CN103420846B - Production method of isopropylamine - Google Patents
Production method of isopropylamine Download PDFInfo
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- CN103420846B CN103420846B CN201210150940.XA CN201210150940A CN103420846B CN 103420846 B CN103420846 B CN 103420846B CN 201210150940 A CN201210150940 A CN 201210150940A CN 103420846 B CN103420846 B CN 103420846B
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Abstract
The invention relates to a production method of isopropylamine, and puts forward that: segmentally loading a fixed bed reactor with catalysts of different properties, loading an entrance end with a spherical nickel-base catalyst of moderate activity, loading an outlet end with a strip-type nickel-based catalyst of higher activity, under suitable reaction conditions, performing an hydrogen ammoniation reaction of acetone to produce the isopropylamine, and thus obtaining a isopropylamine product via necessary separation and refining. Through use of the production method of the isopropylamine, circulation of diisopropylamine and isopropyl alcohol can be avoided, energy consumption can be reduced, and a diisopropylamine distillation system inconvenient to operate can be omitted; and the production method of the isopropylamine is simple, feasible and easy to implement, and has considerable industrial application value and economic benefit.
Description
Technical field
The present invention relates to a kind of method of producing amine, more particularly, the present invention relates to a kind of method of producing Isopropylamine.
Technical background
Isopropylamine is the important source material of production Multiple Pesticides such as G-30027, isofenphos_methyl and Buprofezin etc.; Also can be used for producing washing composition such as Witco 1298 Soft Acid isopropyl amine salt etc.; Also widespread use in rubber industry and medicine industry.
The production method of people's p-isopopylaniline has carried out large quantity research, and some is also applied in the industry maturely.Wherein mainly contain: (1) Virahol gas phase ammoniation process, the method take Virahol as raw material, under copper, nickel or cobalt catalyst exist, Virahol and ammonia react and generate Isopropylamine under hydro condition, disclosed in United States Patent (USP) No. 2349461, No. 2636902, reaction conditions is: temperature 180 ~ 250 DEG C, pressure 1.0 ~ 2.5MPa, and volume space velocity is 0.2h-1; (2) acetone hydrogen ammonating process, the method take acetone as raw material, and use Ni catalyzer, acetone and hydrogen, ammonia carry out hydrogen aminating reaction, generates Isopropylamine.The nickel catalyzator produced as used Beijing Chemical Research Institute, makes acetone carry out hydrogen aminating reaction in fixed-bed reactor, and this catalyst technology is ripe, has industrially used for many years.
Although acetone hydrogen ammonating process is very ripe, in fixed-bed reactor, acetone 100% ground Isopropylamine be can not be changed into, Diisopropylamine, Virahol is inevitably generated.Conventional mode is that Diisopropylamine, Virahol are looped back reactor and continue reaction generation Isopropylamine, cause energy consumption to increase, reactor for treatment amount strengthens, and a large amount of Diisopropylamine that circulates easily produces coking, reduce catalyst activity, also can result in blockage reactor and pipeline.Thus circulate in a large number Diisopropylamine, Virahol is not basic terms of settlement.For this reason, CN 95102074.9 proposes to increase an auxiliary reactor in technical process, and the temperature of reaction of auxiliary reactor is 140 ~ 150 DEG C, and main reactor adopts sectional temperature-controlled, and epimere temperature is 90 ~ 150 DEG C, and hypomere temperature is 50 ~ 90 DEG C.Adopt sectional temperature-controlled object to be carry out gas-solid phase reaction in epimere, hypomere temperature of reaction reduces, and makes reaction be converted into gas-liquid-solid phase reaction, can improve purity and the yield of product like this.In auxiliary reactor, the Diisopropylamine of unreacted acetone, generation, iso-propanol conversion are become Isopropylamine.This patent adopts major-minor two reactors, does not need Diisopropylamine, Virahol to be recycled to main reactor.But owing to using two reactors, facility investment increases, and running cost also strengthens, and does not thus also have industrial application at present.
