CN109422657A - The method of the separation while coproduction Carbox amide of methylamine mixed gas - Google Patents
The method of the separation while coproduction Carbox amide of methylamine mixed gas Download PDFInfo
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- CN109422657A CN109422657A CN201710769459.1A CN201710769459A CN109422657A CN 109422657 A CN109422657 A CN 109422657A CN 201710769459 A CN201710769459 A CN 201710769459A CN 109422657 A CN109422657 A CN 109422657A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/82—Purification; Separation; Stabilisation; Use of additives
- C07C209/86—Separation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/08—Preparation of carboxylic acid amides from amides by reaction at nitrogen atoms of carboxamide groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/10—Preparation of carboxylic acid amides from compounds not provided for in groups C07C231/02 - C07C231/08
Abstract
The present invention relates to the methods of the separation while coproduction Carbox amide of methylamine mixed gas, by methylamine gaseous mixture, monomethyl amine and dimethylamine and CO especially in the high methylamine gaseous mixture of monomethyl amine and dimethylamine ratio are carbonylated and are turned amidation process, after separation conversion, obtain high purity trimethylamine, the method of coproduction formamide and n,N-Dimethylformamide simultaneously.Using the mixed gas of CO gas and methylamine as reactant, in Ru/CeO2Under the action of catalyst; monomethyl amine is selective to occur carbonylation generation formamide with CO, and then formamide and dimethylamine turn acylation reaction generation n,N-Dimethylformamide; to achieve the purpose that purify trimethylamine, while two kinds of Carbox amides of coproduction.Catalyst after use can be reused after carrying out roasting reduction.Method of the invention is easy to operate, at low cost, can be used for scale separation methylamine mixed gas, and high yield coproduction formyl class compound.
Description
Technical field
The present invention relates to a kind of methods for separating methylamine mixed gas, and in particular to by the first in methylamine gaseous mixture
After amine and dimethylamine and the conversion of CO Reaction Separation, the method for obtaining high purity trimethylamine, the i.e. separation of methylamine mixed gas are simultaneously
The method of coproduction Carbox amide, while coproduction Carbox amide.
Background technique
Methylamine mixed gas is the mixture common name of monomethyl amine (MMA), dimethylamine (DMA) and trimethylamine (TMA).Wherein one
Methylamine is mainly used for pesticide, medicine, dyestuff, surfactant, aqueous gels, fuel, photographic process medicine, gas purifying agent and
Industrial solvent.Dimethylamine is mainly used for pesticide, medicine, rubber accelerator, fat tertiary amine, industrial solvent (DMF), dimethylacetamide
Amine (DMA) etc. and organic intermediate.Trimethylamine is also smaller at present as the dosage of feed addictive, but what it increased
Space is also very big.Methylamine be mainly used for stink additive of pesticide, choline chloride, natural gas etc. (Yang Deqin methylamine technology newly into
Exhibition [J] fine chemical material and intermediate, 2007, (11): 8-10).
The mixed gas multi-pass of methylamine crosses the acquisition of methanol ammoniation process at present.Using methanol and ammonia as raw material vapor phase method synthesis of methylamines
Process study, start from 1958, after years development, formd balanced type and unbalanced type methylamine catalyst
And technique two major classes.Found in research process, the technological parameter during methanol ammonification, such as reaction temperature, time of contact and
Charge ratio etc. is able to achieve the distribution of three kinds of components in methylamine mixed gas.Therefore, three kinds of methylamine molecules of preparative separation need by
Complicated rectification section.Due between methylamine molecule there are azeotropism, have biggish energy consumption in separation process.Therefore
A kind of method for developing simply and effectively separation methylamine molecule, has important researching value and potential application background.
