CN102030666B - New process for synthesizing diethanol amine - Google Patents
New process for synthesizing diethanol amine Download PDFInfo
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- CN102030666B CN102030666B CN 201010546889 CN201010546889A CN102030666B CN 102030666 B CN102030666 B CN 102030666B CN 201010546889 CN201010546889 CN 201010546889 CN 201010546889 A CN201010546889 A CN 201010546889A CN 102030666 B CN102030666 B CN 102030666B
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Abstract
The invention provides a method for synthesizing diethanol amine, which comprises the steps of tubular reaction, excessive ammonia separation, reaction distillation and collection of the high-purity product of diethanol amine from a reaction distillation towel. Compared with the prior art, the process has the advantages of greatly increasing the selectivity of diethanol amine, enhancing the course, directly utilizing reaction heat energy and obviously improving the economical efficiency of the technology.
Description
Technical field
The invention belongs to technical field of chemical engineering, is a kind of novel process of synthetic diethanolamine.
Background technology
Thanomin is the general name of Monoethanolamine MEA BASF (MEA), diethanolamine (DEA), trolamine (TEA), is one of important derivatives of oxyethane.Because the thanomin molecule has amino (alkalescence) and hydroxyl (wetting ability) simultaneously, the chemical property of amine and alcohol is arranged, so this product has purposes widely, can be used as tensio-active agent, gas absorbent, washing composition, cement intensifier etc.Wherein diethanolamine is mainly as analytical reagent, the industrial gas purifying such as acid gas absorbent, coke gas, washing composition, lubricant, tenderizer, tensio-active agent and organic gas are synthetic etc., its consumption accounts for 42% of thanomin total amount, is the product of consumption maximum in three kinds of thanomin.
The thanomin production process route is mainly the oxyethane ammonolysis process in the world at present, and the technique that adopts is mainly pipe reaction and rectifying separation technique.This technique is take ammoniacal liquor and oxyethane as raw material, synthetic MEA, DEA, TEA and some byproducts in tubular reactor (or tower reactor), and mixture obtains high purity product through after rectifying separation.Patent 200910098497 has been reported the abbreviated system of producing about thanomin, take liquefied ammonia and oxyethane as raw material, produces thanomin under the existence of a small amount of water catalyzer.Patent 96100557 has been reported the waterless tubular reaction process of producing about thanomin, this technique is also with liquid phase epoxidation ethane and liquefied ammonia low temperature pre-mixing by a certain percentage, send into tubular reactor and carry out reaction under high pressure, then steam and reclaim excess of ammonia through step-down.Patent 90103426 and patent 20091098498 are reported all relates to the liquid-liquid tube reaction ethanolamine production method.
There are several technological difficulties problems in existing thanomin synthesis technique.(1) boiling point of thanomin very high (MEA:170 ℃, DEA:268.8 ℃, TEA:360 ℃), product rectifying need to be carried out under high vacuum, and system energy consumption is very high; (2) the thanomin building-up reactions is strong exothermal reaction (thermal discharge of every moles of ethylene oxide ring-opening reaction is 92 kJ), existing technique must in time shift out a large amount of reaction heat from reactor, shift out reaction heat and not only cause the reduction of energy utilization efficiency, and jeopardize reactive system safety and device smooth running, become the hidden danger of safety in production; (3) due to the diethanolamine in the thanomin product be the intermediate product of consecutive reaction, existing synthesis technique is difficult to the diethanolamine selectivity (being no more than 30%) that reaches high, thereby has limited the raising (diethanolamine is the product of consumption maximum in three kinds of thanomin) of its output.So if can significantly improve the selectivity of diethanolamine in the process of synthesizing ethanolamine, this will be highly profitable to increasing this product production and reducing the later separation cost.
Summary of the invention
The object of the invention is to: provide a kind of new diethanolamine synthetic method, the problem that product separation is difficult, reaction heat is utilized and the diethanolamine selectivity is low that exists to solve existing technique.
