CN102190588A - Method for preparing ethylenediamine from glycol and ammonia - Google Patents
Method for preparing ethylenediamine from glycol and ammonia Download PDFInfo
- Publication number
- CN102190588A CN102190588A CN2010101247535A CN201010124753A CN102190588A CN 102190588 A CN102190588 A CN 102190588A CN 2010101247535 A CN2010101247535 A CN 2010101247535A CN 201010124753 A CN201010124753 A CN 201010124753A CN 102190588 A CN102190588 A CN 102190588A
- Authority
- CN
- China
- Prior art keywords
- ethylene glycol
- ammonia
- catalyzer
- reaction
- quadrol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention provides a method for preparing ethylenediamine from reactants of glycol and ammonia in the presence of a solid catalyst with a main component of copper through a hydrogenation and amination one-step method. The method comprises the following steps of: making glycol containing water or not containing water and ammonia enter a reactor filled with the catalyst with a main component of copper, performing dehydrogenation to obtain the ethylenediamine and water and an ethanolamine byproduct, and separating the mixture obtained through reaction to obtain the product of ethylenediamine.
Description
Technical field
The present invention relates in the presence of copper class solid catalyst, prepare the method for quadrol by ethylene glycol and ammonia hydrogenating amination.Reaction equation is as follows:
HOCH
2CH
2OH+2NH
3---＞NH
2CH
2CH
2NH
2+2H
2O
By product comprises the dimerization or the polymer (ethyleneamines) of thanomin and quadrol, and reaction equation is as follows:
HOCH
2CH
2OH+NH
3---＞HOCH
2CH
2NH
2+H
2O
2HOCH
2CH
2OH+3NH
3---＞NH
2CH
2CH
2NHCH
2CH
2NH
2+4H
2O
nHOCH
2CH
2OH+(n+1)NH
3---＞NH
2CH
2CH
2(NHCH
2CH
2)
n-1NH
2+2nH
2O
Technical background
Quadrol is the important chemical basic material, as solvent, stablizer, sequestrant, synthetic resins, medicine, inhibitor.In recent years, heighten along with being used for free phosphate detergent TEAD (tetraacetyl ethylene diamine) demand, quadrol is as the corresponding increase of raw materials requirement amount of TEAD.
The method for preparing quadrol and other ethyleneamines has been described in the document.
Before ethylene glycol or the thanomin hydrogenating amination technology, generally adopt ethylene dichloride and ammonia prepared in reaction quadrol under alkaline condition.
According to PEP Report No.138, " alkylamine ", SRI International, in March, 1981, especially the 7th, 8,13～16,43～107,113,117 page, ethylene dichloride and ammonia generate quadrol with mol ratio reaction in 1: 15, and productive rate surpasses 20%.
The shortcoming of this method is to use a large amount of bronsted lowry acids and bases bronsted lowries in the production process, and the by-product muriate damages environment.
Technology by thanomin and ammonia hydrogenating amination system quadrol is the main technique of producing quadrol at present.
There is active not high shortcoming in the catalyzer that girbotol process uses based on hydrogen type molecular sieve.
USP4918233 discloses thanomin and ammonia is the catalyzer of raw material synthesis of ethylenediamine.Catalyzer is a hydrogen type molecular sieve, 300～340 degrees centigrade of temperature of reaction, and thanomin liquid air speed is 0.15h
-1, transformation efficiency is 54%, the selectivity 56% of quadrol, and the yield of quadrol is up to 30%.
Patent 200610167715.1 discloses a kind of improved hydrogen type molecular sieve as catalyzer, on forming, outside the hydrogen type molecular sieve, add aluminum oxide and/or metal ion Sb, Zn, Nb, Zr, Mo, the transformation efficiency of thanomin reaches 68%, and the yield of quadrol reaches 44.1%.
