CN108129330A - A kind of cyclopropylamine continuous production system and production method - Google Patents
A kind of cyclopropylamine continuous production system and production method Download PDFInfo
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- CN108129330A CN108129330A CN201711492500.1A CN201711492500A CN108129330A CN 108129330 A CN108129330 A CN 108129330A CN 201711492500 A CN201711492500 A CN 201711492500A CN 108129330 A CN108129330 A CN 108129330A
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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
- C07C209/54—Preparation of compounds containing amino groups bound to a carbon skeleton by rearrangement reactions
- C07C209/58—Preparation of compounds containing amino groups bound to a carbon skeleton by rearrangement reactions from or via amides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
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Abstract
The invention belongs to chemical production fields, and in particular to a kind of cyclopropylamine continuous production system and production method.The cyclopropylamine continuous production system includes the following process units connected in order：First order reaction distillation still, second order reaction distillation still, ammoniation reactor, deamination tank, flash tank, eparating methanol tower, phase-splitter and degradation reaction device.The method that the cyclopropylamine continuous production system carries out cyclopropylamine production is the present invention relates to the use of, solves the problems, such as existing cyclopropylamine intermittence production；It improves in cyclization, ammonification, ammonification distillation process, material fluidity and filterability；Ring propyl formamide degradation technique is improved, while ensures reaching for high conversion and high cyclopropylamine yield, realizes the continuous production of cyclopropylamine.
Description
Technical field
The invention belongs to chemical production fields, and in particular, to a kind of cyclopropylamine continuous production system and production method.
Background technology
Cyclopropylamine (CPA) is the fatty amine of three-membered ring, belongs to important medicine intermediate, is widely used in medicine, pesticide
The fields of grade can be used for synthesizing Ciprofloxacin, Enrofloxacin, the antibacterials such as Sparfloxacin, it can also be used to prepare ring pretilachlor,
The chemical herbicides such as cyprazine.
One of method of plant produced cyclopropylamine is at present：Chloro methyl butyrate is used as raw material, through the ring with sodium methoxide
Close reaction generation cyclopropanecarboxylic acid methyl esters, cyclopropanecarboxylic acid methyl esters generates ring propyl formamide (CPCA), ring third after medium temperature and medium pressure ammonification
Formamide carries out Hofmann degradation to get to cyclopropylamine after ammonification is distilled with sodium hypochlorite.
Industrially, due to various technical problems, entire cyclopropylamine production procedure is intermittent operation, and there is no real
The production of existing serialization.And existing cyclopropylamine intermittence production system and reaction condition are as follows：
Device in existing cyclopropylamine Batch Process system mainly has：Ring-closure reaction kettle, high pressure ammoniated reaction kettle, methanol
Dimethylbenzene distillation still, slightly steams preposition distillation still, cyclopropylamine crude steam kettle and cyclopropylamine rectifying still group at ring propyl formamide degradation reaction kettle
Into more than equipment is required for carrying out intermittent operation.First, sodium methoxide and chloro methyl butyrate carry out ring in ring-closure reaction kettle
Reaction generation cyclopropanecarboxylic acid methyl esters is closed, is then sent material to high pressure aminating reaction kettle, the liquid feeding ammonia into high pressure ammoniated reaction kettle
Carry out aminating reaction, then move and expect methanol dimethylbenzene distillation still, distill to material in kettle in after semisolid plus water, water layer send to
Ring propyl formamide degradation reaction kettle；Lye is added in ring propyl formamide degrades kettle and liquor natrii hypochloritis carries out degradation reaction,
Material is then moved to preposition distillation still is slightly steamed, cyclopropylamine crude steam kettle and cyclopropylamine rectifying still are operated, and rectifying obtains cyclopropylamine product.