For the main component dimethylamine in methylamine gaseous mixture, important industrial application is to pass through carbonylation with CO
Prepare N,N-dimethylformamide.This patent is directed to the characteristics of methylamine mixed gas, by the approach of catalysis selection reaction, especially
It is the weaker front three amine gas of separation reactivity in the gaseous mixture for high dimethylamine gas ratio, and using carbonylation and turns
The reaction such as acylated, coproduction Carbox amide, due to being gas under Carbox amide normal temperature and pressure, with unreacted
Front three amine gas be easily isolated, and reaction process is simple, and used catalyst preparation is easy, and stability is preferable, is suitble to work
Industry metaplasia produces.
Summary of the invention
Meaning of the present invention is the separation process for overcoming traditional front three amine gas cumbersome, expeditiously from methylamine gaseous mixture
Trimethylamine, and high yield coproduction Carbox amide are purified in body.
Separation methylamine mixed gas of the present invention is realized by following scheme: by the monomethyl amine in methylamine mixed gas
After separating conversion with CO gas reaction with dimethylamine, high purity trimethylamine, the method for coproduction Carbox amide, by Ru are obtained
The metal oxide catalyst of load is filled in fixed bed reactors, is introduced methylamine gaseous mixture and CO gas, is passed through a first
The carbonylation and dimethylamine of amine and CO turn acylation reaction with product formamide, to reach the mesh of purifying trimethylamine
's.
Gas after reaction is front three amine gas after purification, and liquid phase is the Carbox amide of coproduction, chromatography detection
Liquid product, solid-phase catalyst are recycled through simple roasting and reduction process.
The metal oxide catalyst of the Ru load, wherein metal oxide is MoO3、CuO、Co3O4、Nb2O5、
Fe2O3、VO2、CeO2One or more of；Ru content of metal are as follows: 0.5wt%~10wt%；The metal oxygen of the Ru load
The preparation of compound catalyst uses immersion reduction method or coprecipitation.Loading catalyst thickness of bed layer is in the reaction tube
5mm~30mm, the flow velocity of methylamine mixed gas are as follows: 5~33mLmin-1, the flow velocity of CO gas are as follows: 5~33mLmin-1, instead
Answer pressure for 0.5~4MPa, 150 DEG C~250 DEG C of reaction temperature；The preferable thickness of bed layer of loading catalyst is in the reaction tube
10mm~15mm, the preferable flow velocity of methylamine mixed gas are as follows: 10~25mLmin-1, the preferable flow velocity of CO gas are as follows: 10~
25mL·min-1, reacting preferable pressure is 1~3MPa, and preferable reaction temperature is 150 DEG C~200 DEG C of reaction temperature.
This method is using the mixed gas of CO gas and methylamine as reactant, under the action of Ru catalyst, monomethyl amine
Selective that carbonylation generation formamide occurs with CO, then formamide and dimethylamine turn acylation reaction generation N, N- bis-
Methylformamide, to achieve the purpose that purify trimethylamine, while two kinds of Carbox amides of coproduction.
Its reaction process is as follows: Ru catalyst being filled in fixed bed reactors, methylamine gaseous mixture and CO gas are introduced
Body, the flow velocity of methylamine mixed gas are as follows: 5~33mLmin-1, the flow velocity of CO gas are as follows: 5~33mLmin-1, reaction pressure
For 0.5~4MPa, 150 DEG C~250 DEG C of reaction temperature, from the 10%~50% of the reaction initial stage, highest can increase CO concentration
It is dense to 90% or more.Liquid product is mainly Carbox amide, selectivity up to 99%.Catalyst after use
It can be reused after carrying out roasting reduction.Method of the invention is easy to operate, at low cost, and less energy consumption can be used for scale
Separate methylamine mixed gas, and high yield coproduction formyl class compound.