Thanomin is made by oxyethane and ammonia react, and oxyethane is made by ethene and oxygen reaction, and its main raw material is from oil.And ethylene glycol can make barkite by the methyl alcohol carbonylation, and repeated hydrogenation makes, and its main raw material is from coal.
In recent years, ethylene glycol is directly made quadrol becomes a kind of more excellent technology.
A kind of method of being produced ethyleneamines and thanomin by ethylene glycol is disclosed in the patent 2007800005568.0 of BASF European Co.,Ltd's application.Use two-stage reaction technology, first section can be used all known catalyzer, and second section use is main catalyzer by ruthenium and cobalt, pressure 200 crust, 150～170 degrees centigrade of temperature, the transformation efficiency 46% of ethylene glycol.
This patent uses with the catalyzer of copper as main ingredient, and ethylene glycol and ammonia prepare quadrol through single step reaction, do not use precious metal.As auxiliary agent, increased the stability of copper catalyst with lanthanum, zirconium, zinc, titanium, cerium, made activity of such catalysts steady in a long-term under 300 degrees centigrade, reacted after 1000 hours, catalyst activity and live catalyst are suitable.
Summary of the invention
Method of the present invention is, at the oxide compound with copper or copper is in the presence of the solid catalyst of main ingredient, the method of the prepared in reaction quadrol of ethylene glycol and ammonia, comprise the steps: ethylene glycol and ammonia, incorporate the hydrogen that pressure is not less than 0.1Mpa into, entering filling is the reactor of the catalyzer of main ingredient with the oxide compound of copper or copper, carries out the hydrogenating amination reaction, generate quadrol, other ethyleneamines beyond by-product thanomin and the quadrol.Reaction solution is through after the rectifying, and to reactor, hydrogen and excess of ammonia then loop back reactor by gas phase to other ethyleneamines beyond by product thanomin and the quadrol through liquid-phase reflux.Temperature of reaction is controlled at 150～350 degrees centigrade, and preferred 200～300 degrees centigrade, ethylene glycol charging air speed is at 0.01～10 gram ethylene glycol/gram catalyzer, and preferred 0.1～5 restrains ethylene glycol/gram catalyzer, reaction pressure 0.3～3Mpa, preferred 1～2Mpa.The pressure of hydrogen is not less than 0.1Mpa.
The advantage of this technology is that raw material is easy to get, and ethylene glycol belongs to large chemicals, and coal or Sweet natural gas or oil field tail gas generate synthetic gas, generates ethylene glycol by synthetic gas again; Catalyzer does not contain precious metal for the solid catalyst based on copper; The yield of the quadrol of reaction is higher, can reach 50%.
Description of drawings
Embodiment
Ethylene glycol and ammonia are incorporated the hydrogen that pressure is not less than 0.1Mpa into, and entering filling is the reactor of the catalyzer of main ingredient with the oxide compound of copper or copper, carry out the hydrogenating amination reaction, generate quadrol, other ethyleneamines beyond by-product thanomin and the quadrol.Reaction solution is through after the rectifying, and to reactor, hydrogen and excess of ammonia then loop back reactor by gas phase to other ethyleneamines beyond by product thanomin and the quadrol through liquid-phase reflux.Temperature of reaction is controlled at 150～350 degrees centigrade, and preferred 200～300 degrees centigrade, ethylene glycol charging air speed is at 0.01～10 gram ethylene glycol/gram catalyzer, and preferred 0.1～5 restrains ethylene glycol/gram catalyzer, reaction pressure 0.3～3Mpa, preferred 1～2Mpa.The pressure of hydrogen is not less than 0.1Mpa.
In present method, the mol ratio of ethylene glycol and ammonia is 1: 2～30.
Hereinafter, except that special declaration, content is represented with mass percent.
Ethylene glycol can be moisture or not moisture, and water content is not limit.
Another raw material is liquefied ammonia or ammonia, can be moisture.