In first step ring-closure reaction, there is a large amount of NaCl to generate, and salt can increase in the presence of organic phase (such as dimethylbenzene)
The viscosity of big reaction solution, reduces its mobility, makes troubles to continuous production and parameter.The ring third of second step aminating reaction generation
Formamide solubility in solvent (such as dimethylbenzene) is smaller, so ring propyl formamide can also be precipitated when temperature is relatively low so that anti-
Liquid mobility is answered to become worse.The Hofmann degradation of third step is last of existing common cyclopropylamine (CPA) production technology
A reaction and yield are relatively low, a more link of parameter.Hofmann degradation process actually contains substitution, disappears
Except (rearrangement) and hydrolysis three phases or two stages of chlorination and decarburization (rearrangement product easily hydrolyzes, thus can will eliminate and
Two stages of hydrolysis, which merge, is known as " decarburization " stage).During Hofmann degradation, two side reactions can produce the yield of CPA
Raw important influence, one is the hydrolysate (such as carbon dioxide) of ring propyl formamide (CPCA), the second is superfluous sodium hypochlorite
The impurity such as the oxidation generation nitrile to raw material, intermediate product and target product.The content of alkali in solution, reaction temperature and has
The addition of chlorine is imitated, there is different degrees of influence to three phases during Hofmann degradation, there is reaction yield very big
Parameter, bring the problem of many to the realization of continuous operation.
So far, due to there are above-mentioned various technical problems, intermittent operation technique that the industrialized production of cyclopropylamine uses,
Low production efficiency, product yield is low and unstable, also there is many rooms for promotion.
Therefore, a kind of system and method for continuous production cyclopropylamine are developed, are received to improving production efficiency and promoting product
Rate is of great significance.
Invention content
In order to solve the above-mentioned technical problem, one of the objects of the present invention is to provide a kind of cyclopropylamine continuous production systems
System.It can be with continuous production cyclopropylamine using the production system.
To achieve these goals, cyclopropylamine continuous production system provided by the invention connects in order including following
Process units：First order reaction distillation still, ammoniation reactor, deamination tank, flash tank, eparating methanol tower, is divided at second order reaction distillation still
Phase device and degradation reaction device.
Wherein, the ammoniation reactor is autoclave ammoniation reactor or tubular type ammoniation reactor.It is preferred that tubular type aminating reaction
Device.
Wherein, the degradation reaction device is autoclave degradation reaction device or tubular type degradation reaction device, preferably tubular type degradation reaction
Device.
Cyclopropylamine continuous production system provided by the invention, further includes continuous coarse destilling tower and company after degradation reaction device
Continuous essence destilling tower.
Cyclopropylamine continuous production system provided by the invention further includes pipeline, the control instrument for connecting each process units
And.Automatic control system uses the control based on DCS (Distributed Control System, dcs)
Technology.
Wherein, the attachment is the attachmentes such as heat supply, cooling, safety.
It is continuous using above-mentioned cyclopropylamine another object of the present invention is to provide a kind of cyclopropylamine continuous production method
Change production system, including：
Step a) chloros methyl butyrate, sodium methoxide and solvent continuously enter first order reaction distillation still, chloro methyl butyrate and
Sodium methoxide carries out cyclization generation cyclopropanecarboxylic acid methyl esters, and methanol, the kettle of first order reaction distillation still are constantly steamed in reaction process
Bottom product enters second order reaction distillation still further reaction and distillating carbinol；
The methanol and second order reaction distillation still that step b) first order reactions distillation still and second order reaction distillation still steam come out
Material and NH3It is mixed into ammoniation reactor, cyclopropanecarboxylic acid methyl esters and NH3Carry out aminating reaction generation ring propyl formamide, reaction
Material sequentially enters deamination tank, flash tank and eparating methanol tower removing NH after being come out from ammoniation reactor3And methanol；
The material that step c) comes out from eparating methanol tower bottom adds water to mix, and extracts ring propyl formamide into phase-splitter and detaches
Oil phase and water phase；
The water phase that step d) phase-splitters come out is mixed into degradation reaction device with NaClO, NaOH aqueous solution and degrade instead
Cyclopropylamine should be generated.
Cyclopropylamine continuous production method provided by the invention, the cyclopropylamine that step d) is obtained are crude product cyclopropylamines, the life
Production method further includes：
Step e) from degradation reaction device come out material through continuous coarse destilling tower and the isolated ring third of continuous fine destilling tower
Amine purified product.
