CN101648875B - Method for continuously preparing di-sec-butylamine - Google Patents

Method for continuously preparing di-sec-butylamine Download PDF

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Publication number
CN101648875B
CN101648875B CN2009101526988A CN200910152698A CN101648875B CN 101648875 B CN101648875 B CN 101648875B CN 2009101526988 A CN2009101526988 A CN 2009101526988A CN 200910152698 A CN200910152698 A CN 200910152698A CN 101648875 B CN101648875 B CN 101648875B
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butanone
sec
butylamine
ammonia
ketone
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CN101648875A (en
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陈国建
兰昭洪
南巍冈
伍伟伟
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ZHEJIANG XINHUA CHEMICAL CO Ltd
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ZHEJIANG XINHUA CHEMICAL CO Ltd
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

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Abstract

The invention discloses a chemical synthesizing method, in particular a method for continuously preparing di-sec-butylamine using butanone as a raw material. In the invention, the butanone is used as the raw material, and the butanone is pumped into a pre-heater to mix with ammonia and hydrogen to preheat and evaporate; Ni-Cu/gamma-Al2O3-diatomite is used as a catalyst, the temperature with a certain pressure is controlled, after reaction, the materials are condensed and cooled to separate gas and liquid, the gas phase enters a reactor by circulating to be used repeatedly; the liquid phase enters a rectifying tower to separate and purify the di-sec-butylamine to obtain the product; the separated ammonia, butanone and sec-butylamine return to a feeding system and enter the reactor to react with the supplementary hydrogen, the ammonia and the butanone. The invention has advantages of simple process, high conversion rate, good selectivity, simple process of separating, low consumption of energy and raw materials and low production cost.