Employed catalyzer is a solid catalyst, and wherein main ingredient is the oxide compound of copper or copper, and the content of copper is 5～65%, is preferably 15～45%.Beyond the copper removal, also contain be selected from lanthanum, zirconium,, other components of zinc, titanium, cerium or its oxide compound.Their content can be 0～15% lanthanum, 0～45% zirconium, 0～50% zinc, 0～30% titanium, 0～10% cerium.
Catalyzer can contain carrier also can not contain carrier, and carrier is selected from activated alumina, gac, magnesium oxide, zirconium dioxide, silicon-dioxide, molecular sieve or its mixture.
Carrier-free catalyzer synthetic can be adopted general coprecipitation method or some component wherein of choosing earlier remix after co-precipitation respectively, also can use pickling process.
Coprecipitation method is specially, dispose the salpeter solution of other metals of copper nitrate solution, 0.5～1 mol of 0.5～1 mol respectively, composition according to the target catalyzer mixes, 80 degrees centigrade of temperature, under the stirring of 2000 rev/mins of rotating speeds, drip the sodium hydroxide or the sodium carbonate solution of 0.5～1 mol, generate precipitation, the PH of control terminal point is 9～11.Ageing 0.5～1 hour is precipitated to specific conductivity below 200 μ s/cm with deionized water wash.Under 120 degrees celsius, toasted 5 hours, 500 degrees centigrade of following roastings 12 hours, after the pulverizing, use the tabletting machine moulding.
The catalyzer that contains carrier can adopt general pickling process.The salpeter solution of the copper nitrate solution of difference 0.5～1 mol, other metals of 0.5～1 mol, composition according to the target catalyzer mixes, add support powder, 80 degrees centigrade of temperature, under the stirring of 2000 rev/mins of rotating speeds, drip the sodium hydroxide or the sodium carbonate solution of 0.5～1 mol, generate precipitation, the PH of control terminal point is 9～11.Ageing 0.5～1 hour is precipitated to specific conductivity below 200 μ s/cm with deionized water wash.Under 120 degrees celsius, toasted 5 hours, 500 degrees centigrade of following roastings 12 hours, after the pulverizing, use the tabletting machine moulding.The difference of pickling process is to add support powder before the precipitation in metallic solution, under the condition that support powder exists, adds alkali and precipitates.
The charging air speed of ethylene glycol be 0.01～10 the gram pure every gram catalyzer per hour, be preferably 0.1～5 the gram pure every gram catalyzer per hour.
Temperature of reaction is 150～350 ℃, preferred 200～300 ℃.
Reaction pressure is 0.3～3Mpa, is preferably 1～2Mpa.
Be reflected in the fixed-bed reactor and carry out, be preferably shell and tube reactor, the heat of reaction needed is provided by steam or deep fat.
Following examples are all selected single Φ 45 * 3 * 4000mm reaction tubes for use, the outer heat that reaction needed is provided by deep fat of pipe.The reaction times of following examples is no less than 10 hours, after the reaction, collects liquid phase material, in gas Chromatographic Determination internal mark method determination component.Among the embodiment 6 to embodiment 11, the ratio of ethylene glycol and ammonia is 1: 10.
Embodiment 1
It is 95% ethylene glycol that raw material is chosen concentration, contains 5% water, and another raw material is a liquefied ammonia, the mol ratio of ethylene glycol and ammonia is 1: 2,275 ℃ of temperature of reaction, reaction pressure 0.5Mpa, catalyzer consist of copper 35%, zirconium 10%, zinc 25%, titanium 30%, loading catalyst 4.2kg, the air speed of charging of alcohol be the pure every gram catalyzer of 0.5 gram per hour, be 2.1kg/h, reaction result shows that the per pass conversion of ethylene glycol is 60%, the yield 32.2% of quadrol.