Compared with existing method, the present invention has following advantage:
1, it is effectively reduced the methods of traditional rectifying separation huge energy consumption of bring, equipment is simple, is suitble to large-scale
Commercial process；
2, the selectivity of coproduction product Carbox amide is high, can reach 95% or more；
3, catalyst preparation is simple, can be by existing chemical engineering unit operation, and stability is preferable and can be for a long time
Operation uses；
The present invention relates to one kind to pass through catalysis reaction, by the monomethyl amine in methylamine gaseous mixture, dimethylamine and CO Reaction Separation
After conversion, the method that separation obtains high purity trimethylamine, while coproduction Carbox amide, realize the mechanism of the above process such as
Shown in Fig. 1:
Detailed description of the invention
Fig. 1 is illustrated by the reaction process that Reaction Separation obtains high purity trimethylamine while coproduction Carbox amide
Figure；With Ru/CeO2For catalyst, it is as follows to describe above-mentioned reaction process respectively: Ru is as active site while activating monomethyl amine,
Carbonylation occurs for dimethylamine and CO molecule, generates formamide and n,N-Dimethylformamide (reacting 1 and 2)；Support C eO2
As reducibility oxide, there is certain acid-base property after reduction, can be catalyzed formamide and dimethylamine to turn acylation reaction (anti-
It answers 3).Compared with monomethyl amine and dimethylamine, for trimethylamine due to the presence of not no N-H, the carbonylation that can not be carried out between N-H is anti-
Should with turn acylation reaction, therefore it is last be still used as gas, reactor is left, to achieve the purpose that separation.
Specific embodiment
In order to which the present invention will be described in further detail, several specific implementation cases are given below, but the present invention is unlimited
In these embodiments.
Embodiment 1
Weigh 20g MoO3It is immersed in 48.6mmolL-1Hydrate ruthenium trichloride solution in, stir 20h at room temperature,
130 DEG C of dryings restore 3h under 350 DEG C of hydrogen atmospheres, and 2wt%Ru/MoO is made3, molding sieve take 14-25 mesh catalyst fill to
In reaction tube, 15mm bed is filled, under the pressure of 3.0MPa, the flow velocity of methylamine mixed gas is 10mLmin-1, wherein one
Methylamine: dimethylamine: trimethylamine=1:2:1 (volume ratio), the flow velocity of raw material CO are 10mLmin-1.It is reacted at 200 DEG C, every
2h sampling, the concentration of trimethylamine increase to 73%；Chromatography, the overall selectivity of Carbox amide are 90%.
Embodiment 2
It weighs 20g CuO and is immersed in 48.6mmolL-1Hydrate ruthenium trichloride solution in, stir 20h at room temperature, 130
DEG C drying restores 3h under 350 DEG C of hydrogen atmospheres, 2wt%Ru/CuO is made, molding sieve takes 14-25 mesh catalyst to fill to reaction
Guan Zhong fills 15mm bed, reaction tube is placed in fixed bed reactors after catalyst filling in reaction tube, 3.0MPa's
Under pressure, the flow velocity of methylamine mixed gas is 10mLmin-1, wherein monomethyl amine: dimethylamine: trimethylamine=1:2:1 (volume
Than), the flow velocity of raw material CO is 10mLmin-1.It reacts at 200 DEG C, is sampled every 2h, the concentration of trimethylamine increases to 78%；
Chromatography, the overall selectivity of Carbox amide are 92%.
Embodiment 3
Weigh 20g Co3O4It is immersed in 48.6mmolL-1Hydrate ruthenium trichloride solution in, stir 20h at room temperature,
130 DEG C of dryings restore 3h under 350 DEG C of hydrogen atmospheres, and 2wt%Ru/Co is made3O4, molding sieve take 14-25 mesh catalyst fill to
In reaction tube, 15mm bed is filled, reaction tube is placed in fixed bed reactors after catalyst filling in reaction tube,
Under the pressure of 3.0MPa, the flow velocity of methylamine mixed gas is 10mLmin-1, wherein monomethyl amine: dimethylamine: trimethylamine=1:2:1
(volume ratio), the flow velocity of raw material CO are 10mLmin-1.It reacts at 200 DEG C, is sampled every 2h, the concentration of trimethylamine increases to
86%；Chromatography, the overall selectivity of Carbox amide are 89%.
