CN103664649B - Method for preparing monoethanolamine from ethylene glycol - Google Patents
Method for preparing monoethanolamine from ethylene glycol Download PDFInfo
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- CN103664649B CN103664649B CN201310674922.6A CN201310674922A CN103664649B CN 103664649 B CN103664649 B CN 103664649B CN 201310674922 A CN201310674922 A CN 201310674922A CN 103664649 B CN103664649 B CN 103664649B
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Abstract
The invention discloses a method for preparing monoethanolamine from ethylene glycol. A reaction system consists of ethylene glycol, liquid ammonia and hydrogen gas; a catalyst takes one or more of aluminum oxide, silicon dioxide, active carbon and a molecular sieve as carriers; at least two of active ingredients including Ru, Ni, Pd, Pt, Co, Mo, Fe, Mn, Sn, Zn and B are loaded; ethylene glycol and liquid ammonia can be converted into monoethanolamine at high activity and high selectivity under the action of the catalyst, and ethylenediamine, piperazine and the like are coproduced. The method is easy to operate, and the yield of monoethanolamine is high.
Description
Technical field
The invention belongs to the preparing technical field of thanomin, be specifically related to a kind of with ethylene glycol and ammonia for the method for Monoethanolamine MEA BASF prepared by raw material.
Background technology
Thanomin is the general name of Monoethanolamine MEA BASF, diethanolamine and trolamine.It is as one of the important derivatives of oxyethane, it is most important product in amino alcohol, output accounts for 90% ~ 95% of amino alcohol ultimate production, is widely used in the fields such as tensio-active agent, gas sweetening, liquid deicer, printing and dyeing, medicine, agricultural chemicals, building and military project.
At present, the production of thanomin is mainly that under the condition of catalyzer, oxyethane and ammonia react generate the mixture of Monoethanolamine MEA BASF, diethanolamine and trolamine at water.The ratio of the three kinds of thanomins generated is primarily of the ratio-dependent of oxyethane and ammonia.React as follows:
The sharpest edges of this universal method are that technique is simple, but the greatest drawback of this method is exactly rely on serious to feed ethylene and oxyethane, and the selection in thanomin production equipment place simultaneously and raw material supply etc. are also seriously restricted.
Prepare ethylene glycol from raw coal, more above-mentioned defect can be avoided by preparing thanomin to the operational path of its amination.But the method preparing thanomin from ethylene glycol also seldom has report, so far, prepare in the research of thanomin at ethylene glycol amination reaction, the correlative study work only having patent 200780005568.0 to report ethylene glycol Study on Catalytic Amination of Alcohols to prepare thanomin.This technique adopts two ends reaction process, first stage reacts on hydrogenating amination catalyzer, subordinate phase uses ruthenium and cobalt to be main loaded catalyst, and under the reaction conditions of pressure 200bar, temperature 150 ~ 170 DEG C, the transformation efficiency of ethylene glycol is up to 42.6%.There is the defects such as high, the ethylene glycol reforming rate of reaction pressure is low in this method.
Summary of the invention
Technical problem to be solved by this invention is to overcome existing thanomin preparation method Problems existing, provide a kind of with ethylene glycol and ammonia for the method for Monoethanolamine MEA BASF prepared by raw material.
Solving the problems of the technologies described above adopted technical scheme is: with ethylene glycol, liquefied ammonia, hydrogen for raw material, in the presence of a catalyst, 200 ~ 350 DEG C are reacted 1 ~ 6 hour, reaction pressure is 3 ~ 18MPa, the mol ratio of liquefied ammonia and ethylene glycol is 5 ~ 30:1, the mol ratio of hydrogen and ethylene glycol is 0.01 ~ 0.3:1, and the add-on of catalyzer is 1% ~ 10%. of quality of glycol
Above-mentioned catalyzer is with any one in aluminum oxide, silicon-dioxide, gac, molecular sieve or two or more for carrier, at least two kinds in load active component Ru, Ni, Pd, Pt, Co, Mo, Fe, Mn, Sn, Zn, B, the charge capacity of active ingredient is 0.1% ~ 20% of catalyst quality, catalyzer can adopt this area the conventional catalyst preparation method that is familiar be prepared from, as the combination of the precipitator method, pickling process, hydrothermal synthesis method or aforesaid method.