Embodiment 2
Raw material is chosen concentration and is no water glycol, and another raw material is saturated ammoniacal liquor, and the mol ratio of ethylene glycol and ammonia is 0.1: 1,300 ℃ of temperature of reaction, reaction pressure 0.3Mpa, catalyzer consist of copper 15%, zirconium 30%, zinc 25%, titanium 30%, loading catalyst 4.1kg, the air speed of charging of alcohol be the pure every gram catalyzer of 2 grams per hour, i.e. 8.2kg/h, reaction result shows, the per pass conversion of ethylene glycol is 71%, the yield 30.5% of quadrol.。
Embodiment 3
It is 80% ethylene glycol that raw material is chosen concentration, contains 20% water, and another raw material is a liquefied ammonia, the mol ratio of ethylene glycol and ammonia is 1: 30,250 ℃ of temperature of reaction, reaction pressure 3Mpa, catalyzer consist of copper 45%, zirconium 5%, zinc 50%, loading catalyst 4.2kg, the air speed of charging of alcohol be the pure every gram catalyzer of 0.5 gram per hour, i.e. 2.1kg/h, reaction result shows, the per pass conversion of ethylene glycol is 90%, and the yield of quadrol is 55.4%.
Embodiment 4
It is 50% ethylene glycol that raw material is chosen concentration, contains 50% water, and another raw material is a liquefied ammonia, the mol ratio of ethylene glycol and ammonia is 1: 10,280 ℃ of temperature of reaction, reaction pressure 1Mpa, catalyzer consist of copper 30%, zirconium 45%, zinc 25%, loading catalyst 4.1kg, the air speed of charging of alcohol be the pure every gram catalyzer of 5 grams per hour, i.e. 20.5kg/h, reaction result shows, the per pass conversion of ethylene glycol is 76%, the yield 47.5% of quadrol.
Embodiment 5
Raw material is chosen ethylene glycol, and another raw material is a liquefied ammonia, and the mol ratio of ethylene glycol and ammonia is 10: 1,350 ℃ of temperature of reaction, reaction pressure 2Mpa, catalyzer consist of copper 45%, lanthanum 15%, zirconium 20%, zinc 20%, carrier is the ZSM-5 molecular sieve, loading catalyst 5kg, the air speed of the charging of ethylene glycol be 10 the gram pure every gram catalyzer per hour, be 50kg/h, reaction result shows that the per pass conversion of ethylene glycol is 23%, and the yield of quadrol is 17%.
Embodiment 6
Raw material is chosen moisture 5% ethylene glycol, and another raw material is an ammonia, 150 ℃ of temperature of reaction, reaction pressure 2Mpa, catalyzer consist of copper 30%, zirconium 45%, zinc 5%, cerium 20%, carrier are gac, loading catalyst 4.5kg, the air speed of the charging of ethylene glycol be the pure every gram catalyzer of 0.01 gram per hour, i.e. 0.045kg/h, reaction result shows, the per pass conversion of ethylene glycol is 30%, the yield 26.4% of quadrol.
Embodiment 7
Raw material is chosen ethylene glycol, and another raw material is a liquefied ammonia, 300 ℃ of temperature of reaction, reaction pressure 1Mpa, catalyzer consist of copper 45%, zirconium 25%, titanium 15%, zinc 15%, carrier are silicon-dioxide, loading catalyst 4.5kg, the air speed of the charging of ethylene glycol be the pure every gram catalyzer of 1 gram per hour, i.e. 4.5kg/h, reaction result shows that the per pass conversion of ethylene glycol is 84%, and the quadrol yield is 44.3%.
Embodiment 8
Raw material is chosen ethylene glycol, and another raw material is a liquefied ammonia, 250 ℃ of temperature of reaction, reaction pressure 3Mpa, catalyzer consist of copper 30%, zirconium 35%, cerium 15%, zinc 20%, carrier are magnesium oxide, loading catalyst 4.5kg, the air speed of the charging of ethylene glycol be the pure every gram catalyzer of 2 grams per hour, i.e. 9kg/h, reaction result shows, the per pass conversion of ethylene glycol is 72%, and the yield of quadrol is 48.6%.