Description

A kind of continuous preparation method of di-sec-butylamine
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 di-sec-butylamine of raw material with the butanone.
Background technology
Di-sec-butylamine is a kind of organic chemical industry's midbody, is mainly used in to produce weedicide (like thiocarbazides), also can be used for aspects such as medicine, dyestuff, inhibiter, flotation agent, thiofide.
The working method of di-sec-butylamine mainly is a methyl ethyl ketoxime ammonification evaporation.Related data report, this method are to be main raw material with the methyl ethyl ketoxime, are catalyzer high pressure (2.5Mpa) operation under autoclave with the Raney's nickel; Operational condition is relatively harsher; Long reaction time (5-6h), and the productivity ratio of di-sec-butylamine is lower is unfavorable for that industry applies.
Summary of the invention
The inventor has accomplished the present invention through number of research projects.
It is high to the purpose of this invention is to provide a kind of transformation efficiency, and 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 di-sec-butylamine.
The present invention solves its technical problem through following technical proposals:
A kind of continuous preparation method of di-sec-butylamine is characterized in that comprising the steps:
1) is raw material with the butanone, and pumps into preheater to butanone, with ammonia, hydrogen mixing preheating vaporization;
2) preheating vaporization back gets into reactor drum, with Ni-Cu/ γ-Al 2O 3-zeyssatite is catalyzer, and control pressure is normal pressure-3.0Mpa, and temperature is 110-250 ℃, and the ketone liquid hourly space velocity is 0.3-2.5h -1, ammonia ketone mol ratio is 2.0-8.5: 1, and hydrogen ketone mol ratio is 7.0-16.0: 1, catalyst levels is 0.25-2.0m 3Ketone/(hrm 3Catalyzer) reacts under the condition;
Wherein, the composition of catalyzer (weight ratio) is: Ni is 1.0-25.0%, and Cu is 1.0-15.0%, and Cr is 1.0-15.0%, and Mn is 1.5-13.0%, and Zn is 1.0-11.0%, and Fe is 0-10.0%, and all the other are γ-Al 2O 3With one of diatomaceous mixture or both.
3) reacting rear material is through condensation cooling, gas-liquid separation, and gas phase gets into the reactor cycles utilization through circulation;
Liquid phase gets into rectifying tower and separates the purification di-sec-butylamine, can get product; The ammonia of separating, butanone, sec.-butylamine turn back to feed system, get into reactor drum again, react with the hydrogen, ammonia and the butanone that replenish entering.
As preferably, the Ni-Cu/ γ-Al described in the above-mentioned preparation method 2O 3The composition of-zeyssatite catalyzer (weight ratio) is: Ni is 5.0-20.0%, and Cu is 3.0-13.0%, and Cr is 2.0-11.0%, and Mn is 2.0-10.5%, and Zn is 2.5-8.0%, and Fe is 2.0-7.5%, and all the other are γ-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 0.3-1.5Mpa, and temperature is 120-210 ℃; The ketone liquid hourly space velocity is 0.5-1.0h-1; Ammonia ketone mol ratio is 3.0-7.0: 1, and hydrogen ketone mol ratio is 8.0-12.0: 1, catalyst levels is 0.35-1.2m 3Ketone/(hrm 3Catalyzer).
As preferably, the preparation procedures system described in the above-mentioned preparation method is carried out closed cycle, material recycle.
The preparation method of this di-sec-butylamine is a raw material with the butanone, with Ni-Cu/ γ-Al 2O 3-zeyssatite catalyzer is a catalyzer, wherein Ni-Cu/ γ-Al 2O 3Consisting of of-zeyssatite catalyzer: Ni is 1.0-25.0%, and Cu is 1.0-15.0%, and Cr is 1.0-15.0%, and Mn is 1.5-13.0%, and Zn is 1.0-11.0%, and Fe is 0-10.0%, and all the other are γ-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 is normal pressure-3.0Mpa, and temperature is 110-250 ℃, and the ketone liquid hourly space velocity is 0.3-2.5h -1, ammonia ketone mol ratio is 2.0-8.5: 1, and hydrogen ketone mol ratio is 7.0-16.0: 1, catalyst levels is 0.25-2.0m 3Ketone/(hrm 3Catalyzer).Butanone by volume pump squeeze into preheater and with ammonia, hydrogen mixing preheating after vaporization back get into the fixed-bed reactor reaction, reacting rear material is through condensation cooling, gas-liquid separation; Gas phase is utilized through the recycle compressor compression cycle, and liquid phase gets into rectifying tower and separates purification: di-sec-butylamine is as the product extraction; Ammonia, butanone turn back to feed system, and replenish a certain amount of hydrogen, ammonia and butanone, to keep the mol ratio of above-mentioned ammonia, hydrogen, butanone; The by product sec.-butylamine or through the back of purifying as by-product sale or return synthetic feed system circulation and continue generation 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 ammonification of raw material continuous catalysis, dehydration, the synthetic di-sec-butylamine of hydrogenation with the butanone.Present method technical process is simple, and transformation efficiency is high, and selectivity is good, 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 di-sec-butylamine (C 8H 19N) preparation method:
With the γ-Al that buys on the market 2O 3A certain amount of zeyssatite of middle adding mixes, and through extrusion molding, drying, roasting, obtains diameter 4mm, strip γ-Al of long 3～7mm 2O 3-diatomite support is processed mixed solution with the nitrate salt of Ni, Cu, Cr, Mn, Zn, Fe, in proportion to γ-Al 2O 3-diatomite support floods, and puts into muffle furnace roasting 24h after the drying, and making content is that Ni is 14.5%, and Cu is 12.5%, and Cr is 6.1%, and Mn is 5.3%, and Zn is 5.0%, and Fe is 4.1%, and all the other are γ-Al 2O 3With diatomaceous mixture Ni-Cu γ-Al 2O 3-zeyssatite catalyzer.
With institute's controlling catalyst diameter of packing into is 32 * 3mm, the stainless steel reactor of length 1320mm.The stainless steel temperature-measuring casing of ∮ 8 * 1mm is set in the reactor drum, and catalyst packing height is 835mm, and loaded catalyst is 400ml.
Reaction mass is 1: 4: 8 ratio charging in the mol ratio of butanone and ammonia, hydrogen, 140 ℃ of temperature, and pressure (gauge pressure) 0.6MPa, butanone charging air speed 0.5h -1Carry out building-up reactions under the condition, the butanone reaction conversion ratio is 89%, and the di-sec-butylamine selectivity is 63%.
Embodiment 2
Press condition and the step of embodiment 1, change its operational condition and be: 160 ℃ of temperature, pressure (gauge pressure) 0.6MPa, the butanone reaction conversion ratio is 95%, the di-sec-butylamine selectivity is 68%.
Embodiment 3
Press condition and the step of embodiment 1, change its operational condition and be: 160 ℃ of temperature, pressure (gauge pressure) 0.8MPa, the butanone reaction conversion ratio is 96%, the di-sec-butylamine selectivity is 71%.
Embodiment 4
Press condition and the step of embodiment 1; Changing its operational condition is: 160 ℃ of temperature, pressure (gauge pressure) 0.8MPa, butanone charging air speed 0.5h-1; The charging proportioning is a butanone: ammonia: hydrogen=mol ratio butanone reaction conversion ratio was 98% in 1: 6: 8, and the di-sec-butylamine selectivity is 66%.
Embodiment 5
Press condition and the step of embodiment 1; Changing its operational condition is: 180 ℃ of temperature, pressure (gauge pressure) 0.8MPa, butanone charging air speed 0.5h-1; The charging proportioning is a butanone: ammonia: hydrogen=mol ratio butanone reaction conversion ratio was 98% in 1: 6: 8, and the di-sec-butylamine selectivity is 72%.
Embodiment 6
Press condition and the step of embodiment 1; Changing its operational condition is: 180 ℃ of temperature, pressure (gauge pressure) 0.8MPa, butanone charging air speed 0.5h-1; The charging proportioning is a butanone: ammonia: hydrogen=mol ratio butanone reaction conversion ratio was 98.5% in 1: 6: 10, and the di-sec-butylamine selectivity is 72%.
Embodiment 7
Press condition and the step of embodiment 1; Changing its operational condition is: 180 ℃ of temperature, pressure (gauge pressure) 0.8MPa, butanone charging air speed 0.7h-1; The charging proportioning is a butanone: ammonia: hydrogen=mol ratio butanone reaction conversion ratio was 89.5% in 1: 6: 10, and the di-sec-butylamine selectivity is 70%.
The present invention is applicable to di-sec-butylamine but is not limited to the preparation of di-sec-butylamine; Be equally applicable to one, the preparation of one or several product in the di-sec-butylamine series product; With reference to the method for the invention, through adjustment, change that partial parameters in the operational condition according to the invention can realize one, the preparation of one or several product in the di-sec-butylamine series product.

