CN101619025A - Continuous preparation method for n-pentylamine - Google Patents
Continuous preparation method for n-pentylamine Download PDFInfo
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- CN101619025A CN101619025A CN200910101302A CN200910101302A CN101619025A CN 101619025 A CN101619025 A CN 101619025A CN 200910101302 A CN200910101302 A CN 200910101302A CN 200910101302 A CN200910101302 A CN 200910101302A CN 101619025 A CN101619025 A CN 101619025A
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Abstract
The invention discloses a continuous preparation method for n-pentylamine, which comprises the following steps: taking n-amyl alcohol as a raw material and Cu-Co/Al2O3-diatomite as catalysts; under the conditions of certain pressure and temperature, putting the n-amyl alcohol into a preheater to be mixed with ammonia gas and hydrogen to perform preheating and gasification; conveying the gasified mixture into a fixed reactor for reaction; performing condensation and cooling, and gas-liquid separation on the reacted materials to obtain the n-pentylamine as a product; and recycling the system materials. The continuous preparation method has the advantages of simple process flow, high conversion rate, good selectivity, simple separation flow, low energy and material consumption and low production cost of the product; in addition, the generation quantity of byproducts can be controlled by adjusting the proportion of materials.
Description
Technical field
The present invention relates to a kind of chemical synthesis process, referring in particular to a kind of is the continuous preparation method of the n-amylamine of raw material with the Pentyl alcohol.
Background technology
N-amylamine is a kind of chemical intermediate, is used for aspects such as medicine, dyestuff, emulsifying agent, anticorrosive agent, solvent, oxidation inhibitor, flotation agent, thiofide, simultaneously also as the chemosynthesis intermediate.Another name: 1-aminopentane, molecular formula: C
5H
13N, molecular weight: 87.16.As a kind of chemical intermediate, its production also is in the starting stage, and the preparation method also is in and gropes the development phase.
Summary of the invention
The inventor has finished the present invention by number of research projects.
The purpose of this invention is to provide a kind of transformation efficiency height, selectivity is good, and by product is few, and flow process is simple, and production cost is low, is fit to the continuous preparation method of industrial n-amylamine.
The present invention solves its technical problem by following technical proposals:
A kind of continuous preparation method of n-amylamine is characterized in that comprising the steps:
1) is raw material with the Pentyl alcohol, and Pentyl alcohol is pumped into preheater, with ammonia, hydrogen mixing preheating vaporization;
2) enter reactor after the preheating vaporization, with Cu-Co/Al
2O
3-diatomite is catalyzer, and control pressure is normal pressure～4.0Mpa, and temperature is 100～280 ℃, and pure liquid hourly space velocity is 0.3～2.5h
-1, ammonia alcohol mol ratio is 3.0～12.5: 1, and hydrogen alcohol mol ratio is 1.5～12.0: 1, and catalyst levels is 0.15～1.5m
3Alcohol/(hrm
3Catalyzer) reacts under the condition;
Wherein, the composition of catalyzer (weight ratio) is: Cu is 1.0～30.0%, and Co is 1.0～50.0%, and Ru is 0.005～0.3%, and Mg is 0.01～0.7%, and Cr is 0.1～5.0%, and all the other are Al
2O
3With one of diatomaceous mixture or both;
3) reacting rear material is through condensation cooling, gas-liquid separation, and gas phase enters the reactor cycles utilization through circulation;
Liquid phase enters rectifying tower and separates the purification n-amylamine, can get product; The ammonia of separating, Pentyl alcohol, two n-amylamines, tri-n-amyl amine turn back to feed system, enter reactor again, react with additional hydrogen, ammonia and the Pentyl alcohol that enters.
As preferably, the Cu-Co/Al described in the above-mentioned preparation method
2O
3The composition of-diatomite catalyzer (weight ratio) is: Cu is 2.0～20.0%, and Co is 2.0～40.0%, and Ru is 0.005～0.3%, and Mg is 0.01～0.7%, and Cr is 0.1～5.0%, and all the other are Al
2O
3With one of diatomaceous mixture or both.
As preferably, the operational condition among above-mentioned a kind of preparation method is: pressure is 0.3～1.8Mpa, and temperature is 120～220 ℃, and pure liquid hourly space velocity is 0.4～1.0h
-1, ammonia alcohol mol ratio is 6.0～10.0: 1, and hydrogen alcohol mol ratio is 4.0～8.0: 1, and catalyst levels is 0.3～1.0m
3Alcohol/(hrm
3Catalyzer).