Embodiment 4
Weigh 20g Nb2O5It is immersed in 48.6mmolL-1Hydrate ruthenium trichloride solution in, stir 20h at room temperature,
130 DEG C of dryings restore 3h under 350 DEG C of hydrogen atmospheres, and 2wt%Ru/Nb is made2O5, molding sieve take 14-25 mesh catalyst fill to
In reaction tube, 15mm bed is filled, reaction tube is placed in fixed bed reactors after catalyst filling in reaction tube,
Under the pressure of 3.0MPa, the flow velocity of methylamine mixed gas is 10mLmin-1, wherein monomethyl amine: dimethylamine: trimethylamine=1:2:1
(volume ratio), the flow velocity of raw material CO are 10mLmin-1.It reacts at 200 DEG C, is sampled every 2h, the concentration of trimethylamine increases to
88%；Chromatography, the overall selectivity of Carbox amide are 94%.
Embodiment 5
Weigh 20g Fe2O3It is immersed in 48.6mmolL-1Hydrate ruthenium trichloride solution in, stir 20h at room temperature,
130 DEG C of dryings restore 3h under 350 DEG C of hydrogen atmospheres, and 2wt%Ru/Fe is made2O3, molding sieve take 14-25 mesh catalyst fill to
In reaction tube, 15mm bed is filled, reaction tube is placed in fixed bed reactors after catalyst filling in reaction tube,
Under the pressure of 3.0MPa, the flow velocity of methylamine mixed gas is 10mLmin-1, wherein monomethyl amine: dimethylamine: trimethylamine=1:2:1
(volume ratio), the flow velocity of raw material CO are 10mLmin-1.It reacts at 200 DEG C, is sampled every 2h, the concentration of trimethylamine increases to
70%；Chromatography, the overall selectivity of Carbox amide are 85%.
Embodiment 6
Weigh 20g VO2It is immersed in 48.6mmolL-1Hydrate ruthenium trichloride solution in, stir 20h at room temperature, 130
DEG C drying restores 3h under 350 DEG C of hydrogen atmospheres, 2wt%Ru/VO is made2, molding, which is sieved, takes 14-25 mesh catalyst to fill to reaction
Guan Zhong fills 15mm bed, reaction tube is placed in fixed bed reactors after catalyst filling in reaction tube, 3.0MPa's
Under pressure, the flow velocity of methylamine mixed gas is 10mLmin-1, wherein monomethyl amine: dimethylamine: trimethylamine=1:2:1 (volume
Than), the flow velocity of raw material CO is 10mLmin-1.It reacts, is sampled every 2h, chromatography at 200 DEG C, the concentration of trimethylamine increases
Add to 79%；Chromatography, the overall selectivity of Carbox amide are 90%.
Embodiment 7
Weigh 20g CeO2It is immersed in 48.6mmolL-1Hydrate ruthenium trichloride solution in, stir 20h at room temperature,
130 DEG C of dryings restore 3h under 350 DEG C of hydrogen atmospheres, and 2wt%Ru/CeO is made2, molding sieve take 14-25 mesh catalyst fill to
In reaction tube, 15mm bed is filled, reaction tube is placed in fixed bed reactors after catalyst filling in reaction tube,
Under the pressure of 3.0MPa, the flow velocity of methylamine mixed gas is 10mLmin-1, wherein monomethyl amine: dimethylamine: trimethylamine=1:2:1
(volume ratio), the flow velocity of raw material CO are 10mLmin-1.It reacts, is sampled every 2h, chromatography at 200 DEG C, trimethylamine
Concentration increases to 90%；Chromatography, the overall selectivity of Carbox amide are 99%.
