CN104262173B - A kind of method of being synthesized diglycolamine by glycol ether low-pressure process - Google Patents
A kind of method of being synthesized diglycolamine by glycol ether low-pressure process Download PDFInfo
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- CN104262173B CN104262173B CN201410442739.8A CN201410442739A CN104262173B CN 104262173 B CN104262173 B CN 104262173B CN 201410442739 A CN201410442739 A CN 201410442739A CN 104262173 B CN104262173 B CN 104262173B
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Abstract
The invention discloses a kind of method of being synthesized diglycolamine by glycol ether low-pressure process, the air in nitrogen replacement reactor is first used before reaction feeds intake, then the hydrogen of preheating is continued to pass in reactor, make that the catalyst temperature in reactor rises to 180-240 DEG C, pressure in reactor rises to 1.60-1.75MPa; Gas mixture is mixed to get and preheating with hydrogen by after liquid ammonia vaporization; Glycol ether and soft water are mixed to get mixed solution and preheating; Gas mixture after preheating and the mixed solution after preheating are sent in reactor, the reaction of liquid phase catalytic ammoniation is carried out in the presence of a catalyst at 1.60-1.75MPa, 180-240 DEG C, obtain crude product, through gas-liquid separator separates gas and liquid after obtained crude product cooling, liquid is thick diglycolamine.Diglycolamine content in the thick diglycolamine that the present invention obtains is high, diethylene glycol conversion rate up to more than 85%, diglycolamine yield more than 70%.
Description
One, technical field
The present invention relates to a kind of synthetic method of known compound, specifically a kind of method of being synthesized diglycolamine by glycol ether low-pressure process.
Two, background technology
Diglycolamine, also known as 2-(2-amino ethoxy) ethanol, molecular formula C
4h
11nO
2, being colorless syrup liquid, is a kind of important solvent and organic raw material, energy and water dissolution, can dissolve aromatic hydrocarbons and absorb sour gas (H
2s and CO
2).Diglycolamine is mainly used as the absorption agent of sour gas, tensio-active agent and wetting agent, sweetening agent, also can be used as the raw material of polymkeric substance, extensive at industrial applications such as metal, electronics, medicine.
Also not having a kind of at home under prior art can be the industrialized producing technology method of Material synthesis diglycolamine with glycol ether, liquefied ammonia, hydrogen and soft water, only at the report of product in laboratory diglycolamine, but its yield is low, the many and difficult separation of by product, can not be used for suitability for industrialized production.
Can there is catalytic ammoniation by glycol ether and ammonia and be obtained by reacting in diglycolamine, reaction process is as follows under catalyzer existent condition:
Main reaction:
Side reaction:
In addition due to the structure of glycol ether, by product N-methylmorpholine, N-ethylmorpholine can be produced in the reaction, and methane etc., prepare in diglycolamine process at glycol ether catalytic ammoniation in a word, the control of reaction conditions is very crucial.
Be not difficult to find from above side reaction:
In the building-up process of 1, diglycolamine, by product generates many, not easily removes;
2, with glycol ether and liquefied ammonia for raw material, the technology of low pressure ammoniation process synthesis diglycolamine, reaction relates to multistep catalytic process, the change of proportioning raw materials and reaction conditions, larger on reaction process impact.
Three, summary of the invention
The present invention aims to provide and a kind ofly synthesizes the method for diglycolamine by glycol ether low-pressure process, makes diglycolamine product at home can suitability for industrialized production, fills the domestic gaps, breaks foreign technology monopolization.
The present invention synthesizes the method for diglycolamine by glycol ether low-pressure process, and detailed process is as follows:
1, before reaction feeds intake, first use the air in nitrogen replacement reactor, then the hydrogen of preheating is continued to pass in reactor, make that the catalyst temperature in reactor rises to 180-240 DEG C, pressure in reactor rises to 1.60-1.75MPa;
2, gas mixture is mixed to get after liquid ammonia vaporization with hydrogen, by described charge heating to 240-280 DEG C;
3, glycol ether and soft water are mixed to get mixed solution, described mixed solution is preheated to 230-280 DEG C;
4, the mixed solution after the gas mixture after step 2 preheating and step 3 preheating is sent in the reactor of step 1, liquid phase catalytic ammoniation reaction (reaction is successive reaction) is carried out in the presence of a catalyst at 1.60-1.75MPa, 180-240 DEG C, obtain crude product, through gas-liquid separator separates gas and liquid after obtained crude product cooling, gas main component is hydrogen and ammonia, can recycle; Liquid is thick diglycolamine, the content of diglycolamine about 35% in thick diglycolamine, sends into separation and purification system subsequently.Because side reaction is few, diglycolamine purity >=99% after refining.
