CN110172029A - A kind of method of continuous synthesis 2-amino-2-methyl-1-propanol - Google Patents

A kind of method of continuous synthesis 2-amino-2-methyl-1-propanol Download PDF

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CN110172029A
CN110172029A CN201910572119.9A CN201910572119A CN110172029A CN 110172029 A CN110172029 A CN 110172029A CN 201910572119 A CN201910572119 A CN 201910572119A CN 110172029 A CN110172029 A CN 110172029A
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methyl
fixed bed
bed reactors
liquid
amino
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CN110172029B (en
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陈健
张书
杭建荣
周健韬
芮伟
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NANJING HONGBAOLI ALKYLOL AMINE CHEMICAL Co Ltd
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NANJING HONGBAOLI ALKYLOL AMINE CHEMICAL Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

The invention discloses a kind of methods of continuous synthesis 2-amino-2-methyl-1-propanol, its specifically: 2- nitro-2- methyl-1-propyl alcohol dissolution is formed into material liquid in a solvent, then the material liquid is passed into fixed bed reactors, reduction reaction is carried out using hydrogen under the effect of the catalyst, the reaction mass being discharged from fixed bed reactors is subjected to rectifying, obtains 2-amino-2-methyl-1-propanol.Before material liquid is passed through fixed bed reactors, hydrogen is passed into fixed bed reactors first, and is heated up, is passed into fixed bed reactors, is reacted when the temperature in fixed bed reactors reaches reaction temperature, then by material liquid；Reaction mass is cooled down from the discharge of the bottom of fixed bed reactors, then into being separated in gas-liquid separator, gas recycling and reusing, liquid enters in collecting tank and timing sampling analysis, liquid reactants obtain 2-amino-2-methyl-1-propanol after distillation is handled.

