CN115819247A - Ethylenediamine and continuous preparation method thereof - Google Patents
Ethylenediamine and continuous preparation method thereof Download PDFInfo
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- CN115819247A CN115819247A CN202211656009.9A CN202211656009A CN115819247A CN 115819247 A CN115819247 A CN 115819247A CN 202211656009 A CN202211656009 A CN 202211656009A CN 115819247 A CN115819247 A CN 115819247A
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Abstract
The invention provides a continuous preparation method of ethylenediamine, which comprises the following steps: s1: under the condition of controlling adiabatic reaction, the molar ratio is (1.5-10): 1, reacting ammonia and hydroxy acetonitrile to obtain a reaction mixture; s2: carrying out flash evaporation treatment on the reaction mixture; s3: after the flash evaporation ammonia treatment, evaporating the residual volatile liquid in the reaction mixture, condensing and recovering the generated steam to obtain a glycine nitrile mixture; s4: adding a catalyst into the glycine nitrile mixture, adding the catalyst to perform hydrogenation reaction, and continuously preparing mixture of ethylenediamine, N-methyl ethylenediamine and diethylenetriamine; s5: and decompressing the mixture, introducing the mixture into a deamination tower for deamination, passing the reaction product through a solvent recovery tower, then through an N-methyl ethylenediamine separation tower, and then passing the reaction product through a product purification tower after dehydration to obtain ethylenediamine. The invention provides a continuous preparation method of ethylenediamine with strong production capacity and high purity.
Description
Technical Field
The invention relates to the field of ethylenediamine preparation, and particularly relates to ethylenediamine and a continuous preparation method thereof.
Background
Ethylenediamine (EDA), also known as 1, 2-diaminoethane, diaminoethylene, ethylenediamine, is characterized by strong basicity and surface activity. EDA is an important fine organic chemical intermediate, and is widely applied to the fields of manufacturing chelating agents, surfactants, fabric softeners, lubricating oil additives, insecticides, bactericides, resin polymers and the like.
The conventional EDA production processes mainly include a dichloroethane method, a formaldehyde-hydrogen cyanide method, an ethanolamine (MEA) condensation amination method and a reductive amination method. The dichloroethane method takes dichloroethane and ammonia water as raw materials, a large amount of sodium chloride is produced as a byproduct in the reaction process, and equipment corrosion and environmental pollution are serious; the MEA reductive amination method takes MEA and liquid ammonia as raw materials, is carried out under the action of metal Ni and Co catalysts, and reaction products except water can be sold as products after being separated and purified. However, the reaction process needs to be carried out under the conditions of high pressure (17-30 MPa) and hydrogen, and the investment of production devices is high; and catalytic active components such as Ni, co and the like are easy to generate complex reaction with ammonia/amine, so that EDA products are polluted by heavy metals, and the requirements of high-end markets are difficult to meet.
The condensation amination method is to selectively synthesize EDA by taking solid acid as a catalyst and taking MEA and NH3 as raw materials under the condition of medium and low pressure (2-4 MPa). However, since MEA has 2 functional groups with close activity, the reaction with NH3 is complicated, and intramolecular or intermolecular series reaction is likely to occur, thereby generating a series of chain or cyclic by-products; meanwhile, dehydrogenation reaction can also occur in the reaction to generate pyrazine compounds, so the process technology for synthesizing EDA by condensation amination reaction still faces challenges.
US patents US20110207873A1, US20100094057A1 disclose a process for the preparation of bis (aminoacetonitrile) and a process for the preparation of ethylenediamine by reaction of formaldehyde with hydrocyanic acid, heating the aminoacetonitrile formed with an aqueous ammonia solution or liquid ammonia, followed by catalytic hydrogenation to yield ethylenediamine. The disadvantage of this process is that the intermediate product is unstable and gives a rapid dark polymerization and coagulation product, with a low yield of ethylenediamine obtained by hydrogenation.
