CN101704753A - Method for preparing ethylene diamine from ethanolamine and ammonia serving as raw materials under hydrogen condition - Google Patents
Method for preparing ethylene diamine from ethanolamine and ammonia serving as raw materials under hydrogen condition Download PDFInfo
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- CN101704753A CN101704753A CN200910237771A CN200910237771A CN101704753A CN 101704753 A CN101704753 A CN 101704753A CN 200910237771 A CN200910237771 A CN 200910237771A CN 200910237771 A CN200910237771 A CN 200910237771A CN 101704753 A CN101704753 A CN 101704753A
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- ammonia
- thanomin
- ethanolamine
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- catalyzer
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a method for preparing ethylene diamine from ethanolamine and ammonia serving as raw materials under a hydrogen condition. A reaction system consists of the ethanolamine, the ammonia, hydrogen and a catalyst, wherein the reaction temperature is 100 to 190 DEG C, the reaction pressure is 6.0 to 25.0MPa, the molar ratio of the ammonia to the ethanolamine is 1-20 and the molar ratio of the H2 to the ethanolamine is 0.008-0.05, and the air speed of the ethanolamine liquid is 0.1 to 1.5h-1; the catalyst takes Al2O3 or SiO2 as a carrier and one or more of Ru, Ni, Pd, B, Fe, Co, Re and Cu as carried active components; and the ethanolamine and the liquid ammonia can be transformed into the ethylene diamine (EDA) in high activity and high selectivity, along with by products such as diethylenetriamine (DETA), a piperazine (PIP), an aminoethylpipe (AEP), a hydroxyethylpiperazine (HEP), a hydroxyethyl ethylene diamine (AEEA) and the like under the hydrogen condition and the action of the catalyst.
Description
Technical field
The present invention relates to a kind of is raw material prepares quadrol under hydro condition method with thanomin and ammonia, at length be to be used under the hydro condition Monoethanolamine MEA BASF and ammonia to be converted into quadrol (EDA) be main by a kind of, and the method for coproduction diethylenetriamine (DETA), piperazine (PIP), aminoethyl piperazine (AEP), hydroxyethyl piperazine (HEP) and hydroxyethylethylene diamine (AEEA) etc.
Background technology
The ethyleneamines series product are to comprise quadrol, diethylenetriamine, triethylene tetramine and polyethylene polyamine etc., wherein the most important thing is quadrol, for the well sold and in short supply industrial chemicals in market, has purposes widely in fields such as epoxy curing agent, agricultural chemicals, high molecular polymers.Quadrol mainly contains two kinds of preparation methods, and the one, dichloroethane law (EDC); The 2nd, Monoethanolamine MEA BASF (MEA) method.Relative merits are respectively arranged.Domestic a plurality of producers all adopt the EDC method at present, the sodium-chlor that this method by-product is a large amount of, and equipment corrosion is serious, and energy consumption is big, is in end-of-life state basically.The domestic never industrialized unit of MEA process.Therefore, the consumption of China's quadrol about 50,000 tons, mainly relies on import at present.
The sixties in last century, BASF AG realized the industrialization of MEA process, under high pressure (greater than 20.0Mpa), reacting under the effect of hydrogen catalyst neutralisation by Monoethanolamine MEA BASF and ammonia, main products is quadrol (EDA), and coproduction diethylenetriamine (DETA), piperazine (PIP), aminoethyl piperazine (AEP), hydroxyethyl piperazine (HEP) and hydroxyethylethylene diamine (AEEA) etc., adopt trickle-bed reactor, adopt catalyzer such as Ni, Co and Cu.U.S.'s union carbide corporation then adopts Ni-Re-B/Al
2O
3Catalyzer, reaction conditions be gentle (15.0-18.0MPa and 140-160 ℃) relatively.