Description

A kind of method of continuous synthesis 2-amino-2-methyl-1-propanol
Technical field
The present invention relates to a kind of methods of continuous synthesis 2-amino-2-methyl-1-propanol.
Background technique
2-amino-2-methyl-1-propanol is white crystals or colourless viscous liquid, water-miscible, is dissolved in ethyl alcohol.Its mesh Before be widely used for the multiple fields such as intermetallic composite coating, coating, adhesive, rubber, personal nursing, CCS, water process.Compared to similar Some other organic base, 2-amino-2-methyl-1-propanol has the superiority such as pH stability is good, be not easy xanthochromia, small toxicity Energy.
Currently, the production of 2-amino-2-methyl-1-propanol is generally using 2- nitro-2- methyl-1-propyl alcohol as raw material, with bone Frame nickel or noble metal do hydrogenation catalyst, using batch tank hydrogenation synthesis.But autoclave hydroprocessing is complicated, the stability of reaction Difference, it is also necessary to consume more hydrogen to be replaced, also result in more tail gas pollutions.Importantly, autoclave adds hydrogen It is unfavorable for improving production efficiency, increases labor intensity, increase material consumption energy consumption.
In addition that there is also hydrogenation times is long for skeleton nickel, and fine particulate skeletal nickel catalyst recycles relative difficulty, catalyst damage It loses the problems such as larger, and the noble metals such as ruthenium, palladium are then expensive.
Summary of the invention
The purpose of the present invention is overcoming, complicated for operation, stability is poor, environmental pollution, catalyst activity is low, loses big ask Topic, to provide a kind of method of continuous synthesis 2-amino-2-methyl-1-propanol, this method high, stability with reaction efficiency Well, the features such as catalyst is cheap efficiently, pollution is small, simple to operation, is suitable for industrialized production.
To achieve the above object the present invention adopts the following technical scheme:
A kind of method of continuous synthesis 2-amino-2-methyl-1-propanol, specifically:
2- nitro-2- methyl-1-propyl alcohol dissolution is formed into material liquid in a solvent, the material liquid is then passed into fixation In bed reactor, reduction reaction, the reactant that will be discharged from fixed bed reactors are carried out using hydrogen under the effect of the catalyst Material carries out rectifying, obtains 2-amino-2-methyl-1-propanol.
Before material liquid is passed through fixed bed reactors, hydrogen is passed into fixed bed reactors first, and is risen Temperature is passed into fixed bed reactors when the temperature in fixed bed reactors reaches reaction temperature, then by material liquid, is carried out anti- It answers；Reaction mass is cooled down from the discharge of the bottom of fixed bed reactors, then into being separated in gas-liquid separator, gas Body recycling and reusing, liquid enters in collecting tank and timing sampling analysis, liquid reactants obtain 2- ammonia after distillation is handled Base-2- methyl-1-propyl alcohol.
Preferably, the solvent is methanol, ethyl alcohol, isopropanol, ethylene glycol, water, n,N-dimethylacetamide, acetone or two At least one of methyl sulfoxide.
In the present invention, using fixed bed reactors, carry out the mode of continuously hydrogen adding, to 2- nitro-2- methyl-1-propyl alcohol into Row reduction reaction can be such that production smoothly carries out after the corresponding parameter of determination, and product produced is made to have height consistent Performance parameter.And in the prior art, when being interrupted production using autoclave mode, due to being required to readjust technique ginseng every time Number, even if the adjustment of technological parameter is more smooth, also due to the slight error adjusted every time and lead to the mass parameter of product It fluctuates, even if product quality meets the requirements, the uniformity of product index can also be lower than quantity-produced product index.
In process of production, since the displacement repeatedly of hydrogen by the way of continuously hydrogen adding, can be reduced, and hydrogen is thus reduced The cost recovery of gas, while the loss of hydrogen can be reduced.
It is produced using continous way, while improving uniform in quality, the reaction time can also be shortened, improve production Efficiency reduces labor intensity.
Using the present invention, feed stock conversion can be made up to 99%, selectivity improves the utilization of raw material up to 95% Rate, to be effectively reduced product cost.
Specifically, to control reaction speed, side reaction is reduced, reaction temperature is 50~190 DEG C.Reaction pressure be 0.5~ 6.0MPa。
For the conversion ratio for guaranteeing raw material, the liquid hourly space velocity (LHSV) of material liquid is 0.3~10h-1。
For control reaction speed, avoiding reacting too fast, reaction temperature raising is too fast, in material liquid, 2- nitro -2- methyl - The mass concentration of 1- propyl alcohol is 10~50%.
Further, 2- nitro-2- methyl-1-propyl alcohol to react residence time in fixed bed reactors be 10~ 100min.In above-mentioned time range, it can guarantee the conversion ratio of raw material substantially.
It is 1.0 to guarantee that nitro is reduced sufficiently as amino, hydrogen and 2- nitro-2- methyl-1-propyl alcohol molar ratio ~30.0:1.
Further, in this method, used catalyst is iron/Al catalysts, and wherein iron/aluminium molar ratio is 0.01~1.It urges The loadings of agent are the 5~25% of fixed bed reactors total volume.Retain sufficient airflow channel, it is anti-in fixed bed for raw material Olderly flowage in device is answered, and is come into full contact with catalyst, to guarantee catalytic effect.Iron/Al catalysts, activity is high, conversion ratio It is higher with selectivity, and comparison Raney's nickel and noble metal are cheap.Iron/Al catalysts are able to carry out continuously hydrogen adding reaction, It does not need the operation such as to be filtered catalyst, recycle, reduces catalyst consumption.
Specific embodiment
The present invention will be further described combined with specific embodiments below.
In following embodiment, nitroalcohol is 2- nitro-2- methyl-1-propyl alcohol.
Embodiment 1
The nitroalcohol ethanol solution that configuration quality percentage concentration is 50%, and in charging feedstock tank.Again in fixed bed reaction Iron/Al catalysts are added in device, iron/aluminium molar ratio is 0.05, and loadings are the 25% of fixed bed reactors total volume.It adjusts Hydrogen flowing quantity is warming up to 50 DEG C, after temperature is stablized, liquid charging stock is continuously added into fixed bed reactors with pump, liquid Raw material passes through fixed bed reactors after mixing with hydrogen from top to bottom.Controlling liquid hourly space velocity (LHSV) simultaneously is 0.6h-1, hydrogen and 2- ammonia Base-2- methyl-1-propyl alcohol molar ratio is 30.0:1, reaction pressure 6MPa, reaction time 100min.Reaction mass From reactor bottom come out after it is cooling through cooling coil, subsequently into gas-liquid separator, gas recycling and reusing, liquid reactants Material then enters collecting tank and timing sampling analysis, and the conversion ratio of raw material is 90.1%, and selectivity is 92.3%.Reaction mass passes through Rectification process obtains 2-amino-2-methyl-1-propanol.