An industrial still use reactor at present, carry out single hop and control, Discrete control, does not loop back reactor by the Diisopropylamine of generation and Virahol, with hydrogen, ammonia react together with fresh acetone, generates Isopropylamine.But because reactor adopts single hop to control, be suitable for the hydrogen aminating reaction of acetone, temperature of reaction concerning Diisopropylamine generate Isopropylamine reaction still lower, thus the Diisopropylamine looped back can not change into Isopropylamine ideally, thus cause the concentration of Diisopropylamine in production equipment more and more higher, namely there is accumulation, at least need the distillation system opening separation Diisopropylamine termly with the Diisopropylamine concentration in reduction system, but the separation of Diisopropylamine uses Diisopropylamine, isopropyl alcohol and water forms the principle of ternary azeotrope, thus the distillation system operation being separated Diisopropylamine is very difficult, be easy to cause general tower, thus increase manufacturing cost.
In sum, existing Isopropylamine industrial installation also exists and generates the undesirable problem of the selectivity of Isopropylamine.
Summary of the invention
The present invention in order to overcome the defect of prior art, and considers industrial easy realization, proposes in fixed-bed reactor, to load the different catalyzer of two kinds of performances, for the building-up reactions of Isopropylamine.
Concrete technical scheme is as follows:
The method of production Isopropylamine of the present invention is: in fixed-bed reactor, catalyst based near inlet end filling spherical nickel, near exit end filling bar shaped nickel-base catalyst, the specific surface area that described spherical nickel is catalyst based and pore volume are respectively 170 ~ 220m2/g and 0.5 ~ 0.8ml/g, specific surface area and the pore volume of described bar shaped nickel-base catalyst are respectively 140 ~ 170m2/g and 0.3 ~ 0.5ml/g, the catalyst based loading height of described spherical nickel is 1/4 ~ 1/2 of fixed-bed reactor bed height, under the existence of described two kinds of catalyzer, acetone, hydrogen and ammonia carry out hydrogen aminating reaction and generate the reaction product that Isopropylamine is master, temperature of reaction is 80 ~ 150 DEG C, reaction pressure is 0.7 ~ 1.6MPa, acetone solution hourly space velocity is 0.1 ~ 1.2h-1, acetone: hydrogen: the mol ratio of ammonia is 1: 1 ~ 4: 1 ~ 6.
It is an exothermic process that acetone hydrogen aminating reaction produces Isopropylamine, and thermal discharge is larger.Adopt the catalyzer that single activity is higher, at reactor inlet end, violent thermopositive reaction occurs, be difficult to liberated heat to shift out, cause local reaction temperature higher like this, side reaction is more, and the Diisopropylamine amount of generation is more.In the present invention, catalyst based in the active moderate spherical nickel of reactor inlet end filling, make the response intensity of inlet end moderate, reaction heat can be shifted out in time, thus effectively can control temperature of reaction, correspondingly reduce side reaction.Through reaction to a certain degree, acetone concentration reduces, and speed of reaction reduces, and at this moment enters active higher bar shaped nickel-base catalyst bed, thus improves conversion rate, enhance productivity.The catalyst for isopropylamine BC-A-30 that the catalyst based preferred Beijing Chemical Research Institute of described spherical nickel produces, the XH-3 catalyzer that the preferred ZheJiang XinHua Chemical Engineering Co., Ltd of described bar shaped nickel-base catalyst produces.
The conversion rate of acetone is not only relevant to temperature of reaction, and be subject to the activity influence of catalyzer, for improving the production efficiency of whole reactor and controlling reaction conditions to improve reaction preference, the catalyst based loading height of described spherical nickel is preferably 1/4 ~ 1/3 of fixed-bed reactor bed height.