United States Patent (USP) 4,642,303 have reported that under the effect of Ni-Cu-Cr catalyzer, the MEA aminating reaction helps the generation of EDA at low temperatures.United States Patent (USP) 3,068,290 have disclosed when Ni is catalyst based to be gone up the ammonia dividing potential drop and be 13-17Mpa, the selectivity of EDA is 70-90%, the ammonia dividing potential drop during less than 8.0Mpa the selectivity of EDA have only about 40%.United States Patent (USP) 5,068,330 have delivered and have added Ir as auxiliary agent in Ni is catalyst based, have obtained good effect.United States Patent (USP) 4,992,587 adopt Ni and Co as active ingredient, and porous metal oxide is a carrier, is auxiliary agent with Ru, and the per pass conversion of the catalyzer MEA that makes by continuous impregnating, drying is more than 50%, and EDA compounds selectivity is about 70%.United States Patent (USP) 5,750,790 adopt transition phase Al
2O
3Load Ni and Re catalyzer, the selectivity of MEA reactive activity and EDA all is improved, about 60%.United States Patent (USP) 6,534,441 have found at Ni-Re/Al
2O
3In added active ingredient B after, the selectivity of EDA is brought up to more than 70%.
Summary of the invention
The purpose of this invention is to provide a kind of is raw material prepares quadrol under hydro condition method with thanomin and ammonia.
For achieving the above object, the method for preparing quadrol provided by the invention prepares quadrol with feed ethanol amine and ammonia under hydro condition; Reaction system of the present invention is made up of thanomin, ammonia, hydrogen and catalyzer; Reaction conditions is:
Temperature of reaction is 100～190 ℃ (preferable temperature of reaction is 130～160 ℃); Reaction pressure is that (preferable reaction pressure is 7.0～22.0MPa) to 6.0～25.0MPa, and the mol ratio of ammonia/thanomin is 1～20 (preferable mol ratio is 1～15), H
2/ thanomin=0.008～0.05 (preferable mol ratio is 0.010～0.025) thanomin liquid air speed is 0.1～1.5h
-1(preferable liquid air speed is 0.2～1.0h
-1).
Described catalyzer is with Al
2O
3Or SiO
2Be carrier, one or more among active ingredient Ru, Ni, Pd, B, Fe, Co, Re and the Cu, the loading of active ingredient are the 0.1-30.0% of catalyst weight.
Described thanomin is a Monoethanolamine MEA BASF, and ammonia is liquefied ammonia, and major product is quadrol (EDA), and coproduction diethylenetriamine (DETA), piperazine (PIP), aminoethyl piperazine (AEP), hydroxyethyl piperazine (HEP) and hydroxyethylethylene diamine (AEEA) etc.
Catalyzer of the present invention is made up of carrier and the active ingredient that is supported on the carrier.Carrier can be Al
2O
3Or SiO
2Active ingredient can be one or more among active ingredient Ru, Ni, Pd, B, Fe, Co, Re and the Cu.The catalyzer that contains said components can adopt conventional catalyst preparation method that this area is familiar with as: the precipitator method, pickling process, hydrothermal synthesis method or aforesaid method are used in combination.
The present invention can significantly reduce reaction pressure and energy consumption compared with prior art, improves that thanomin and ammonia are that feedstock production is the selectivity of quadrol under hydro condition.
Embodiment
The invention provides a kind of is raw material prepares quadrol under hydro condition method with thanomin and ammonia, be about to thanomin and ammonia are catalytically conveted to quadrol under hydro condition process, this process coproduction diethylenetriamine (DETA), piperazine (PIP), aminoethyl piperazine (AEP), hydroxyethyl piperazine (HEP) and hydroxyethylethylene diamine (AEEA) etc.Reaction system is made up of thanomin, ammonia, hydrogen and catalyzer.To be separately converted to quadrol (EDA) with high reactivity, highly selective after catalyzer contacts certain hour under certain temperature and hydrogen pressure be main for thanomin and ammonia in above-mentioned system, and coproduction diethylenetriamine (DETA), piperazine (PIP), aminoethyl piperazine (AEP), hydroxyethyl piperazine (HEP) and hydroxyethylethylene diamine (AEEA) etc.
The present invention can directly pump into liquefied ammonia and thanomin mixed solution in the preheater, and and H
2Enter into fixed-bed reactor after mixing preheating.Need not to add any solvent in this process dissolves or dilutes.
Reaction process of the present invention can adopt fixed-bed reactor, also can adopt paste state bed reactor.Wherein preferred fixed-bed reactor.
Catalyzer of the present invention can activate by the hydrogen treat under the certain condition before using.Preferable condition with the hydrogen deactivated catalyst is: GHSV=2400h
-1, normal pressure, 375 ℃, 5 hours recovery times.