The mol ratio of glycol ether, liquefied ammonia and soft water is 1:5:5.
Described catalyzer is copper-nickel catalyst, and producing 1 ton of diglycolamine needs spent catalyst 0.003m3.
In catalytic ammoniation process, hydrogen does not participate in reaction, and it act as maintenance system pressure.
Compared with the prior art, beneficial effect of the present invention is embodied in:
Diglycolamine content in the thick diglycolamine that the present invention obtains is high, diethylene glycol conversion rate up to more than 85%, diglycolamine yield more than 70%; Equipment and catalyzer are production domesticization, can realize suitability for industrialized production.
Because side reaction is few, the thick diglycolamine that the inventive method prepares can obtain the diglycolamine product of purity more than 99% after separation and purification.
Four, accompanying drawing explanation
Fig. 1 is process flow diagram of the present invention.
In figure, 1 liquid ammonia storage tank, 2 liquefied ammonia surge tanks, 3 liquid ammonia gasifiers, 4 glycol ether storage tanks, 5 glycol ether surge tanks, 6 soft water storage tanks, 7 soft water surge tanks, 8 glycol ethers and soft water mixing tank, 9 well heaters, 10 heat exchangers, 11 steam heaters, 12 electric heaters, 13 reactors, 14 condensers, 15 water coolers, 16 gas-liquid separators, 17 circulation gas tanks, 18 circulation gas surge tanks, 19 recycle gas compressors, 20 circulation gas by-pass valves, 21 thick diglycolamine storage tanks, 22 tensimeters, 23 is temperature measurers, 24 under meters, 25 volume pumps.
Five, embodiment
Below in conjunction with accompanying drawing, the invention will be further described.
As shown in Figure 1, before reaction feeds intake, first use the air in nitrogen replacement reactor 13, then the hydrogen of preheating is continued to pass in reactor 13, make the catalyzer temperature-elevating in reactor 13 to 180-240 DEG C, reactor 13 boosts to 1.60-1.75MPa, when catalyst temperature, tower internal pressure rise to temperature of reaction, pressure, stop hydrogen recycle.
Liquefied ammonia in liquid ammonia storage tank 1 pumps into after liquefied ammonia surge tank 2 buffering through volume pump 25, liquid ammonia gasifier 3 is entered with after under meter 24 accurate measurement, after gasification gas ammonia out with mix with the circulating hydrogen from circulation gas tank 18 after under meter 24 accurate measurement after, enter heat exchanger 10, heat exchange is carried out with reactor 13 crude product out, mixed gas after heat exchange preheating enters steam heater 11 and heats, enter electric heater 12 again and be heated to 240-280 DEG C, enter reactor 13 subsequently and participate in reaction.Enter the mixture temperature before reactor 13 to be measured by temperature measurer 23.
Pump into glycol ether surge tank 5 by the glycol ether in glycol ether storage tank 4 through volume pump 25, bottom glycol ether surge tank 5, glycol ether out enters mixing tank 8 after under meter 24 accurate measurement; Soft water in soft water storage tank 6 pumps into soft water surge tank 7 through volume pump 25, bottom soft water surge tank 7, soft water out enters mixing tank 8 after under meter 24 accurate measurement, soft water fully mixes in mixing tank 8 with glycol ether, bottom mixing tank 8 mixture out in well heater 9 by steam heating to after 230-280 DEG C, enter reactor 13 and participate in reaction.Enter the mixture temperature before reactor 13 to be measured by temperature measurer 23, adjust according to process requirements.