Acetone generates Isopropylamine through hydrogen aminating reaction, for obtaining Isopropylamine product, needing through required separation and refining, said method comprising the steps of:
(1) synthesis of Isopropylamine:
In fixed-bed reactor, catalyst based near inlet end filling spherical nickel, near exit end filling bar shaped nickel-base catalyst, the specific surface area that described spherical nickel is catalyst based and pore volume are respectively 170 ~ 220m2/g and 0.5 ~ 0.8ml/g, specific surface area and the pore volume of described bar shaped nickel-base catalyst are respectively 140 ~ 170m2/g and 0.3 ~ 0.5ml/g, the catalyst based loading height of described spherical nickel is 1/4 ~ 1/2 of fixed-bed reactor bed height, under the existence of described two kinds of catalyzer, raw material acetone, hydrogen and ammonia carry out hydrogen aminating reaction and generate the reaction product that Isopropylamine is master, reaction conditions is: temperature of reaction is 80 ~ 150 DEG C, and reaction pressure is 0.7 ~ 1.6MPa, and acetone solution hourly space velocity is 0.1 ~ 1.2h-1, acetone: hydrogen: the mol ratio of ammonia is 1: 1 ~ 4: 1 ~ 6,
(2) material of self-retaining bed bioreactor cools in the future, and carry out gas-liquid separation, gas returns reactor through compressor recirculated compressed, and liquid sends into deammoniation tower, isolates ammonia, delivers to reactor, be rich in the material of Isopropylamine from tower reactor extraction from tower top;
(3) material being rich in Isopropylamine from deamination tower reactor is incorporated into Isopropylamine tower, in Isopropylamine tower through refinery distillation from overhead extraction Isopropylamine product, tower reactor extraction contains the material of Diisopropylamine, isopropyl alcohol and water;
(4) Isopropylamine tower reactor is contained the material introducing film separating system of Diisopropylamine, isopropyl alcohol and water, after the dehydration of film separating system film, be used as the raw material of production Diisopropylamine containing the organic phase of Virahol, Diisopropylamine.
Reactor of the present invention can be upper feeding mode, also can be lower feeding manner.
In the method for the invention, cooling carrys out substantially identical with existing full scale plant of the water cooler of material of autoreactor, gas-liquid separator, Isopropylamine tower and dehydration tower.Content disclosed in CN 95102074.9 is all introduced reference.
The method simple possible of synthesizing isopropamide of the present invention, only need a reactor, Diisopropylamine distillation system is not built in whole device, as long as the catalyzer that segmentation filling performance is different in fixed-bed reactor just can improve the selectivity of reaction greatly, thus method of the present invention easily realizes, and can omit Diisopropylamine distillation system, greatly reduce cost of investment and running cost, and convenient operation, method is simple, has considerable economic benefit.
Embodiment
Explain and illustrate the method for production Isopropylamine of the present invention below by way of example further, but method of the present invention is not limited to cited embodiment.
Embodiment 1
Fixed-bed reactor are the stainless steel reactor of 32 × 3mm, length 1350mm.The stainless steel temperature-measuring casing of ∮ 8 × 1mm is set in reactor, the trade mark that filling Beijing Chemical Research Institute produces successively is from top to bottom the trade mark that BC-A-30 ball-type catalyst for isopropylamine and ZheJiang XinHua Chemical Engineering Co., Ltd produce is XH-3 stripe shape catalyzer, catalyst loading total height is 960mm, wherein ball shape catalyst loading height is 270mm, stripe shape catalyst packing height is 690mm, and loaded catalyst is 510ml.Reaction raw materials is upper entering and lower leaving, and the material flowed out from reactor bottom enters separator after condensing cooling, and vapor phase ammonia, hydrogen are discharged from separator top, bottom liquid phases timing sampling.
Temperature of reaction is 105 DEG C, and reaction pressure is 0.8MPa, and acetone liquid hourly space velocity is 0.5L acetone/(L catalyzer hour), acetone: hydrogen: the mol ratio of ammonia is 1: 3: 3.Reaction result: acetone conversion 99%, Isopropylamine selectivity is about 95%, Diisopropylamine selectivity about 3.3%, Virahol selectivity about 1.7%.