The present invention will be further described below by specific embodiment.
Embodiment 1
The catalyzer that adopts is Ni-Re-B/Al
2O
3Catalyst weight consists of: Ni=15%, and Re=1.6%, B=1.2%, all the other are carrier A l
2O
3Carrier adopts commodity Al
2O
3, and catalyst activity component Ni and auxiliary agent Re and B are supported on carrier A l by conventional pickling process
2O
3(Al
2O
3Granularity be 20～40 orders) on.8.0 through the hydrogen activation, activation condition is gram (about 10ml) catalyzer: GHSV=2400h before reaction
-1, normal pressure, 375 ℃, 5 hours recovery times.Select fixed-bed reactor for use.Temperature of reaction is 155 ℃, and hydrogen pressure is 8.0MPa, and ammonia/thanomin mol ratio is 10, H
2/ thanomin mol ratio is that 0.015 thanomin liquid air speed is 0.5h
-1, the reaction times is 50h, sampling analysis.Sample adopts gas chromatographic analysis, HP-15 capillary chromatographic column, fid detector.Dimethyl formamide (DMFA) carries out quantitative analysis for interior mark.
Embodiment 2
Adopting thanomin liquid air speed is 0.3h
-1, other condition is identical with embodiment 1.
Embodiment 3
Adopting thanomin liquid air speed is 0.7h
-1, other condition is identical with embodiment 1.
Embodiment 4
Adopting temperature of reaction is 145 ℃, and other condition is identical with embodiment 1.
Embodiment 5
Adopting temperature of reaction is 160 ℃, and other condition is identical with embodiment 1.
Embodiment 6
Adopting hydrogen pressure is 9.0, and other condition is identical with embodiment 1.
Embodiment 7
Adopting hydrogen pressure is 10.0, and other condition is identical with embodiment 1.
Embodiment 8
Adopting hydrogen pressure is 12.0, and other condition is identical with embodiment 1.
Embodiment 9
Adopt H
2/ thanomin mol ratio is 0.01, and other condition is identical with embodiment 1.
Embodiment 10
Adopt H
2/ thanomin mol ratio is 0.03, and other condition is identical with embodiment 1.
Embodiment 11
Adopting ammonia/thanomin mol ratio is 5, and other condition is identical with embodiment 1
Embodiment 12
Adopting ammonia/thanomin mol ratio is 15, and other condition is identical with embodiment 1
Embodiment 13
Adopt 200 milliliters of stirring-type slurry attitude beds, the granularity of 8.0 gram catalyzer is that 150-200 order and 100ml thanomin/liquefied ammonia (mix in advance, ammonia/thanomin mol ratio is 10) pump into 200ml slurry attitude bed autoclave reactor, charges into H again
2To pressure be 10.0MPa, other condition is identical with embodiment 1.
Thanomin of the present invention and ammonia are that raw material prepares the reacting ethylenediamine evaluation result and is summarised in the table 1 under hydro condition.
Press the catalyzer of embodiment 1, reaction conditions and raw material are formed, and have carried out more than 500 hour stability test, face hydrogen ammonification activity and selectivity and remain unchanged basically.
Adopt the Al of 2-3mm
2O
3Bead is as carrier, the activity of such catalysts component is identical with embodiment 4 with auxiliary agent content, carry out the catalyzer feather weight and amplified preparation, and at liter level single tube fixed-bed reactor (internal diameter is 25mm, height is 3000mm, and material is 316L, and the catalyzer loading amount is 1 liter, fill magnet ring for two sections) carried out reaction conditions and embodiment 1 identical scale-up, the result shows: activity of such catalysts and selectivity are basic identical.
Table 1: Monoethanolamine MEA BASF and ammonia are converted into the condition optimizing evaluation result of quadrol under the hydro condition
Claims (9)
1. one kind is raw material prepares quadrol under hydro condition method with thanomin and ammonia, and reaction system is made up of thanomin, ammonia, hydrogen and catalyzer; Reaction conditions is:
Temperature of reaction is 100～190 ℃, and reaction pressure is 6.0～25.0MPa, and the mol ratio of ammonia/thanomin is 1～20, H
2/ thanomin=0.008～0.05, thanomin liquid air speed is 0.1～1.5h
-1
Described catalyzer is with Al
2O
3Or SiO
2Be carrier, active ingredient is one or more among Ru, Ni, Pd, B, Fe, Co, Re, the Cu, and the loading of active ingredient is the 0.1-30.0% of catalyst weight.