Embodiment 9
Raw material is chosen ethylene glycol, and another raw material is a liquefied ammonia, 250 ℃ of temperature of reaction, reaction pressure 3Mpa, catalyzer consist of copper 40%, zirconium 25%, cerium 20%, titanium 15%, carrier are magnesium oxide, loading catalyst 4.5kg, the air speed of the charging of ethylene glycol be the pure every gram catalyzer of 2 grams per hour, i.e. 9kg/h, reaction result shows, the per pass conversion of ethylene glycol is 77%, and the yield of quadrol is 51.3%.
Embodiment 10
Raw material is chosen ethylene glycol, and another raw material is a liquefied ammonia, 300 ℃ of temperature of reaction, reaction pressure 2Mpa, catalyzer consist of copper 40%, zinc 20%, cerium 20%, titanium 20%, carrier are gac, loading catalyst 4.5kg, the air speed of the charging of ethylene glycol be the pure every gram catalyzer of 4 grams per hour, i.e. 18kg/h, reaction result shows, the per pass conversion of ethylene glycol is 75%, and the yield of quadrol is 49.5%.
Embodiment 11
Raw material is chosen ethylene glycol, and another raw material is a liquefied ammonia, 250 ℃ of temperature of reaction, reaction pressure 2Mpa, catalyzer consist of copper 40%, cerium 20%, titanium 40%, carrier is a silicon-dioxide, loading catalyst 4.5kg, the air speed of the charging of ethylene glycol be 4 the gram pure every gram catalyzer per hour, be 18kg/h, reaction result shows that the per pass conversion of ethylene glycol is 78%, and the yield of quadrol is 53%.
Claims (10)
1. one kind is being in the presence of the solid catalyst of main ingredient with copper, by being selected from the reactant of ethylene glycol and ammonia, carry out the hydrogenating amination single stage method and prepare the method for quadrol, comprise the steps: that it is the reactor of the catalyzer of main ingredient with copper that moisture or water-free ethylene glycol and ammonia enter filling, carry out the hydrogenating amination reaction, generate quadrol, water, the by-product thanomin, post reaction mixture obtains the product quadrol after separating.
2. according to the method for claim 1, described raw material can be thanomin.
3. according to the method for claim 1, described raw material ammonia is liquefied ammonia or ammonia.
4. according to the method for claim 1, described catalyzer, wherein the weight content of copper is 5～65%, is preferably 15～45%.
5. according to the method for claim 4, described catalyzer also contains other components that are selected from lanthanum, zirconium, zinc, titanium, its oxide compound of cerium.
6. according to the method for claim 1, described catalyzer can load on the carrier, and carrier is selected from activated alumina, gac, magnesium oxide, silicon-dioxide, molecular sieve or its mixture.
7. according to the process of claim 1 wherein that the mol ratio of ethylene glycol and ammonia is 1: 2～30.
8. according to the method for claim 1,150～350 ℃ of temperature of reaction, preferred 200～300 ℃.
9. according to the method for claim 1, it is characterized in that, the charging air speed of ethylene glycol be 0.01～10 gram ethylene glycol every gram catalyzer per hour, per hour be preferably the every gram catalyzer of 0.1～5 gram ethylene glycol.