Embodiment 8
It weighs 60g cerium nitrate hexahydrate to be dissolved in 60mL water, a certain amount of hydrate ruthenium trichloride is added, stirring is straight at room temperature
To being mixed thoroughly, ammonium hydroxide is added dropwise to dropwise in above-mentioned solution, adjusts pH=10, is continued to stir 4h at room temperature, is separated by filtration,
130 DEG C of dryings restore 3h under 350 DEG C of hydrogen atmospheres, and 2wt%Ru/CeO is made2, molding sieve take 14-25 mesh catalyst fill to
In reaction tube, 15mm bed is filled, reaction tube is placed in fixed bed reactors after catalyst filling in reaction tube,
Under the pressure of 3.0MPa, the flow velocity of methylamine mixed gas is 10mLmin-1, wherein monomethyl amine: dimethylamine: trimethylamine=1:2:1
(volume ratio), the flow velocity of raw material CO are 10mLmin-1.It reacts, is sampled every 2h, chromatography at 200 DEG C, trimethylamine
Concentration increases to 85%；Chromatography, the overall selectivity of Carbox amide are 93%.
Embodiment 9
It weighs 60g cerium nitrate hexahydrate to be dissolved in 60mL water, a certain amount of hydrate ruthenium trichloride is added, stirring is straight at room temperature
To being mixed thoroughly, ammonium hydroxide is added dropwise to dropwise in above-mentioned solution, adjusts pH=11, is continued to stir 4h at room temperature, is separated by filtration,
130 DEG C of dryings restore 3h under 350 DEG C of hydrogen atmospheres, and 5wt%Ru/CeO is made2, molding sieve take 40-60 mesh catalyst fill to
In reaction tube, 10mm bed is filled, reaction tube is placed in fixed bed reactors after catalyst filling in reaction tube,
Under the pressure of 2.0MPa, the flow velocity of methylamine mixed gas is 5mLmin-1, wherein monomethyl amine: dimethylamine: trimethylamine=1:2:1
(volume ratio), the flow velocity of raw material CO are 5mLmin-1.Reacted at 150 DEG C, every 2h sample, chromatography, trimethylamine it is dense
Degree increases to 65%；Chromatography, the overall selectivity of Carbox amide are 95%.
Embodiment 10
It weighs 60g cerium nitrate hexahydrate to be dissolved in 60mL water, a certain amount of hydrate ruthenium trichloride is added, stirring is straight at room temperature
To being mixed thoroughly, ammonium hydroxide is added dropwise to dropwise in above-mentioned solution, adjusts pH=11, is continued to stir 4h at room temperature, is separated by filtration,
130 DEG C of dryings restore 3h under 350 DEG C of hydrogen atmospheres, and 5wt%Ru/CeO is made2, molding sieve take 40-60 mesh catalyst fill to
In reaction tube, 10mm bed is filled, reaction tube is placed in fixed bed reactors after catalyst filling in reaction tube,
Under the pressure of 2.0MPa, the flow velocity of methylamine mixed gas is 5mLmin-1, wherein monomethyl amine: dimethylamine: trimethylamine=1:2:1
(volume ratio), the flow velocity of raw material CO are 5mLmin-1.Reacted at 250 DEG C, every 2h sample, chromatography, trimethylamine it is dense
Degree increases to 85%；Chromatography, the overall selectivity of Carbox amide are 85%.
Embodiment 11
It weighs 60g cerium nitrate hexahydrate to be dissolved in 60mL water, a certain amount of hydrate ruthenium trichloride is added, stirring is straight at room temperature
To being mixed thoroughly, ammonium hydroxide is added dropwise to dropwise in above-mentioned solution, adjusts pH=11, is continued to stir 4h at room temperature, is separated by filtration,
130 DEG C of dryings restore 3h under 350 DEG C of hydrogen atmospheres, and 5wt%Ru/CeO is made2, molding sieve take 40-60 mesh catalyst fill to
In reaction tube, 20mm bed is filled, reaction tube is placed in fixed bed reactors after catalyst filling in reaction tube,
Under the pressure of 4.0MPa, the flow velocity of methylamine mixed gas is 25mLmin-1, wherein monomethyl amine: dimethylamine: trimethylamine=1:2:1
(volume ratio), the flow velocity of raw material CO are 25mLmin-1.It reacts, is sampled every 2h, chromatography at 200 DEG C, trimethylamine
Concentration increases to 76%；Chromatography, the overall selectivity of Carbox amide are 90%.