When the active ingredient of above-mentioned catalyzer is Pt, Ru and Co, wherein the charge capacity of Pt is 1%, the mol ratio of Ru and Pt is 1:1, the mol ratio of Co and Pt is 2:1, the optimum condition preparing Monoethanolamine MEA BASF from ethylene glycol is: with ethylene glycol, liquefied ammonia, hydrogen for raw material, 230 ~ 270 DEG C are reacted 2 ~ 5 hours, reaction pressure is 5 ~ 9MPa, the mol ratio of liquefied ammonia and ethylene glycol is 15 ~ 25:1, the mol ratio of hydrogen and ethylene glycol is 0.05 ~ 0.3:1, and the add-on of catalyzer is 2% ~ 10% of quality of glycol.
When the active ingredient of upper catalyzer is Pd and Ru, wherein the charge capacity of Pd is 1%, the mol ratio of Ru and Pd is 1:1, the optimum condition preparing Monoethanolamine MEA BASF from ethylene glycol is: with ethylene glycol, liquefied ammonia, hydrogen for raw material, 290 ~ 330 DEG C are reacted 1 ~ 3 hour, and reaction pressure is 8 ~ 11MPa, and the mol ratio of liquefied ammonia and ethylene glycol is 15 ~ 30:1, the mol ratio of hydrogen and ethylene glycol is 0.1 ~ 0.3:1, and the add-on of catalyzer is 2% ~ 10% of quality of glycol.
When the active ingredient of above-mentioned catalyzer is Ru, Co and Ni, wherein the charge capacity of Ru is 1%, the mol ratio of Ru and Co, Ni is 1:1:1, the optimum condition preparing Monoethanolamine MEA BASF from ethylene glycol is: with ethylene glycol, liquefied ammonia, hydrogen for raw material, 250 ~ 270 DEG C are reacted 2 ~ 4 hours, and reaction pressure is 6 ~ 11MPa, and the mol ratio of liquefied ammonia and ethylene glycol is 10 ~ 20:1, the mol ratio of hydrogen and ethylene glycol is 0.01 ~ 0.3:1, and the add-on of catalyzer is 1% ~ 10% of quality of glycol.
When the active ingredient of above-mentioned catalyzer is Ru, Sn and Fe, wherein the charge capacity of Ru is 1%, the mol ratio of Ru and Sn, Fe is 1:1:1, the optimum condition preparing Monoethanolamine MEA BASF from ethylene glycol is: with ethylene glycol, liquefied ammonia, hydrogen for raw material, 200 ~ 250 DEG C are reacted 3 ~ 5 hours, and reaction pressure is 10 ~ 12MPa, and the mol ratio of liquefied ammonia and ethylene glycol is 20 ~ 30:1, the mol ratio of hydrogen and ethylene glycol is 0.05 ~ 0.3:1, and the add-on of catalyzer is 1% ~ 10% of quality of glycol.
When the active ingredient of above-mentioned catalyzer is Pt, Mo and Sn, wherein the charge capacity of Pt is 1%, the mol ratio of Mo and Pt is 2:1, the mol ratio of Sn and Pt is 1:2, the optimum condition preparing Monoethanolamine MEA BASF from ethylene glycol is: with ethylene glycol, liquefied ammonia, hydrogen for raw material, 200 ~ 230 DEG C are reacted 3 ~ 6 hours, reaction pressure is 13 ~ 15MPa, the mol ratio of liquefied ammonia and ethylene glycol is 6 ~ 20:1, the mol ratio of hydrogen and ethylene glycol is 0.01 ~ 0.2:1, and the add-on of catalyzer is 2% ~ 10% of quality of glycol.
The present invention prepares the method for Monoethanolamine MEA BASF from ethylene glycol, has high ethylene glycol reforming rate and Monoethanolamine MEA BASF yield.