10. according to the method for claim 1, reaction pressure 0.3～3Mpa is preferably 1～2Mpa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101247535A CN102190588A (en) | 2010-03-16 | 2010-03-16 | Method for preparing ethylenediamine from glycol and ammonia |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101247535A CN102190588A (en) | 2010-03-16 | 2010-03-16 | Method for preparing ethylenediamine from glycol and ammonia |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102190588A true CN102190588A (en) | 2011-09-21 |
Family
ID=44599551
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010101247535A Pending CN102190588A (en) | 2010-03-16 | 2010-03-16 | Method for preparing ethylenediamine from glycol and ammonia |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102190588A (en) |
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103724210A (en) * | 2012-10-11 | 2014-04-16 | 浙江新化化工股份有限公司 | Production method of N-ethyl-n-butylamine |
| CN105503613A (en) * | 2014-09-26 | 2016-04-20 | 中国科学院大连化学物理研究所 | Method for preparing polyamine by direct ammoniation of polyhydroxy compound |
| WO2017152413A1 (en) * | 2016-03-11 | 2017-09-14 | Rhodia Operations | Production of amines utilizing zeolite catalysts |
| WO2018099967A1 (en) | 2016-11-30 | 2018-06-07 | Basf Se | Process for the conversion of ethylene glycol to ethylenediamine employing a zeolite catalyst |
| WO2018099966A1 (en) | 2016-11-30 | 2018-06-07 | Basf Se | Process for the conversion of monoethanolamine to ethylenediamine employing a nanocrystalline zeolite of the mor framework structure |
| 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 |
| WO2018108698A1 (en) | 2016-12-15 | 2018-06-21 | Basf Se | Method for producing ethanolamines and/or ethyleneamines |
| WO2018157395A1 (en) * | 2017-03-03 | 2018-09-07 | Rhodia Operations | Process for preparing an amine via a direct amination reaction |
| WO2018202765A1 (en) | 2017-05-03 | 2018-11-08 | Basf Se | Process for the conversion of ethylene oxide to monoethanolamine and ethylenediamine employing a zeolite |
| WO2018224321A1 (en) | 2017-06-09 | 2018-12-13 | Basf Se | Method for the production of ethyleneamines |
| WO2018224316A1 (en) | 2017-06-09 | 2018-12-13 | Basf Se | Method for the production of ethyleneamines |
| WO2018224315A1 (en) | 2017-06-09 | 2018-12-13 | Basf Se | Method for producing ethyleneamines |
| WO2019081284A1 (en) | 2017-10-27 | 2019-05-02 | Basf Se | Separation of n-methylethylenediamine from eda-containing mixtures |
| WO2019081285A1 (en) | 2017-10-27 | 2019-05-02 | Basf Se | Method for producing ethyleneamines |
| WO2019081283A1 (en) | 2017-10-27 | 2019-05-02 | Basf Se | Method for the production of ethyleneamines |
| WO2019081286A1 (en) | 2017-10-27 | 2019-05-02 | Basf Se | Method for the production of ethyleneamines |
| WO2020178085A1 (en) | 2019-03-06 | 2020-09-10 | Basf Se | Method for the production of ethyleneamines |
| WO2021115907A1 (en) | 2019-12-13 | 2021-06-17 | Basf Se | Separation of n-methylethylenediamine from eda-containing mixtures |
| WO2023135035A1 (en) | 2022-01-14 | 2023-07-20 | Basf Se | Method for the manufacture or conversion of alkanolamines |
| WO2024002748A1 (en) | 2022-06-29 | 2024-01-04 | Basf Se | Method for manufacture of ethyleneamines |
| WO2024002740A1 (en) | 2022-06-29 | 2024-01-04 | Basf Se | Method for manufacture of ethyleneamines |
-
2010
- 2010-03-16 CN CN2010101247535A patent/CN102190588A/en active Pending
Cited By (35)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103724210A (en) * | 2012-10-11 | 2014-04-16 | 浙江新化化工股份有限公司 | Production method of N-ethyl-n-butylamine |