2. method according to claim 1, wherein, thanomin and ammonia are respectively Monoethanolamine MEA BASF and liquefied ammonia; The product of preparation is a quadrol, and by product is diethylenetriamine, piperazine, aminoethyl piperazine, hydroxyethyl piperazine and hydroxyethylethylene diamine.
3. method according to claim 1, wherein, reaction pressure is 7.0～22.0MPa.
4. method according to claim 1, wherein, temperature of reaction is 140～160 ℃.
5. method according to claim 1, wherein, thanomin liquid air speed is 0.2～1.0h
-1
6. method according to claim 1, wherein, ammonia/thanomin mol ratio is 1～15
7. method according to claim 1, wherein, H
2/ thanomin mol ratio is 0.010～0.035
8. method according to claim 1, wherein, the combination that catalyzer adopts the precipitator method, pickling process, hydrothermal synthesis method or aforesaid method with active constituent loading on carrier.
9. method according to claim 7, wherein, catalyzer is used H before use
2In-situ reducing activates.
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|---|---|---|---|
| CN200910237771A CN101704753A (en) | 2009-11-17 | 2009-11-17 | Method for preparing ethylene diamine from ethanolamine and ammonia serving as raw materials under hydrogen condition |
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|---|---|---|---|
| CN200910237771A CN101704753A (en) | 2009-11-17 | 2009-11-17 | Method for preparing ethylene diamine from ethanolamine and ammonia serving as raw materials under hydrogen condition |
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|---|---|
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ID=42375019
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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 |
| CN102531915A (en) * | 2011-12-16 | 2012-07-04 | 淮北科达化工有限责任公司 | Method for preparing ethylene diamine through condensation and ammoniation by using bronsted acid ion liquid to catalyze ethanolamine |
| 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 |
| WO2013152548A1 (en) * | 2012-04-13 | 2013-10-17 | 中国科学院大连化学物理研究所 | Catalyst for synthesizing ethylene amine and method for preparing ethylene amine |
| CN103819344A (en) * | 2013-12-18 | 2014-05-28 | 西安近代化学研究所 | Synthesis method of 1,2-propane diamine |
| CN106608825A (en) * | 2015-10-22 | 2017-05-03 | 中国石油化工股份有限公司 | Method for producing ethylenediamine by ethanolamine method |
| CN109239208A (en) * | 2017-07-11 | 2019-01-18 | 四川科瑞德凯华制药有限公司 | A kind of quality determining method of Syprine Hydrochloride |
| CN110116004A (en) * | 2019-06-11 | 2019-08-13 | 吉林化工学院 | A kind of catalyst and its preparation and application of monoethanolamine prepared by nitrate and liquefied ammonia reduction amination synthesis ethyleneamines |
| CN110201671A (en) * | 2019-06-11 | 2019-09-06 | 吉林化工学院 | A kind of catalyst and its preparation and application preparing monoethanolamine and liquefied ammonia reduction amination synthesis ethyleneamines with ammino-complex |
| CN112044447A (en) * | 2020-08-18 | 2020-12-08 | 西安近代化学研究所 | Catalyst for synthesizing monoethylamine, preparation method and application |
| CN114433064A (en) * | 2020-11-05 | 2022-05-06 | 中国石油化工股份有限公司 | Method for preparing piperazine and ethylenediamine from hydroxyethyl ethylenediamine |
| CN114433096A (en) * | 2020-11-05 | 2022-05-06 | 中国石油化工股份有限公司 | Method for preparing ethylenediamine and piperazine by virtue of disproportionation of diethylenetriamine |
| CN114605268A (en) * | 2022-03-22 | 2022-06-10 | 中国科学院大连化学物理研究所 | Method for catalytically synthesizing polyethylene polyamine |
| CN114700078A (en) * | 2022-04-07 | 2022-07-05 | 西安近代化学研究所 | Active metal-silicon dioxide catalyst and preparation method of tetramethyl diethylenetriamine |