Specifically, the aqueous solution containing cyclopropylamine is obtained from the material that degradation reaction device comes out through continuous coarse distillation column distillation,
Cyclopropylamine aqueous solution is into the isolated pure cyclopropylamine product of continuous fine destilling tower, i.e. cyclopropylamine purified product.Present invention purification
The effect of two stage rectification be：Since a step rectifying tower is excessively high and complicated, it is extremely difficult to ideal separating effect；Two-stage
Rectification effect is preferable.
Wherein, step a) solvent for use can select dimethylbenzene, it is also an option that toluene, trimethylbenzene etc..It is preferred that dimethylbenzene.
Wherein, the molar ratio of step a) chloros methyl butyrate, sodium methoxide and solvent is 1：(1~1.5)：(0.5~2), object
Expect mobility and filterability enhancing.
Wherein, the reaction temperature of step a) cyclizations is 65~150 DEG C, and reaction pressure is 80~150Kpa.As excellent
Choosing, reaction temperature are 90~110 DEG C, and reaction pressure is 90~110Kpa.
(i.e. first order reaction distillation still and two level are anti-in the reaction distillation kettle of two-stage series connection for the cyclization of step a) of the present invention
Answer distillation still) in carry out, side border ring steams methanol, and cyclization is made to balance to direction shifting generate conducive to cyclopropanecarboxylic acid methyl esters
It is dynamic, back-mixing can be reduced using two-stage reaction distillation still compared with first order reaction distillation still, improve reaction rate and yield.
Wherein, the material come out through second order reaction distillation still includes cyclopropanecarboxylic acid methyl esters and solvent.
Wherein, the reaction temperature of step b) aminating reactions is 35~100 DEG C, and reaction pressure is 0.8~2MPa.As excellent
Choosing, preferably 70~90 DEG C of reaction temperature, reaction pressure are 1~1.5Mpa.
Wherein, step b) reaction masses include ring propyl formamide, NH3And methanol.
Production method of the present invention, using deamination tank, flash tank and eparating methanol tower removing ammonia after aminating reaction
And methanol.That is：
Step b) aminating reactions of the present invention, reaction product sequentially enter deamination tank and flash tank after being come out from ammoniation reactor
Remove NH3With part methanol, the material come out from flash tank bottom further removes remaining methanol into eparating methanol tower.
Wherein, the material come out from flash tank bottom includes：Ring propyl formamide, dimethylbenzene, methanol and sodium chloride.
Step b) aminating reactions of the present invention are pressure and the removing stablized in ammoniation reactor 3 using the effect of deamination tank 4
Part NH3。
Step b) aminating reactions of the present invention remove remaining NH using flash tank 5, eparating methanol tower 63With remaining methanol.
Step c) of the present invention detaches the aqueous solution of solvent and ring propyl formamide using phase-splitter 7.The present invention is extracted using water
Ring propyl formamide, and dimethylbenzene oil phase and water phase rich in ring propyl formamide are detached with phase-splitter, so as to take off solvent (such as diformazan
Benzene).
Wherein, the reaction temperature of step d) degradation reactions is -15~30 DEG C, and reaction pressure is 80~150Kpa.As excellent
Choosing, reaction temperature are 5~15 DEG C, and reaction pressure is 110~130Kpa.
Production method of the present invention, chloro methyl butyrate and NH3Raw materials components mole ratio be 1:(1~3).
The raw materials components mole ratio of production method of the present invention, step c) plus water extraction, ring propyl formamide and water is 1:(2~
5)。
Production method of the present invention, ring propyl formamide and sodium hypochlorite (count) raw materials components mole ratio as 1 using effective chlorine:(1.1
~2.5).
The raw materials components mole ratio 1 of production method of the present invention, ring propyl formamide and sodium hydroxide:(2~4).
Production method of the present invention, NH3Charging can be ammonia, liquefied ammonia or ammonium hydroxide, preferably liquefied ammonia.