However, the above process has the disadvantages of strict reaction conditions, poor intrinsic safety, low product quality and purity, low production capacity and the like.
Disclosure of Invention
The invention aims to solve the technical problem of providing a continuous preparation method of ethylenediamine, which aims to solve the defects of low purity and low production capacity of ethylenediamine produced by the conventional preparation method.
In order to solve the problems, the invention provides a continuous preparation method of ethylenediamine, which comprises the following steps:
s1: under the condition of controlling adiabatic reaction, the molar ratio is (1.5-10): 1, reacting ammonia and hydroxy acetonitrile at 120-180 ℃ to obtain a reaction mixture;
s2: carrying out flash evaporation treatment on the reaction mixture prepared in the step S1 to remove ammonia;
s3: after the ammonia flash evaporation treatment in the step S2, evaporating the residual volatile liquid in the reaction mixture, condensing and recovering the generated steam to obtain a glycine nitrile mixture;
s4: adding a catalyst into the glycine nitrile mixture obtained in the step S3, and adding the catalyst in the presence of water and/or an organic solvent to perform hydrogenation reaction, wherein the catalyst is a Raney catalyst, so as to continuously prepare a mixture of ethylenediamine, N-methyl ethylenediamine and diethylenetriamine;
s5: decompressing the mixture prepared in the step, introducing the mixture into a deamination tower for deamination, passing the reaction product through a solvent recovery tower, then through an N-methyl ethylenediamine separation tower, and then passing the reaction product through a product purification tower after dehydration to obtain ethylenediamine.
Preferably, in the step S1, the ammonia is 80-100% by mass.
Preferably, in the step S1, the reaction temperature is 140-150 ℃, the reaction pressure is 20-30 bar, and the reaction time is 8-20 seconds.
Preferably, in step S3, the recovering to obtain glycine nitrile includes: glycine nitrile is separated and recovered from said ammonia flashed from the reaction mixture and from said remaining liquid.
Preferably, in step S4, the doped element of the raney catalyst is one of Cr, mo, ni and Fe.
In the preparation process of the present invention, a raney catalyst, preferably a raney cobalt or nickel catalyst, particularly preferably a raney cobalt catalyst doped with at least one of the elements Cr, ni or Fe or a raney nickel catalyst doped with at least one of the elements Mo, cr or Fe, is used as the catalyst having a hydrogenation function. The amount of catalyst actually used is determined by its activity.
Preferably, in step S4, the organic solvent is tetrahydrofuran or methanol.
Preferably, in step S4, the hydrogenation reaction conditions are as follows: pressure: 40-160 bar, temperature: 80-140 ℃.
Preferably, in the step S1, the reaction is performed in a tubular reactor; in the steps S2 to S5, the reaction is carried out in a stirring reactor, a loop reactor or other back mixing type reactors.
Preferably, in step S3, after the flash evaporation treatment, an operation of recycling the ammonia gas obtained by the flash evaporation is further included; in the step S4, the operation of recycling redundant hydrogen generated by hydrogenation treatment is also included; the step S5 further includes an operation of recycling the solvent recovered by the solvent recovery tower.
The invention aims to solve another technical problem of providing the ethylenediamine so as to solve the problem of low purity of the conventional ethylenediamine.
In order to solve the above problems, the present invention provides ethylenediamine prepared by the preparation method.
In the process of the present invention, we continuously produced glycinonitrile product by introducing hydroxyacetonitrile and ammonia to react in a tubular reactor under essentially controlled adiabatic reaction conditions to obtain good yields of glycinonitrile. The main reaction is as follows:
HOCH 2 CN+NH 3 ----H 2 NCH 2 CN+HN(CH 2 CN) 2 +H 2 O；
glycine nitriles are important intermediates for the preparation of ethylenediamine and glycine. Thus, impurities in glycine nitrile, such as Iminodiacetonitrile (IDAN), are often detrimental, affecting the purity and yield of ethylenediamine or glycine,
in the process of the present invention, impurities such as Iminodiacetonitrile (IDAN) are still produced in the tubular reactor, but IDAN and other impurities are non-volatile and can be separated from the volatile glycinonitrile by distillation, preferably by means of a wiped-film evaporator (wiped-film evaporator), since the contact time of such an apparatus is very short and since glycinonitrile is unstable, especially at elevated temperatures, the typical batch distillation is not suitable and significant decomposition losses occur.
