CN116082172B - Method for producing isopropanolamine - Google Patents
Method for producing isopropanolamine Download PDFInfo
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- CN116082172B CN116082172B CN202310381686.2A CN202310381686A CN116082172B CN 116082172 B CN116082172 B CN 116082172B CN 202310381686 A CN202310381686 A CN 202310381686A CN 116082172 B CN116082172 B CN 116082172B
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- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/04—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reaction of ammonia or amines with olefin oxides or halohydrins
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- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/10—Separation; Purification; Stabilisation; Use of additives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
- C07C215/02—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C215/04—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated
- C07C215/06—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated and acyclic
- C07C215/08—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated and acyclic with only one hydroxy group and one amino group bound to the carbon skeleton
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- C07C215/02—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C215/04—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated
- C07C215/06—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated and acyclic
- C07C215/12—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated and acyclic the nitrogen atom of the amino group being further bound to hydrocarbon groups substituted by hydroxy groups
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Abstract
The invention provides a method for producing isopropanolamine, which comprises the steps of reacting propylene oxide with liquid ammonia under the action of a water absorbing sieve, and then deaminizing, deaminizing and rectifying a mixture of the mixed isopropanolamine obtained by the reaction to obtain monoisopropanolamine. The method is simple and convenient, and the water absorbing sieve is used as the catalyst, so that the water consumption for catalysis is greatly reduced, the energy consumption is reduced, the liquid ammonia can be directly used as the raw material, and the material cost and the operation cost are reduced. Meanwhile, the method also improves the reaction rate and the conversion rate of propylene oxide, reduces the generation of impurities, avoids the decomposition of products, improves the purity (more than 99 percent) of the isopropanolamine, and is suitable for large-scale production. In addition, the method reduces the amount of the monoisopropanolamine carried in the circulating process of the liquid ammonia, and improves the selectivity (up to 93.3%) of the monoisopropanolamine.
Description
Technical Field
The invention belongs to the technical field of preparation of organic matters, and particularly relates to a production method of isopropanolamine.
Background
The current industrialized production method of monoisopropanolamine mostly adopts low-concentration ammonia water and epoxypropane as raw materials, uses water in the ammonia water as a catalyst, coproduces diisopropanolamine and triisopropanolamine, ensures that the selectivity of monoisopropanolamine is about 60%, has low and unstable purity, and has high energy consumption for post-treatment dehydration. In recent years, with the rapid downstream development of monoisopropanolamine, the demand for monoisopropanolamine is increasing, and the demand for quality is also increasing. In order to reduce the water consumption in the production process and improve the selectivity of the monoisopropanolamine, manufacturers in China often seek breakthrough in specific reactors or specific catalysts.
Patent CN105348118A discloses a method for producing isopropanolamine, which comprises the steps of simultaneously feeding ammonia water and propylene oxide into a fixed bed tubular reactor for reaction, using water in the ammonia water as a catalyst, and performing a series of post-treatment to obtain isopropanolamine. The method saves the total energy consumption of deamination and dehydration, but the purity of the obtained monoisopropanolamine is only 85-96%.
Patent CN109748804a discloses a method for producing isopropanolamine, which adopts a two-stage fixed bed reactor, firstly, liquid ammonia and propylene oxide are introduced into a tubular fixed bed reactor for reaction, a non-binder ZSM-5 zeolite molecular sieve is used as a catalyst, then, a reaction product and ammonia water are reacted in an adiabatic tubular reactor by using water as a catalyst, and finally, isopropanolamine is obtained. Patent CN109748805a discloses a method for producing isopropanolamine, after mixing liquid ammonia and propylene oxide, introducing the mixture into a tubular fixed bed reactor for reaction, and then continuing the reaction in the adiabatic fixed bed reactor, wherein in the two steps of reaction, a non-binder ZSM-5 zeolite molecular sieve is used as a catalyst, and finally the isopropanolamine is obtained. In the two patents, a non-binder ZSM-5 zeolite molecular sieve (containing phosphorus and lanthanum) is used as a catalyst, the components and the production process of the catalyst are complex, the catalyst is applied to industrial production, the cost is high, and the selectivity of the prepared isopropanolamine is low.
Disclosure of Invention
In view of the above, an object of the present invention is to provide a method for producing isopropanolamine. The method can improve the selectivity and purity of the monoisopropanolamine, and is suitable for large-scale production.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a process for the production of isopropanolamine comprising the steps of:
s1: propylene oxide and liquid ammonia react under the action of a water absorption sieve;
s2: carrying out deamination treatment on the reaction product obtained in the step S1 through flash evaporation;
s3: deamination is carried out again on the tank bottom material obtained by flash evaporation through first rectification, and then second rectification is carried out on the tower bottom material obtained by the first rectification, so that monoisopropanolamine is obtained.
Preferably, the water absorbing sieve is obtained by water absorbing treatment of a molecular sieve.
Preferably, the molecular sieve is selected from any one or more of sodium X-type molecular sieve, calcium X-type molecular sieve, sodium Y-type molecular sieve or calcium Y-type molecular sieve.
Preferably, step S1 is: propylene oxide, liquid ammonia and ammonia water react under the action of a water absorbing sieve.
Preferably, the tank bottom material obtained after the flash evaporation is finished is subjected to ammonia distillation treatment, and the tower bottom material obtained after the ammonia distillation treatment is subjected to deamination treatment again through first rectification.
Preferably, the pressure of the flash evaporation is 1.4-2.0 MPa.
Preferably, the tank top material and the tank bottom material obtained after the flash evaporation are subjected to ammonia distillation treatment, and the tower bottom material after the ammonia distillation treatment is subjected to deamination again through first rectification.
Preferably, the molar ratio of propylene oxide to ammonia is 1 (5-20).
Preferably, the reaction temperature is 100-140 ℃ and the pressure is 8-15 MPa.
Preferably, the pressure of the ammonia distillation treatment is 1.4-2.0 MPa, and the bottom temperature of the ammonia distillation treatment is less than or equal to 170 ℃.
Preferably, after the deamination treatment is finished, the tower bottom material obtained by the first rectification is dehydrated, and then the tower bottom material obtained by the dehydration treatment is rectified for the second time to obtain the isopropanolamine.
Preferably, the pressure of the first rectification is 0.01-0.3 MPa, and the bottom temperature of the first rectification is less than or equal to 170 ℃.
Preferably, the pressure of the second rectification is 2-5 kPa, and the bottom temperature of the second rectification is less than or equal to 180 ℃.