| CN103724210B (en) * | 2012-10-11 | 2016-03-02 | 浙江新化化工股份有限公司 | The production method of N-ethyl-n-butylamine |
| CN105503613A (en) * | 2014-09-26 | 2016-04-20 | 中国科学院大连化学物理研究所 | Method for preparing polyamine by direct ammoniation of polyhydroxy compound |
| WO2017152413A1 (en) * | 2016-03-11 | 2017-09-14 | Rhodia Operations | Production of amines utilizing zeolite catalysts |
| US11104637B2 (en) | 2016-11-30 | 2021-08-31 | Basf Se | Process for the conversion of monoethanolamine to ethylenediamine employing a copper-modified zeolite of the MOR framework structure |
| 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 |
| WO2018099966A1 (en) | 2016-11-30 | 2018-06-07 | Basf Se | Process for the conversion of monoethanolamine to ethylenediamine employing a nanocrystalline zeolite of the mor framework structure |
| US11091425B2 (en) | 2016-11-30 | 2021-08-17 | Basf Se | Process for the conversion of ethylene glycol to ethylenediamine employing a zeolite catalyst |
| JP2020503261A (en) * | 2016-11-30 | 2020-01-30 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | Method for converting ethylene glycol to ethylenediamine using zeolite catalyst |
| CN109996781A (en) * | 2016-11-30 | 2019-07-09 | 巴斯夫欧洲公司 | Using zeolite catalyst by the ethylene glycol reforming method for ethylenediamine |
| WO2018099967A1 (en) | 2016-11-30 | 2018-06-07 | Basf Se | Process for the conversion of ethylene glycol to ethylenediamine employing a zeolite catalyst |
| US10836704B2 (en) | 2016-12-15 | 2020-11-17 | Basf Se | Method for producing ethanolamines and/or ethyleneamines |
| WO2018108698A1 (en) | 2016-12-15 | 2018-06-21 | Basf Se | Method for producing ethanolamines and/or ethyleneamines |
| JP2020514255A (en) * | 2016-12-15 | 2020-05-21 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | Method for producing ethanolamine and / or ethyleneamine |
| WO2018157395A1 (en) * | 2017-03-03 | 2018-09-07 | Rhodia Operations | Process for preparing an amine via a direct amination reaction |
| WO2018202765A1 (en) | 2017-05-03 | 2018-11-08 | Basf Se | Process for the conversion of ethylene oxide to monoethanolamine and ethylenediamine employing a zeolite |
| US10774034B2 (en) | 2017-05-03 | 2020-09-15 | Basf Se | Process for the conversion of ethylene oxide to monoethanolamine and ethylenediamine employing a zeolite |
| US11208373B2 (en) | 2017-06-09 | 2021-12-28 | Basf Se | Method for the production of ethyleneamines |
| US11214535B2 (en) | 2017-06-09 | 2022-01-04 | Basf Se | Method for producing ethyleneamines |
| WO2018224315A1 (en) | 2017-06-09 | 2018-12-13 | Basf Se | Method for producing ethyleneamines |
| WO2018224316A1 (en) | 2017-06-09 | 2018-12-13 | Basf Se | Method for the production of ethyleneamines |
| WO2018224321A1 (en) | 2017-06-09 | 2018-12-13 | Basf Se | Method for the production of ethyleneamines |
| WO2019081286A1 (en) | 2017-10-27 | 2019-05-02 | Basf Se | Method for the production of ethyleneamines |
| US11021434B2 (en) | 2017-10-27 | 2021-06-01 | Basf Se | Method for producing ethyleneamines |
| WO2019081283A1 (en) | 2017-10-27 | 2019-05-02 | Basf Se | Method for the production of ethyleneamines |
| WO2019081285A1 (en) | 2017-10-27 | 2019-05-02 | Basf Se | Method for producing ethyleneamines |
| WO2019081284A1 (en) | 2017-10-27 | 2019-05-02 | Basf Se | Separation of n-methylethylenediamine from eda-containing mixtures |
| US11225455B2 (en) | 2017-10-27 | 2022-01-18 | Basf Se | Separation of n-methylethylenediamine from EDA-containing mixtures |
| US11339117B2 (en) | 2017-10-27 | 2022-05-24 | Basf Se | Method for the production of ethyleneamines |
| US11492324B2 (en) | 2017-10-27 | 2022-11-08 | Basf Se | Method for the production of ethyleneamines |
