Method for producing isopropylamine

Abstract

The invention discloses a method for producing isopropylamine, which belongs to the technical field of
amine. To solve the problem that the prior isopropylamine industrial production device cannot
effectively convert diisopropylamine into the isopropylamine, a reactor for an acetone hydroamination
reaction performs the sectional control of the reaction temperature, the reaction temperature of a first
section positioned at an inlet of the reactor is between 110 and 150 DEG C, and the reaction
temperature of a downstream section is 5 to 30 DEG C higher than that of an upstream section which is
adjacent to the downstream section. Along with the gradual reduction of the concentration of acetone
along a bed, the reaction temperature is improved section by section, which is favorable for converting
the diisopropylamine and isopropanol into the isopropylamine, thereby reducing the circulation of the
diisopropylamine and the isopropanol, reducing energy consumption, and preventing the
diisopropylamine from being gradually accumulated in a system so as not to need operating a
diisopropylamine rectification system with difficult operation. The method is simple, feasible and easy to
realize,and has considerable industrial application value and economic benefit.

Description

translated from Chinese

Amphetamine production methods

Wood technology field

The present invention relates to a process for producing amines and more particularly, the
present invention relates to a process for the production of isopropylamine. Background
technique

Important raw material for the production of isopropylamine more pesticides, for example,
atrazine, isofenphos-methyl buprofezin and the like; for example, also be used for the production
of detergents isopropylamine salt of dodecylbenzenesulfonic acid and the like; and in rubber
industry the pharmaceutical industry is also widely used.

People amphetamine production methods a lot of research, and some have also been applied in a
mature industry. Which are: (1) isopropyl alcohol vapor phase amination method which
isopropanol as starting material in the presence of copper, nickel or cobalt catalysts, isopropanol,
isopropylamine and ammonia generated in the reaction under the presence of hydrogen, as
described in US Patent No. 2,349,461, the reaction conditions disclosed in No. 2,636,902 are: a
temperature of 180~250 ° C, a pressure 1.0~ 2.5MPa, LHSV of 0.2h "; (2) a hydrogen acetone
amide, the method is as raw materials acetone using a Ni catalyst, acetone and hydrogen,
ammonia, hydrogen amination reaction, generating isopropylamine. the nickel catalyst Beijing
Research Institute of Chemical production, hydrogen amination acetone in a fixed bed reactor,
the catalyst technology is mature, It has been used for many years in the industry.

Although the amide hydrogen of acetone method is well established, however, in a fixed bed
reactor can not be converted into 100% acetone isopropylamine, diisopropylamine is inevitably
generated, isopropanol. Is a common way of diisopropylamine, isopropanol recycled to the
reactor to continue the reaction of isopropylamine, resulting in increased energy consumption,
increased processing capacity of the reactor, a large number of cycles diisopropylamine prone to
coking, the catalyst activity decreased, but also cause clogging of the reactor and piping. Thus a
large number of cycle diisopropylamine, isopropyl alcohol is not a fundamental solution. For this
purpose, CN 95102074.9 proposes to increase a secondary reactor in the process flow, the
temperature of the secondary reactor the reaction is 140~150 ° C, with sub main reactor
temperature, the temperature of the upper 90~15 (TC, lower temperatures 50~ 90 ° C. the
purpose of piecewise temperature gas-solid phase reaction is carried out in the previous
paragraph, the lower the reaction temperature is lowered, the reaction into the reaction gassed,
this can increase the purity and yield of the product. in acetone in the secondary reactor
unreacted, generated diisopropylamine, isopropylamine converted into isopropanol. this patent
vice- two reactors, the cycle does not require diisopropylamine, isopropanol into the main
reactor. However, due to the use of two reactors, increased investment in equipment, operating
costs also increased, so there is no industrial applications.

Still industrial use one reactor, the implementation of a single control section, and not separately
controlled raw

3 percent of diisopropylamine and isopropanol recycled to the reactor, and fresh acetone with
hydrogen, is reacted with ammonia to generate isopropylamine. However, since the single-stage
reactor employs a control, suitable hydrogen amination of acetone, the reaction temperature is
relatively low for the reaction is diisopropylamine isopropylamine, diisopropylamine thus not
recycled to the treatment

Like converted into isopropylamine, diisopropylamine concentration resulting in increasing the

production device, i.e. the presence of accumulated, at least necessary to periodically open the
separation of diisopropylamine distillation system to reduce the system - the concentration of
isopropylamine , but the separation is the use of diisopropylamine diisopropylamine, principle
ternary azeotrope of isopropanol and water is formed, and thus the separation of
diisopropylamine distillation system operation is very difficult, it is likely to cause extensive
column, thereby increasing the cost of generation.