As preferably, the preparation process system described in above-mentioned a kind of preparation method carries out closed cycle, material recycle.
The preparation method of this n-amylamine is a raw material with the Pentyl alcohol, with Cu-Co/Al
2O
3-diatomite catalyzer is a catalyzer; Cu-Co/Al wherein
2O
3Consisting of of-diatomite catalyzer: Cu is 1.0～30.0%, and Co is 1.0～50.0%, and Ru is 0.005～0.3%, and Mg is 0.01～0.7%, and Cr is 0.1～5.0%, and all the other are Al
2O
3With one of diatomaceous mixture or both.This is reflected at vapour phase and carries out, and adopts the continous way process, and its concrete operations condition is pressure: normal pressure～4.0Mpa, temperature: 100～280 ℃, and pure liquid hourly space velocity: 0.3～2.5h
-1, ammonia alcohol mol ratio: 3.0～12.5, hydrogen alcohol mol ratio: 1.5～12.0, catalyst levels: 0.15～1.5m
3Alcohol/(hrm
3Catalyzer).Pentyl alcohol by volume pump squeeze into preheater and with ammonia, hydrogen mixing preheating after enter fixed-bed reactor reactions after the vaporization, reacting rear material is through condensation cooling, gas-liquid separation; Gas phase is utilized through the recycle compressor compression cycle, and liquid phase enters rectifying tower and separates purification: n-amylamine is as the product extraction; Ammonia, Pentyl alcohol turn back to feed system, and replenish a certain amount of hydrogen, ammonia and Pentyl alcohol, to keep the mol ratio of above-mentioned ammonia, hydrogen, isooctyl alcohol; Minor by-products two n-amylamines (abbreviation diamines) and tri-n-amyl amine (abbreviation triamine) or after purifying as by-product sale or return synthetic feed system circulation and continue to produce in order to suppress by product; Waste water purifies to the emission standard discharging.
The effect that the present invention is useful is: be the synthetic n-amylamine of raw material continuous catalysis ammonification dehydration with the Pentyl alcohol.Present method technical process is simple, the transformation efficiency height, and selectivity is good, and by product is few, and separation process is simple and clear, and energy consumption, raw material consumption are low, and the products production cost is low.
Embodiment
Below in conjunction with embodiment the present invention is further described.
Embodiment 1: this n-amylamine (C
4H
11NO) preparation method:
At first prepare catalyzer:
Industrial Cu-Co/Al
2O
3-diatomite catalyzer is a catalyzer, is numbered A1, and the composition of catalyzer (weight ratio) is: Cu is 1.0%, and Co is 20.0%, and Ru is 0.05%, and Mg is 0.07%, and Cr is 1.5%, and all the other are Al
2O
3Respectively account for 50% mixture with diatomite.
Industrial Cu-Co/Al
2O
3-diatomite catalyzer is a catalyzer, is numbered A2, and the composition of catalyzer (weight ratio) is: Cu is 3.0%, and Co is 15.0%, and Ru is 0.05%, and Mg is 0.07%, and Cr is 2.0%, and all the other are Al
2O
3Respectively account for 50% mixture with diatomite.
Industrial Cu-Co/Al
2O
3-diatomite catalyzer is a catalyzer, is numbered A3, and the composition of catalyzer (weight ratio) is: Cu is 15.0%, and Co is 30.0%, and Ru is 0.1%, and Mg is 0.09%, and Cr is 2.0%, and all the other are Al
2O
3Account for 30% and diatomite account for 70% mixture.
Industrial Cu-Co/Al
2O
3-diatomite catalyzer is a catalyzer, is numbered A4, and the composition of catalyzer (weight ratio) is: Cu is 15.0%, and Co is 40.0%, and Ru is 0.2%, and Mg is 0.1%, and Cr is 2.0%, and all the other are Al
2O
3Account for 20% and diatomite account for 80% mixture.
Industrial Cu-Co/Al
2O
3-diatomite catalyzer is a catalyzer, is numbered A5, and the composition of catalyzer (weight ratio) is: Cu is 10.0%, and Co is 30.0%, and Ru is 0.1%, and Mg is 0.1%, and Cr is 4.0%, and all the other are Al
2O
3Account for 60% and diatomite account for 40% mixture.
Industrial Cu-Co/Al
2O
3-diatomite catalyzer is a catalyzer, is numbered A6, and the composition of catalyzer (weight ratio) is: Cu is 5.0%, and Co is 25.0%, and Ru is 0.3%, and Mg is 0.6%, and Cr is 4.0%, and all the other are Al
2O
3Respectively account for 50% mixture with diatomite.