Preferably, after the second rectification is finished, the method further comprises rectifying the tower bottom material obtained by the second rectification for the third time to obtain diisopropanolamine and triisopropanolamine.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a method for producing isopropanolamine, which comprises the steps of reacting propylene oxide with liquid ammonia under the action of a water absorbing sieve, and then deaminizing, deaminizing and rectifying a mixture of the mixed isopropanolamine obtained by the reaction to obtain monoisopropanolamine. The method is simple and convenient, and the water absorbing sieve is used as the catalyst, so that the water consumption for catalysis is greatly reduced, the energy consumption is reduced, and the liquid ammonia is directly used as the raw material, so that the material cost and the operation cost are reduced. Meanwhile, the method also improves the reaction rate and the conversion rate of propylene oxide, reduces the generation of impurities, avoids the decomposition of products, improves the purity (more than 99 percent) of the isopropanolamine, and is suitable for large-scale production. In addition, the method reduces the amount of the monoisopropanolamine carried in the circulating process of the liquid ammonia, and improves the selectivity (up to 93.3%) of the monoisopropanolamine.
Drawings
FIG. 1 is a schematic diagram of an isopropanolamine production device according to the present invention;
FIG. 2 is a schematic diagram of a second embodiment of the isopropanolamine production apparatus of the present invention;
FIG. 3 is a schematic diagram III of the isopropanolamine production device of the present invention;
FIG. 4 is a schematic structural view of an isopropanolamine production apparatus in a comparative example;
wherein 1 is a fixed bed reactor; 2 is a mixer; 3 is a heat exchanger, 3-1 is a liquid ammonia heat exchanger, 3-2 is a propylene oxide heat exchanger, and 3-3 is an ammonia water heat exchanger; 4 is a feed pump, 4-1 is a liquid ammonia feed pump, 4-2 is a propylene oxide feed pump, and 4-3 is an ammonia feed pump; 5-1 is a liquid ammonia storage tank; 5-2 is a propylene oxide storage tank; 5-3 is an ammonia water storage tank; 6 is a flash tank; 7 is a deamination tower; 8 is a isopropanolamine rectifying tower; 9 is a diisopropanolamine rectifying tower; 10 is a compressor; 11 is an ammonia still; 12 is a dehydration tower;
FIG. 5 is a gas chromatographic test chart of monoisopropanolamine as a product in example 6 of the present invention.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Aiming at the problems of high preparation cost, low selectivity and low purity of the isopropanolamine in the prior art, the invention provides a production method of the isopropanolamine, which can be realized through a device shown in fig. 1, 2 or 3, wherein 1 is a fixed bed reactor; 2 is a mixer; 3 is a heat exchanger, 3-1 is a liquid ammonia heat exchanger, 3-2 is a propylene oxide heat exchanger, and 3-3 is an ammonia water heat exchanger; 4 is a feed pump, 4-1 is a liquid ammonia feed pump, 4-2 is a propylene oxide feed pump, and 4-3 is an ammonia feed pump; 5-1 is a liquid ammonia storage tank; 5-2 is a propylene oxide storage tank; 5-3 is an ammonia water storage tank; 6 is a flash tank; 7 is a deamination tower; 8 is a isopropanolamine rectifying tower; 9 is a diisopropanolamine rectifying tower; 10 is a compressor; 11 is an ammonia still; and 12 is a dehydration tower. The method can improve the purity and selectivity of the monoisopropanolamine and specifically comprises the following steps:
S1: propylene oxide and liquid ammonia react under the action of a water absorption sieve;
s2: carrying out deamination treatment on the reaction product obtained in the step S1 through flash evaporation;
s3: deamination is carried out again on the tank bottom material obtained by flash evaporation through first rectification, and then second rectification is carried out on the tower bottom material obtained by the first rectification, so that monoisopropanolamine is obtained.
According to the invention, propylene oxide and liquid ammonia are reacted under the action of a water absorbing sieve to obtain a reaction product comprising mixed isopropanolamine. In the present invention, the reaction is carried out in a fixed bed reactor, which is preferably a tubular fixed bed reactor, and the specifications of the tubular fixed bed reactor may be selected according to actual production requirements. In the invention, the water absorption sieve is obtained by water absorption treatment of a molecular sieve, wherein the water absorption treatment can be soaking water absorption or showering water absorption, the molecular sieve has stronger water absorption, a certain amount of water can be stably absorbed, and the water amount which is stably absorbed is the saturated water absorption of the molecular sieve. The molecular sieve is preferably selected from any one or more of a sodium X-type molecular sieve, a calcium X-type molecular sieve, a sodium Y-type molecular sieve or a calcium Y-type molecular sieve, and more preferably from a sodium X-type molecular sieve and/or a calcium X-type molecular sieve. The invention discovers that controlling the pore diameter of the molecular sieve within a proper range is beneficial to improving the selectivity of the monoisopropanolamine, so that the pore diameter of the molecular sieve is preferably 0.8-1 nm, such as 0.8 nm, 0.85nm, 0.90 nm, 0.95 nm or 1 nm. In some embodiments of the present invention, the molar ratio of ammonia to propylene oxide is preferably (5-20): 1, such as 5:1, 8:1, 10:1, 12:1, 15:1, 18:1 or 20:1, and one molecule of ammonia can react with three molecules of propylene oxide at most, and the obtained reaction product includes monoisopropanolamine, diisopropanolamine and triisopropanolamine. Through researches, the generation of diisopropanolamine and triisopropanolamine can be reduced by increasing the amount of ammonia, but the higher the amount of ammonia, the higher the energy consumption for recovery and the higher the cost. Therefore, in order to achieve both the selectivity and the energy consumption of the monoisopropanolamine product, the molar ratio of propylene oxide to ammonia is preferably controlled to be 1 (7-15). In some embodiments of the invention, propylene oxide and liquid ammonia are introduced into a fixed bed reactor provided with a water absorption molecular sieve according to the proportion, the temperature is preferably controlled to be 100-140 ℃, the pressure is preferably controlled to be 8-15 Mpa, and the reaction is preferably carried out, so that the service life of the catalyst water absorption molecular sieve can be prolonged while the rapid reaction of the liquid ammonia and the propylene oxide is ensured, the generation of impurities is reduced, and the temperature in the reaction process is preferably controlled to be 110-130 ℃ and the pressure is preferably controlled to be 9-13 Mpa. In some embodiments of the invention, in order to avoid overlarge temperature difference between the catalyst and the material contacted by the water absorption molecular sieve, prolong the service life of the catalyst and improve the reaction rate at the same time, the invention prefers that the propylene oxide and the liquid ammonia are preheated before entering the fixed bed reactor, and the preheating temperature is 80-140 ℃, preferably 90-120 ℃.
According to the invention, after the reaction in the fixed bed reactor is completed, the reaction product obtained is deaminated by flash evaporation. In the invention, the flash evaporation is preferably performed in a flash tank, and the operation pressure of the flash tank is 1.4-2.0 MPa.