In summary, the conventional industrial production means there are isopropylamine,

diisopropylamine isopropylamine not efficiently converted to the problem.
SUMMARY

For the present invention, the above-described problems, and considering easy to implement
industrially, temperature raised reactor segment, the reaction temperature is higher than the
downstream section of the upstream section of the reaction temperature. Specific technical
solutions are as follows.

The method of the present invention is the production of isopropylamine, in a fixed bed reactor,
in the presence of a nickel based catalyst, acetone, hydrogen and ammonia to generate hydrogen
amination isopropylamine, diisopropylamine, and isopropanol, wherein diisopropylamine
isopropanol and separated recycled to the reactor, wherein the reactor is controlled to implement
piecewise

The reaction temperature of the reaction system temperature, located in the first stage reactor
inlet is 110~150 ° C, the reaction temperature is higher than the downstream section of the
upstream section adjacent to the high reaction temperature 5~30 ° C.

The reaction temperature is preferably upstream section, a downstream section of the reaction
temperature is higher than the adjacent 10~20 ° C. For ease of industrialization, the fixed bed
reactor and more preferably 2 to 3 minutes the reaction temperature control section, the reaction
temperature is higher than the downstream section of the upstream section adjacent to the high
reaction temperature 10~20 ° C. In particular, the production method of the present invention
comprising isopropylamine steps of:

(1) and recycled to the acetone diisopropylamine, hydrogen and ammonia isopropanol, and
heated to the reaction temperature in the first, fed to a fixed bed reactor containing a nickel-based
catalyst amination reaction with hydrogen in the feed acetone: hydrogen: ammonia molar ratio of
1: 2 ~ 4: ~ 4, a liquid hourly space velocity of acetone 0.1~0.5 h ", as the reactor to carry out one
of the points in any of claims 1 ~ 3 section temperature control;

(2) the material is cooled from the reactor, gas-liquid separation, gas compressed by the
compressor is recycled back to the reactor, the liquid is fed deaminase column, ammonia is
separated from the top of the column to the reactor, from the tower bottom Produced
amphetamine-rich material;

4 (3) from the column bottom material deamination isopropylamine introduced into the column,
the column isopropylamine action leavened fine after recovery from the overhead product
isopropylamine, recovery column reactor containing diisopropylamine, isopropanol and water
materials;

(4) Isopropylamine column bottom material is introduced into the dehydration tower, separating
diisopropylamine to overhead and isopropyl

Alcohol-based materials, recycled to the reactor, column reactor is discharged wastewater.

Preferably, deamination overhead condenser is not provided, the additional feed liquid ammonia
is fed directly to the top of the ammonia removal column as a cold source, it is condensed
components except the ammonia stream into a liquid reflux in the column, ammonia gasification
ammonia gas

Taken out and fed to the reactor from the top of the column. More preferably, the deamination
column blocks having a theoretical plate 20~40 overhead temperature of 25~40 ° C, the column
top pressure was 1.1~1.4MPa.

The reactor may be employed according to the present invention operates at atmospheric
pressure, the pressing operation may be, for example, operating pressure 0.6~1.0MPa. Upper
feed mode may be, may be a lower feed mode.

In the method of the present invention, the material is cooled from the reactor a cooler, a gas-
liquid separator, isopropylamine column and a dehydration column in the conventional plant is
substantially the same. The CN 95102074.9 disclosed fully incorporated by reference.

Initially, the industrial production process isopropylamine fractionator design is complete, in

addition to the previously described separation column, the column further comprising
diisopropylamine, isopropanol and the like towers. To simplify the process, CN 95102074.9
proposes to increase a side reaction is generated, and isopropanol conversion of
diisopropylamine, isopropylamine, diisopropylamine column to cancel, isopropanol tower.
However, since multiple devices in an industrial reactor, the investment and operating costs will
increase, and thus no two reactors are used in industry, is still circulating diisopropylamine and
isopropyl

alcohol. Accordingly, current industrial device further required separate set of diisopropylamine
rectification system until diisopropylamine at higher concentrations in the system, opening the
system to prevent the separation of diisopropylamine catalyst diisopropylamine caused by
inactivation of and clogging of the system. The inventors after intensive studies, found that the
conversion reaction temperature diisopropylamine require a higher ratio of acetone to isopropyl
amine hydrogen amination reaction temperature, thus the conventional plant, the reactor
temperature can not be implemented over the single stage conversion of two isopropylamine, but
increase the temperature of the reactor does not help acetone hydrogen selective amination
reaction, which appears in the system, the concentration of diisopropylamine increasingly high,
the need to run diisopropylamine rectification system periodically.