Embodiment 2
1) being raw material with the Pentyl alcohol, is catalyzer with A1;
2) this is reflected at vapour phase and carries out, and adopts the continous way process, and its concrete operations condition is pressure: 0.7～0.9Mpa, temperature: 160～190 ℃, and pure liquid hourly space velocity: 0.6～0.8h
-1, ammonia alcohol mol ratio: 8.0～9.0, hydrogen alcohol mol ratio: 6.0～7.0.
3) Pentyl alcohol by volume pump squeeze into preheater and with ammonia, hydrogen mixing preheating after enter fixed-bed reactor reactions after the vaporization, reacting rear material is through condensation cooling, gas-liquid separation; Gas phase is utilized through the recycle compressor compression cycle, and liquid phase enters rectifying tower and separates purification: n-amylamine is as the product extraction; Ammonia, Pentyl alcohol turn back to feed system, and replenish a certain amount of hydrogen, ammonia and Pentyl alcohol, to keep the mol ratio of above-mentioned ammonia, hydrogen, Pentyl alcohol; Minor by-products two n-amylamines (abbreviation diamines) and tri-n-amyl amine (abbreviation triamine) or after purifying as by-product sale or return synthetic feed system circulation and continue to produce in order to suppress by product; Waste water purifies to the emission standard discharging.
Embodiment 2---and embodiment 12:
With the diameter of packing into of catalyzer among the embodiment 1 is 32 * 3mm, the stainless steel reactor of length 1350mm.The stainless steel temperature-measuring casing of ∮ 8 * 1mm is set in the reactor, and catalyst packing height is 835mm, and loaded catalyst is 400ml.Reaction raw materials is to go out under enterprising, enters the separator after the condensation cooling from the effusive material of reactor bottom, and vapor phase ammonia, hydrogen are discharged the bottom liquid phases timing sampling from the separator top.Form concrete reaction conditions and the results are shown in following table with gas chromatographic analysis.
Reaction conditions and result
Data are reacted under present inventor's processing condition as can be known in the table thus, and the result all has higher transformation efficiency and selectivity preferably.
Embodiment 13---and embodiment 17
According to embodiment 2～12 described devices, flow process, filling 400ml A4 catalyzer carries out 240 hours stable service tests.Reaction pressure: 0.8MPa, temperature: 180 ℃, pure liquid hourly space velocity: 0.6h
-1, ammonia alcohol mol ratio: 8.5, hydrogen alcohol mol ratio: 6.5.Form concrete reaction conditions and the results are shown in following table with liquid-phase chromatographic analysis.
240 hours stable service tests
Show data thus as can be known, under these processing condition, the transformation efficiency of reaction is higher than 74%, and selectivity is higher than 95%, and catalyzer has stability preferably simultaneously.
The present invention is applicable to n-amylamine but is not limited to the preparation of n-amylamine, be equally applicable to one, two, the preparation of one or several product in the tri-n-amyl amine series product, with reference to the method for the invention, can realize one, two by adjusting, change partial parameters in the operational condition of the present invention, the preparation of one or several product in the tri-n-amyl amine series product.
The present invention is applicable to described catalyzer but is not limited to described catalyzer that being equally applicable to copper-cobalt is other copper-cobalt series catalysts of main active ingredient.
Claims (4)
1, a kind of continuous preparation method of n-amylamine is characterized in that comprising the steps:
1) is raw material with the Pentyl alcohol, and Pentyl alcohol is pumped into preheater, with ammonia, hydrogen mixing preheating vaporization;
2) enter reactor after the preheating vaporization, with Cu-Co/Al
2O
3-diatomite is catalyzer, and control pressure is normal pressure～4.0Mpa, and temperature is 100～280 ℃, and pure liquid hourly space velocity is 0.3～2.5h
-1, ammonia alcohol mol ratio is 3.0～12.5: 1, and hydrogen alcohol mol ratio is 1.5～12.0: 1, and catalyst levels is 0.15～1.5m
3Alcohol/(hrm
3Catalyzer) reacts under the condition;
Wherein, by weight calculating, the consisting of of catalyzer: Cu is 1.0～30.0%, and Co is 1.0～50.0%, and Ru is 0.005～0.3%, and Mg is 0.01～0.7%, and Cr is 0.1～5.0%, and all the other are Al
2O
3With one of diatomaceous mixture or both;
3) reacting rear material is through condensation cooling, gas-liquid separation, and gas phase enters the reactor cycles utilization through circulation;
Liquid phase enters rectifying tower and separates the purification n-amylamine, can get product; The ammonia of separating, Pentyl alcohol, two n-amylamines, tri-n-amyl amine turn back to feed system, enter reactor again, react with additional hydrogen, ammonia and the Pentyl alcohol that enters.