Embodiment 2
The nitroalcohol ethylene glycol solution that configuration quality percentage concentration is 40%, and in charging feedstock tank.It is anti-in fixed bed again Addition iron/Al catalysts in device are answered, iron/aluminium molar ratio is 0.1, and loadings are the 20% of fixed bed reactors total volume.It adjusts Hydrogen flowing quantity is saved, is warming up to 70 DEG C, after temperature is stablized, liquid charging stock is continuously added into fixed bed reactors with pump, liquid Body raw material passes through fixed bed reactors after mixing with hydrogen from top to bottom.Controlling liquid hourly space velocity (LHSV) simultaneously is 0.8h-1, hydrogen and 2- ammonia Base-2- methyl-1-propyl alcohol molar ratio is 20.0:1, reaction pressure 5MPa, reaction time 80min.Reaction mass From reactor bottom come out after it is cooling through cooling coil, subsequently into gas-liquid separator, gas recycling and reusing, liquid reactants Material then enters collecting tank and timing sampling analysis, and the conversion ratio of raw material is 94.5%, and selectivity is 94.8%.Reaction mass passes through Rectification process obtains 2-amino-2-methyl-1-propanol.
Embodiment 3
The nitroalcohol methanol solution that configuration quality percentage concentration is 30%, and in charging feedstock tank.Again in fixed bed reaction Iron/Al catalysts are added in device, iron/aluminium molar ratio is 0.2, and loadings are the 15% of fixed bed reactors total volume.It adjusts Hydrogen flowing quantity is warming up to 90 DEG C, after temperature is stablized, liquid charging stock is continuously added into fixed bed reactors with pump, liquid Raw material passes through fixed bed reactors after mixing with hydrogen from top to bottom.Controlling liquid hourly space velocity (LHSV) simultaneously is 2h-1, hydrogen and 2- amino- 2- methyl-1-propyl alcohol molar ratio is 15.0:1, reaction pressure 4MPa, reaction time 30min.Reaction mass is from anti- Cooling through cooling coil after answering device bottom to come out, subsequently into gas-liquid separator, gas recycling and reusing, liquid reactions material is then Into collecting tank and timing sampling analysis, the conversion ratio of raw material is 97.8%, and selectivity is 95.2%.Reaction mass passes through rectifying Processing obtains 2-amino-2-methyl-1-propanol.
Embodiment 4
The nitroalcohol methanol solution that configuration quality percentage concentration is 20%, and in charging feedstock tank.Again in fixed bed reaction Iron/Al catalysts are added in device, iron/aluminium molar ratio is 0.2, and loadings are the 10% of fixed bed reactors total volume.It adjusts Hydrogen flowing quantity is warming up to 110 DEG C, after temperature is stablized, liquid charging stock is continuously added into fixed bed reactors with pump, liquid Raw material passes through fixed bed reactors after mixing with hydrogen from top to bottom.Controlling liquid hourly space velocity (LHSV) simultaneously is 3h-1, hydrogen and 2- amino- 2- methyl-1-propyl alcohol molar ratio is 10.0:1, reaction pressure 3MPa, reaction time 30min.Reaction mass is from anti- Cooling through cooling coil after answering device bottom to come out, subsequently into gas-liquid separator, gas recycling and reusing, liquid reactions material is then Into collecting tank and timing sampling analysis, the conversion ratio of raw material is 99.1%, and selectivity is 95.1%.Reaction mass passes through rectifying Processing obtains 2-amino-2-methyl-1-propanol.
Embodiment 5
The nitroalcohol n,N-dimethylacetamide solution that configuration quality percentage concentration is 20%, and in charging feedstock tank.Again Iron/Al catalysts are added in fixed bed reactors, iron/aluminium molar ratio is 0.5, and loadings are fixed bed reactors total volume 10%.Hydrogen flowing quantity is adjusted, is warming up to 110 DEG C, after temperature is stablized, is continuously added to liquid charging stock with pump anti-to fixed bed It answers in device, liquid charging stock passes through fixed bed reactors after mixing with hydrogen from top to bottom.Controlling liquid hourly space velocity (LHSV) simultaneously is 3h-1, hydrogen The molar ratio of gas and 2-amino-2-methyl-1-propanol is 10.0:1, reaction pressure 2MPa, reaction time 20min. Reaction mass from reactor bottom come out after it is cooling through cooling coil, subsequently into gas-liquid separator, gas recycling and reusing, liquid Precursor reactant material then enters collecting tank and timing sampling analysis, and the conversion ratio of raw material is 98.5%, and selectivity is 94.6%.Reaction Material obtains 2-amino-2-methyl-1-propanol by rectification process.
Embodiment 6
The nitro alcohol solution that configuration quality percentage concentration is 10%, and in charging feedstock tank.Again in fixed bed reactors Middle addition iron/Al catalysts, iron/aluminium molar ratio are 0.8, and loadings are the 5% of fixed bed reactors total volume.Adjust hydrogen Flow is warming up to 130 DEG C, after temperature is stablized, liquid charging stock is continuously added into fixed bed reactors with pump, liquid charging stock Pass through fixed bed reactors after mixing with hydrogen from top to bottom.Controlling liquid hourly space velocity (LHSV) simultaneously is 1.5h-1, hydrogen and 2- amino -2- Methyl-1-propyl alcohol molar ratio is 5.0:1, reaction pressure 2MPa, reaction time 40min.Reaction mass is from reaction Device bottom is cooling through cooling coil after coming out, subsequently into gas-liquid separator, gas recycling and reusing, liquid reactions material then into Enter collecting tank and timing sampling analysis, the conversion ratio of raw material is 98.9%, and selectivity is 89.4%.Reaction mass passes through at rectifying Reason obtains 2-amino-2-methyl-1-propanol.
Embodiment 7
The nitroalcohol dimethyl sulphoxide solution that configuration quality percentage concentration is 10%, and in charging feedstock tank.Again in fixation Iron/Al catalysts are added in bed reactor, iron/aluminium molar ratio is 1.0, and loadings are the 5% of fixed bed reactors total volume. Hydrogen flowing quantity is adjusted, is warming up to 150 DEG C, after temperature is stablized, liquid charging stock is continuously added into fixed bed reactors with pump, Liquid charging stock passes through fixed bed reactors after mixing with hydrogen from top to bottom.Controlling liquid hourly space velocity (LHSV) simultaneously is 6h-1, hydrogen and 2- ammonia Base-2- methyl-1-propyl alcohol molar ratio is 2.0:1, reaction pressure 1MPa, reaction time 10min.Reaction mass from Reactor bottom is cooling through cooling coil after coming out, subsequently into gas-liquid separator, gas recycling and reusing, liquid reactions material Then enter collecting tank and timing sampling analysis, the conversion ratio of raw material is 99.1%, and selectivity is 80.9%.Reaction mass passes through essence It evaporates processing and obtains 2-amino-2-methyl-1-propanol.