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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 |
| CN102040523B (en) * | 2010-11-24 | 2013-03-27 | 山西玉龙化工有限公司 | Method for inhibiting coking of ethylenediamine reaction liquid |
| 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 |
| CN103159630B (en) * | 2011-12-14 | 2015-05-20 | 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 |
| CN102531915A (en) * | 2011-12-16 | 2012-07-04 | 淮北科达化工有限责任公司 | Method for preparing ethylene diamine through condensation and ammoniation by using bronsted acid ion liquid to catalyze ethanolamine |
| CN102531915B (en) * | 2011-12-16 | 2013-08-07 | 淮北科达化工有限责任公司 | Method for preparing ethylene diamine through condensation and ammoniation by using bronsted acid ion liquid to catalyze ethanolamine |
| WO2013152548A1 (en) * | 2012-04-13 | 2013-10-17 | 中国科学院大连化学物理研究所 | Catalyst for synthesizing ethylene amine and method for preparing ethylene amine |
| CN103819344A (en) * | 2013-12-18 | 2014-05-28 | 西安近代化学研究所 | Synthesis method of 1,2-propane diamine |
| CN103819344B (en) * | 2013-12-18 | 2016-04-27 | 西安近代化学研究所 | A kind of synthetic method of 1,2-propylene diamine |
| CN106608825A (en) * | 2015-10-22 | 2017-05-03 | 中国石油化工股份有限公司 | Method for producing ethylenediamine by ethanolamine method |
| CN106608825B (en) * | 2015-10-22 | 2018-10-23 | 中国石油化工股份有限公司 | The method that Girbotal process produces ethylenediamine |
| CN109239208A (en) * | 2017-07-11 | 2019-01-18 | 四川科瑞德凯华制药有限公司 | A kind of quality determining method of Syprine Hydrochloride |
| CN110116004A (en) * | 2019-06-11 | 2019-08-13 | 吉林化工学院 | A kind of catalyst and its preparation and application of monoethanolamine prepared by nitrate and liquefied ammonia reduction amination synthesis ethyleneamines |
| CN110201671A (en) * | 2019-06-11 | 2019-09-06 | 吉林化工学院 | A kind of catalyst and its preparation and application preparing monoethanolamine and liquefied ammonia reduction amination synthesis ethyleneamines with ammino-complex |
| CN110116004B (en) * | 2019-06-11 | 2022-02-25 | 吉林化工学院 | Catalyst for synthesizing ethylene amine by reductive amination of monoethanolamine and liquid ammonia prepared from nitrate and preparation and use methods thereof |
| CN112044447A (en) * | 2020-08-18 | 2020-12-08 | 西安近代化学研究所 | Catalyst for synthesizing monoethylamine, preparation method and application |
| CN112044447B (en) * | 2020-08-18 | 2023-02-14 | 西安近代化学研究所 | Catalyst for synthesizing monoethylamine, preparation method and application |
| CN114433064A (en) * | 2020-11-05 | 2022-05-06 | 中国石油化工股份有限公司 | Method for preparing piperazine and ethylenediamine from hydroxyethyl ethylenediamine |
| CN114433096A (en) * | 2020-11-05 | 2022-05-06 | 中国石油化工股份有限公司 | Method for preparing ethylenediamine and piperazine by virtue of disproportionation of diethylenetriamine |
| CN114433064B (en) * | 2020-11-05 | 2023-11-10 | 中国石油化工股份有限公司 | Method for preparing piperazine and ethylenediamine from hydroxyethyl ethylenediamine |
| CN114433096B (en) * | 2020-11-05 | 2023-12-08 | 中国石油化工股份有限公司 | Method for preparing ethylenediamine and piperazine by disproportionation of diethylenetriamine |
| CN114605268A (en) * | 2022-03-22 | 2022-06-10 | 中国科学院大连化学物理研究所 | Method for catalytically synthesizing polyethylene polyamine |
| CN114605268B (en) * | 2022-03-22 | 2023-02-28 | 中国科学院大连化学物理研究所 | Method for catalytically synthesizing polyethylene polyamine |
| CN114700078A (en) * | 2022-04-07 | 2022-07-05 | 西安近代化学研究所 | Active metal-silicon dioxide catalyst and preparation method of tetramethyl diethylenetriamine |
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Application publication date: 20100512 |