In the process of the present invention, relatively pure glycine nitrile mixture solution can be obtained by distilling glycine nitrile resulting solution, and ethylene diamine can be prepared by hydrogenation in the presence of catalyst. The method enters a subsequent fractionation and purification scheme of the ethylenediamine, can obtain higher yield of the ethylenediamine, and improves the purity of the ethylenediamine on the premise of improving the yield of the ethylenediamine.
The main reaction is as follows:
H 2 NCH 2 CN+H 2 -------H 2 NCH 2 CNH 2
the invention provides a simple and continuous method for preparing ethylenediamine, and the obtained ethylenediamine has high yield, high purity, and higher commercial value and industrial popularization value.
Detailed Description
The technical solutions of the present invention will be described clearly and completely below, and it should be apparent that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the process of the invention, the hydroxyacetonitrile solution used, in the usual case, contains about 30% to 51% of hydroxyacetonitrile, but the hydroxyacetonitrile can also be used in highly concentrated form, for example in a form of from 60% to 80% or even more, such as 90%, or anhydrous form, completely or partially dehydrated by evaporation.
Example 1:
this example provides a continuous method for preparing ethylenediamine, comprising the following steps:
s1: under the condition of controlling adiabatic reaction, the molar ratio of 1.5:1, reacting ammonia with hydroxyacetonitrile at the temperature of 120 ℃ to obtain a reaction mixture; the ammonia accounts for 80 percent of the mass of the ammonia; the reaction pressure is 20 bar, the reaction time is 8 seconds, and the reaction is carried out in a tubular reactor;
s2: carrying out flash evaporation treatment on the reaction mixture prepared in the step S1 to remove ammonia;
s3: after the ammonia flash evaporation treatment in the step S2, recycling the ammonia obtained by flash evaporation again, evaporating the residual volatile liquid in the reaction mixture, condensing and recovering the generated steam, and recovering to obtain a glycine nitrile mixture; the recovery of glycine nitrile comprises: glycine nitrile is separated and recovered from the ammonia flashed from the reaction mixture and from the remaining liquid.
S4: adding a catalyst into the glycine nitrile mixture obtained in the step S3, adding the catalyst in the presence of water and/or an organic solvent for hydrogenation reaction, and recycling redundant hydrogen, wherein the catalyst is a Raney catalyst, and the doped element of the Raney catalyst is one of Cr, mo, ni and Fe, so as to continuously prepare a mixture of ethylenediamine, N-methyl ethylenediamine and diethylenetriamine; the organic solvent is tetrahydrofuran or methanol;
the conditions of the hydrogenation reaction are as follows: pressure: 40 bar, temperature: 80 deg.C
S5: decompressing the mixture prepared in the step, introducing the mixture into a deamination tower for deamination, passing the reaction product through a solvent recovery tower, recycling the solvent recovered by the solvent recovery tower, passing the solvent through an N-methyl ethylenediamine separation tower, dehydrating the reaction product, and passing the reaction product through a product purification tower to obtain ethylenediamine.
In the step S1, the reaction is carried out in a tubular reactor; in the steps S2 to S5, the reaction is carried out in a stirring reactor, a loop reactor or other back mixing type reactors.
The invention also provides ethylenediamine prepared by the preparation method.