The inventors in order to solve this problem fundamentally, is proposed and CN 95102074.9
disclosed the primary reactor segment temperature and the lower the reaction temperature is
opposite to a temperature lower aspect ratio of the upper stage of the reaction, i.e., the production
process is provided only one reactor, the reactor Sub-heated, but the downstream section of the
reaction temperature is higher than the reaction temperature of the upstream section. As the
hydrogen amination reaction with acetone, the acetone content of the catalyst bed along getting
low, then increasing the reaction temperature, acetone was little effect on the selectivity of the
amination reaction of hydrogen, the reaction temperature is increased in favor of
diisopropylamine isopropanol and converted to the isopropylamine, thereby reducing the amount
of circulation of diisopropylamine and isopropanol, lower energy consumption, help to improve
the processing capacity of the apparatus, while preventing the accumulation of diisopropylamine
in the system, can completely cancel diisopropylamine distillation system.

Furthermore, additional liquid ammonia was added at the top of the column system deamination
omitted deaminase column overhead condenser, on the one hand does not require a low off
overhead condenser cooling source of ammonia, on the other hand additional liquid ammonia
deamidation vaporized column liquid ammonia save heat in the gasifier, thereby reducing energy
consumption and production cost of the apparatus.

Isopropylamine generating method according to the invention is simple and feasible, requires
only one reactor, in the construction of the entire apparatus is not diisopropylamine distillation
system, so long as it is divided into sections of the reactor to control the reaction temperature can
be, that is, dividing the shell into paragraphs, with water at different temperatures are controlled
to the reaction temperature of each stage, and thus the method of the present invention is easy to
implement, however, diisopropylamine rectification system of the present invention the method
may be omitted, significantly reduce investment and operating costs, and easy to operate.
Therefore, the method is simple, but it has a very considerable economic benefits.

I is a schematic flow diagram of FIG producing method of the present invention isopropylamine.

Symbol Description:

1. preheater; 2 reactor; 3. cooler; 4 gas-liquid separator;. Deamination column 5; 6

isopropylamine column; 7. dehydration column.

Detailed ways

Isopropylamine explained further below producing method of the present invention in

conjunction with the accompanying drawings. 1, the tubular fixed bed reactor equipped with a
nickel-based catalyst temperature control mode implementation segment. Material flow reactor
shown in Figure 1 is the progress under, divided into three temperature control. At the first inlet

Temperature control in the reaction section 110~15 (TC range, e.g. 120~125.C. The reaction
temperature for the second higher than the first section 5~30.C, preferably 10~20.C, e.g.
controlled 135~ 140.C range. the reaction temperature of the third stage higher than the second
section 5~3 (TC, preferably 10~20.C, e.g. 145~15 control (TC in the range of reaction
temperatures given above and adjacent the temperature difference between the two is merely
illustrative, and can be carried out according to the initial use of a catalyst, adjusting the middle
and the end. in order to prevent the formation of polymer, the reaction temperature of the last
section of the outlet of the reactor should not be too high, such as no more than 19 ( TC.

Acetone, additional hydrogen recycle gas from the gas-liquid separator, the gas from the
overhead deaminase ammonia and liquid circulation through the preheater 1 from the dewatering
overhead preheat the incoming segment of the fixed bed reactor temperature 2 hydrogen
amination. 2 out from the reactor 3 is cooled by passage through cooler material, separated in the
gas-liquid separator 4 into gas and liquid, gas compressed by the compressor as the recycle gas
returned to the reactor using liquid into deaminase

Tower 5. Material from the deamination of the autoclave through the separation column 5
deamination in column 5, separated from the top outlet of ammonia, deamination overhead
condenser is not provided, at the top of liquid ammonia was added supplemented as necessary as
the deamination of the column 5 cold source, together with additional liquid ammonia into the
gasification and the material isolated from the gas-liquid separator 4 from the gas ammonia
reactor 2, column 5 deaminase recovery tank isopropylamine rich material. Isopropylamine
enriched material is introduced into the column 6 isopropylamine, diisopropylamine product
taken out from the top, the bottoms discharge, isopropanol, water and trace amounts of materials
containing isopropylamine diisopropylamine. The autoclave discharge material 6 is introduced
into the column 7 isopropylamine, circulating water is separated from the liquid bottoms from
the dehydration column top product containing diisopropylamine, isopropylamine and traces of
isopropanol, and the circulating liquid to the reactor.

