CN101215239A - Combined preparation method for ethylene diamine and aminoethylpiperazine - Google Patents
Combined preparation method for ethylene diamine and aminoethylpiperazine Download PDFInfo
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- CN101215239A CN101215239A CNA2008100007683A CN200810000768A CN101215239A CN 101215239 A CN101215239 A CN 101215239A CN A2008100007683 A CNA2008100007683 A CN A2008100007683A CN 200810000768 A CN200810000768 A CN 200810000768A CN 101215239 A CN101215239 A CN 101215239A
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- thanomin
- piperazine
- quadrol
- ammonia
- ethyl piperazidine
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Abstract
The invention discloses a combined preparation process of ethane diamine and aminoethyl piperazine, aiming to solve the problem low yield when prepared associated ethane diamine and aminoethyl piperazine. The invention comprises the steps as flowed that firstly mixing ethane diamine and ammonia to react under the conditions of the exist of mordenite of condensed amination catalyst phosphorous modification, 2.0MPa-5.0MPa pressure, 300-350 DEG C temperature, 6-12:1 of ammonia and aminoethyl alcohol weight ratio, 20-30 seconds of reaction contact time, distilling and separating product liquid to obtain aminoethyl alcohol product, secondly reacting piperazine which is obtained in first step and aminoethyl alcohol under the conditions of the exist of ZSM-5 zeolite of condensed amination catalyst silicon modification, 4.0MPa-8.0MPa pressure, 350-400 DEG C temperature, 0.5-1.5:1 of piperazine and aminoethyl alcohol weight ratio, and 10-20 seconds of reaction contact time, distilling and separating product liquid to obtain aminoethyl piperazine product. The invention is mainly combined to be used to prepare ethane diamine and aminoethyl piperazine.
Description
Technical field
The present invention relates to the combined preparation process of a kind of quadrol and amine ethyl piperazidine.
Technical background
Quadrol and amine ethyl piperazidine are two kinds of well sold and in short supply industrial chemicals of market, have purposes widely in fields such as epoxy curing agent, agricultural chemicals, high molecular polymers.
Among the preparation method of quadrol, be raw material when carrying out amination reaction with thanomin, ammonia and hydrogen, aminate is a quadrol, and generates with a certain amount of piperazine, amine ethyl piperazidine.Among the preparation method of amine ethyl piperazidine, be raw material when carrying out amination reaction with thanomin and piperazine, aminate is the amine ethyl piperazidine.
Generally, because the intermediate amine that amination reaction generates has higher reactive behavior than ammonia, itself and thanomin further react the generation cyclic amine, cause aminate comparatively complicated.Therefore in order to improve the utilization ratio of cyclic amine, make the cyclic amine piperazine be converted into the amine ethyl piperazidine, developed the method for carrying out combined preparation quadrol and amine ethyl piperazidine with the piperazine for the raw material reduction amination.US 3793397 discloses a kind of reduction amination preparation method of amine ethyl piperazidine.This method is a raw material with thanomin, ammonia, hydrogen, in the presence of the reduction amination catalyzer, at 200 ℃～300 ℃, 6.5MPa carry out reductive amination process under the～22.5MPa condition, the product that generates is quadrol, piperazine, amine ethyl piperazidine, diethylenetriamine, the aminate flow point that will contain piperazine from or without separation, be recycled in the starting raw material and react, generate the amine ethyl piperazidine.The main chemical reactions that is taken place is:
In this method, generate the diethylenetriamine by product greater than 6% in the aminate, cause quadrol and amine ethyl piperazidine yield not high, wherein the quadrol yield is up to 15.5%, and amine ethyl piperazidine yield is up to 31.7%, and total recovery is no more than 47.2%.
By retrieval, do not retrieve the data of condensation amination combined preparation quadrol and amine ethyl piperazidine.
Summary of the invention
Technical problem to be solved by this invention is to overcome the deficiency that exists in the background technology, and the combined preparation process of high quadrol of a kind of yield and amine ethyl piperazidine is provided.