Above-mentioned purpose of the present invention is achieved through the following technical solutions:
A kind of synthetic method of diethanolamine is provided, and flow process comprises pipe reaction workshop section, excess ammonia centrifugal station and reactive distillation workshop section as shown in Figure 1, and its concrete grammar is as follows:
1) tubular reactor workshop section
Ammoniacal liquor and oxyethane, react in tubular reactor under the pressure of the temperature of reaction of 50 ~ 70 ℃ and 2.5 ~ 3.0MPa with the mol ratio of 10:1 ~ 15:1, until oxyethane transforms fully, generate Monoethanolamine MEA BASF, diethanolamine and trolamine mixture; The tubular reactor outlet material comprises unconverted ammonia, water and described three kinds of thanomin products;
The raw material of this segment process is that strong aqua and oxyethane enter tubular reactor after mixing tank mixes, and the target of reaction is that oxyethane transforms in reactor fully, and the turnout of TEA is the least possible simultaneously.This step has realized above-mentioned target by device parameter and the operating parameters of optimizing reactor;
2) excess ammonia centrifugal station
Step 1) tubular reactor outlet material first through the step-down of flash tank multistage flash evaporation, isolate 20 ~ 30% unreacted ammonia, and then enter ammonia still and steam remaining ammonia, the product that obtains at the bottom of the tower of ammonia still is MEA, DEA, H
2O and TEA;
3) reactive distillation workshop section
Step 2) bottom product of ammonia still enters the top of reaction fractionating tower, introduce oxyethane from the middle part of reaction fractionating tower simultaneously, at the bottom of oxyethane and ammonia still tower, the mixture raw materials components mole ratio is 1:1 ~ 1.5, two strands of materials carry out chemical reaction and product separation simultaneously in reaction fractionating tower, the working pressure of reaction fractionating tower is 0.3 ~ 0.6atm, and temperature of reaction is 100 ~ 120 ℃, and reboil ratio is 8.0, reaction fractionating tower overhead extraction water, the highly purified diethanolamine product of tower reactor extraction;
In this step, oxyethane can rise along tower as light constituent, with the ethanolamine mixtures contact reacts; The large calorimetric that reaction is emitted also makes light constituent water in ethanolamine mixtures and MEA steam along tower simultaneously to rise, wherein, water vapour constantly is plucked out of from tower top after rising, MEA is continuous reacting ethylene oxide with together rising in uphill process, finally transform fully, and purer heavy constituent DEA can descend along tower, constantly is plucked out of from tower reactor.In whole process, a small amount of water of carrying secretly in ethanolamine mixtures also can be used as catalyzer and heat-carrying agent plays a role.In addition, the reaction of reaction fractionating tower is homogeneous reaction, and the reactant Monoethanolamine MEA BASF itself has katalysis, does not need separately to add catalyzer;
In this step, by the processing parameter of design reaction fractionating tower, make oxyethane and MEA realize transforming fully in tower, from overhead extraction water, can obtain purity at the bottom of tower at the DEA more than 80%.
The ammonia concn that step 1) adopts is preferred more than 90%.
The mol ratio of the described ammoniacal liquor of step 1) and oxyethane is preferably 10:1.
The described reaction pressure of step 1) is preferably 3MPa.
Step 2) the ammonia preferred cycle that steams of the described ammonia still tubular reactor that returns step 1) continues to use.
The described reaction fractionating tower working pressure of step 3) is preferably 0.5atm.
The described highly purified diethanolamine product that step 3) preferably will obtain is refining through a rectifying tower again, finally obtains pure diethanolamine.
In method of the present invention, tubular reactor, step 2 that step 1) is used) flash tank and the ammonia still that use, and the reaction fractionating tower that step 3) is used is existing equipment.
Compared with prior art, beneficial effect of the present invention has been to significantly improve the selectivity of diethanolamine.The Main Means that the present invention adopts is to introduce reaction rectification technique in synthesizing ethanolamine technique.Reactive distillation (Reactive Distillation, RD) is the technology of same equipment that the unit operation of chemical reaction and these two chemical process most criticals of rectifying separation is coupled in, and is the strong means that traditional technology is strengthened and improved to chemical process.Reaction rectification technique is introduced in the thanomin synthesis technique, can be utilized rectificating method that reactant is in time separated with product, thereby improve transformation efficiency and the selectivity of reaction, improve simultaneously plant capacity.On the other hand, the reaction heat of emitting does not need to shift out reactor, but the phegma in the rectifying that is used to vaporize, heat obtains fully effectively utilizing.And compare with other techniques, method of the present invention does not need separately to increase a dehydration tower and comes Separation of Water, has not only simplified flow process, has greatly reduced running cost simultaneously.Synthetic method of the present invention is tower-coupled with tubular reactor and reactive distillation, and synthesis of selective can significantly improve, and in product, diethanolamine content can reach more than 80%.