Production method of the present invention, the sodium hypochlorite and sodium hydroxide that cyclopropylamine degradation reaction uses can be solid
Can be its respective aqueous solution, preferably its respective aqueous solution.
Production method of the present invention, entire production procedure are operated for continuity.Trend of the material in each device be：Profit
With above-mentioned continuous production system, material and second order reaction distillation still that first order reaction distillation still and second order reaction distillation still steam
Enter ammoniation reactor after the material mixing that bottom comes out, the material of the generation of ammoniation reactor sequentially enters deamination tank, flash distillation
Tank, eparating methanol tower and phase-splitter, the material of phase-splitter enter degradation reaction device and obtain cyclopropylamine crude product, and cyclopropylamine crude product enters ring
Propylamine continuous coarse destilling tower, cyclopropylamine continuous fine destilling tower obtain cyclopropylamine purified product.
The invention has the advantages that：The production system and production method of the present invention is reacted using two-stage series connection and steamed
It evaporates kettle, ammoniation reactor, deamination tank, flash tank, phase-splitter, degradation reaction device and continuous coarse and steams tower and rectifying tower, it can
It is operated continuously, conducive to cyclopropylamine yield and production efficiency is improved, realizes the continuous production of whole process.
The present invention obtains the high cyclopropylamine product of purity, and cyclopropylamine total recovery is height.Product quality is high and stablizes, and labour is strong
Spend low, device production efficiency height.
The present invention solves the problems, such as existing cyclopropylamine intermittence production；It improves in cyclization, ammonification, ammonification distillation process,
Material fluidity and filterability；Ring propyl formamide degradation technique is improved, while ensures that high conversion and high cyclopropylamine height are received
Rate is reached, and realizes the continuous production of cyclopropylamine.
Description of the drawings
Fig. 1 is the connection diagram of cyclopropylamine continuous production system.
Wherein, 1 it is first order reaction distillation still, 2 be second order reaction distillation still, 3 be ammoniation reactor, 4 be deamination tank, 5 is
Flash tank, 6 be eparating methanol tower, 7 be phase-splitter, 8 be degradation reaction device, 9 be continuous coarse destilling tower and 10 be continuous fine destilling tower.
Specific embodiment
The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention..
Unmentioned operation is the routine operation of this field in the present invention, in the present invention material that refers to be can be from
The conventional material being commercially available in the market.
Embodiment 1
The production system of continuous production cyclopropylamine includes the following process units connected in order：First order reaction distillation still
1 and second order reaction distillation still 2, tubular type ammoniation reactor 3, deamination tank 4, flash tank 5, eparating methanol tower 6, phase-splitter 7, tubular type degradation
Reactor 8, cyclopropylamine continuous coarse destilling tower 9, cyclopropylamine continuous fine destilling tower 10, equipment connecting pipeline, control instrument and attachment
(heat supply, cooling, safety etc.).
Above-mentioned each device is linked in sequence successively, and trend of the material in each device is (as shown in Figure 1)：First order reaction is distilled
Material (the ring that the material (methanol) that kettle 1 and second order reaction distillation still 2 steam comes out through pipeline and 2 bottom of second order reaction distillation still
Third methyl formate and solvent xylene) the laggard tubular type ammoniation reactor 3 of mixing, the material (ring of the generation of tubular type ammoniation reactor 3
Propyl formamide, NH3And methanol) sequentially enter deamination tank 4, flash tank 5, eparating methanol tower 6 and phase-splitter 7, the material of phase-splitter 7
(ring propyl formamide) obtains cyclopropylamine crude product into tubular type degradation reaction device 8, and cyclopropylamine crude product enters the continuous simple distillation of cyclopropylamine
Tower 9, cyclopropylamine continuous fine destilling tower 10 obtain cyclopropylamine purified product.