In the thanomin reductive amination process, generate the diethylenetriamine by product inevitably, its reason is because the dehydrogenation-hydrogenation performance of reduction amination catalyzer causes.In order to solve quadrol and the not high problem of amine ethyl piperazidine yield, must avoid diethylenetriamine production of by-products in the amination reaction.Discover through the inventor, adopting the mordenite of phosphorus modification modification is the condensation amination catalysis, when carrying out the condensation amination reaction by thanomin and ammonia, the product that generates is quadrol, piperazine, amine ethyl piperazidine, avoid the diethylenetriamine production of by-products, can improve the yield of quadrol and amine ethyl piperazidine.
Combined preparation quadrol of the present invention and amine ethyl piperazidine, synthetic route is as follows:
Reaction formula (2)
The combined preparation process of quadrol of the present invention and amine ethyl piperazidine may further comprise the steps:
A. thanomin and ammonia are mixed, the preheating vaporization, feed in the fixed-bed reactor, in the presence of the condensation amination catalysis, pressure 2.0MPa～5.0MPa, 300 ℃～350 ℃ of temperature, ammonia and thanomin weight ratio 6～12: 1, reaction contact time reacted under the condition in 20 seconds～30 seconds, and the condensation amination catalysis is the mordenite of phosphorus modification, and its weight percent consists of: mordenite 99%～97%, phosphorus 1%～3%, product stream is quadrol, piperazine, amine ethyl piperazidine and unreacted ammonia, thanomin, to product stream fractionation by distillation, gets the product quadrol;
B. piperazine that step a is obtained and thanomin preheating vaporization, feed in the fixed-bed reactor, in the presence of the condensation amination catalysis, pressure 4.0MPa～8.0MPa, 350 ℃～400 ℃ of temperature, piperazine and thanomin weight ratio 0.5～1.5: 1, reaction contact time reacted under the condition in 10 seconds～20 seconds, and the condensation amination catalysis is the ZSM-5 zeolite of silicon modification, its weight percent consists of: ZSM-5 zeolite 99%～95%, silicon 1%～5% to product stream fractionation by distillation, obtains the amine ethyl piperazidine.
The combined preparation process of preferred quadrol of the present invention and amine ethyl piperazidine may further comprise the steps:
A. thanomin and ammonia are mixed, the preheating vaporization, feed in the fixed-bed reactor, react in the presence of the mordenite of condensation amination catalysis phosphorus modification, pressure is 4.0MPa, temperature is 330 ℃, ammonia and thanomin weight ratio are 8: 1, and reaction contact time is 24 seconds, and product stream is quadrol, piperazine, amine ethyl piperazidine and unreacted ammonia, thanomin, product stream is separated, get the product quadrol;
B. piperazine that step a is obtained and thanomin preheating vaporization, feed in the fixed-bed reactor, in the presence of the ZSM-5 zeolite of condensation amination catalysis silicon modification, react, pressure is 6.0MPa, temperature is 380 ℃, and piperazine and thanomin weight ratio are 1.0: 1, and reaction contact time is 15 seconds, product stream is separated, obtain the amine ethyl piperazidine.
Condensation amination catalysis used in the present invention can be phosphorus modified mordenite, silicon modified ZSM-5 zeolite, also mordenite, ZSM-5 zeolite or the chabazite of phosphorus, silicon or boron modification can be, phosphoric acid salt, monohydric phosphate, dihydrogen phosphate and various Mo, the W of metal V, Ti, Fe, Co, Ni, Cu, Zn, Mg, the heteropolyacid salt of V can also be.
Advantage of the present invention:
The present invention is a raw material with thanomin and ammonia, in the presence of condensation amination catalysis phosphorus modified mordenite, silicon modified ZSM-5 zeolite, when carrying out two step condensation amination reactions, does not produce the diethylenetriamine by product, has improved the yield of quadrol and amine ethyl piperazidine.To consume the unit weight thanomin is benchmark, and the target product total recovery can reach 77.8%, and the quadrol yield is 32.6%, and amine ethyl piperazidine yield is 45.2%.
Embodiment
Embodiment 1
1.1 Preparation of catalysts
A. phosphorus modified mordenite
Get the 80g mordenite and add 20g aluminum oxide and 5mL water, granulation, moulding is pressed into Φ 5 * 5mm cylinder shape particle, dries back 500 ℃ of roasting 2h, obtains catalyst precursor;
Get in the solution that the 50g catalyst precursor joins the preparation of 54mL normal hexane and 3.4g trimethyl phosphite 99 and flood, remove normal hexane 90 ℃ of distillations.Residuum behind the evaporate to dryness with 3 ℃/min, is warming up to 550 ℃ in retort furnace, behind the roasting 5h, naturally cooling gets 1.5% phosphorus modified mordenite.