Description of drawings
Fig. 1 is the schema of diethanolamine synthesis technique of the present invention.
Embodiment
Embodiment 1.
1) take the ammoniacal liquor of oxyethane and 90% concentration as raw material, mole proportioning at 3.0MPa, 50 ℃, ammoniacal liquor and oxyethane is under the condition of 10:1, at first react by tubular reactor, until oxyethane transforms fully, the synthesizing ethanolamine mixing prod, product forms (by a mole mark): MEA54.25%, DEA27.59%, TEA18.16%;
2) mixing prod that step 1) is obtained first passes through the step-down of flash tank multistage flash evaporation, isolate 20 ~ 30% unreacted ammonia, and then enter ammonia still and steam remaining ammonia, the product that obtains at the bottom of the tower of ammonia still (by a mole mark) is: MEA71.51%, DEA18.18%, H
2O2.33% and TEA7.98%;
3) product that step 2) obtains at the bottom of the ammonia still tower enters the top of reaction fractionating tower, introduce oxyethane from the middle part of reaction fractionating tower simultaneously, oxyethane and ammonia still bottom product raw materials components mole ratio are 1:1, two strands of materials carry out chemical reaction and product separation simultaneously in reaction fractionating tower, the working pressure of reaction fractionating tower is 0.5atm, temperature of reaction is 100 ℃, reboil ratio is 8.0, reaction fractionating tower overhead extraction water, the highly purified diethanolamine product of tower reactor extraction, by a mole mark, group of products becomes DEA 82.36%, and TEA 17.64%.
Embodiment 2.
1) take the ammoniacal liquor of oxyethane and 95% concentration as raw material, mole proportioning at 2.5MPa, 60 ℃, ammoniacal liquor and oxyethane is under the condition of 12:1, at first react by tubular reactor, until oxyethane transforms fully, the synthesizing ethanolamine mixing prod, product forms (by a mole mark): MEA56.78%, DEA28.97%, TEA14.25%;
2) mixing prod that step 1) is obtained first passes through the step-down of flash tank multistage flash evaporation, isolate 20 ~ 30% unreacted ammonia, and then enter ammonia still and steam remaining ammonia, the product that obtains at the bottom of the tower of ammonia still (by a mole mark) is: MEA74.52%, DEA19.13%, H
2O1.37% and TEA4.98%;
3) product that step 2) obtains at the bottom of the ammonia still tower enters the top of reaction fractionating tower, introduce oxyethane from the middle part of reaction fractionating tower simultaneously, oxyethane and ammonia still bottom product raw materials components mole ratio are 1:1.5, two strands of materials carry out chemical reaction and product separation simultaneously in reaction fractionating tower, the working pressure of reaction fractionating tower is 0.3atm, temperature of reaction is 120 ℃, reboil ratio is 8.0, reaction fractionating tower overhead extraction water, the highly purified diethanolamine product of tower reactor extraction, by a mole mark, group of products becomes DEA 84.32%, and TEA 15.68%.
Embodiment 3.
1) take the ammoniacal liquor of oxyethane and 90% concentration as raw material, mole proportioning at 3.0MPa, 70 ℃, ammoniacal liquor and oxyethane is under the condition of 15:1, at first react by tubular reactor, until oxyethane transforms fully, the synthesizing ethanolamine mixing prod, product forms (by a mole mark): MEA56.32%, DEA29.46%, TEA14.22%;
2) mixing prod that step 1) is obtained first passes through the step-down of flash tank multistage flash evaporation, isolate 20 ~ 30% unreacted ammonia, and then enter ammonia still and steam remaining ammonia, the product that obtains at the bottom of the tower of ammonia still (by a mole mark) is: MEA74.68%, DEA18.79%, H
2O2.02% and TEA4.51%;
3) product that step 2) obtains at the bottom of the ammonia still tower enters the top of reaction fractionating tower, introduce oxyethane from the middle part of reaction fractionating tower simultaneously, oxyethane and ammonia still bottom product raw materials components mole ratio are 1:1.2, two strands of materials carry out chemical reaction and product separation simultaneously in reaction fractionating tower, the working pressure of reaction fractionating tower is 0.6atm, temperature of reaction is 110 ℃, reboil ratio is 8.0, reaction fractionating tower overhead extraction water, the highly purified di-alcohol product of tower reactor extraction, by a mole mark, group of products becomes DEA 83.97%, and TEA 16.03%.
