CN1123273A - Method for preparation of N-methyl formamide - Google Patents
Method for preparation of N-methyl formamide Download PDFInfo
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- CN1123273A CN1123273A CN 95113010 CN95113010A CN1123273A CN 1123273 A CN1123273 A CN 1123273A CN 95113010 CN95113010 CN 95113010 CN 95113010 A CN95113010 A CN 95113010A CN 1123273 A CN1123273 A CN 1123273A
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- methylformamide
- preparation
- methyl
- formiate
- oxide
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Abstract
The preparation method uses a two-step continuous technological process. First step is to prepare methyl formate by making methyl alcohol pass through the process of catalytic dehydrogenation, and second step is to make methyl formate and methylamine pass through the aminating reaction, then the product is separated and refined. ADVANTAGE-. the technological process is simple, and can make continuous production; the percent conversion of its dehydrogenation catalyst is high, selectivity is high, and its service life can be up to above 2.5 years.
Description
The present invention relates to a kind of preparation method of organic compound, particularly relate to a kind of preparation method of N-methylformamide.
N-methylformamide is a kind of high boiling solvent, is commonly used for pesticide intermediate and organic synthesis raw material.Prior preparation method mainly contains three kinds, the first, and carbon monoxide and one step of methylamine high pressure catalysis synthesis process, though operational path is short, product separation and catalyst recirculation flow process are complicated, and high pressure reactor is had relatively high expectations, and technology difficulty is big.It two is, formic acid and methylamine one-step synthesis, and technology is simple, but the formic acid seriously corroded, the separating device investment is bigger.It three is, methyl alcohol and formic acid synthesize methyl-formiate, and with synthetic N-methylformamide of two steps of methylamine, small-scale production adopts this method more again, but expense of raw materials is higher, periodical operation, and technology falls low, has had the formic acid corrosion and has contained problem such as sour sewage disposal.
The object of the present invention is to provide a kind of is raw material with methyl alcohol, adopts the preparation method of the N-methylformamide of two step method continuous processing.
The preparation method of N-methylformamide of the present invention is, with methyl alcohol is raw material, at first enter vaporizer, be heated and be vaporized into steam, enter dehydrogenation reactor after overheated and carry out catalytic dehydrogenation, reaction conditions is 150～350 ℃ of temperature, and pressure 0～0.2MPa, catalyzer are the composite catalysts that contains multiple oxide compound.The required heat of dehydrogenation reaction can be supplied with by the thermal cyclic carrier heating system that process furnace provides, and enters the separation and purification system after the reaction product cooling, generally carries out in distillation tower.Return vaporizer after wherein unconverted methyl alcohol separates and recycle, hydrogen containing tail gas can be delivered to PSA-H
2Carry hydrogen production device and reclaim pure hydrogen, content greater than/equal that 97% refining methyl-formiate is delivered to the amination reaction device and anhydrous methylamine carries out amination reaction.The condition of amination reaction is 0～90 ℃ of a temperature, and pressure 0～1.5MPa, optimum operation condition are 20～60 ℃ of temperature, and pressure 0.1～0.6MPa also can carry out under normal pressure.Its proportion of raw materials is a methyl-formiate: methylamine=1.02～1.15: 1.The selectivity of amination reaction is greater than 99%.The amination reaction product enters separation system, generally in distillation tower, carry out, a small amount of superfluous amination reaction thing returns the amination reaction device and recycles, N-methylformamide crude product carry out rectifying again, make purity at last greater than refining N-methylformamide product of 99.5%.
Among the preparation method of N-methylformamide of the present invention, the composite catalyst component that the methanol dehydrogenation reaction is adopted comprises (with weight %) cupric oxide 8～88, zinc oxide 5～40, aluminum oxide 5～44, Vanadium Pentoxide in FLAKES 1～10, sodium oxide 0.1～0.5.