Claims (4)

1. the continuous preparation method of a di-sec-butylamine is characterized in that comprising the steps:
1) is raw material with the butanone, and pumps into preheater to butanone, with ammonia, hydrogen mixing preheating vaporization;
2) preheating vaporization back gets into reactor drum, with Ni-Cu-Cr-Mn-Zn-Fe/ γ-Al 2O 3-zeyssatite is catalyzer, and control pressure is normal pressure～3.0Mpa, and temperature is 110～250 ℃, and the ketone liquid hourly space velocity is 0.3～2.5h -1, ammonia ketone mol ratio is 2.0～8.5: 1, and hydrogen ketone mol ratio is 7.0～16.0: 1, and catalyst levels is 0.25～2.0m 3Ketone/(hrm 3Catalyzer) reacts under the condition;
Wherein, consisting of of catalyzer: Ni is 1.0-25.0%, and Cu is 1.0-15.0%, and Cr is 1.0-15.0%, and Mn is 1.5-13.0%, and Zn is 1.0-11.0%, and Fe is 0-10.0%, and all the other are γ-Al 2O 3With diatomaceous mixture, aforementioned proportion is a weight ratio;
3) reacting rear material is through condensation cooling, gas-liquid separation, and gas phase gets into the reactor cycles utilization through circulation; Liquid phase gets into rectifying tower and separates the purification di-sec-butylamine, can get product; The ammonia of separating, butanone, sec.-butylamine turn back to feed system, get into reactor drum again, react with the hydrogen, ammonia and the butanone that replenish entering.
2. a kind of preparation method according to claim 1 is characterized in that described Ni-Cu-Cr-Mn-Zn-Fe/ γ-Al 2O 3Consisting of of-zeyssatite catalyzer: Ni is 5.0-20.0%, and Cu is 3.0-13.0%, and Cr is 2.0-11.0%, and Mn is 2.0-10.5%, and Zn is 2.5-8.0%, and Fe is 2.0-7.5%, and all the other are γ-Al 2O 3With diatomaceous mixture, aforementioned proportion is weight percentage.
3. a kind of preparation method according to claim 1, it is characterized in that described operational condition is: pressure is 0.3-1.5Mpa, and temperature is 120-210 ℃, and the ketone liquid hourly space velocity is 0.5-1.0h -1, ammonia ketone mol ratio is 3.0-7.0: 1, and hydrogen ketone mol ratio is 8.0-12.0: 1, catalyst levels is 0.35-1.2m 3Ketone/(hrm 3Catalyzer).
4. a kind of preparation method according to claim 1 is characterized in that described preparation procedures system implementation closed cycle, the material recycle.
CN2009101526988A 2009-09-21 2009-09-21 Method for continuously preparing di-sec-butylamine Active CN101648875B (en)

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CN102145290A (en) * 2011-01-26 2011-08-10 中国科学院青岛生物能源与过程研究所 Catalyst for preparing low carbon polylol from corncob and method for preparing low carbon polylol
CN102898312A (en) * 2011-07-28 2013-01-30 泰州石油化工有限责任公司 Method for preparing sec-butylamine through methyl ethyl ketone catalytic ammonization hydrogenation

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2937325A1 (en) * 1979-09-14 1981-04-09 Institutul De Cercetari Produse Auxiliare Organice, Medias Low aliphatic prim. and sec. amine(s) prodn. - by reductive ammonolysis of low alcohol(s) and ketone(s) over a nickel and cobalt contg. catalyst

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2937325A1 (en) * 1979-09-14 1981-04-09 Institutul De Cercetari Produse Auxiliare Organice, Medias Low aliphatic prim. and sec. amine(s) prodn. - by reductive ammonolysis of low alcohol(s) and ketone(s) over a nickel and cobalt contg. catalyst

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Akira Miyazawa,et al.Reaction of primary amines with Pt/C catalyst in water under microwave irradiation: a convenient synthesis of secondary amines from primary amines.《Tetrahedron Letters》.2006,第47卷1437-1439. *

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