Embodiment
Below in conjunction with embodiment, the present invention is described in more detail, but the invention is not restricted to these embodiments.
Embodiment 1
The mol ratio being 15:1, hydrogen and ethylene glycol by the mol ratio of liquefied ammonia and ethylene glycol is 0.1:1, in the intermittent high-pressure reactor of 200mL, add 24.8g(0.4mol) ethylene glycol, 1g Pt-Ru-Co/Al
2o
3inflated with nitrogen is taken a breath after 3 times, in intermittent high-pressure reactor, be filled with hydrogen to 0.5MPa, then in above-mentioned system, squeeze into 102g(6mol with volume pump) liquefied ammonia, be warming up to 250 DEG C, regulate reacting kettle inner pressure to 8MPa with nitrogen, react cooling after 3 hours, sampling, sample adopts Agilent 7890A gas-chromatography to carry out analyzing (HP-1 capillary chromatographic column, fid detector), the transformation efficiency of ethylene glycol is 58%, and the yield of Monoethanolamine MEA BASF is 38%.
Catalyst Pt-the Ru-Co/Al of the present embodiment
2o
3be prepared from by conventional pickling process, carrier A l
2o
3adopt commercial, the charge capacity of Pt be 1%, Ru and Pt mol ratio be the mol ratio of 1:1, Co and Pt be 2:1.
Embodiment 2
The temperature of reaction of the present embodiment is 270 DEG C, and other condition is identical with embodiment 1, and the transformation efficiency of ethylene glycol is 65%, and the yield of Monoethanolamine MEA BASF is 37%.
Embodiment 3
The temperature of reaction of the present embodiment is 350 DEG C, and other condition is identical with embodiment 1, and the transformation efficiency of ethylene glycol is 93%, and the yield of Monoethanolamine MEA BASF is 18%.
Embodiment 4
In the present embodiment, be 25:1 according to the mol ratio of liquefied ammonia and ethylene glycol, in reaction system, squeeze into 170g(10mol with volume pump) liquefied ammonia, other condition is identical with embodiment 1, and the transformation efficiency of ethylene glycol is 73%, and the yield of Monoethanolamine MEA BASF is 46%.
Embodiment 5
In the present embodiment, be 0.2:1 according to the mol ratio of hydrogen and ethylene glycol, inflated with nitrogen is taken a breath in 3 backward intermittent high-pressure reactors and is filled with hydrogen to 1MPa, and other condition is identical with embodiment 1, and the transformation efficiency of ethylene glycol is 61%, and the yield of Monoethanolamine MEA BASF is 39%.
Embodiment 6
In the present embodiment, the mol ratio being 25:1, hydrogen and ethylene glycol according to the mol ratio of liquefied ammonia and ethylene glycol is 0.1:1, in the intermittent high-pressure reactor of 200mL, add 24.8g(0.4mol) ethylene glycol, 2gPt-Ru-Co/Al
2o
3, inflated with nitrogen is taken a breath after 3 times, in intermittent high-pressure reactor, be filled with hydrogen to 0.5MPa, in above-mentioned system, 170g(10mol is squeezed into again with volume pump) liquefied ammonia, other condition is identical with embodiment 1, and the transformation efficiency of ethylene glycol is 85%, and the yield of Monoethanolamine MEA BASF is 51%.
Embodiment 7
The mol ratio being 20:1, hydrogen and ethylene glycol according to the mol ratio of liquefied ammonia and ethylene glycol is 0.1:1, in the intermittent high-pressure reactor of 200mL, add 24.8g(0.4mol) ethylene glycol, 2g Ru-Co-Ni/Al
2o
3catalyzer, inflated with nitrogen is taken a breath after 3 times, hydrogen is filled with to 0.5MPa in intermittent high-pressure reactor, in above-mentioned system, 136g(8mol is squeezed into again with volume pump) liquefied ammonia, be warming up to 270 DEG C, regulate reacting kettle inner pressure to 8MPa with nitrogen, react 3 hours, the transformation efficiency of ethylene glycol is 71%, and the yield of Monoethanolamine MEA BASF is 41%.