The method of continuous production cyclopropylamine includes：
Step a) chloros methyl butyrate and sodium methoxide solid and dimethylbenzene in molar ratio 1：1.2：1 continuously enters first order reaction
Distillation still, wherein dimethylbenzene are solvents, and chloro methyl butyrate and sodium methoxide carry out cyclization generation cyclopropanecarboxylic acid methyl esters, reaction
104 DEG C, pressure 100kPa of temperature constantly steams methanol in reaction process, and it is further that bottom product enters second order reaction distillation still
React simultaneously distillating carbinol；
Methanol that step b) first order reactions distillation still and second order reaction distillation still steam and comprising second order reaction distillation still
The material (cyclopropanecarboxylic acid methyl esters and dimethylbenzene) of bottom product is mixed into tubular type ammoniation reactor, cyclopropanecarboxylic acid methyl esters with liquefied ammonia
With NH3(chloro methyl butyrate and NH3Raw materials components mole ratio be 1:2) aminating reaction generation ring is carried out in tubular type ammoniation reactor
Propyl formamide, 80 DEG C, 1~1.3MPa of pressure of reaction temperature, reaction product come out laggard successively into deamination tank from ammoniation reactor
NH is removed with flash tank3With part methanol, the material come out from flash tank bottom further pulls out remaining first into eparating methanol tower
Alcohol；
The material that step c) comes out from eparating methanol tower bottom adds water, and (raw materials components mole ratio of ring propyl formamide and water is 1:3) it mixes
It closes, ring propyl formamide is extracted, and detach oil phase and water phase into phase-splitter；
Water phase and the (charging of ring propyl formamide and sodium hypochlorite of NaClO, NaOH aqueous solution that step d) comes out from phase-splitter
Molar ratio is 1：2, the raw materials components mole ratio of ring propyl formamide and sodium hydroxide is 1:3) tubular type degradation reaction device is mixed into 10
~13 DEG C, pressure 120Kpa progress degradation reaction generation cyclopropylamines；
Step e) from degradation reaction device come out material through the isolated water containing cyclopropylamine of cyclopropylamine continuous coarse destilling tower
Solution, the cyclopropylamine solution that cyclopropylamine continuous coarse distillation tower top steams obtain purity into cyclopropylamine continuous fine destilling tower rectifying and are
99.95% cyclopropylamine product, total recovery 93%.
Embodiment 2
The present embodiment and 1 other content all same of embodiment, difference：Sodium methoxide charging uses during cyclization
30% methanol solution of sodium methylate.Cyclopropylamine product purity is 99.95%, total recovery 92%.
Embodiment 3
The present embodiment and 1 other content all same of embodiment, difference：The reactor of degradation reaction uses still reaction
Device, reaction temperature are controlled at 0~13 DEG C.Cyclopropylamine product purity is 99.95%, total recovery 91%.
Embodiment 4
The present embodiment and 1 other content all same of embodiment, difference：Chloro methyl butyrate and sodium methoxide solid and two
Toluene is 1 in molar ratio：1.5：2.Cyclopropylamine product purity is 99.95%, total recovery 91%.
Step a) solvent for use of the present invention replaces with toluene or trimethylbenzene, can also realize corresponding effect.
Comparative example
Cyclopropylamine intervalization production process is：In ring-closure reaction kettle, chloro methyl butyrate and 30% methanolic sodium methoxide are molten
Liquid and dimethylbenzene in molar ratio 1：1.2：1 adds in, and sodium methoxide and chloro methyl butyrate react generation cyclopropanecarboxylic acid first in a solvent
Ester, reaction kettle temperature control system fully react postcooling at 140 DEG C or so, then by sodium chloride-containing, the cyclopropanecarboxylic acid first after reaction
The material of ester, dimethylbenzene and methanol is sent to high pressure aminating reaction kettle；Into high pressure ammoniated reaction kettle, liquid feeding ammonia carries out aminating reaction,
Reaction carries out under heat-retaining condition, and temperature is controlled at 70~85 DEG C, 0.5~1.5MPa of pressure, has reacted cooling and has arranged extra ammonia,
Then it moves and expects methanol dimethylbenzene distillation still, distill to material in kettle in water is added after semisolid, water layer, which is sent to ring propyl formamide, to drop
Solution reaction kettle；Lye is added in ring propyl formamide degrades kettle and liquor natrii hypochloritis carries out degradation reaction, reaction temperature is kept
At -10~0 DEG C, material is fully moved after reaction to slightly steaming preposition distillation still；Preposition distillation still distillation procedure is slightly steamed to 115 DEG C of knots of kettle temperature
Beam, containing sodium carbonate, sodium chloride raffinate be emptied to geosyncline；Product of distillation of the raw material of cyclopropylamine crude steam kettle from upper step, ring third
Part is to positive part aqueous basin of degrading, time 2h before being steamed after the throwing piece alkali ammonia excretion of amine crude steam kettle, then steams positive part and store to positive part aqueous is slightly steamed
Tank is steamed to the 80 DEG C of end of top temperature；The positive part aqueous basin of slightly steaming of the cyclopropylamine rectifying still raw material from upper step, steams after adding piece alkali ammonia excretion
It evaporates to interior 80 DEG C or so of temperature and obtains refined cyclopropylamine product.
