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(CN1130621) Process for producing isopropyl amine

Method for producing isopropylamine

         The invention relates to a preparation method of isopropylamine, and more specifically, relates to acetone as a raw
material, in the presence of a catalyst, by virtue of a gas-phase hydrogen amination reaction, the method for preparing the
isopropylamine comprises the following steps:

         As is well known, isopropylamine is used for producing a variety of pesticides such as atrazine, methyl isosalix,
buprofezin and other important raw materials; and can also be used for producing detergents such as sodium dodecyl
benzene sulfonate and the like; is widely applied to the rubber industry and the medicine industry.

         Method for preparing important chemical raw materials for a long time, a large amount of research is carried out on
people, and a wide variety of preparation methods are provided. The method mainly comprises the following steps: (1)
isopropanol is used as a raw material, and isopropyl alcohol is used as a raw material, in the presence of hydrogen and cu, ni
or co catalysts, isopropyl alcohol and ammonia to generate isopropylamine, as shown in US pat. no. 234,961, 2636902; the
reaction conditions are as follows: 180-250 DEG c, the pressure of 1.0-2.5 mpa and the load of the catalyst are 0.2 liters of
isopropyl alcohol/liter of catalyst / (2) An acetone hydrogen ammoniation method, wherein acetone is used as a raw
material, and hydrogen and ammonia are greatly excess, a ni/Al2O3 catalyst is adopted, so that the acetone is subjected to a
hydrogen ammoniation reaction to generate the isopropylamine. The invention further discloses a production method of the
isopropylamine, the method comprises the following steps: taking acetone as a raw material, and adopting a 5 * 5 mm
ni/Al2O3 catalyst Hydrogenation reaction of acetone in fixed bed reactor. According to the method disclosed by the
invention, the conversion of 100% of raw materials is not possible, residual raw materials, side reaction products such as
diisopropylamine, isopropanol and water, so that a complex system is formed, so that the purity and the yield of the product
isopropylamine are reduced, and the azeotropic distillation is adopted, extraction and distillation and the like, so that the
process is complex, the energy consumption is increased, and the wastewater containing organic matters is difficult to
discharge;

         Therefore, aiming at the defects existing in the prior art, a lot of research work is carried out to complete the method

         The invention aims to provide an improved method for preparing isopropylamine. The method disclosed by the
invention can be used for producing high isopropylamine selectivity and yield and simplifying the production process, low
in energy consumption and the content of organic matters in the wastewater is lower than that of the emission standard;

         The method disclosed by the invention is carried out, namely pumping acetone into water, is heated in the heater 3
together with H2 and NH3 from the outlet of the compressor, and enabling the mixture to reach the reaction temperature;
and adding the gasified acetone, H2 and NH3 according to a ratio of slightly greater than the stoichiometric ratio a main
reactor 4 which is provided with a Ni/Al2O3 catalyst and is in sectional control is added, and carrying out a hydrogenation
reaction; and introducing a reaction product of the main reactor into a condenser 6, the gas-liquid separator 7 is used for
obtaining a liquid phase with isopropylamine as a main component and a gas phase taking hydrogen and nitrogen as main
components; (4) and the liquid phase is guided into a deamination tower 8 to obtain a liquid phase rich in isopropyl amine
capable of removing NH3, the gas-phase ammonia separated from the tower top is subjected to water cooling, ammonia
cooling and partial condensation, and is separated by a gas-liquid separator 11 the liquid ammonia flows back into the tower
8 through the pump 12, and the uncondensed gas-phase ammonia and the gas-phase ammonia evaporated by the ammonia
condenser are returned to the compressor together. The method comprises the following steps: introducing the deamination-
rich liquid phase rich in isopropylamine into a distillation tower 13, and carrying out distillation, and the tower top distillate
is obtained from the tower top to obtain the product isopropylamine; (6) the kettle liquid of the distillation tower 13 is added
into a stripping tower 15, and the tower top distillate is condensed to obtain the diisopropylamine, isopropanol and water;
(7) and enabling the azeotrope to enter a secondary reactor 5 together with the h2 and NH3 mixed gas to carry out a
hydrogenation reaction to obtain the same product as the main reactor

         The catalyst used in the method disclosed by the invention is the same as the catalyst described in the czhu patent
131353, the description part of related catalysts in the literature is introduced into the literature as a reference

         The conditions of the method are as follows: acetone: ammonia: hydrogen = 1: (2-5): (2-5) is 1: 3: 3, and the reaction
temperature is 50-150 DEG c, preferably 100-120 DEG c, and the pressure is 0.4-1.2 Mpa, preferably 0.8-1.2 Mpa, and the
air speed of the acetone solution is 0.4-0.6 liters/liter of the catalyst/time. The preparation method comprises the following
steps:

         The reactor used by the method is a fixed bed reactor, preferably a tubular fixed bed reactor, and the reaction
temperature is controlled in a segmented manner, and the reaction temperature is 90-150 DEG c at the height of about 1/2 of
the height of the bed layer, and carrying out gas-solid reaction at the temperature; and the reaction temperature at the rest
1/2 is 50-90 DEG c, so that the reaction is gradually converted into a gas-liquid-solid three-phase reaction. Therefore, two
types of reactions are realized in the same reactor, the purity and the yield of the product are improved, and the conversion
rate of acetone is close to 100%. Diisopropylamine generated by side reactions, isopropyl alcohol and a small amount of
acetone converted at tail end of catalyst life, under the condition of the same gas composition as the main reactor, a heat
insulation reactor with the same catalyst is adopted, when the liquid space velocity is 0.4-1.6 liters/liter of catalyst/hour, the
pressure is 0.4-1.2 MPa, the temperature is 140-150 DEG c, and the temperature is 100%, and 70% of diisopropylamine and
isopropyl alcohol are converted into isopropylamine. Therefore, by adopting about 1-fold diisopropylamine and the
circulation amount of isopropyl alcohol, the method disclosed by the invention is mainly used, the two reactors can be used
for completely producing isopropylamine, residual diisopropylamine and acetone (trace amount)), and the isopropanol is
separated. Therefore, the acetone single consumption of the isopropylamine can be close to the theoretical equivalent. (1-
Ton of isopropylamine/1-ton of acetone) The method disclosed by the invention has the advantages that the content of the
organic matters in the wastewater is lower than that of the emission standard.

         The separation of hydrogen and ammonia in the method adopts water cooling, and a low-temperature cold source
refrigeration system does not need to be adopted, namely cooling the reaction product mixture at the temperature of 0.8-0.1
mpa and the temperature of 30-35 DEG c, and carrying out ammonia-cooling condensation on the isopropylamine and the
feed amount of 1/3 into a liquid, and almost about 1/3 of hydrogen and about 1/3 of ammonia are separated out in a gas
phase, and is circulated back to the reaction system after being boosted by the compressor

         According to the method disclosed by the invention, the deamination step is a distillation tower adopting 25 theoretical
plates, and the conditions are as follows: reflux ratio 1, the tower top temperature is about 15-20 DEG c, and the kettle
temperature is about 160-170 DEG c, the tower pressure is 0.8-0.9 mpa, and ammonia is separated from the tower top, and
the temperature of the tower top is 1/3 of the amount of ammonia (about 1/3 of the feeding amount)) evaporating and
refrigerating, wherein the separated ammonia gas and hydrogen are returned to the compressor together, is recycled after
being boosted and does not need to be externally provided with a refrigeration system.

         The present invention is further described by referring to FIG. 1 (isopropylamine production process flow diagram)

         After being compressed by the compressor 1, the hydrogen and the circulating gas are heated in an evaporation heater
3 together with acetone from the pump 2, the acetone is vaporized and is preheated to the reaction temperature together with
the h2 and the NH3, and then enters a main reactor with a ni/AL2O3 catalyst, and is subjected to hydrogen ammoniation
reaction Reaction product (including unreacted raw material and reaction product)) and reacting with a reaction product
from the auxiliary reactor 5 into a water condenser 6, isopropylamine and diisopropylamine, acetone, isopropanol and the
like, and is separated by a gas-liquid separator 7, the gas-phase ammonia and hydrogen are returned to the compressor 1,
and the liquid phase enters the deamination tower 8, the residual gas-phase ammonia is separated from the tower top, and
the residual gas-phase ammonia is discharged through a water condenser 9 and then passes through an ammonia condenser
10, is partially condensed and is separated by a gas-liquid separator 11, and liquid ammonia flows back into the tower 8
through a pump 12, and the uncondensed gas-phase ammonia and the gas-phase ammonia evaporated by the ammonia
condenser are returned to the compressor 1 together, a condensing agent system of the ammonia condenser is used for
supplementing and adding the raw material liquid ammonia The liquid phase of the deamination tower 8 is led into the
distillation tower 13, and the top distillate is cooled through a condenser 14 to obtain the product isopropylamine,
introducing the kettle liquid into a gas stripping tower 15, and cooling the tower top distillate through a condenser 16 to
obtain diisopropylamine, isopropanol and water, and the azeotrope is used as a raw material of the auxiliary reactor 5
through a pump 17, and discharging the water generated by the reaction from the tower kettle, wherein the hydrogen-
ammonia gas composition of the gas phase of the secondary reactor is the same as that of the main reactor;
         The present invention is further described below with some examples, but the present invention is not limited thereto.
The percentages used are in percentage by weight unless otherwise indicated. The novel features of the invention are set
forth in the claims, and some modifications or improvements made by those skilled in the art can be realized by those
skilled in the art, the method disclosed by the invention is within the scope of the invention without departing from the spirit
of the invention.