The present embodiment catalyzer Ru-Co-Ni/Al
2o
3preparation method identical with embodiment 1, wherein the mol ratio of the charge capacity of Ru to be the mol ratio of 1%, Ru and Co be 1:1, Co and Ni is 1:1.
Embodiment 8
The mol ratio being 20:1, hydrogen and ethylene glycol according to the mol ratio of liquefied ammonia and ethylene glycol is 0.1:1, in the intermittent high-pressure reactor of 200mL, add 24.8g(0.4mol) ethylene glycol, 2g Ru-Sn-Fe/Al
2o
3inflated with nitrogen is taken a breath after 3 times, hydrogen is filled with to 0.5MPa in intermittent high-pressure reactor, in above-mentioned system, 204g(12mol is squeezed into again with volume pump) liquefied ammonia, be warming up to 220 DEG C, regulate reacting kettle inner pressure to 11MPa with nitrogen, react 3 hours, the transformation efficiency of ethylene glycol is 65%, and the yield of Monoethanolamine MEA BASF is 34%.
The present embodiment catalyzer Ru-Sn-Fe/Al
2o
3preparation method identical with embodiment 1, wherein the mol ratio of the charge capacity of Ru to be the mol ratio of 1%, Ru and Sn be 1:1, Sn and Fe is 1:1.
Embodiment 9
The mol ratio being 18:1, hydrogen and ethylene glycol according to the mol ratio of liquefied ammonia and ethylene glycol is 0.1:1, in the intermittent high-pressure reactor of 200mL, add 24.8g(0.4mol) ethylene glycol, 2g Pt-Mo-Sn/Al
2o
3inflated with nitrogen is taken a breath after 3 times, hydrogen is filled with to 0.5MPa in intermittent high-pressure reactor, in above-mentioned system, 122.4g(7.2mol is squeezed into again with volume pump) liquefied ammonia, be warming up to 220 DEG C, regulate reacting kettle inner pressure to 13MPa with nitrogen, react 3 hours, the transformation efficiency of ethylene glycol is 75%, and the yield of Monoethanolamine MEA BASF is 53%.
The present embodiment catalyst Pt-Mo-Sn/Al
2o
3preparation method identical with embodiment 1, wherein the mol ratio of the charge capacity of Pt to be the mol ratio of 1%, Mo and Pt be 2:1, Sn and Pt is 0.5:1.
Embodiment 10
The mol ratio being 25:1, hydrogen and ethylene glycol according to the mol ratio of liquefied ammonia and ethylene glycol is 0.1:1, in the intermittent high-pressure reactor of 200mL, add 24.8g(0.4mol) ethylene glycol, 2g Pd-Ru/Al
2o
3inflated with nitrogen is taken a breath after 3 times, hydrogen is filled with to 0.5MPa in intermittent high-pressure reactor, in above-mentioned system, 122.4g(7.2mol is squeezed into again with volume pump) liquefied ammonia, be warming up to 310 DEG C, regulate reacting kettle inner pressure to 9MPa with nitrogen, react 3 hours, the transformation efficiency of ethylene glycol is 89%, and the yield of Monoethanolamine MEA BASF is 23%.
The present embodiment catalyst P d-Ru/Al
2o
3preparation method identical with embodiment 1, wherein the charge capacity of Pd is the mol ratio of 1%, Ru and Pd is 1:1.
Support of the catalyst Al in above-described embodiment
2o
3also silicon-dioxide, gac or molecular sieve can be used to replace; at least two kinds in these carrier loaded active ingredient Ru, Ni, Pd, Pt, Co, Mo, Fe, Mn, Sn, Zn, B; the catalyzer obtained all can be used for the present invention; what more than enumerate is only specific embodiments of the invention, and all distortion that those of ordinary skill in the art can directly derive from content disclosed by the invention or associate are all in protection scope of the present invention.