Entire production procedure each unit is intermittent operation, and the product purity finally obtained is 90.9%, and yield is about
79%.
Although above the present invention is described in detail with a general description of the specific embodiments,
On the basis of the present invention, it can be made some modifications or improvements, this will be apparent to those skilled in the art.Cause
This, these modifications or improvements, belong to the scope of protection of present invention without departing from theon the basis of the spirit of the present invention.
Claims (10)
1. a kind of cyclopropylamine continuous production system, including the following process units connected in order：First order reaction distillation still
(1), second order reaction distillation still (2), ammoniation reactor (3), deamination tank (4), flash tank (5), eparating methanol tower (6), phase-splitter (7)
With degradation reaction device (8).
2. cyclopropylamine continuous production system according to claim 1, which is characterized in that the system is after degradation reaction device
Further include simple distillation tower (9) and smart destilling tower (10).
3. a kind of cyclopropylamine continuous production method, using cyclopropylamine continuous production system described in claim 1, including：
Step a) chloros methyl butyrate, sodium methoxide and solvent continuously enter first order reaction distillation still, chloro methyl butyrate and methanol
Sodium carries out cyclization generation cyclopropanecarboxylic acid methyl esters, and methanol, the bottom production of first order reaction distillation still are constantly steamed in reaction process
Object enters second order reaction distillation still further reaction and distillating carbinol；
The object that the methanol and second order reaction distillation still that step b) first order reactions distillation still and second order reaction distillation still steam come out
Material and NH3It is mixed into ammoniation reactor, cyclopropanecarboxylic acid methyl esters and NH3Carry out aminating reaction generation ring propyl formamide, reaction mass
Deamination tank, flash tank and eparating methanol tower removing NH are sequentially entered after being come out from ammoniation reactor3And methanol；
The material that step c) comes out from eparating methanol tower bottom adds water to mix, and extracts ring propyl formamide into phase-splitter and detaches oil phase
And water phase；
The water phase that step d) phase-splitters come out is mixed into degradation reaction device with NaClO, NaOH aqueous solution and carries out degradation reaction life
Into cyclopropylamine.
4. cyclopropylamine continuous production method according to claim 3, which is characterized in that the cyclopropylamine that step d) is obtained is
Cyclopropylamine crude product, the production method further include：
Step e) is from the material that degradation reaction device comes out through simple distillation tower and the isolated cyclopropylamine purified product of smart destilling tower.
5. cyclopropylamine continuous production method according to claim 3 or 4, which is characterized in that solvent is dimethylbenzene, toluene
Or trimethylbenzene.
6. cyclopropylamine continuous production method according to claim 3 or 4, which is characterized in that step a) chloro butyric acid first
The molar ratio of ester, sodium methoxide and solvent is 1：(1~1.5)：(0.5~2).
7. cyclopropylamine continuous production method according to claim 3 or 4, which is characterized in that step a) cyclizations
Reaction temperature is 65~150 DEG C, and reaction pressure is 80~150Kpa；
The reaction temperature of step b) aminating reactions is 35~100 DEG C, and reaction pressure is 0.8~2Mpa；
The reaction temperature of step d) degradation reactions is -15~30 DEG C, and reaction pressure is 80~150Kpa.