Claims (10)

1. a kind of method of continuous synthesis 2-amino-2-methyl-1-propanol, which is characterized in that by 2- nitro-2- methyl-1-the third Alcohol dissolution forms material liquid in a solvent, then the material liquid is passed into fixed bed reactors, under the effect of the catalyst Reduction reaction is carried out using hydrogen, the reaction mass being discharged from fixed bed reactors is subjected to rectifying, obtains 2- amino-2-methyl- 1- propyl alcohol.
2. the method according to claim 1, wherein the solvent be methanol, ethyl alcohol, isopropanol, ethylene glycol, At least one of water, n,N-dimethylacetamide, acetone or dimethyl sulfoxide.
3. the method according to claim 1, wherein reaction temperature is 50~190 DEG C.
4. the method according to claim 1, wherein
The liquid hourly space velocity (LHSV) of material liquid is 0.3~10h-1。
5. the method according to claim 1, wherein
Reaction pressure is 0.5~6.0MPa.
6. the method according to claim 1, wherein
In material liquid, 2- nitro-2- methyl-1-propyl alcohol mass concentration is 10~50%.
7. the method according to claim 1, wherein
2- nitro-2- methyl-1-propyl alcohol is 10~100min reacting the residence time in fixed bed reactors.
8. the method according to claim 1, wherein
Hydrogen and 2- nitro-2- methyl-1-propyl alcohol molar ratio are 1.0~30.0:1.
9. the method according to claim 1, wherein
The catalyst is iron/Al catalysts, and wherein iron/aluminium molar ratio is 0.01~1.
10. the method according to claim 1, wherein
The loadings of catalyst are the 5~25% of fixed bed reactors total volume.
CN201910572119.9A 2019-06-28 2019-06-28 Method for continuously synthesizing 2-amino-2-methyl-1-propanol Active CN110172029B (en)

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