Example 2:
the embodiment provides a continuous preparation method of ethylenediamine, which comprises the following steps:
s1: under the condition of controlling adiabatic reaction, the molar ratio of 1.5:10, reacting ammonia with hydroxy acetonitrile at the temperature of 180 ℃ to obtain a reaction mixture; the ammonia accounts for 100 percent of the mass of the ammonia; the reaction pressure is 30 bar, the reaction time is 20 seconds, and the reaction is carried out in a tubular reactor;
s2: carrying out flash evaporation treatment on the reaction mixture prepared in the step S1 to remove ammonia;
s3: after the ammonia flash evaporation treatment in the step S2, recycling the ammonia obtained by flash evaporation again, evaporating the residual volatile liquid in the reaction mixture, condensing and recovering the generated steam, and recovering to obtain a glycine nitrile mixture; the recovery of glycine nitrile comprises: glycine nitrile is separated and recovered from the ammonia flashed from the reaction mixture and from the remaining liquid.
S4: adding a catalyst into the glycine nitrile mixture obtained in the step S3, adding the catalyst in the presence of water and/or an organic solvent for hydrogenation reaction, and recycling redundant hydrogen, wherein the catalyst is a Raney catalyst, and the doped element of the Raney catalyst is one of Cr, mo, ni and Fe, so as to continuously prepare a mixture of ethylenediamine, N-methyl ethylenediamine and diethylenetriamine; the organic solvent is tetrahydrofuran or methanol;
the conditions of the hydrogenation reaction are as follows: pressure: 160 bar, temperature: 140 deg.C
S5: decompressing the mixture prepared in the step, introducing the mixture into a deamination tower for deamination, passing the reaction product through a solvent recovery tower, recycling the solvent recovered by the solvent recovery tower, passing the solvent through an N-methyl ethylenediamine separation tower, dehydrating the reaction product, and passing the reaction product through a product purification tower to obtain ethylenediamine.
In the step S1, the reaction is carried out in a tubular reactor; in the steps S2 to S5, the reaction is carried out in a stirring reactor, a loop reactor or other back mixing type reactors.
The invention also provides ethylenediamine prepared by the preparation method.
Example 3:
this example provides a continuous method for preparing ethylenediamine, comprising the following steps:
s1: under the condition of controlling adiabatic reaction, the molar ratio of 1.5:6, reacting ammonia with hydroxyacetonitrile at 145 ℃ to obtain a reaction mixture; the ammonia is 80 mass percent of ammonia; the reaction pressure was 25 bar and the reaction time was 14 seconds, the reaction being carried out in a tubular reactor;
s2: carrying out flash evaporation treatment on the reaction mixture prepared in the step S1 to remove ammonia;
s3: after the ammonia flash evaporation treatment in the step S2, recycling the ammonia obtained by flash evaporation again, evaporating the residual volatile liquid in the reaction mixture, condensing and recovering the generated steam, and recovering to obtain a glycine nitrile mixture; the recovery of glycine nitrile comprises: glycine nitrile is separated and recovered from the ammonia flashed from the reaction mixture and from the remaining liquid.
S4: adding a catalyst into the glycine nitrile mixture obtained in the step S3, adding the catalyst in the presence of water and/or an organic solvent to perform a hydrogenation reaction, and recycling redundant hydrogen, wherein the catalyst is a Raney catalyst doped with one of Cr, mo, ni and Fe, so as to continuously prepare a mixture of ethylenediamine, N-methyl ethylenediamine and diethylenetriamine; the organic solvent is tetrahydrofuran or methanol;
the conditions of the hydrogenation reaction are as follows: pressure: 100 bar, temperature: 110 deg.C
S5: decompressing the mixture prepared in the step, introducing the mixture into a deamination tower for deamination, passing the reaction product through a solvent recovery tower, recycling the solvent recovered by the solvent recovery tower, passing the solvent through an N-methyl ethylenediamine separation tower, dehydrating the reaction product, and passing the reaction product through a product purification tower to obtain ethylenediamine.
In the step S1, the reaction is carried out in a tubular reactor; in the steps S2 to S5, the reaction is carried out in a stirring reactor, a loop reactor or other back mixing type reactors.