B. silicon modified ZSM-5 zeolite catalyzer
Get 80g ZSM-5 zeolite and add 20g aluminum oxide and 5mL water, granulation, moulding is pressed into Φ 5 * 5mm cylinder shape particle, dries back 500 ℃ of roasting 2h, obtains catalyst precursor;
Get in the solution that the 50g catalyst precursor joins the preparation of 96mL normal hexane and 7.0g phenyltrimethoxysila,e and flood, remove normal hexane 90 ℃ of distillations.Residuum behind the evaporate to dryness with 3 ℃/min, is warming up to 550 ℃ in retort furnace, behind the roasting 3h, naturally cooling gets 2.0% silicon modified ZSM-5 zeolite catalyzer.
1.2 amination reaction
Thanomin and ammonia are mixed, the preheating vaporization, feed in the fixed-bed reactor, in the presence of condensation amination catalysis 1.5% phosphorus modified mordenite, react, pressure is 4.0MPa, temperature is 330 ℃, ammonia and thanomin weight ratio are 8: 1, reaction contact time is 24 seconds, and product stream is quadrol, piperazine, amine ethyl piperazidine and unreacted ammonia, thanomin, remove ammonia after, contain quadrol 32.6% through the gas phase gas chromatography-mass spectrometry analysis, piperazine 28.0%, amine ethyl piperazidine 3.8%, thanomin 28.4%.Product stream is carried out fractionation by distillation, obtain the product quadrol, purity is 99.5%.
Separated piperazine and the thanomin preheating vaporization that obtains the last step, feed in the fixed-bed reactor, react in the presence of condensation amination catalysis 2.0% silicon modified ZSM-5 zeolite, pressure is 6.0MPa, and temperature is 380 ℃, piperazine and thanomin weight ratio are 1.0: 1, reaction contact time is 15 seconds, and the product gas phase gas chromatography-mass spectrometry analysis of flowing through contains quadrol 1.6%, piperazine 18.3%, amine ethyl piperazidine 68.8%, thanomin 10.4%.Product stream is separated, obtain the amine ethyl piperazidine, purity is 98.7%.
To consume the unit weight thanomin is benchmark, and the quadrol yield is 32.6%, and amine ethyl piperazidine yield is that 45.2%, two kind of target product total recovery can reach 77.8%.
Embodiment 2
2.1 Preparation of catalysts
A. phosphorus modified mordenite
Catalyst preparation process is substantially the same manner as Example 1, and difference is to flood with the solution that 58mL normal hexane and 4.7g trimethyl phosphite 99 are prepared, and gets 2.1% phosphorus modified mordenite.
B. silicon modified ZSM-5 zeolite catalyzer:
Catalyst preparation process is substantially the same manner as Example 1, and difference is to flood with the solution that 50mL normal hexane and 17.5g phenyltrimethoxysila,e are prepared, and gets 5.0% silicon modified ZSM-5 zeolite catalyzer.
2.2 amination reaction
Thanomin and ammonia are mixed, the preheating vaporization, feed in the fixed-bed reactor, in the presence of condensation amination catalysis 2.1% phosphorus modified mordenite, react, pressure is 5.0MPa, temperature is 300 ℃, ammonia and thanomin weight ratio are 6: 1, reaction contact time is 20 seconds, and product stream is quadrol, piperazine, amine ethyl piperazidine and unreacted ammonia, thanomin, remove ammonia after, contain quadrol 48.6% through the gas phase gas chromatography-mass spectrometry analysis, piperazine 13.1%, amine ethyl piperazidine 4.2%, thanomin 24.4%.Product stream is carried out fractionation by distillation, obtain the product quadrol, purity is 99.7%.
Separated piperazine and the thanomin preheating vaporization that obtains the last step, feed in the fixed-bed reactor, react in the presence of amination catalysis 5.0% silicon modified ZSM-5 zeolite, pressure is 4.0MPa, and temperature is 400 ℃, piperazine and thanomin weight ratio are 0.5: 1, reaction contact time is 10 seconds, and the product gas phase gas chromatography-mass spectrometry analysis of flowing through contains quadrol 5.8%, piperazine 3.7%, amine ethyl piperazidine 63.5%, thanomin 17.4%.Product stream is separated, obtain the amine ethyl piperazidine, purity is 97.9%.