2, a kind of preparation method according to claim 1 is characterized in that described Cu-Co/Al
2O
3Consisting of of-diatomite catalyzer: Cu is 2.0～20.0%, and Co is 2.0～40.0%, and Ru is 0.005～0.3%, and Mg is 0.01～0.7%, and Cr is 0.1～5.0%, and all the other are Al
2O
3With one of diatomaceous mixture or both, above-mentioned counting by weight percentage.
3, a kind of preparation method according to claim 1, it is characterized in that described operational condition is: pressure is 0.3～1.8Mpa, and temperature is 120～220 ℃, and pure liquid hourly space velocity is 0.4～1.0h
-1, ammonia alcohol mol ratio is 6.0～10.0: 1, and hydrogen alcohol mol ratio is 4.0～8.0: 1, and catalyst levels is 0.3～1.0m
3Alcohol/(hrm
3Catalyzer).
4, a kind of preparation method according to claim 1 is characterized in that described preparation process system carries out closed cycle, material recycle.
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|---|---|---|---|
| CN200910101302A CN101619025A (en) | 2009-07-29 | 2009-07-29 | Continuous preparation method for n-pentylamine |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910101302A CN101619025A (en) | 2009-07-29 | 2009-07-29 | Continuous preparation method for n-pentylamine |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102336672A (en) * | 2011-09-21 | 2012-02-01 | 浙江建业化工股份有限公司 | Method for producing isoamyl amine |
| CN102344373A (en) * | 2011-09-30 | 2012-02-08 | 陈国建 | Method for preparing 2-methyl, 5-pentamethylenediamine |
| CN102633648A (en) * | 2012-03-27 | 2012-08-15 | 巨化集团技术中心 | Preparation method of n-butylamine |
| CN103664633A (en) * | 2013-12-27 | 2014-03-26 | 大连百傲化学股份有限公司 | Synthetic method of n-octylamine |
| WO2018157395A1 (en) * | 2017-03-03 | 2018-09-07 | Rhodia Operations | Process for preparing an amine via a direct amination reaction |
| CN110302790A (en) * | 2019-07-26 | 2019-10-08 | 山东达民化工股份有限公司 | The n-hexylamine production technology of catalyst and preparation method thereof and application catalyst |
| CN113831250A (en) * | 2020-06-23 | 2021-12-24 | 中国科学院过程工程研究所 | Method, device and catalyst for preparing 1, 2-butanediamine |
-
2009
- 2009-07-29 CN CN200910101302A patent/CN101619025A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102336672A (en) * | 2011-09-21 | 2012-02-01 | 浙江建业化工股份有限公司 | Method for producing isoamyl amine |
| CN102336672B (en) * | 2011-09-21 | 2014-06-18 | 浙江建业化工股份有限公司 | Method for producing isoamyl amine |
| CN102344373A (en) * | 2011-09-30 | 2012-02-08 | 陈国建 | Method for preparing 2-methyl, 5-pentamethylenediamine |
| CN102633648A (en) * | 2012-03-27 | 2012-08-15 | 巨化集团技术中心 | Preparation method of n-butylamine |
| CN102633648B (en) * | 2012-03-27 | 2014-08-27 | 巨化集团技术中心 | Preparation method of n-butylamine |
| CN103664633A (en) * | 2013-12-27 | 2014-03-26 | 大连百傲化学股份有限公司 | Synthetic method of n-octylamine |
| CN103664633B (en) * | 2013-12-27 | 2015-08-19 | 大连百傲化学股份有限公司 | A kind of synthetic method of n-octyl amine |
| WO2018157395A1 (en) * | 2017-03-03 | 2018-09-07 | Rhodia Operations | Process for preparing an amine via a direct amination reaction |
| CN110302790A (en) * | 2019-07-26 | 2019-10-08 | 山东达民化工股份有限公司 | The n-hexylamine production technology of catalyst and preparation method thereof and application catalyst |
| CN113831250A (en) * | 2020-06-23 | 2021-12-24 | 中国科学院过程工程研究所 | Method, device and catalyst for preparing 1, 2-butanediamine |
| CN113831250B (en) * | 2020-06-23 | 2024-05-03 | 中国科学院过程工程研究所 | Method, device and catalyst for preparing 1, 2-butanediamine |
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Application publication date: 20100106 |