Claims (6)
1. prepare the method for Monoethanolamine MEA BASF from ethylene glycol for one kind, it is characterized in that: with ethylene glycol, liquefied ammonia, hydrogen for raw material, in the presence of a catalyst, 200 ~ 350 DEG C are reacted 1 ~ 6 hour, reaction pressure is 3 ~ 18MPa, the mol ratio of liquefied ammonia and ethylene glycol is 5 ~ 30:1, and the mol ratio of hydrogen and ethylene glycol is 0.01 ~ 0.3:1, and the add-on of catalyzer is 1% ~ 10% of quality of glycol;
Above-mentioned catalyzer is for carrier with any one in aluminum oxide, silicon-dioxide, gac, molecular sieve, at least two kinds in load active component Ru, Pd, Pt, Co, Mo, Fe, Sn, Zn, the total loading amount of active ingredient is 0.1% ~ 20% of catalyst quality.
2. the method preparing Monoethanolamine MEA BASF from ethylene glycol according to claim 1, it is characterized in that: the active ingredient of described catalyzer is Pt, Ru and Co, wherein the charge capacity of Pt is 1%, the mol ratio of Ru and Pt is 1:1, the mol ratio of Co and Pt is 2:1, with ethylene glycol, liquefied ammonia, hydrogen for raw material, 230 ~ 270 DEG C are reacted 2 ~ 5 hours, reaction pressure is 5 ~ 9MPa, the mol ratio of liquefied ammonia and ethylene glycol is 15 ~ 25:1, the mol ratio of hydrogen and ethylene glycol is 0.05 ~ 0.3:1, and the add-on of catalyzer is 2% ~ 10% of quality of glycol.
3. the method preparing Monoethanolamine MEA BASF from ethylene glycol according to claim 1, it is characterized in that: the active ingredient of described catalyzer is Pd and Ru, wherein the charge capacity of Pd is 1%, the mol ratio of Ru and Pd is 1:1, with ethylene glycol, liquefied ammonia, hydrogen for raw material, 290 ~ 330 DEG C are reacted 1 ~ 3 hour, reaction pressure is 8 ~ 11MPa, the mol ratio of liquefied ammonia and ethylene glycol is 15 ~ 30:1, the mol ratio of hydrogen and ethylene glycol is 0.1 ~ 0.3:1, and the add-on of catalyzer is 2% ~ 10% of quality of glycol.
4. the method preparing Monoethanolamine MEA BASF from ethylene glycol according to claim 1, it is characterized in that: the active ingredient of described catalyzer is Ru, Sn and Fe, wherein the charge capacity of Ru is 1%, the mol ratio of Ru and Sn, Fe is 1:1:1, with ethylene glycol, liquefied ammonia, hydrogen for raw material, 200 ~ 250 DEG C are reacted 3 ~ 5 hours, reaction pressure is 10 ~ 12MPa, the mol ratio of liquefied ammonia and ethylene glycol is 20 ~ 30:1, the mol ratio of hydrogen and ethylene glycol is 0.05 ~ 0.3:1, and the add-on of catalyzer is 1% ~ 10% of quality of glycol.
5. the method preparing Monoethanolamine MEA BASF from ethylene glycol according to claim 1, it is characterized in that: the active ingredient of described catalyzer is Pt, Mo and Sn, wherein the charge capacity of Pt is 1%, the mol ratio of Mo and Pt is 2:1, the mol ratio of Sn and Pt is 1:2, with ethylene glycol, liquefied ammonia, hydrogen for raw material, 200 ~ 230 DEG C are reacted 3 ~ 6 hours, reaction pressure is 13 ~ 15MPa, the mol ratio of liquefied ammonia and ethylene glycol is 6 ~ 20:1, the mol ratio of hydrogen and ethylene glycol is 0.01 ~ 0.2:1, and the add-on of catalyzer is 2% ~ 10% of quality of glycol.
6. the method preparing Monoethanolamine MEA BASF from ethylene glycol according to Claims 1 to 5 any one, is characterized in that: described catalyzer adopts the conventional precipitator method, pickling process or hydrothermal method to be prepared from.
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