Then, according to the invention, the tank bottom material obtained from the flash tank is subjected to deamination treatment again through first rectification. In some embodiments of the present invention, the first rectification is preferably performed in a deamination tower, the deamination tower has an operating pressure of 0.01-0.3 MPa, preferably 0.01-0.1 MPa, a tower bottom temperature of 170 ℃ or less, preferably 140-170 ℃, more preferably 150-160 ℃, a tower top temperature of 20-60 ℃, preferably 30-55 ℃, and ammonia discharged from the top of the deamination tower is preferably compressed by a compressor and then returned to a liquid ammonia storage tank. In some embodiments of the invention, the material obtained from the bottom of the flash tank after the flash evaporation is finished is preferably subjected to ammonia distillation treatment, and the bottom material after the ammonia distillation treatment is subjected to deamination again through first rectification. The ammonia distillation is preferably carried out in an ammonia distillation column. As a more preferable technical scheme, in order to avoid that isopropanolamine carried by circulating liquid ammonia returns to a reaction system to continuously react with propylene oxide and reduce the selectivity of monoisopropanolamine, the top material (ammonia) and the bottom material (isopropanolamine containing ammonia) obtained after flash evaporation are subjected to ammonia distillation treatment, and then the bottom material after the ammonia distillation treatment is subjected to deamination treatment again through first rectification. According to the invention, ammonia discharged from the top of the flash tank and isopropanolamine containing ammonia discharged from the bottom of the flash tank are fed into the ammonia still from the lower part and the middle part of the ammonia still respectively for ammonia distillation, because part of isopropanolamine is contained in the ammonia discharged from the top of the flash tank, the ammonia still is fed into the ammonia still again for the purpose of distilling pure ammonia, the product isopropanolamine is refluxed to the tower kettle, and then the ammonia discharged from the top of the ammonia still is returned to the liquid ammonia storage tank. The operation pressure of the ammonia still is 1.4-2.0 MPa, preferably 1.6-1.9 MPa, the bottom temperature of the ammonia still is less than or equal to 170 ℃, preferably 155-170 ℃, further preferably 160-170 ℃, and the top temperature of the ammonia still is 39-50 ℃, preferably 41-48 ℃.
Then, according to the invention, the bottom material obtained after the first rectification treatment is subjected to the second rectification, namely, the bottom material of the deamination tower is fed into a isopropanolamine rectifying tower to carry out the second rectification, and the monoisopropanolamine is obtained from the top of the tower. The operation pressure of the monoisopropanolamine rectifying tower is 2-5 kPa, the temperature of the tower bottom is less than or equal to 180 ℃, preferably 165-180 ℃, more preferably 170-180 ℃, the temperature of the tower top is 65-85 ℃, and preferably 70-80 ℃.
In some embodiments of the present invention, after the second rectification is finished, the method preferably further comprises feeding the bottom material obtained by the second rectification, that is, the bottom material of the monoisopropanolamine rectification tower, into the diisopropanolamine rectification tower to perform third rectification, obtaining diisopropanolamine from the top of the tower, and obtaining triisopropanolamine from the bottom of the tower. The operation pressure of the diisopropanolamine rectifying tower is 1-3 kPa, the temperature of the tower bottom is less than or equal to 200 ℃, preferably 180-200 ℃, more preferably 185-195 ℃, the temperature of the tower top is 144-164 ℃, and preferably 150-160 ℃. According to the preferable technical scheme, the tower top material of the diisopropanolamine rectifying tower enters the monoisopropanolamine rectifying tower from the lower part of the monoisopropanolamine rectifying tower to be rectified again, diisopropanolamine is obtained from the upper side line of the diisopropanolamine rectifying tower, and triisopropanolamine is obtained from the tower bottom.
In some embodiments of the present invention, step S1 preferably further includes feeding ammonia water, wherein the ammonia water, the liquid ammonia and the propylene oxide are preheated and mixed and then enter a fixed bed reactor provided with a water absorption molecular sieve, the concentration of the ammonia water is not higher than 30%, and the water inflow is not higher than 5% of the mass of the propylene oxide. In one embodiment of the invention, ammonia water and liquid ammonia are respectively preheated and then combined or ammonia water and liquid ammonia are combined and then preheated, and then the mixture is mixed with the preheated epoxypropane in a mixer uniformly and then introduced into a fixed bed reactor provided with a water absorption molecular sieve. In another embodiment of the invention, ammonia water, liquid ammonia and propylene oxide are respectively preheated and then enter a mixer for mixing, and the mixture is introduced into a fixed bed reactor provided with a water absorption molecular sieve for reaction. It should be noted that when the ammonia water is fed in step S1, dehydration treatment is preferably added after the ammonia distillation treatment, that is, the tower bottom material of the ammonia distillation tower is sequentially subjected to the first rectification treatment, the dehydration treatment, the second rectification and the third rectification to obtain products of monoisopropanolamine, diisopropanolamine and triisopropanolamine. The dehydration treatment is carried out in a dehydration tower, namely, the tower bottom material of the deamination tower enters the dehydration tower to carry out dehydration treatment, the operating pressure of the dehydration tower is 50-100 kPa, the tower bottom temperature of the dehydration tower is 120-170 ℃, preferably 140-160 ℃, the tower top temperature of the dehydration tower is 20-50 ℃, preferably 30-45 ℃, and ammonia water discharged from the tower top of the dehydration tower returns to an ammonia water storage tank for recycling.
It should be noted that, according to the above technical scheme, when the ammonia water is fed in step S1, the bottom material of the deamination tower is preferably fed into the dewatering tower for dewatering treatment, the ammonia water discharged from the top of the dewatering tower returns to the ammonia water storage tank for recycling, the bottom material of the dewatering tower is fed into an isopropanolamine rectifying tower for rectifying treatment, the monoisopropanolamine is obtained from the top of the tower, the bottom material of the bottom material is fed into a diisopropanolamine rectifying tower for rectifying treatment, the diisopropanolamine is obtained from the top of the tower, and the triisopropanolamine is obtained from the bottom of the tower. Tests prove that the purity of the monoisopropanolamine obtained from the top of the monoisopropanolamine rectifying tower and the purity of the diisopropanolamine obtained from the top of the diisopropanolamine rectifying tower can reach 99% or more.
In the invention, because the monoisopropanolamine is easy to decompose and generate tar-like substances at a higher temperature, for example, at a temperature higher than 170 ℃, the purity and the yield of the product are reduced, and therefore, the temperature is not higher than 170 ℃ in the deamination and dehydration processes before rectifying the monoisopropanolamine, namely, the temperature of a distillation tower, a deamination tower and a dehydration tower when ammonia water participates in, and the temperature of a tower bottom is not higher than 170 ℃. Similarly, in order to avoid pyrolysis or coking of diisopropanolamine and triisopropanolamine, the temperature of the tower bottom of the monoisopropanolamine rectifying tower is not higher than 180 ℃, and the temperature of the tower bottom of the diisopropanolamine rectifying tower is not higher than 200 ℃. In some embodiments, the parameters of tray number, reflux ratio, etc. for the rectification column of the present invention can be determined by simulation using various industrial software (e.g., aspen Plus from Aspen tech).
