of N,-N-diethyl-formamide |
Non-Patent Citations (1)
| Title |
|---|
| Facile N-formylation of amines using Lewis acids as novel catalysts;A. Chandra Shekhar et al;《Tetrahedron Letters》;20091008;第50卷;第7099-7101页 * |
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Inventor after: Song Guoquan Inventor after: Xiao Qiang Inventor after: Yang Li Inventor after: Yan Guangxue Inventor after: Wu Yanbin Inventor after: Wu Zhengling Inventor before: Song Guoquan Inventor before: Xiao Qiang Inventor before: Yang Li Inventor before: Yan Guangxue |
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