The characteristics of this composite catalyst are that low temperature active is good, have good active in 180～280 ℃ of scopes.Selectivity reaches 82～97%, and transformation efficiency reaches 30～45%, methyl-formiate and unconverted methyl alcohol is only arranged, separate easily in the reaction liquid phase; Contain 80～85% hydrogen in the gas phase, through PSA～H
2Carry and to produce pure hydrogen behind the hydrogen production device and directly make fuel etc. as commodity selling or gaseous products.Industrially take all factors into consideration its selectivity, transformation efficiency and yield, 210～240 ℃ of general controlled temperature.In addition, catalyzer reaches more than 2.5 years work-ing life.The raw material of this composite catalyst is easy to get, the oxyhydroxide of its metal, and inorganic salt and organic salt all can be used as the preparation raw material, avoid using precious metal.The preparation method be with copper, zinc, aluminium salt on request ratio be dissolved in the water, use the yellow soda ash co-precipitation, after filtration, the washing after, be to add in the dry process phosphoric acid salt, sodium oxide etc., again through the calcining, compressing tablet makes, and uses H before the use
2Or activation such as CO gas activity.
N of the present invention-methylformamide preparation method's advantage is to adopt serialization production, compares with the old technology of intermittent type, has not only improved production efficiency greatly, and constant product quality, be significantly improved, raw material sources are convenient, simple to operate, productive expense is low, and the three wastes of methanol dehydrogenation reaction are few.Catalyst selectivity height, transformation efficiency height, long service life.
Describe the embodiment of the invention in detail below in conjunction with accompanying drawing.
Fig. 1: process flow diagram of the present invention
Embodiment 1:
Preparation of Catalyst
Take by weighing 105.5 gram Cn (NO
3)
2, 3H
2O, 36.6 gram Zn (NO
3)
26H
2O, 37.4 gram Al (NO
3)
39H
2O is soluble in water; Take by weighing 75 gram Na
2CO
3Soluble in water, to incorporate into after the preheating respectively in the reactor, reaction finishes after wash, filters, drying, adds AlPO again
4, after processing such as calcining, make cylindrical catalyst again.The result is as shown in table 1 for this catalyst test.
In fixed bed dehydrogenation reactor, fill above-mentioned dehydrogenation catalyst 1000 grams, methyl alcohol enters in the reactor after overheated through vaporizing with the 1390g/h flow velocity, 190 ℃ of control reaction temperature, pressure 0.1MPa, reaction product enters distillation tower and carries out separation and purification, make the methyl-formiate of purity 97%, enter the amination reaction device with the 440g/h flow again, anhydrous methylamine steam adds with the 2670ml/min flow velocity, the amination reaction temperature is 40 ℃, carry out under the normal pressure, reaction product gets N-methylformamide crude product through fractionation by distillation, get the refining N-methylformamide product of purity 99.9% again after rectifying, its quality index is as shown in table 3.
Embodiment 2:
Preparation of Catalyst
Take by weighing 126.5 gram Cn ((NO
3)
2, 3H
2O, 32.9 gram Zn (NO
3)
26H
2O, 67.3 gram Al (NO
3)
39H
2O is soluble in water; Take by weighing 108 gram Na
2CO
3Soluble in water, its in preparation process with embodiment 1.The result is as shown in table 2 for this catalyst test.
In fixed bed dehydrogenation reactor, fill above-mentioned dehydrogenation catalyst 1050 grams, methyl alcohol enters in the reactor after overheated through vaporizing with 1408 gram/h flow velocitys, 230 ℃ of control reaction temperature, pressure is normal pressure, reaction product enters distillation tower and carries out separation and purification, make the methyl-formiate of purity 97%, enter the amination reaction device with the 445g/h flow again, anhydrous methylamine steam adds with the 2688ml/min flow velocity, the amination reaction temperature is 60 ℃, pressure is 0.6MPa, and reaction product gets N-methylformamide crude product through fractionation by distillation, get the refining N-methylformamide product of purity 99.9% again after rectifying, its quality index is as shown in table 3.