In some embodiments of the invention, a fixed bed reactor is filled with a molecular sieve which is soaked in water in advance, after nitrogen replacement, liquid ammonia is firstly filled, propylene oxide is filled after the liquid ammonia takes away unadsorbed water in the molecular sieve and reacts with the liquid ammonia, a product obtained from the fixed bed reactor enters a flash tank, ammonia discharged from the top of the tank and ammonia-containing isopropanolamine discharged from the bottom of the tank enter the ammonia still from the lower part and the middle part of the ammonia still respectively for ammonia still, the ammonia discharged from the top of the ammonia still returns to a liquid ammonia storage tank, the bottom material of the ammonia still is filled into a deamination tower for deamination treatment, the ammonia discharged from the top of the deamination tower returns to the liquid ammonia storage tank after being compressed by a compressor, the bottom material of the deamination tower is filled into an isopropanolamine rectifying tower, the isopropanolamine is obtained from the top of the tower, the bottom material is filled into a diisopropanolamine rectifying tower, and the diisopropanolamine is obtained from the top of the tower.
In some other embodiments of the present invention, after a dry molecular sieve is filled in a fixed bed reactor, steam or water is firstly introduced to flush the molecular sieve, nitrogen is substituted after the molecular sieve absorbs water, then liquid ammonia, ammonia water and propylene oxide are introduced to react, products obtained from the fixed bed reactor enter a flash tank, ammonia discharged from the top of the tank and isopropanolamine containing ammonia discharged from the bottom of the tank enter the ammonia still from the lower part and the middle part of the ammonia still respectively to be distilled again, ammonia discharged from the top of the ammonia still returns to a liquid ammonia storage tank, the bottom material of the ammonia still is introduced into a deamination tower to be deaminated, ammonia discharged from the top of the deamination tower returns to the liquid ammonia storage tank after being compressed by a compressor, the bottom material of the deamination tower is introduced into a dewatering tower to be dehydrated, the ammonia water discharged from the top of the dewatering tower returns to be recycled to the liquid ammonia storage tank, the bottom material of the dewatering tower enters an isopropanolamine rectifying tower to obtain isopropanolamine, the bottom material of the dewatering tower is introduced into the diisopropanolamine rectifying tower to obtain diisopropanolamine, and the bottom material of the diisopropanolamine is obtained.
The propylene oxide and the liquid ammonia are reacted under the condition that single water or a molecular sieve is used as a catalyst, and the subsequent deamination and rectification treatment steps in the technical scheme can be combined to obtain the monoisopropanolamine with high selectivity and purity.
The preparation method of the isopropanolamine comprises the steps of reacting propylene oxide with liquid ammonia under the action of a water absorbing sieve, and then deaminizing, deaminizing and rectifying a mixture of the mixed isopropanolamine obtained by the reaction again to obtain the monoisopropanolamine. The method is simple and convenient, and the water absorbing sieve is used as the catalyst, so that the water consumption for catalysis is greatly reduced, the energy consumption is reduced, and the liquid ammonia is directly used as the raw material, so that the material cost is reduced, and the running cost is also reduced. Meanwhile, the method also improves the reaction rate and the conversion rate of propylene oxide, reduces the generation of impurities, avoids the decomposition of products, improves the purity of the isopropanolamine, and is suitable for large-scale production. In addition, the method reduces the amount of the monoisopropanolamine carried in the liquid ammonia in the circulating process and improves the selectivity of the monoisopropanolamine.
Through tests, in the product obtained by adopting the preparation method, the selectivity of the monoisopropanolamine is higher and can reach more than 75 percent, the highest can reach 93.3 percent, the purity of the monoisopropanolamine and the purity of the diisopropanolamine can reach more than 99 percent, and the downstream application of the monoisopropanolamine is facilitated.
The monoisopropanolamine provided by the invention can be used for synthesizing industrial detergents, surfactants, plasticizers, emulsifying agents, cleaning agents or various auxiliary agents, and can also be used for preparing organic synthetic solvents.
In order to further illustrate the present invention, the following examples are provided. The experimental materials used in the following examples of the present invention are commercially available or prepared according to conventional preparation methods well known to those skilled in the art.
Example 1
The embodiment provides a production device of isopropanolamine, the structural schematic diagram of which is shown in figure 1, and 1 is a fixed bed reactor; 2 is a mixer; 3 is a heat exchanger, 3-1 is a liquid ammonia heat exchanger, 3-2 is a propylene oxide heat exchanger, and 3-3 is an ammonia water heat exchanger; 4 is a feed pump, 4-1 is a liquid ammonia feed pump, 4-2 is a propylene oxide feed pump, and 4-3 is an ammonia feed pump; 5-1 is a liquid ammonia storage tank; 5-2 is a propylene oxide storage tank; 5-3 is an ammonia water storage tank; 6 is a flash tank; 7 is a deamination tower; 8 is a isopropanolamine rectifying tower; 9 is a diisopropanolamine rectifying tower; 10 is a compressor; and 12 is a dehydration tower. The inlet of the feed pump is communicated with the outlet of the storage tank, the outlet of the feed pump is communicated with the inlet of the heat exchanger, the outlet of the heat exchanger is communicated with the inlet of the mixer, the outlet of the mixer is communicated with the inlet of the fixed bed reactor, the outlet of the fixed bed reactor is communicated with the inlet of the flash tank, the top outlet of the flash tank is communicated with the inlet of the liquid ammonia storage tank, the bottom outlet of the flash tank is communicated with the inlet of the deamination tower, the top outlet of the deamination tower is communicated with the inlet of the compressor, the outlet of the compressor is communicated with the inlet of the liquid ammonia storage tank, the bottom outlet of the deamination tower is communicated with the inlet of the dewatering tower, the top outlet of the dewatering tower is communicated with the inlet of the ammonia storage tank, the top outlet of the dewatering tower is communicated with the inlet of the isopropanolamine rectifying tower, the top of the isopropanolamine rectifying tower obtains isopropanolamine, the bottom outlet of the isopropanolamine rectifying tower is communicated with the inlet of the diisopropanolamine rectifying tower, the top of the diisopropanolamine rectifying tower is obtained at the top of the isopropanolamine rectifying tower.
Example 2
The embodiment provides a production device of isopropanolamine, the structural schematic diagram of which is shown in fig. 2, and 1 is a fixed bed reactor; 2 is a mixer; 3 is a heat exchanger, 3-1 is a liquid ammonia heat exchanger, and 3-2 is a propylene oxide heat exchanger; 4 is a feed pump, 4-1 is a liquid ammonia feed pump, and 4-2 is a propylene oxide feed pump; 5-1 is a liquid ammonia storage tank; 5-2 is a propylene oxide storage tank; 6 is a flash tank; 7 is a deamination tower; 8 is a isopropanolamine rectifying tower; 9 is a diisopropanolamine rectifying tower; 10 is a compressor; 11 is an ammonia still. The inlet of the feed pump is communicated with the outlet of the storage tank, the outlet of the feed pump is communicated with the inlet of the heat exchanger, the outlet of the heat exchanger is communicated with the inlet of the mixer, the outlet of the mixer is communicated with the inlet of the fixed bed reactor, the outlet of the fixed bed reactor is communicated with the inlet of the flash tank, the top outlet of the flash tank is communicated with the inlet at the lower part of the ammonia still, the bottom outlet of the flash tank is communicated with the inlet at the middle part of the ammonia still, the bottom outlet of the ammonia still is communicated with the inlet of the deamination tower, the top outlet of the deamination tower is communicated with the inlet of the compressor, the outlet of the compressor is communicated with the inlet of the liquid ammonia storage tank, the bottom outlet of the deamination tower is communicated with the inlet of the monoisopropanolamine rectifying tower, the top of the monoisopropanolamine rectifying tower is communicated with the inlet of the diisopropanolamine rectifying tower, the top of the diisopropanolamine rectifying tower is obtained, and the bottom of the diisopropanolamine rectifying tower is obtained.