Embodiment 12
It weighs 60g cerium nitrate hexahydrate to be dissolved in 60mL water, a certain amount of hydrate ruthenium trichloride is added, stirring is straight at room temperature
To being mixed thoroughly, ammonium hydroxide is added dropwise to dropwise in above-mentioned solution, adjusts pH=11, is continued to stir 4h at room temperature, is separated by filtration,
130 DEG C of dryings restore 3h under 350 DEG C of hydrogen atmospheres, and 5wt%Ru/CeO is made2, molding sieve take 40-60 mesh catalyst fill to
In reaction tube, 20mm bed is filled, reaction tube is placed in fixed bed reactors after catalyst filling in reaction tube,
Under the pressure of 2.0MPa, the flow velocity of methylamine mixed gas is 15mLmin-1, wherein monomethyl amine: dimethylamine: trimethylamine=1:2:1
(volume ratio), the flow velocity of raw material CO are 15mLmin-1.It reacts, is sampled every 2h, chromatography at 200 DEG C, trimethylamine
Concentration increases to 86%；Chromatography, the overall selectivity of Carbox amide are 92%.
Embodiment 13
Weigh 20g CeO2It is immersed in 48.6mmolL-1Hydrate ruthenium trichloride solution in, stir 20h at room temperature,
130 DEG C of dryings restore 3h under 350 DEG C of hydrogen atmospheres, and 2wt%Ru/CeO is made2, molding sieve take 14-25 mesh catalyst fill to
In reaction tube, 15mm bed is filled, reaction tube is placed in fixed bed reactors after catalyst filling in reaction tube,
Under the pressure of 3.0MPa, the flow velocity of methylamine mixed gas is 10mLmin-1, wherein monomethyl amine: dimethylamine: trimethylamine=1:2:3
(volume ratio), the flow velocity of raw material CO are 10mLmin-1.It reacts, is sampled every 2h, chromatography at 200 DEG C, trimethylamine
Concentration increases to 95%；Chromatography, the overall selectivity of Carbox amide are 99%.
Embodiment 14
Weigh 20g CeO2It is immersed in 48.6mmolL-1Hydrate ruthenium trichloride solution in, stir 20h at room temperature,
130 DEG C of dryings restore 3h under 350 DEG C of hydrogen atmospheres, and 2wt%Ru/CeO is made2, molding sieve take 14-25 mesh catalyst fill to
In reaction tube, 15mm bed is filled, reaction tube is placed in fixed bed reactors after catalyst filling in reaction tube,
Under the pressure of 3.0MPa, the flow velocity of methylamine mixed gas is 10mLmin-1, wherein monomethyl amine: dimethylamine: trimethylamine=1:8:1
(volume ratio), the flow velocity of raw material CO are 10mLmin-1.It reacts, is sampled every 2h, chromatography at 200 DEG C, trimethylamine
Concentration increases to 75%；Chromatography, the overall selectivity of Carbox amide are 99%.
Embodiment 15
Weigh 20g CeO2It is immersed in 48.6mmolL-1Hydrate ruthenium trichloride solution in, stir 20h at room temperature,
130 DEG C of dryings restore 3h under 350 DEG C of hydrogen atmospheres, and 2wt%Ru/CeO is made2, molding sieve take 14-25 mesh catalyst fill to
In reaction tube, 15mm bed is filled, reaction tube is placed in fixed bed reactors after catalyst filling in reaction tube,
Under the pressure of 3.0MPa, the flow velocity of methylamine mixed gas is 10mLmin-1, wherein monomethyl amine: dimethylamine: trimethylamine=1:1:1
(volume ratio), the flow velocity of raw material CO are 10mLmin-1.It reacts, is sampled every 2h, chromatography at 200 DEG C, trimethylamine
Concentration increases to 85%；Chromatography, the overall selectivity of Carbox amide are 99%.