Example 1

The present examples serve to illustrate various embodiments of acetone, diisopropylamine,

isopropylamine into isopropanol reaction temperature. Using a fixed bed reactor in the
laboratory, using isopropylamine catalyst Beijing Research Institute of Chemical Production,

Loading level of 50 ml, gas phase reaction.

Test L: acetone as starting material for the synthesis of hydrogen isopropylamine amination
reaction, reaction conditions were: liquid acetone

The molar ratio of ammonia: a volume space velocity of 0.5h ", atmospheric pressure, reaction
temperature of 152t :, acetone: Hydrogen

1: 3: 3. The test results are shown in Table 1.

Test 2: In order to simulate the material in the plant, each of diisopropylamine and isopropanol
50wt. /. The mixed material as a raw material, in the presence of hydrogen, which is reacted with
ammonia conversion are isopropylamine, industrial apparatus according to the quality of fresh
acetone and circulating fluid ratio of about 3/1, and thus in the present embodiment,
diisopropylamine and iso propanol

Mixed material liquid hourly space velocity is set to o.nh-1, other reaction conditions were:
atmospheric pressure, the reaction

The temperature was 152. C or 17 (TC, (isopropanol diisopropylamine +): Hydrogen: ammonia
molar ratio of 1: 3: 3 The test results are shown in Table l <table> table see original document
page 7 </ column. > </ row> <table> as can be seen from the data in table l, at LHSV simulated
industrial apparatus, i.e. acetone 0.5 h ", as the circulating liquid 0.17h", i.e. in the same reaction
temperature of 152 "C , the conversion of acetone to a higher conversion rate of
diisopropylamine and isopropanol. If the reaction temperature is increased, diisopropylamine and
isopropanol conversion rate also increases. thus the implementation of the single-stage
temperature control in current industrial reactor, conversion of the circulating fluid. Therefore, in
actual industrial production, the amount of circulating fluid will be more than the conversion rate
of acetone, continuously or at least periodically to run diisopropylamine rectification system.
Example 2

The present embodiment serve to explain Sub-heated hydrogen amination reaction of the present
invention.

To simulate industrial plant reactor temperature control segment, in a laboratory reactor divided
into two sections, i.e.,

Two beds, each segment 50 ml isopropylamine were packed catalyst Beijing Research Institute
of Chemical production, respectively, two

Temperature, gas phase reaction.

Feed containing 75wt. /. Acetone, 12.5wt. /. Diisopropylamine and 12.5wt. /. The reaction
temperature of the mixed materials isopropanol, acetone volume of the liquid space velocity
0.5h-, the reaction temperature in the first bed is controlled 152t :, controlling the second stage
bed 17 (TC, atmospheric pressure, (acetone + isopropanol diisopropylamine +): hydrogen:
ammonia molar ratio of 1: 3: 3 content of the reaction product of the components set forth in
table 2.

Further, the reaction temperatures of the two bed are controlled at 152 ° C, subjected to the same
test, the conversion rate and the content of each component in the reaction product are shown in
Table 2.

And the content of Table 2, the conversion of the components of the reaction product of

The reaction temperature of the contents of diisopropylamine acetone aqueous isopropanol

diisopropylamine

The content of the raw wt. /. 75 12.5 12.5 00

152/170 ° C the reaction product content Wt. / C 0.93 6.46 7.67 65.99 18.95

98.45 33.33 23.81% conversion / /

152/152 ° C the reaction product content wt. /. 1.41 10.65 10.71 58.86 18.37

Conversion rate. /. 97.67 -8.33 -4.76 / /

As can be seen from Table 2, with two reactors, but the reaction temperature in two stages, ie the
same equivalent as compared to a single stage reactor bed, the reactor bed into two sections, and
the reaction temperature lower than the upper bed bed reactor high temperature 18'C, slightly
improved the conversion rate of acetone, isopropanol and diisopropylamine transition from
negative to positive conversion rate conversion, i.e., the conversion increases to decrease. Thus,
the method of the present invention can prevent accumulation of diisopropylamine and isopropyl
alcohol in the system, can completely cancel diisopropylamine rectification system, and easy to
implement.