Example 3
The embodiment provides a production device of isopropanolamine, the structural schematic diagram of which is shown in fig. 3, and 1 is a fixed bed reactor; 2 is a mixer; 3 is a heat exchanger, 3-1 is a liquid ammonia heat exchanger, 3-2 is a propylene oxide heat exchanger, and 3-3 is an ammonia water heat exchanger; 4 is a feed pump, 4-1 is a liquid ammonia feed pump, 4-2 is a propylene oxide feed pump, and 4-3 is an ammonia feed pump; 5-1 is a liquid ammonia storage tank; 5-2 is a propylene oxide storage tank, and 5-3 is an ammonia water storage tank; 6 is a flash tank; 7 is a deamination tower; 8 is a isopropanolamine rectifying tower; 9 is a diisopropanolamine rectifying tower; 10 is a compressor; 11 is an ammonia still; and 12 is a dehydration tower. The inlet of the feed pump is communicated with the outlet of the storage tank, the outlet of the feed pump is communicated with the inlet of the heat exchanger, the outlet of the heat exchanger is communicated with the inlet of the mixer, the outlet of the mixer is communicated with the inlet of the fixed bed reactor, the outlet of the fixed bed reactor is communicated with the inlet of the flash tank, the top outlet of the flash tank is communicated with the lower inlet of the ammonia still, the bottom outlet of the flash tank is communicated with the middle inlet of the ammonia still, the bottom outlet of the ammonia still is communicated with the inlet of the deamination still, the top outlet of the deamination still is communicated with the inlet of the compressor, the outlet of the compressor is communicated with the inlet of the liquid ammonia storage tank, the bottom outlet of the deamination still is communicated with the inlet of the dehydration still, the top outlet of the dehydration still is communicated with the inlet of the isopropanolamine rectifying still, the top of the isopropanolamine rectifying still is obtained, the bottom outlet of the isopropanolamine rectifying still is communicated with the inlet of the diisopropanolamine rectifying still, and the bottom of the diisopropanolamine rectifying still is obtained.
Example 4
Using the apparatus of example 1 above, isopropanolamine was produced as follows:
after filling a calcium X-type molecular sieve (water absorption of 230 mg/g) soaked and absorbed in water into a fixed bed reactor, and after nitrogen replacement, controlling the temperature of the fixed bed reactor to be 140 ℃ and the pressure to be 15 MPa, respectively mixing and preheating propylene oxide in the material flowing out of the fixed bed reactor to be a mixture of mixed isopropanolamine, ammonia and water, wherein the selectivity of isopropanolamine in the mixed isopropanolamine is 75.5%, the material after the reaction enters a flash tank, the pressure is reduced to 1.4 MPa, at the flow rates of 8.3 kg/h, 10.8 kg/h and 1.66 kg/h (the mole ratio of ammonia in the liquid ammonia to the propylene oxide is 5:1, the water inflow is 3% of propylene oxide, the liquid ammonia is a mixture of fresh liquid ammonia and circulating liquid ammonia, and the ammonia is circulating ammonia) respectively, the propylene oxide in the material flowing out of the fixed bed reactor is completely reacted, the reacted material components are the mixture of the mixed isopropanolamine, the water and the isopropanolamine in the mixed isopropanolamine are 75.5%, ammonia discharged from the top of the flash tank is returned to the liquid ammonia storage tank, the tank bottom material of the flash tank is introduced into a deamination tower to carry out deamination treatment under the conditions of 0.08 MPa and the temperature of a tower kettle of 160 ℃, ammonia discharged from the top of the deamination tower is compressed by a compressor and then returned to the liquid ammonia storage tank, the tower bottom material of the deamination tower is introduced into a dehydration tower to carry out dehydration treatment under the conditions of 50 kPa and the temperature of a tower kettle of 120 ℃, ammonia discharged from the top of the dehydration tower is returned to the ammonia water storage tank for cyclic application, the tower bottom material of the dehydration tower enters into an isopropanolamine rectifying tower to carry out rectifying separation under the conditions of 3 kPa and the temperature of the tower kettle of 170 ℃, the isopropanolamine with the purity of 99.6 percent is obtained from the top of the tower, the tower bottom material is introduced into the diisopropanolamine rectifying tower to carry out rectifying separation under the conditions of 3 kPa and the temperature of the tower kettle of 185 ℃, the tower top material is returned to the monoisopropanolamine rectifying tower from the lower part to carry out rectifying separation, diisopropanolamine is obtained from the side line of the upper part of the diisopropanolamine rectifying tower, and triisopropanolamine is obtained from the bottom of the diisopropanolamine rectifying tower, wherein the purity of the triisopropanolamine is 99.5% and 82.4% respectively.
Example 5
By using the apparatus in the above example 3, isopropanolamine was produced as follows:
the method comprises the steps of filling a sodium X-type molecular sieve (water absorption of 230 mg/g) soaked and absorbed in water into a fixed bed reactor, after nitrogen replacement, controlling the temperature of the fixed bed reactor to be 110 ℃ and the pressure to be 9 MPa, respectively mixing propylene oxide, liquid ammonia and 5% ammonia water at flow rates of 3.35 kg/h, 5.62 kg/h and 1.34 kg/h (the mole ratio of ammonia in the liquid ammonia to the ammonia water to propylene oxide is 7:1, the water inflow is 2% of propylene oxide, the liquid ammonia is a mixture of fresh liquid ammonia and circulating liquid ammonia, the ammonia water is circulating ammonia water), preheating to 100 ℃, introducing the mixture into the reactor to react, completely taking propylene oxide in the material flowing out of the fixed bed reactor to react, mixing isopropanolamine, mixing the mixture of ammonia and water, the selectivity of isopropanolamine in the mixed isopropanolamine is 80.3%, introducing the reacted material into a flash tank, reducing the pressure to 1.6 MPa, ammonia discharged from the top of the flash tank and isopropanolamine containing ammonia discharged from the bottom of the flash tank enter the ammonia distillation tower from the lower part and the middle part of the ammonia distillation tower respectively, ammonia is distilled again under the conditions of 1.6 MPa and 160 ℃ of the tower kettle temperature, ammonia discharged from the top of the ammonia distillation tower returns to a liquid ammonia storage tank, tower bottom materials of the ammonia distillation tower are introduced into the ammonia distillation tower to be subjected to deamination under the conditions of 0.08 MPa and 160 ℃ of the tower kettle temperature, ammonia discharged from the top of the ammonia distillation tower is compressed by a compressor and then returns to the liquid ammonia storage tank, tower bottom materials of the ammonia distillation tower are introduced into the dehydration tower to be subjected to dehydration under the conditions of 80 kPa and 160 ℃ of the tower kettle temperature, ammonia water discharged from the tower top of the ammonia distillation tower returns to be circularly used, the tower bottom materials of the ammonia distillation tower enter an isopropanolamine rectification tower to be separated under the conditions of 2 kPa and 175 ℃ of the tower kettle temperature, the purity of the isopropanolamine is 99.5%, and introducing the tower bottom material into a diisopropanolamine rectifying tower to carry out rectifying separation under the conditions of 2 kPa and the tower bottom temperature of 190 ℃, obtaining diisopropanolamine at the tower top, and obtaining triisopropanolamine at the tower bottom, wherein the purities of the triisopropanolamine are 99.2% and 82.3% respectively.