Material molar ratio controls at glycol ether: liquefied ammonia: soft water=1:5:5, is controlled by under meter 24 accurate measurement.In reactor 13, the temperature of reaction of material is measured by temperature measurer 23, in reactor 13, reaction pressure is measured by tensimeter 22, temperature of reaction in reactor 13 controls between 180-240 DEG C, and pressure-controlling between 1.60-1.75MPa, and needs to regulate according to technique.Mixed gas from electric heater 12 and the mixture from well heater 9, in reactor 13, carry out the reaction of liquid phase catalytic ammoniation, generate thick diglycolamine under the effect of copper-nickel catalyst.Bottom reactor 13, thick diglycolamine is out in heat exchanger 10, after lowering the temperature from the gas mixture heat exchange in liquid ammonia gasifier 3 and circulation gas tank 18, is then cooled to through condenser 14, water cooler 15 and enters gas-liquid separator 16 after below 40 DEG C and be separated.Bottom gas-liquid separator 16, thick diglycolamine out enters thick diglycolamine storage tank 20, delivers to separation and purification system afterwards.Enter the thick diglycolamine temperature before gas-liquid separator 16 to be measured by temperature measurer 23, adjust according to process requirements.Gas-liquid separator 16 top gas out, enters circulation gas tank 17, according to process requirements, the emptying of part circulation gas is carried hydrogen retrieval to pressure-variable adsorption and is utilized, a part, after circulator 19 pressurizes, enters circulation gas surge tank 18 and mixes with the fresh hydrogen of supplementing, recycle.
In process of production, the aperture of circulation gas by-pass valve 20 is regulated, to meet Production requirement.
Claims (1)
1. synthesized a method for diglycolamine by glycol ether low-pressure process, it is characterized in that comprising the following steps:
1) before reaction feeds intake, first use the air in nitrogen replacement reactor, then the hydrogen of preheating is continued to pass in reactor, make that the catalyst temperature in reactor rises to 180-240 DEG C, pressure in reactor rises to 1.60-1.75MPa;
2) gas mixture is mixed to get after liquid ammonia vaporization with hydrogen, by described charge heating to 240-280 DEG C;
3) glycol ether and soft water are mixed to get mixed solution, described mixed solution is preheated to 230-280 DEG C;
4) by step 2) gas mixture after preheating and the mixed solution after step 3) preheating send in reactor, the reaction of liquid phase catalytic ammoniation is carried out in the presence of a catalyst at 1.60-1.75MPa, 180-240 DEG C, obtain crude product, through gas-liquid separator separates gas and liquid after obtained crude product cooling, liquid is thick diglycolamine, sends into separation and purification system subsequently;
Described catalyzer is copper-nickel catalyst;
The mol ratio of glycol ether, liquefied ammonia and soft water is 1:5:5.
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| CN201410442739.8A CN104262173B (en) | 2014-09-02 | 2014-09-02 | A kind of method of being synthesized diglycolamine by glycol ether low-pressure process |
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| CN201410442739.8A CN104262173B (en) | 2014-09-02 | 2014-09-02 | A kind of method of being synthesized diglycolamine by glycol ether low-pressure process |
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| CN104262173A CN104262173A (en) | 2015-01-07 |
| CN104262173B true CN104262173B (en) | 2016-04-06 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3755692B1 (en) | 2018-02-22 | 2022-04-06 | Basf Se | Method for the depletion of 2-methoxyethanol (moe) |
| HUE058943T2 (en) | 2018-02-22 | 2022-09-28 | Basf Se | Method for the continuous destillative separation of mixtures comprising morpholine (mo), monoaminodiglycol (adg), ammonia, water and methoxyethanol (moe) |
| US11155516B2 (en) * | 2019-10-14 | 2021-10-26 | Javad Safaei-Ghomi | Synthesis of 2-(2-aminoethoxy) ethanol |
| CN117417262B (en) * | 2023-10-19 | 2024-03-29 | 山东达民化工股份有限公司 | Preparation method of diglycolamine |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101844987A (en) * | 2010-05-25 | 2010-09-29 | 张家港市大伟助剂有限公司 | Preparation method of bi-(2-ethylhexyl) |
| CN102574774A (en) * | 2009-10-06 | 2012-07-11 | 烷基胺化学制品有限公司 | A process for the preparation of 2-(2-aminoethoxy) ethanol (2aee) and morpholine with 2aee: morpholine >3 |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102574774A (en) * | 2009-10-06 | 2012-07-11 | 烷基胺化学制品有限公司 | A process for the preparation of 2-(2-aminoethoxy) ethanol (2aee) and morpholine with 2aee: morpholine >3 |
| CN101844987A (en) * | 2010-05-25 | 2010-09-29 | 张家港市大伟助剂有限公司 | Preparation method of bi-(2-ethylhexyl) |
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