Embodiment 2
Fixed-bed reactor are the stainless steel reactor of 32 × 3mm, length 1350mm.The stainless steel temperature-measuring casing of ∮ 8 × 1mm is set in reactor, the trade mark that filling Beijing Chemical Research Institute produces successively is from top to bottom the trade mark that BC-A-30 ball-type catalyst for isopropylamine and ZheJiang XinHua Chemical Engineering Co., Ltd produce is XH-3 stripe shape catalyzer, catalyst loading total height is 960mm, wherein ball shape catalyst loading height is 305mm, stripe shape catalyst packing height is 655mm, and loaded catalyst is 510ml.Reaction raw materials is upper entering and lower leaving, and the material flowed out from reactor bottom enters separator after condensing cooling, and vapor phase ammonia, hydrogen are discharged from separator top, bottom liquid phases timing sampling.
Temperature of reaction is 105 DEG C, and reaction pressure is 0.8MPa, and acetone liquid hourly space velocity is 0.5L acetone/(L catalyzer hour), acetone: hydrogen: the mol ratio of ammonia is 1: 3: 3.Reaction result: acetone conversion 99%, Isopropylamine selectivity is about 96%, Diisopropylamine selectivity about 2.4%, Virahol selectivity about 1.6%.
Embodiment 3
The catalyst loading pattern of embodiment 3-5 is as embodiment 2.
Temperature of reaction is 115 DEG C, and reaction pressure is 1.0MPa, and acetone liquid hourly space velocity is 0.7L acetone/(L catalyzer hour), acetone: hydrogen: the mol ratio of ammonia is 1: 3: 3.Reaction result: acetone conversion 100%, Isopropylamine selectivity 98.6%, Diisopropylamine selectivity about 1.0%, Virahol selectivity about 0.4%.
Embodiment 4
Temperature of reaction is 125 DEG C, and reaction pressure is 1.2MPa, and acetone liquid hourly space velocity is 0.9L acetone/(L catalyzer hour), acetone: hydrogen: the mol ratio of ammonia is 1: 3: 3.Reaction result: acetone conversion 100%, Isopropylamine selectivity more than 99.3%, Diisopropylamine selectivity about 0.52%, Virahol selectivity about 0.18%.
Embodiment 5
Temperature of reaction is 140 DEG C, and reaction pressure is 1.5MPa, and acetone liquid hourly space velocity is 1.1L acetone/(L catalyzer hour), acetone: hydrogen: the mol ratio of ammonia is 1: 3: 3.Reaction result: acetone conversion 100%, Isopropylamine selectivity is about 98.7%, Diisopropylamine selectivity about 1.1%, Virahol selectivity about 0.2%.
Claims (4)
1. produce a method for Isopropylamine, it is characterized in that, in fixed-bed reactor, catalyst based near inlet end filling spherical nickel, near exit end filling bar shaped nickel-base catalyst, the specific surface area that described spherical nickel is catalyst based and pore volume are respectively 170 ~ 220m
2/ g and 0.5 ~ 0.8ml/g, specific surface area and the pore volume of described bar shaped nickel-base catalyst are respectively 140 ~ 170m
2/ g and 0.3 ~ 0.5ml/g, the catalyst based loading height of described spherical nickel is 1/4 ~ 1/2 of fixed-bed reactor bed height, under the existence of described two kinds of catalyzer, raw material acetone, hydrogen and ammonia carry out hydrogen aminating reaction and generate the reaction product that Isopropylamine is master; Reaction conditions is: temperature of reaction is 80 ~ 150 DEG C, and reaction pressure is 0.7 ~ 1.6MPa, and acetone solution hourly space velocity is 0.1 ~ 1.2h
-1, acetone: hydrogen: the mol ratio of ammonia is 1:1 ~ 4:1 ~ 6; The catalyst based trade mark for Beijing Chemical Research Institute's production of described spherical nickel is BC-A-30 catalyst for isopropylamine, and described bar shaped nickel-base catalyst is the trade mark that ZheJiang XinHua Chemical Engineering Co., Ltd produces is XH-3 catalyzer.
2. the method for production Isopropylamine according to claim 1, is characterized in that, the catalyst based loading height of described spherical nickel is 1/4 ~ 1/3 of fixed-bed reactor bed height.
3. the method for production Isopropylamine according to claim 1, is characterized in that, reactor may optionally be upper feeding mode, or lower feeding manner.