Example 6
By using the apparatus in the above example 3, isopropanolamine was produced as follows:
the method comprises the steps of filling a sodium X-type molecular sieve (water absorption of 230 mg/g) soaked and absorbed in water into a fixed bed reactor, after nitrogen replacement, controlling the temperature of the fixed bed reactor to be 125 ℃ and the pressure to be 11 MPa, respectively mixing propylene oxide, liquid ammonia and 30% ammonia water at flow rates of 5.2 kg/h, 14.8 kg/h and 0.7 kg/h (the mol ratio of ammonia in the liquid ammonia to the ammonia water to propylene oxide is 10:1, the water inflow is 4% of propylene oxide, the liquid ammonia is a mixture of fresh liquid ammonia and circulating liquid ammonia, the ammonia water is circulating ammonia water), preheating to 120 ℃, introducing the mixture into the reactor to react, completely taking propylene oxide in the material flowing out of the fixed bed reactor to react, mixing isopropanolamine, mixing the mixture of ammonia and water, selectively adding isopropanolamine in the mixed isopropanolamine into a flash tank, reducing the pressure to 1.7 MPa, ammonia discharged from the top of the flash tank and isopropanolamine containing ammonia discharged from the bottom of the flash tank enter the ammonia distillation tower from the lower part and the middle part of the ammonia distillation tower respectively, ammonia is distilled again under the conditions of 1.7 MPa and 160 ℃ of the tower kettle temperature, ammonia discharged from the top of the ammonia distillation tower returns to a liquid ammonia storage tank, tower bottom materials of the ammonia distillation tower are introduced into the ammonia distillation tower to be subjected to deamination under the conditions of 0.01 MPa and 140 ℃ of the tower kettle temperature, ammonia discharged from the top of the ammonia distillation tower is compressed by a compressor and then returns to the liquid ammonia storage tank, tower bottom materials of the ammonia distillation tower are introduced into the dehydration tower to be subjected to dehydration under the conditions of 50 kPa and 140 ℃ of the tower kettle temperature, ammonia water discharged from the tower top of the ammonia distillation tower returns to be circularly used, the tower bottom materials of the dehydration tower enter an isopropanolamine rectification tower to be rectified and separated under the conditions of 2 kPa and 165 ℃ of the tower kettle temperature, isopropanolamine is obtained from the tower top, the purity is 99.78%, and introducing the tower bottom material into a diisopropanolamine rectifying tower to carry out rectifying separation under the conditions of 1 kPa and the tower bottom temperature of 180 ℃, obtaining diisopropanolamine at the tower top, and obtaining triisopropanolamine at the tower bottom, wherein the purity of the triisopropanolamine is 99.4% and 85% respectively.
The result of gas chromatography detection of the monoisopropanolamine obtained in example 6 is shown in fig. 5, and the peak with the retention time of 3.056 min is the product monoisopropanolamine.
Example 7
By using the apparatus in the above example 3, isopropanolamine was produced as follows:
the method comprises the steps of filling a fixed bed reactor with a sodium X-type molecular sieve and a sodium Y-type molecular sieve (the mass ratio of which is 1:1 after soaking and water absorption is 115 mg/g and 140 mg/g respectively), after nitrogen replacement, controlling the temperature of the fixed bed reactor to be 130 ℃ and the pressure to be 12.5 MPa, respectively mixing propylene oxide, liquid ammonia and 10% ammonia water at the flow rates of 10.4 kg/h, 29.6 kg/h and 1.04 kg/h (the mole ratio of ammonia in the liquid ammonia and the ammonia water to propylene oxide is 10:1, the water inflow is 1% of propylene oxide, the liquid ammonia is a mixture of fresh liquid ammonia and circulating liquid ammonia, the ammonia water is circulating ammonia water), introducing the mixture into the reactor for reaction, completely participating in the reaction of propylene oxide in the material flowing out of the fixed bed reactor, mixing isopropanolamine and the mixture of ammonia and water, the selectivity of isopropanolamine in the mixture is 88.1%, the reacted materials enter a flash tank, the pressure is reduced to 1.8 MPa, ammonia discharged from the top of the flash tank and isopropanolamine containing ammonia discharged from the bottom of the flash tank enter the ammonia distillation tower from the lower part and the middle part of the ammonia distillation tower respectively, ammonia is distilled again under the conditions of 1.8 MPa and 165 ℃ of the tower kettle temperature, the ammonia discharged from the top of the ammonia distillation tower returns to a liquid ammonia storage tank, the tower bottom material of the ammonia distillation tower is introduced into a deamination tower to be subjected to deamination treatment under the conditions of 0.01 MPa and 150 ℃ of the tower kettle temperature, the ammonia discharged from the top of the deamination tower is compressed by a compressor and then returns to the liquid ammonia storage tank, the tower bottom material of the deamination tower is introduced into a dehydration tower to be subjected to dehydration treatment under the conditions of 80 kPa and 150 ℃ of the tower kettle temperature, the ammonia discharged from the tower top of the dehydration tower returns to the ammonia water storage tank for recycling, the tower bottom material of the dehydration tower enters an isopropanolamine rectification tower to be subjected to rectification separation under the conditions of 3 kPa and 170 ℃, and (3) obtaining monoisopropanolamine with the purity of 99.5% from the tower top, introducing the tower bottom material into a diisopropanolamine rectifying tower for rectifying and separating under the conditions of 2 kPa and the tower bottom temperature of 195 ℃, obtaining diisopropanolamine from the tower top, and obtaining triisopropanolamine from the tower bottom with the purity of 99.3% and 80.4% respectively.