The invention also provides ethylenediamine prepared by the preparation method.
The technical scheme of the invention is described in detail by combining specific experimental data, experimental operation, instruments and the like as follows:
s1: hydroxyacetonitrile (50%) and liquid ammonia (95%) were pumped into a continuous tube reactor for reaction at a molar feed of ammonia and hydroxyacetonitrile of 6, at a reaction temperature of 140 ℃ to 150 ℃ and a pressure of 2.6MPa (G) with a residence time in the tube reactor of about 12 seconds, with the main reaction producing Aminoacetonitrile (ANN) and the by-product being mainly Iminodiacetonitrile (IDAN).
S2: the ammonification reaction product is decompressed and flashed to obtain a large amount of ammonia gas, so that the temperature of the product is reduced by about 100 ℃, the pressure is reduced to about atmospheric pressure, and the ammonia gas can be recycled after being compressed;
s3: the flash liquid phase is purified by a wiped film evaporator and the non-volatile by-products collected at the bottom of the evaporator are removed as a waste stream or can be further processed to recover IDAN. The distillation gave a glycine nitrile solution (sample analyzed by GC, glycine nitrile 47.5%, IDAN0.3%, ammonia 1.8%), yield 91.3% in hydroxyacetonitrile.
S4: and distilling the ammoniated reaction product to obtain glycine nitrile solution, mixing the glycine nitrile solution with the catalyst, pumping the mixture into a hydrogenation reactor, simultaneously adding excessive hydrogen, taking Tetrahydrofuran (THF) as a solvent, and introducing the mixture together at the reaction temperature of 120 ℃ and the pressure of 8MPa (G). The hydrogenation reaction products are Ethylenediamine (EDA), N-methylethylenediamine (N-MeEDA) and Diethylenetriamine (DETA). Excessive hydrogen is discharged from the top of the reactor, condensed and compressed to be recycled, liquid-phase hydrogenation reaction products enter a decanter to separate out the catalyst, and reaction products and solvent carried by the hydrogen enter a subsequent product separation section together with the liquid-phase reaction products after being condensed.
S5: and (2) decompressing the hydrogenation reaction product, then feeding the hydrogenation reaction product into a deamination tower to separate ammonia brought by glycine nitrile, recycling the deaminated reaction product through a two-stage solvent recovery tower, feeding the solvent into an N-MeEDA separation tower, then feeding the solvent into a product purification tower after two-stage dehydration, and collecting a high-quality EDA product from the tower top. The samples were analyzed by GC and showed a constant selectivity of glycine nitrile >95% for EDA and 1% for DETA.
The above examples further demonstrate that the present invention provides a continuous process for the production of ethylene diamine with high purity and high productivity, low impurity content and high selectivity.
Although the present disclosure has been described above, the scope of the present disclosure is not limited thereto. Those skilled in the art can make various changes and modifications without departing from the spirit and scope of the present disclosure, and such changes and modifications will fall within the scope of the present invention.
Claims (10)
1. A continuous preparation method of ethylenediamine is characterized by comprising the following steps: the method comprises the following steps:
s1: under the condition of controlling adiabatic reaction, the molar ratio is (1.5-10): 1, reacting ammonia and hydroxy acetonitrile at 120-180 ℃ to obtain a reaction mixture;
s2: carrying out flash evaporation treatment on the reaction mixture prepared in the step S1 to remove ammonia;
s3: after the ammonia flash evaporation treatment in the step S2, evaporating the residual volatile liquid in the reaction mixture, condensing and recovering the generated steam to obtain a glycine nitrile mixture;
s4: adding a catalyst into the glycine nitrile mixture obtained in the step S3, and adding the catalyst in the presence of water and/or an organic solvent to perform hydrogenation reaction, wherein the catalyst is a Raney catalyst, so as to continuously prepare a mixture of ethylenediamine, N-methyl ethylenediamine and diethylenetriamine;
s5: decompressing the mixture prepared in the step, introducing the mixture into a deamination tower for deamination, passing the reaction product through a solvent recovery tower, then through an N-methyl ethylenediamine separation tower, and then passing the reaction product through a product purification tower after dehydration to obtain ethylenediamine.