Claims (6)
1. the method for the separation while coproduction Carbox amide of methylamine mixed gas is mixed methylamine by catalysis reaction
After monomethyl amine in conjunction gas separates conversion with CO gas reaction with dimethylamine, high purity trimethylamine, coproduction benzamide type are obtained
The method of compound, it is characterised in that: the Ru metal oxide catalyst loaded is filled in fixed bed reactors, introduces first
Amine gaseous mixture and CO gas, turn acylation by the carbonylation and dimethylamine and product formamide of monomethyl amine and CO are anti-
It answers, to achieve the purpose that purify trimethylamine；Gas after reaction is front three amine gas after purification, and liquid phase is the formyl of coproduction
Aminated compounds.
2. according to the method for claim 1, it is characterised in that:
The metal oxide catalyst of the Ru load, wherein metal oxide is MoO3、CuO、Co3O4、Nb2O5、Fe2O3、
VO2、CeO2One of or two kinds or more；Ru content of metal are as follows: 0.5wt%~10wt%.
3. method according to claim 1 or 2, it is characterised in that:
The preparation of the metal oxide catalyst of the Ru load uses immersion reduction method or coprecipitation.
4. according to the method for claim 1, it is characterised in that:
Loading catalyst thickness of bed layer is 5mm~30mm, the flow velocity of methylamine mixed gas are as follows: 5~33mL in the reaction tube
min-1, the flow velocity of CO gas are as follows: 5~33mLmin-1, reaction pressure be 0.5~4MPa, 150 DEG C~250 DEG C of reaction temperature.
5. according to described in claim 1 or 4, it is characterised in that:
Loading catalyst thickness of bed layer is 10mm~15mm, the flow velocity of methylamine mixed gas in the reaction tube are as follows: 10~
25mL·min-1, the flow velocity of CO gas are as follows: 10~25mLmin-1, reaction pressure be 1~3MPa, 150 DEG C of reaction temperature~
200℃。
6. according to the method for claim 1, it is characterised in that: methylamine mixed gas includes monomethyl amine, dimethylamine and front three
Amine, volume group become x:y:z (wherein x, y, z are integer, and meet 0 < x, y, z < 100, and x+y+z=100).
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112898175A (en) * | 2019-11-19 | 2021-06-04 | 中国科学院大连化学物理研究所 | Method for preparing N, N-dimethylformamide |
| CN112898174A (en) * | 2019-11-19 | 2021-06-04 | 中国科学院大连化学物理研究所 | Preparation method of N, N-dimethylformamide |
| CN113842852A (en) * | 2021-10-29 | 2021-12-28 | 聊城鲁西甲胺化工有限公司 | Process and system for annual production of 20 ten thousand tons of methylamine |
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| CN104710321A (en) * | 2013-12-12 | 2015-06-17 | 中国科学院大连化学物理研究所 | Method for preparing N, N-dimethylformamide through dimethylamine carbonylation |
| CN105016937A (en) * | 2014-04-29 | 2015-11-04 | 中国科学院大连化学物理研究所 | Method for preparing formamide by catalytic oxidation of tertiary amine |
| CN106278930A (en) * | 2015-05-13 | 2017-01-04 | 中国科学院大连化学物理研究所 | A kind of dimethylaminocarbonyl prepares the method for N,N-dimethylformamide |
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| CN112898175A (en) * | 2019-11-19 | 2021-06-04 | 中国科学院大连化学物理研究所 | Method for preparing N, N-dimethylformamide |
| CN112898174A (en) * | 2019-11-19 | 2021-06-04 | 中国科学院大连化学物理研究所 | Preparation method of N, N-dimethylformamide |
| CN113842852A (en) * | 2021-10-29 | 2021-12-28 | 聊城鲁西甲胺化工有限公司 | Process and system for annual production of 20 ten thousand tons of methylamine |
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