Example 8
By using the apparatus in the above example 3, isopropanolamine was produced as follows:
filling dry calcium Y-type molecular sieve in a fixed bed reactor, firstly introducing water which is 20% of the molecular sieve in mass, showering the molecular sieve, carrying out nitrogen replacement after the molecular sieve absorbs water, controlling the temperature of the fixed bed reactor to be 135 ℃ and the pressure to be 13.5 MPa, respectively mixing propylene oxide, liquid ammonia and 20% ammonia water at the flow rates of 10.4 kg/h, 28.5 kg/h and 2.6 kg/h (the mole ratio of ammonia in the liquid ammonia and the ammonia water to propylene oxide is 10:1, the water inflow is 5% of the propylene oxide, the liquid ammonia is a mixture of fresh liquid ammonia and circulating liquid ammonia, the ammonia water is circulating ammonia water), introducing the mixture into the reactor for reaction, completely participating in the reaction in propylene oxide in the material flowing out of the fixed bed reactor, the reacted material component is a mixture of mixed isopropanolamine, ammonia and water, the selectivity of the isopropanolamine in the mixed isopropanolamine is 87.9%, the reacted material enters a flash tank, ammonia discharged from the top of the flash tank and isopropanolamine containing ammonia discharged from the bottom of the flash tank are respectively fed into the ammonia distillation tower from the lower part and the middle part of the ammonia distillation tower, ammonia is distilled again under the conditions of 2 MPa and the temperature of a tower kettle of 170 ℃, ammonia discharged from the top of the ammonia distillation tower is returned to a liquid ammonia storage tank, tower bottom materials of the ammonia distillation tower are fed into the ammonia distillation tower to be subjected to deamination under the conditions of 0.3 MPa and the temperature of the tower kettle of 170 ℃, ammonia discharged from the top of the ammonia distillation tower is compressed by a compressor and then is returned to the liquid ammonia storage tank, tower bottom materials of the ammonia distillation tower are fed into the dehydration tower to be subjected to dehydration under the conditions of 100 kPa and the temperature of the tower kettle of 170 ℃, ammonia water discharged from the tower top of the ammonia distillation tower is returned to be circularly applied to the ammonia storage tank, tower bottom materials of the ammonia distillation tower enter into a isopropanolamine rectification tower to be subjected to rectification separation under the conditions of 5 kPa and the temperature of the tower kettle of 180 ℃, isopropanolamine is obtained from the tower top, the purity is 99.2%, the tower bottom material is led into a diisopropanolamine rectifying tower to be rectified and separated under the conditions of 3 kPa and the tower kettle temperature of 200 ℃, diisopropanolamine is obtained at the tower top, triisopropanolamine is obtained at the tower bottom, and the purity is 99% and 78.5% respectively.
Example 9
By using the apparatus in the above example 2, isopropanolamine was produced as follows:
filling a sodium X-type molecular sieve (water absorption of 230 mg/g) after soaking and water absorbing into a fixed bed reactor, after nitrogen replacement, controlling the temperature of the fixed bed reactor to be 120 ℃ and the pressure to be 10.5 MPa, firstly introducing liquid ammonia preheated to 90 ℃ at a flow rate of 16.7 kg/h, introducing ammonia 1 h, introducing propylene oxide preheated to 90 ℃ at a flow rate of 3.8 kg/h (the mol ratio of the liquid ammonia to the propylene oxide is 15:1) to react with the liquid ammonia, completely participating in the reaction of propylene oxide in the material flowing out of the fixed bed reactor, wherein the reacted material comprises a mixture of mixed isopropanolamine, ammonia and water, the selectivity of monoisopropanolamine in the mixed isopropanolamine is 91.4%, the reacted material enters a flash tank, the pressure is reduced to 1.8 MPa, ammonia discharged from the top of the flash tank and isopropanolamine containing ammonia discharged from the bottom of the flash tank enter the ammonia distillation tower from the lower part and the middle part of the ammonia distillation tower respectively, ammonia is distilled again under the conditions of 1.8 MPa and 165 ℃ of the tower kettle temperature, ammonia discharged from the top of the ammonia distillation tower returns to a liquid ammonia storage tank, tower bottom materials of the ammonia distillation tower are introduced into the ammonia distillation tower to be subjected to deamination treatment under the conditions of 0.05 MPa and 155 ℃ of the tower kettle temperature, ammonia discharged from the top of the ammonia distillation tower is compressed by a compressor and then returns to the liquid ammonia storage tank, tower bottom materials of the ammonia distillation tower are introduced into a monoisopropanolamine rectification tower to be subjected to rectification separation under the conditions of 3 kPa and 170 ℃ of the tower kettle temperature, monoisopropanolamine is obtained from the tower top, the purity is 99.5%, tower bottom materials are introduced into a diisopropanolamine rectification tower under the conditions of 2 kPa and 190 ℃ of the tower kettle temperature, and the purity of triisopropanolamine is obtained from the tower top is 99.3%, and 82.6%.
Example 10
By using the apparatus in the above example 2, isopropanolamine was produced as follows:
filling a sodium X-type molecular sieve and a calcium X-type molecular sieve which are soaked and absorbed in water in a mass ratio of 1:1 (the water absorption amount is 115 mg/g), after nitrogen replacement, controlling the temperature of the fixed bed reactor to be 100 ℃ and the pressure to be 8 MPa, firstly introducing liquid ammonia preheated to 80 ℃ at a flow rate of 17.5kg/h, introducing ammonia to be 1 h, introducing propylene oxide preheated to 80 ℃ at a flow rate of 3 kg/h (the molar ratio of the liquid ammonia to the propylene oxide is 20:1) to react with the liquid ammonia, completely participating in the reaction of propylene oxide in the material flowing out of the fixed bed reactor, mixing isopropanolamine with ammonia and water as the material components after the reaction, introducing the material after the reaction into a flash tank with the selectivity of one isopropanolamine of 93.3 percent in the mixed isopropanolamine, and reducing the pressure to 1.9 MPa, ammonia discharged from the top of the flash tank and isopropanolamine containing ammonia discharged from the bottom of the flash tank enter the ammonia distillation tower from the lower part and the middle part of the ammonia distillation tower respectively, ammonia is distilled again under the conditions of 1.9 MPa and the temperature of a tower kettle of 170 ℃, ammonia discharged from the top of the ammonia distillation tower returns to a liquid ammonia storage tank, tower bottom materials of the ammonia distillation tower are introduced into the ammonia distillation tower to be subjected to deamination under the conditions of 0.1 MPa and the temperature of the tower kettle of 170 ℃, ammonia discharged from the top of the ammonia distillation tower is compressed by a compressor and then returns to the liquid ammonia storage tank, tower bottom materials of the ammonia distillation tower are introduced into a monoisopropanolamine rectification tower to be subjected to rectification separation under the conditions of 2 kPa and the temperature of the tower kettle of 175 ℃, monoisopropanolamine is obtained from the tower top, the purity is 99.2%, the tower bottom materials are introduced into a diisopropanolamine rectification tower under the conditions of 2 kPa and the temperature of the tower kettle of 190 ℃, and the purity of triisopropanolamine is respectively 99%, and the purity of the tower bottom materials is 81.5%.