To consume the unit weight thanomin is benchmark, and the quadrol yield is 34.4%, and amine ethyl piperazidine yield is that 40.3%, two kind of target product total recovery can reach 74.7%.
Embodiment 3
3.1 Preparation of catalysts
A. phosphorus modified mordenite
Catalyst preparation process is substantially the same manner as Example 1, and difference is to flood with the solution that 70mL normal hexane and 4.1g trimethyl phosphite 99 are prepared, and gets 1.8% phosphorus modified mordenite.
B. silicon modified ZSM-5 zeolite catalyzer
Catalyst preparation process is substantially the same manner as Example 1, and difference is to flood with the solution that 50mL normal hexane and 8.8g phenyltrimethoxysila,e are prepared, and gets 2.5% silicon modified ZSM-5 zeolite catalyzer.
3.2 amination reaction
Thanomin and ammonia are mixed, the preheating vaporization, feed in the fixed-bed reactor, in the presence of condensation amination catalysis 1.8% phosphorus modified mordenite, react, pressure is 2.0MPa, temperature is 350 ℃, ammonia and thanomin weight ratio are 12: 1, reaction contact time is 30 seconds, and product stream is quadrol, piperazine, amine ethyl piperazidine and unreacted ammonia, thanomin, remove ammonia after, contain quadrol 43.0% through the gas phase gas chromatography-mass spectrometry analysis, piperazine 29.1%, amine ethyl piperazidine 0.6%, thanomin 19.4%.Product stream is carried out fractionation by distillation, obtain the product quadrol, purity is 99.7%.
Separated piperazine and the thanomin preheating vaporization that obtains the last step, feed in the fixed-bed reactor, react in the presence of condensation amination catalysis 2.5% silicon modified ZSM-5 zeolite, pressure is 8.0MPa, and temperature is 350 ℃, piperazine and thanomin weight ratio are 1.5: 1, reaction contact time is 20 seconds, and the product gas phase gas chromatography-mass spectrometry analysis of flowing through contains quadrol 8.1%, piperazine 0.6%, amine ethyl piperazidine 63.2%, thanomin 19.2%.Product stream is separated, obtain the amine ethyl piperazidine, purity is 98.5%.
To consume the unit weight thanomin is benchmark, and the quadrol yield is 35.3%, and amine ethyl piperazidine yield is that 25.2%, two kind of target product total recovery is 60.5%.
Embodiment 4
4.1 Preparation of catalysts
A. phosphorus modified mordenite
Catalyst preparation process is substantially the same manner as Example 1, and difference is to flood with the solution that 90mL normal hexane and 6.8g trimethyl phosphite 99 are prepared, and gets 3.0% phosphorus modified mordenite.
B. silicon modified ZSM-5 zeolite catalyzer
Catalyst preparation process is substantially the same manner as Example 1, and difference is to flood with the solution that 67mL normal hexane and 4.6g phenyltrimethoxysila,e are prepared, and gets 1.3% silicon modified ZSM-5 zeolite catalyzer.
4.2 amination reaction
Thanomin and ammonia are mixed, the preheating vaporization, feed in the fixed-bed reactor, in the presence of condensation amination catalysis 3.0% phosphorus modified mordenite, react, pressure is 4.0MPa, temperature is 330 ℃, ammonia and thanomin weight ratio are 12: 1, reaction contact time is 30 seconds, and product stream is quadrol, piperazine, amine ethyl piperazidine and unreacted ammonia, thanomin, remove ammonia after, contain quadrol 40.0% through the gas phase gas chromatography-mass spectrometry analysis, piperazine 32.1%, amine ethyl piperazidine 0.7%, thanomin 19.3%.Product stream is carried out fractionation by distillation, obtain the product quadrol, purity is 99.7%.
Separated piperazine and the thanomin preheating vaporization that obtains the last step, feed in the fixed-bed reactor, react in the presence of condensation amination catalysis 1.3% silicon modified ZSM-5 zeolite, pressure is 5.0MPa, and temperature is 0370 ℃, piperazine and thanomin weight ratio are 1.4: 1, reaction contact time is 13 seconds, and the product gas phase gas chromatography-mass spectrometry analysis of flowing through contains quadrol 5.1%, piperazine 3.6%, amine ethyl piperazidine 58.2%, thanomin 24.2%.Product stream is separated, obtain the amine ethyl piperazidine, purity is 97.9%.