Table 1: test
Table 1: test
| Numbering | Temperature of reaction ℃ | During air speed-1 | Transformation efficiency % | Selectivity |
| ??1 | ????180 | ????1072 | ????30.2 | ????92.5 |
| ??2 | ????190 | ????1265 | ????30.5 | ????91.6 |
| ??3 | ????200 | ????1220 | ????34.0 | ????88.0 |
| ??4 | ????210 | ????1130 | ????35.1 | ????87.1 |
| ??5 | ????220 | ????1043 | ????37.3 | ????87.2 |
| ??6 | ????230 | ????1064 | ????40.6 | ????84.4 |
| Test number | Temperature of reaction ℃ | During air speed-1 | Transformation efficiency % | Selectivity |
| ????1 | ????200 | ????1032 | ????33.5 | ????93.4 |
| ????2 | ????210 | ????1024 | ????34.6 | ????90.2 |
| ????3 | ????220 | ????1056 | ????36.1 | ????87.1 |
| ????4 | ????230 | ????1018 | ????43.4 | ????85.0 |
| ????5 | ????240 | ????1105 | ????44.2 | ????82.9 |
Table 3:N-methylformamide quality index
| Color and luster (metal plate-cobalt colorimetric) | Content % | Moisture content % | Acidity (in formic acid) % | |
| Embodiment 1 | ????＜15 | ????99.9 | ≤0.048 | ????≤9(PPm) |
| Embodiment 2 | ????＜15 | ????99.9 | ≤0.048 | ????≤9(PPm) |
Claims (4)
1, a kind of preparation method of N-methylformamide is characterized in that adopting the two step method continuous processing, and the first step methyl alcohol is produced methyl-formiate through catalytic dehydrogenation; Second ground beetle acid methyl esters and methylamine reaction generate N-methylformamide.
2, the preparation method of N-methylformamide as claimed in claim 1, it is characterized in that methanol dehydrogenation is reflected in the fixed-bed reactor carries out, reaction conditions is 150～350 ℃ of temperature, pressure 0～0.2MPa, catalyzer is the composite catalyst that contains multiple oxide compound, products therefrom behind separation and purification content greater than/equal 97% methyl-formiate.
3, the preparation method of N-methylformamide as claimed in claim 2 is characterized in that the composite catalyst component comprises (in weight %) cupric oxide 8～88, zinc oxide 5～40, aluminum oxide 5～44, Vanadium Pentoxide in FLAKES 1～10, sodium oxide 0.1～0.5.
4, the preparation method of N-methylformamide as claimed in claim 1, the reaction conditions that it is characterized in that methyl-formiate is 0～90 ℃ of a temperature, pressure 0～1.5MPa, products therefrom through separate, after the rectifying purity greater than/equal the N-methylformamide product more than 99.5%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95113010A CN1049885C (en) | 1995-09-27 | 1995-09-27 | Method for preparation of N-methyl formamide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95113010A CN1049885C (en) | 1995-09-27 | 1995-09-27 | Method for preparation of N-methyl formamide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1123273A true CN1123273A (en) | 1996-05-29 |
| CN1049885C CN1049885C (en) | 2000-03-01 |
Family
ID=5079803
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95113010A Expired - Lifetime CN1049885C (en) | 1995-09-27 | 1995-09-27 | Method for preparation of N-methyl formamide |
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| Country | Link |
|---|---|
| CN (1) | CN1049885C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102942500A (en) * | 2012-11-16 | 2013-02-27 | 常州大学 | Preparation method of N-formamide compound |
| CN102164671B (en) * | 2008-09-26 | 2013-11-06 | 三菱瓦斯化学株式会社 | Methanol dehydrogenation catalyst for producing methyl formate and method for producing methyl formate |
| CN105330559A (en) * | 2015-10-14 | 2016-02-17 | 宿迁新亚科技有限公司 | Electronic-grade formamide compound preparation method |
| CN108892623A (en) * | 2018-06-18 | 2018-11-27 | 苏州盖德精细材料有限公司 | The high-efficiency synthesis method of N-METHYLFORMAMIDE |
-
1995
- 1995-09-27 CN CN95113010A patent/CN1049885C/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102164671B (en) * | 2008-09-26 | 2013-11-06 | 三菱瓦斯化学株式会社 | Methanol dehydrogenation catalyst for producing methyl formate and method for producing methyl formate |
| CN102942500A (en) * | 2012-11-16 | 2013-02-27 | 常州大学 | Preparation method of N-formamide compound |
| CN102942500B (en) * | 2012-11-16 | 2014-08-27 | 常州大学 | Preparation method of N-formamide compound |
| CN105330559A (en) * | 2015-10-14 | 2016-02-17 | 宿迁新亚科技有限公司 | Electronic-grade formamide compound preparation method |
| CN108892623A (en) * | 2018-06-18 | 2018-11-27 | 苏州盖德精细材料有限公司 | The high-efficiency synthesis method of N-METHYLFORMAMIDE |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1049885C (en) | 2000-03-01 |
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