Comparative example 1
The comparative example provides a production device of isopropanolamine, the structural schematic diagram of which is shown in fig. 4, and 1 is a fixed bed reactor; 2 is a mixer; 3 is a heat exchanger, 3-2 is a propylene oxide heat exchanger, and 3-3 is an ammonia water heat exchanger; 4 is a feed pump, 4-2 is a propylene oxide feed pump, and 4-3 is an ammonia feed pump; 5-2 is a propylene oxide storage tank; 5-3 is an ammonia water storage tank; 6 is a flash tank; 7 is a deamination tower; 8 is a isopropanolamine rectifying tower; 9 is a diisopropanolamine rectifying tower; 10 is a compressor; and 12 is a dehydration tower. The inlet of the feed pump is communicated with the outlet of the storage tank, the outlet of the feed pump is communicated with the inlet of the heat exchanger, the outlet of the heat exchanger is communicated with the inlet of the mixer, the outlet of the mixer is communicated with the inlet of the fixed bed reactor, the outlet of the fixed bed reactor is communicated with the inlet of the flash tank, the top outlet of the flash tank is communicated with the inlet of the ammonia water storage tank, the bottom outlet of the flash tank is communicated with the inlet of the deamination tower, the top outlet of the deamination tower is communicated with the inlet of the compressor, the outlet of the compressor is communicated with the inlet of the ammonia water storage tank, the bottom outlet of the deamination tower is communicated with the inlet of the dewatering tower, the top outlet of the dewatering tower is communicated with the inlet of the ammonia water storage tank, the top of the one isopropanolamine rectifying tower obtains one isopropanolamine, the bottom outlet of the one isopropanolamine rectifying tower is communicated with the inlet of the diisopropanolamine rectifying tower, the top of the diisopropanolamine rectifying tower obtains the diisopropanolamine, and the bottom of the one isopropanolamine rectifying tower obtains the triisopropanolamine.
Comparative example 2
The isopropanolamine is produced by using the device in the comparative example 1, and the specific method is as follows:
sequentially loading porous plates, zirconium beads and fixed bed reactors of the porous plates, heating the fixed bed reactors to 140 ℃ after nitrogen replacement, regulating the operation pressure of the fixed bed to 15 MPa, then respectively introducing mixed and preheated epoxypropane and 90% ammonia water (a mixture of fresh ammonia water, circulating liquid ammonia and ammonia water) at the flow rates of 8 kg/h and 12.6 kg/h (the molar ratio of ammonia in the ammonia water to epoxypropane is 5:1) for reaction, further ageing the epoxypropane in the material flowing out of the fixed bed reactors until the epoxypropane completely participates in the reaction, obtaining a mixture of mixed isopropanolamine, ammonia and water, wherein the selectivity of monoisopropanolamine in the mixed isopropanolamine is 51%, the aged material enters a flash tank, the pressure is reduced to 1.7 MPa, and the ammonia discharged from the top of the flash tank directly returns to a storage tank for application, ammonia-containing isopropanolamine discharged from the bottom of a flash tank is introduced into a deamination tower to be deaminated under the conditions of 0.3 MPa and the temperature of a tower kettle of 180 ℃, ammonia discharged from the top of the deamination tower is compressed by a compressor and then returns to an ammonia water storage tank, tower bottom materials of the deamination tower are introduced into the dewatering tower to be dehydrated under the conditions of 100 kPa and the temperature of the tower kettle of 180 ℃, ammonia water removed from the top of the dewatering tower returns to the ammonia water storage tank, tower bottom materials of the dewatering tower enter a monoisopropanolamine rectifying tower to be rectified and separated under the conditions of 5 kPa and the temperature of the tower kettle of 190 ℃, monoisopropanolamine is obtained from the top of the tower, the purity is 98.3%, the tower bottom materials are introduced into a diisopropanolamine rectifying tower to be separated under the conditions of 3 kPa and the temperature of the tower kettle of 220 ℃, triisopropanolamine is obtained from the top of the tower, and the purity of triisopropanolamine is 97.2% and 61.5% respectively.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (8)
1. A method for producing isopropanolamine, comprising the steps of:
s1: propylene oxide and liquid ammonia react under the action of a water absorption sieve;
the water absorption sieve is obtained after water absorption treatment by a molecular sieve;
the molecular sieve is selected from any one or more of sodium X-type molecular sieve, calcium X-type molecular sieve, sodium Y-type molecular sieve or calcium Y-type molecular sieve;
the water absorption capacity of the water absorption sieve is the saturated water absorption capacity of the molecular sieve;
the molar ratio of the propylene oxide to the ammonia is 1 (5-20);
the temperature of the reaction is 100-140 ℃, and the pressure is 8-15 MPa;
s2: carrying out deamination treatment on the reaction product obtained in the step S1 through flash evaporation;
S3: deamination is carried out again on the tank bottom material obtained by flash evaporation through first rectification, and then second rectification is carried out on the tower bottom material obtained by the first rectification, so that monoisopropanolamine is obtained.
2. The method according to claim 1, wherein step S1 is: propylene oxide, liquid ammonia and ammonia water react under the action of a water absorbing sieve.
3. The production method according to claim 1, wherein the tank bottom material obtained after the flash evaporation is finished is subjected to ammonia distillation treatment, and the tower bottom material obtained after the ammonia distillation treatment is subjected to deamination again through first rectification;
the pressure of the flash evaporation is 1.4-2.0 MPa.
4. A production method according to claim 3, wherein the top material and the bottom material obtained after the flash evaporation are subjected to ammonia distillation treatment, and the bottom material obtained after the ammonia distillation treatment is subjected to deamination again through first rectification.
5. The production method according to claim 3 or 4, wherein the pressure of the ammonia distillation treatment is 1.4 to 2.0 MPa;
the bottom temperature of the ammonia distillation treatment is less than or equal to 170 ℃.
6. The production method according to claim 2, wherein after the deamination treatment is completed, the bottom material obtained by the first rectification is dehydrated, and then the bottom material obtained by the dehydration treatment is rectified for the second time to obtain monoisopropanolamine.
7. The production method according to claim 1, wherein the pressure of the first rectification is 0.01 to 0.3mpa;
the bottom temperature of the first rectification is less than or equal to 170 ℃;
the pressure of the second rectification is 2-5 kPa;
the bottom temperature of the second rectification is less than or equal to 180 ℃.
8. The production method according to claim 1, further comprising performing third distillation on the bottom material obtained by the second distillation to obtain diisopropanolamine and triisopropanolamine after the second distillation is completed.
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| CN1176901C (en) * | 2002-11-13 | 2004-11-24 | 南京红宝丽股份有限公司 | Production method of isopropanolamine |
| CN101265196B (en) * | 2008-04-23 | 2011-05-04 | 南京宝淳化工有限公司 | Method of synthesizing monoisopropanolamine |
| CN205024124U (en) * | 2015-09-29 | 2016-02-10 | 浙江精功新材料技术有限公司 | Isopropanolamine production system |
| CN105348118B (en) * | 2015-09-29 | 2017-06-23 | 浙江精功新材料技术有限公司 | A kind of method that utilization fixed-bed tube reactor produces isopropanolamine |
| CN109748804B (en) * | 2017-11-01 | 2021-12-28 | 中国石油化工股份有限公司 | Production method of isopropanolamine |
| CN109748805B (en) * | 2017-11-01 | 2022-02-01 | 中国石油化工股份有限公司 | Method for producing isopropanolamine by liquid ammonia process |
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