| WO2020178085A1 (en) | 2019-03-06 | 2020-09-10 | Basf Se | Method for the production of ethyleneamines |
| WO2021115907A1 (en) | 2019-12-13 | 2021-06-17 | Basf Se | Separation of n-methylethylenediamine from eda-containing mixtures |
| WO2023135035A1 (en) | 2022-01-14 | 2023-07-20 | Basf Se | Method for the manufacture or conversion of alkanolamines |
| WO2024002748A1 (en) | 2022-06-29 | 2024-01-04 | Basf Se | Method for manufacture of ethyleneamines |
| WO2024002740A1 (en) | 2022-06-29 | 2024-01-04 | Basf Se | Method for manufacture of ethyleneamines |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102190588A (en) | Method for preparing ethylenediamine from glycol and ammonia | |
| CN102233272A (en) | Catalyst for preparing ethylene diamine through amination of ethylene glycol and preparation method thereof | |
| CN107794074B (en) | Preparation method of branched alkane in range of gasoline, aviation kerosene or diesel oil | |
| CN110105223A (en) | A kind of method that continuity method prepares 1,3- hexamethylene dimethylamine | |
| JP6242878B2 (en) | Process for producing mono-N-alkyl-piperazine | |
| CN102198935A (en) | Method for preparing hydrogen by reforming methanol and water | |
| CN100503534C (en) | Method for synthesis of isopropanol | |
| CN101659597A (en) | Method for preparing Guerbet alcohol | |
| ES2381470T3 (en) | Method for the production of N, N-substituted 1,3-PROPANE-DIAMINS | |
| CN109745986A (en) | Hydrotalcite composite transition metal catalyst is for the purposes in cyclohexanol ammonolysis reaction | |
| CN107365257B (en) | A kind of 2- methyl cellosolve acetate glutaronitrile adds the method that hydrogen prepares 2 methyl pentamethylenediamine and 3- methyl piperidine | |
| CA2370621A1 (en) | Process for the preparation of carboxylic acid salts from primary alcohols | |
| JP2009214077A (en) | Manufacturing method of catalyst for methanol synthesis and manufacturing method of methanol | |
| CN111056963B (en) | Preparation method of 3-aminopropanol | |
| CN102614881B (en) | Method and used catalytic agent for synthesizing N-butylethylamine | |
| CN115772095B (en) | Method for synthesizing acetonitrile by acetic acid ammonification method in one step | |
| CN103254101A (en) | Method and equipment for preparation of methyl carbamate | |
| CN104974045B (en) | A kind of method for preparing aminated compounds | |
| CN101434551B (en) | Method for synthesizing monoethanolamine | |
| CN114907219B (en) | Method for preparing monoisopropanolamine and diisopropanolamine by cracking triisopropanolamine | |
| CN101239957A (en) | Synthesis method of N-methylpiperazine | |
| CN102295571A (en) | Method for synthesis of amide through ammoxidation of methanol or formaldehyde | |
| CN111036268B (en) | Alumina composite material, preparation method and application thereof, and synthetic method of n-valeronitrile | |
| JPH039772B2 (en) | ||
| CN112608244A (en) | Novel method for preparing monoethanolamine |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| DD01 | Delivery of document by public notice |
Addressee: Zhangjiagang Huier Chemical Technology Co.,Ltd. Liu Sheng Document name: Notification of Publication of the Application for Invention |
|
| DD01 | Delivery of document by public notice |
Addressee: Zhangjiagang Huier Chemical Technology Co.,Ltd. Document name: Notification of before Expiration of Request of Examination as to Substance |
|
| DD01 | Delivery of document by public notice |
Addressee: Zhangjiagang Huier Chemical Technology Co.,Ltd. Document name: Notification that Application Deemed to be Withdrawn |
|
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20110921 |