4. the method for production Isopropylamine according to claim 1, is characterized in that, described method comprises the steps:
(1) synthesis of Isopropylamine:
In fixed-bed reactor, catalyst based near inlet end filling spherical nickel, near exit end filling bar shaped nickel-base catalyst, the specific surface area that described spherical nickel is catalyst based and pore volume are respectively 170 ~ 220m
2/ g and 0.5 ~ 0.8ml/g, specific surface area and the pore volume of described bar shaped nickel-base catalyst are respectively 140 ~ 170m
2/ g and 0.3 ~ 0.5ml/g, the catalyst based loading height of described spherical nickel is 1/4 ~ 1/2 of fixed-bed reactor bed height, under the existence of described two kinds of catalyzer, raw material acetone, hydrogen and ammonia carry out hydrogen aminating reaction and generate the reaction product that Isopropylamine is master; Reaction conditions is: temperature of reaction is 80 ~ 150 DEG C, and reaction pressure is 0.7 ~ 1.6MPa, and acetone solution hourly space velocity is 0.1 ~ 1.2h
-1, acetone: hydrogen: the mol ratio of ammonia is 1:1 ~ 4:1 ~ 6;
(2) material of self-retaining bed bioreactor cools in the future, and carry out gas-liquid separation, gas returns reactor through compressor recirculated compressed, and liquid sends into deammoniation tower, isolates ammonia, delivers to reactor, be rich in the material of Isopropylamine from tower reactor extraction from tower top;
(3) material being rich in Isopropylamine from deamination tower reactor is incorporated into Isopropylamine tower, in Isopropylamine tower through refinery distillation from overhead extraction Isopropylamine product, tower reactor extraction contains the material of Diisopropylamine, isopropyl alcohol and water;
(4) Isopropylamine tower reactor is contained the material introducing film separating system of Diisopropylamine, isopropyl alcohol and water, after the dehydration of film separating system film, be used as the raw material of production Diisopropylamine containing the organic phase of Virahol, Diisopropylamine.
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| CN103965055B (en) * | 2014-05-26 | 2015-11-18 | 浙江建业化工股份有限公司 | The synthetic method of Isopropylamine |
| CN106397219B (en) * | 2016-08-26 | 2018-03-27 | 安徽昊源化工集团有限公司 | A kind of method of acetone hydrogenation ammonification synthesizing isopropamide |
| CN110066223A (en) * | 2018-01-22 | 2019-07-30 | 北京颖泰嘉和生物科技股份有限公司 | The preparation method of 1- methoxyl group -2- propylamine |
| CN110152714B (en) * | 2018-03-20 | 2022-04-01 | 浙江建业化工股份有限公司 | Catalyst for producing isobutylamine and diisobutylamine and use method thereof |
| 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 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040122259A1 (en) * | 2002-12-20 | 2004-06-24 | Till Gerlach | Preparation of an amine |
| CN101684073A (en) * | 2008-09-28 | 2010-03-31 | 中国石油化工股份有限公司 | Method for producing isopropylamine |
| CN101816938A (en) * | 2009-02-27 | 2010-09-01 | 中国石油化工股份有限公司 | Catalyst for preparing isopropamide by aminating acetone as well as preparation method and application thereof |
| CN101880236A (en) * | 2009-05-08 | 2010-11-10 | 中国石油化工股份有限公司 | Method for synthesizing isopropamide |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040122259A1 (en) * | 2002-12-20 | 2004-06-24 | Till Gerlach | Preparation of an amine |
| CN101684073A (en) * | 2008-09-28 | 2010-03-31 | 中国石油化工股份有限公司 | Method for producing isopropylamine |
| CN101816938A (en) * | 2009-02-27 | 2010-09-01 | 中国石油化工股份有限公司 | Catalyst for preparing isopropamide by aminating acetone as well as preparation method and application thereof |
| CN101880236A (en) * | 2009-05-08 | 2010-11-10 | 中国石油化工股份有限公司 | Method for synthesizing isopropamide |
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