Claims (6)
1. the synthetic method of a diethanolamine comprises pipe reaction workshop section, excess ammonia centrifugal station and reactive distillation workshop section, and its concrete grammar is as follows:
1) tubular reactor workshop section
Ammoniacal liquor and oxyethane, react in tubular reactor under the pressure of the temperature of reaction of 50～70 ℃ and 2.5～3.0MPa with the mol ratio of 10:1～15:1, until oxyethane transforms fully, generate Monoethanolamine MEA BASF, diethanolamine and trolamine mixture; The tubular reactor outlet material comprises unconverted ammonia, water and described three kinds of thanomin products;
2) excess ammonia centrifugal station
Step 1) tubular reactor outlet material first through the step-down of flash tank multistage flash evaporation, isolate 20～30% unreacted ammonia, and then enter ammonia still and steam remaining ammonia, the product that obtains at the bottom of the tower of ammonia still is Monoethanolamine MEA BASF, diethanolamine, H
2O and trolamine;
3) reactive distillation workshop section
Step 2) bottom product of ammonia still enters the top of reaction fractionating tower, introduce oxyethane from the middle part of reaction fractionating tower simultaneously, at the bottom of oxyethane and ammonia still tower, the mixture raw materials components mole ratio is 1:1～1.5, two strands of materials carry out chemical reaction and product separation simultaneously in reaction fractionating tower, the working pressure of reaction fractionating tower is 0.3～0.6atm, and temperature of reaction is 100～120 ℃, and reboil ratio is 8.0, reaction fractionating tower overhead extraction water, the highly purified diethanolamine product of tower reactor extraction.
2. the synthetic method of diethanolamine claimed in claim 1, it is characterized in that: ammonia concn that step 1) adopts is more than 90%.
3. the synthetic method of diethanolamine claimed in claim 1, it is characterized in that: the mol ratio of the described ammoniacal liquor of step 1) and oxyethane is 10:1.
4. the synthetic method of diethanolamine claimed in claim 1, it is characterized in that: the described reaction pressure of step 1) is 3MPa.
5. the synthetic method of diethanolamine claimed in claim 1, is characterized in that: step 2) ammonia that steams of the described ammonia still tubular reactor that loops back step 1) continues to use.
6. the synthetic method of diethanolamine claimed in claim 1, it is characterized in that: the described reaction fractionating tower working pressure of step 3) is 0.5atm.
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| CN107778186A (en) * | 2016-08-30 | 2018-03-09 | 中国石油化工股份有限公司 | Catalyst Production and process of regenerating |
| CN107805206B (en) * | 2017-11-21 | 2020-09-04 | 四川之江高新材料股份有限公司 | Method for continuously synthesizing ethanolamine and derivative thereof by virtue of microtubule reaction-rectification coupling |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1049653A (en) * | 1990-07-02 | 1991-03-06 | 浙江大学 | The process for liquid-liquid tube reaction that thanomin is produced |
| CN1139101A (en) * | 1996-04-19 | 1997-01-01 | 浙江大学 | Waterless tubular reaction process for ethanolamine production |
| CN101723840A (en) * | 2008-10-20 | 2010-06-09 | 苏舍化学技术有限公司 | Method and plant for the production of ethanol amines |
| CN101735077A (en) * | 2009-12-11 | 2010-06-16 | 广西壮族自治区化工研究院 | Production method and production equipment for synthesizing ethanolamine by ethylene oxide |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1049653A (en) * | 1990-07-02 | 1991-03-06 | 浙江大学 | The process for liquid-liquid tube reaction that thanomin is produced |
| CN1139101A (en) * | 1996-04-19 | 1997-01-01 | 浙江大学 | Waterless tubular reaction process for ethanolamine production |
| CN101723840A (en) * | 2008-10-20 | 2010-06-09 | 苏舍化学技术有限公司 | Method and plant for the production of ethanol amines |
| CN101735077A (en) * | 2009-12-11 | 2010-06-16 | 广西壮族自治区化工研究院 | Production method and production equipment for synthesizing ethanolamine by ethylene oxide |
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