2. The continuous production method of ethylenediamine according to claim 1, characterized in that: in the step S1, the ammonia is 80-100% by mass.
3. The continuous production method of ethylenediamine according to claim 1, characterized in that: in the step S1, the reaction temperature is 140-150 ℃, the reaction pressure is 20-30 bar, and the reaction time is 8-20 seconds.
4. The continuous production method of ethylenediamine according to claim 1, characterized in that: in the step S3, the recovering to obtain glycine nitrile includes: glycine nitrile is separated and recovered from the remaining liquid by neutralization of the ammonia flashed from the reaction mixture.
5. The continuous production method of ethylenediamine according to claim 1, characterized in that: in the step S4, the doped element of the raney nickel catalyst is one of Cr, mo, ni, and Fe.
6. The continuous production method of ethylenediamine according to claim 1, characterized in that: in the step S4, the organic solvent is tetrahydrofuran or methanol.
7. The continuous production method of ethylenediamine according to claim 1, characterized in that: in the step S4, the conditions of the hydrogenation reaction are as follows: pressure: 40-160 bar, temperature: 80-140 ℃.
8. The continuous production method of ethylenediamine according to claim 1, characterized in that: in the step S1, the reaction is carried out in a tubular reactor; in the steps S2 to S5, the reaction is carried out in a stirring reactor, a loop reactor or other back mixing type reactors.
9. The continuous production method of ethylenediamine according to claim 1, characterized in that: in the step S3, after the flash evaporation treatment, an operation of recycling the ammonia gas obtained by the flash evaporation is further included; in the step S4, the operation of recycling redundant hydrogen generated by hydrogenation treatment is also included; the step S5 further includes an operation of recycling the solvent recovered by the solvent recovery tower.
10. An ethylenediamine characterized by: the ethylenediamine is prepared by the preparation method of any one of the steps 1 to 9.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101622221A (en) * | 2007-03-01 | 2010-01-06 | 巴斯夫欧洲公司 | Method for producing ethylenediamine |
| CN103159630A (en) * | 2011-12-14 | 2013-06-19 | 中国科学院大连化学物理研究所 | A method for preparing ethylenediamine by using ethanolamine and ammonia as raw materials |
| WO2014131620A1 (en) * | 2013-02-28 | 2014-09-04 | Basf Se | Method for producing eda using so2-free hydrocyanic acid |
| CN108884058A (en) * | 2015-11-20 | 2018-11-23 | 阿奇克斯制药公司 | Big ring broad-spectrum antibiotic |
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- 2022-12-22 CN CN202211656009.9A patent/CN115819247A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101622221A (en) * | 2007-03-01 | 2010-01-06 | 巴斯夫欧洲公司 | Method for producing ethylenediamine |
| CN103159630A (en) * | 2011-12-14 | 2013-06-19 | 中国科学院大连化学物理研究所 | A method for preparing ethylenediamine by using ethanolamine and ammonia as raw materials |
| WO2014131620A1 (en) * | 2013-02-28 | 2014-09-04 | Basf Se | Method for producing eda using so2-free hydrocyanic acid |
| CN108884058A (en) * | 2015-11-20 | 2018-11-23 | 阿奇克斯制药公司 | Big ring broad-spectrum antibiotic |
Non-Patent Citations (2)
| Title |
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| ISLAM, SAIDUL; BUCAR, DEJAN-KRESIMIR; POWNER, MATTHEW W.: "Prebiotic selection and assembly of proteinogenic amino acids and natural nucleotides from complex mixtures", NATURE CHEMISTRY, vol. 9, no. 6, pages 584 - 589, XP036932014, DOI: 10.1038/nchem.2703 * |
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