To consume the unit weight thanomin is benchmark, and the quadrol yield is 40.1%, and amine ethyl piperazidine yield is that 22.0%, two kind of target product total recovery is 62.1%.
Claims (2)
1. the combined preparation process of quadrol and amine ethyl piperazidine may further comprise the steps:
A. thanomin and ammonia are mixed, the preheating vaporization, feed in the fixed-bed reactor, in the presence of the condensation amination catalysis, pressure 2.0MPa～5.0MPa, 300 ℃～350 ℃ of temperature, ammonia and thanomin weight ratio 6～12: 1, reaction contact time reacted under the condition in 20 seconds～30 seconds, and the condensation amination catalysis is the mordenite of phosphorus modification, and its weight percent consists of: mordenite 99%～97%, phosphorus 1%～3%, product stream is quadrol, piperazine, amine ethyl piperazidine and unreacted ammonia, thanomin, to product stream fractionation by distillation, gets the product quadrol;
B. piperazine that step a is obtained and thanomin preheating vaporization, feed in the fixed-bed reactor, in the presence of the condensation amination catalysis, pressure 4.0MPa～8.0MPa, 350 ℃～400 ℃ of temperature, piperazine and thanomin weight ratio 0.5～1.5: 1, reaction contact time reacted under the condition in 10 seconds～20 seconds, and the condensation amination catalysis is the ZSM-5 zeolite of silicon modification, its weight percent consists of: ZSM-5 zeolite 99%～95%, silicon 1%～5% to product stream fractionation by distillation, obtains the amine ethyl piperazidine.
2. the combined preparation process of quadrol according to claim 1 and piperazine may further comprise the steps:
A. thanomin and ammonia are mixed, the preheating vaporization, feed in the fixed-bed reactor, react in the presence of the mordenite of condensation amination catalysis phosphorus modification, pressure is 4.0MPa, temperature is 330 ℃, ammonia and thanomin weight ratio are 8: 1, and reaction contact time is 24 seconds, and product stream is quadrol, piperazine, amine ethyl piperazidine and unreacted ammonia, thanomin, product stream is separated, get the product quadrol;
B. piperazine that step a is obtained and thanomin preheating vaporization, feed in the fixed-bed reactor, in the presence of the ZSM-5 zeolite of condensation amination catalysis silicon modification, react, pressure is 6.0MPa, temperature is 380 ℃, and piperazine and thanomin weight ratio are 1.0: 1, and reaction contact time is 15 seconds, product stream is separated, obtain the amine ethyl piperazidine.
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| CN102040523A (en) * | 2010-11-24 | 2011-05-04 | 西安近代化学研究所 | Method for inhibiting coking of ethylenediamine reaction liquid |
| CN102718661A (en) * | 2012-06-26 | 2012-10-10 | 西安近代化学研究所 | Coproduction method of 1, 2-propanediamine and dimethyl piperazine |
| CN103709042A (en) * | 2013-12-11 | 2014-04-09 | 西安近代化学研究所 | Preparation method of ethylene diamine |
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| CN102227414B (en) * | 2008-10-06 | 2016-05-18 | 联合碳化化学品及塑料技术公司 | Prepare the method for cyclic n nitroso compound-aminofunctional triamine |
| WO2018099964A1 (en) | 2016-11-30 | 2018-06-07 | Basf Se | Process for the conversion of monoethanolamine to ethylenediamine employing a copper-modified zeolite of the mor framework structure |
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| US3793397A (en) * | 1971-01-19 | 1974-02-19 | Jefferson Chem Co Inc | Process for the production of aminoethylpiperazine |
| JP5167135B2 (en) * | 2005-09-30 | 2013-03-21 | ビーエーエスエフ ソシエタス・ヨーロピア | Method for producing ethyleneamine |
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| WO2018099964A1 (en) | 2016-11-30 | 2018-06-07 | Basf Se | Process for the conversion of monoethanolamine to ethylenediamine employing a copper-modified zeolite of the mor framework structure |
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