8. cyclopropylamine continuous production method according to claim 3 or 4, which is characterized in that chloro methyl butyrate and NH3
Raw materials components mole ratio be 1:(1~3)；
The raw materials components mole ratio of step c) plus water extraction, ring propyl formamide and water is 1:(2~5)；
Ring propyl formamide and sodium hypochlorite raw materials components mole ratio are 1:(1.1~2.5)；
The raw materials components mole ratio of ring propyl formamide and sodium hydroxide is 1:(2~4).
9. cyclopropylamine continuous production method according to claim 3 or 4, which is characterized in that step b) reaction products from
Ammoniation reactor sequentially enters deamination tank and flash tank removing NH after coming out3With part methanol, the object come out from flash tank bottom
Expect further to remove remaining methanol into eparating methanol tower.
10. a kind of cyclopropylamine continuous production method, described using the cyclopropylamine continuous production system described in claim 2
After the material that first order reaction distillation still and second order reaction distillation still steam is mixed with the material that second order reaction distillation still bottom comes out
Into the ammoniation reactor, the material of the generation of ammoniation reactor sequentially enter the deamination tank, flash tank, eparating methanol tower and
Phase-splitter, the material of phase-splitter obtain cyclopropylamine crude product into the degradation reaction device, and cyclopropylamine crude product enters the simple distillation
Tower, smart destilling tower obtain cyclopropylamine purified product.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3711549A (en) * | 1970-05-19 | 1973-01-16 | Gulf Research Development Co | Process for manufacturing cyclopropylamine |
| JPS51104A (en) * | 1974-06-19 | 1976-01-05 | Takuma Uchida | Aasudoriruniokeru doriringubaketsutosokobutakaihohoho |
| US4590292A (en) * | 1985-06-10 | 1986-05-20 | Ciba-Geigy Corporation | Process for the manufacture of cyclopropylamine |
| CN1125715A (en) * | 1995-09-28 | 1996-07-03 | 金旭虎 | Industrial production method of cyclopropylamine |
| US5728873A (en) * | 1995-06-30 | 1998-03-17 | Huels Aktiengesellschaft | Process for the preparation of cyclopropanamine |
| EP0970943A3 (en) * | 1998-07-09 | 2001-09-12 | Degussa AG | Process for the preparation of the cyclopropylamine |
| CN1498884A (en) * | 2002-11-06 | 2004-05-26 | �Ϻ���ͨ��ѧ | Continuous prepn. of amine |
-
2017
- 2017-12-30 CN CN201711492500.1A patent/CN108129330B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3711549A (en) * | 1970-05-19 | 1973-01-16 | Gulf Research Development Co | Process for manufacturing cyclopropylamine |
| JPS51104A (en) * | 1974-06-19 | 1976-01-05 | Takuma Uchida | Aasudoriruniokeru doriringubaketsutosokobutakaihohoho |
| US4590292A (en) * | 1985-06-10 | 1986-05-20 | Ciba-Geigy Corporation | Process for the manufacture of cyclopropylamine |
| US5728873A (en) * | 1995-06-30 | 1998-03-17 | Huels Aktiengesellschaft | Process for the preparation of cyclopropanamine |
| CN1125715A (en) * | 1995-09-28 | 1996-07-03 | 金旭虎 | Industrial production method of cyclopropylamine |
| EP0970943A3 (en) * | 1998-07-09 | 2001-09-12 | Degussa AG | Process for the preparation of the cyclopropylamine |
| CN1498884A (en) * | 2002-11-06 | 2004-05-26 | �Ϻ���ͨ��ѧ | Continuous prepn. of amine |
Non-Patent Citations (2)
| Title |
|---|
| 郑智宏: "《煤化工生产基础知识》", 31 January 2007 * |
| 陈敏恒等: "《化学反应工程基本原理》", 31 August 1982 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109836334A (en) * | 2019-02-14 | 2019-06-04 | 清华大学 | A method of continuously preparing cyclopropylamine |
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