         Example 1

         Reactor for loading ni/agla2O3 catalyst containing ni as 16% into phi 32 * 3.5 * 600 mm, a thermometer sleeve with
the diameter of 8 mm is arranged in the middle of the reactor, and the height of the bed layer is 212 mm, the reaction
pressure is 0.04MPa, and the reaction temperature is 105 DEG c, acetone: NH3: H2 = 1: 3: 3 (mol), and the air speed of the
acetone solution is 0 3 The reaction result shows that the conversion rate of acetone is 99%, the selectivity of the
isopropylamine is 90%, and the content of the diisopropylamine and the isopropylamine is about 5%

         Example 2

         Catalyst and reactor as well as raw material proportioning the same as example 1, and reaction conditions are as
follows: the reaction temperature is 110 DEG c, and the reaction pressure is 0.8MPa, the air speed of the acetone solution is
0.6 liters of acetone/liter of the catalyst/time, and the temperature of the bed layer is 50 mm every other, the temperature of
the material and the catalyst bed layer is reduced by 10-15 DEG c, and the outlet temperature of the material and the catalyst
bed layer is 50 DEG c, and the reaction result shows that the conversion rate of acetone is about 100%, the selectivity of the
isopropylamine is 94%, the selectivity of the diisopropylamine is 2.4%, the selectivity of the isopropanol is 3.6%,

         Example 3

         Using the same catalyst as example 1, reactor and raw material ratio and reaction conditions: the reaction temperature
is 120 DEG c, and the temperature of the bed layer of the reactor is reduced by 15-20 DEG c every 50 mm, the temperature
of the material outlet catalyst bed layer is 50 DEG c, and the reaction pressure is 0.8MPa, acetone liquid space velocity is
1.2 liters of acetone/liter of catalyst /. The reaction result shows that the conversion rate of acetone is about 100%, and the
selectivity of isopropylamine is more than 92%, the selectivity of the isopropanolamine is 4.3%, the selectivity of the
isoacetone is 3.3%, the selectivity of the diisopropylamine is 4.3%, and the selectivity of the isoacetone is 3.3%.

         Example 4

         The same catalyst and reactor as example 1 are adopted, and the raw materials comprise 5.06% of acetone, 10.22% of
isopropylamine, 11.34% of diisopropylamine, 39.73% of isopropanol and 28.65% of water. The reaction conditions are as
follows: the reaction temperature is 150 DEG c, and the reaction pressure is 0.8MPa, and the liquid space velocity is 0.6
liters of liquid/liter of catalyst /, wherein the ratio of liquid to hydrogen to ammonia is 1: 3: 3 (mol). The reaction result is
that about 100% of acetone is converted into isopropylamine, 70% of diisopropylamine and about 70% of isopropyl alcohol
are converted into isopropylamine;

         Example 5

         Under the reaction conditions of examples 1-4, the reaction product is under the pressure of 0.8MPa, and cooling to
room temperature (25-30 DEG c) through water); the reaction product is partially condensed; and the gas phase contains
0.5-1.0% by volume of isopropylamine); and the rest of the amine 1/2 is in the gas phase, and the other 1/2 is in the liquid
phase. The preparation method comprises the following steps:

         Example 6

         The liquid phase of the water-cooled reaction product is subjected to deamination and distillation, and the distillation
condition is as follows: the pressure is 0.8MPa (tower top), wherein the top temperature is 18 DEG c, the kettle temperature
is 166 DEG c, and the kettle pressure is 0.84 MPa) and 25 theoretical tower plates, wherein the reflux ratio is 1, and the
deamination result is as follows: H (OH) 2 (NO3) 2 (NO3) 2 (H2O) 3 isopropylamine acetone diisopropylamine and
acetone water

                                                                             18. 9 Feed (%)) micro-19.5 54.0 0.2-2.8 4.5

                                                                              (Wt %) tower top (gas phase)) is less than or equal to 99.8% and less than
0.1% (volume) reflux (%)) is less than or equal to 86 and less than 14 microns micro-micro-micro-tower kettle (%) 0.1%
-0.3% of water, 0.1% -0.3% of water, 0.1% -0.3% of water, and 0.1% -0.3% of 5       23. 7

         Example 7

         The reactor of example 1 and the catalyst are adopted, wherein the reaction conditions are as follows: the temperature
is 55 DEG c and the pressure is 0.8MPa, the liquid space velocity is 0.8L/l, and the ratio of acetone to hydrogen to ammonia
is 1: 3: 3, the temperature of the bed layer is reduced to 5 DEG c every 50 ml, and the temperature of the material outlet is
40 DEG c.. the reaction result shows that the acetone conversion rate is 85% and the selectivity of isopropylamine is greater
than 90%.