CN102002019A - Method for removing ethylene glycol monomethyl ether impurity in coarse product of morpholine device - Google Patents
Method for removing ethylene glycol monomethyl ether impurity in coarse product of morpholine device Download PDFInfo
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- CN102002019A CN102002019A CN 201010516869 CN201010516869A CN102002019A CN 102002019 A CN102002019 A CN 102002019A CN 201010516869 CN201010516869 CN 201010516869 CN 201010516869 A CN201010516869 A CN 201010516869A CN 102002019 A CN102002019 A CN 102002019A
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- morpholine
- ethylene glycol
- glycol monomethyl
- monomethyl ether
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Abstract
The invention discloses a method for removing an organic compound impurity, which is a method for removing an ethylene glycol monomethyl ether impurity from tower bottoms of a deamination tower of a morpholine device. The method is characterized by comprising the following steps of: pumping tower bottoms of the deamination tower in the morpholine device to a preheater through a charging pump, then transferring the tower bottoms to the middle of a rectifying tower after being heated, pumping deionized water through a water pump to a vaporizer to gasify, then heating the deionized water by a heater and entering the lower part of the rectifying tower, wherein the bottom temperature of the rectifying tower is 118 DEG C and the tower top pressure of the rectifying tower is atmosphere pressure; cooling vapor at tower top after entering a condensation cooler and then entering a condensate storage tank; reflowing a part of condensate to the rectifying tower, wherein the reflow ratio is (2.0-4.0):1; fractioning in front of the tower top and entering the next step; discharging at the tower top of the rectifying tower and completing coarse morpholine product without ethylene glycol monomethyl ether. The invention has the advantages that the process flow of separation step of the morpholine device is improved and the ethylene glycol monomethyl ether is removed by introducing directly heated vapor in a first dehydrogenation tower without adding other process equipment, thereby preventing ethylene glycol monomethyl ether from entering the subsequent steps and improving the quality of morpholine of the morpholine device.
Description
Technical field
The present invention relates to a kind of way that removes organic compound impurity, remove ethylene glycol monomethyl ether impurity in the morpholine device deamination tower bottoms, prepare the method for high purity morpholine more specifically to a kind of.
Background technology
Morpholine is a kind of important Organic Chemicals, is widely used in to produce rubber accelerator, vulcanizing agent, medicine, agricultural chemicals, inhibiter, petrochemical complex auxiliary agent and chemical polishing agent etc.
At present, adopt the production equipment of glycol ether-liquefied ammonia explained hereafter morpholine, adopt the Ni-Cu/Al2O3 catalyst system mostly, in building-up process, all can produce ethylene glycol monomethyl ether impurity etc., it consists of: water 28%～32%, N-methylmorpholine 1.0%～2.0%, N-ethylmorpholine 2.5%～4.5%, ethylene glycol monomethyl ether 0.3%～0.6%, about morpholine 60%, all the other are high boiling material, and according to the operational circumstances difference, it is formed also otherwise be same.124.5 ℃ of the boiling points of ethylene glycol monomethyl ether, between 128 ℃ of 115.4 ℃ of morpholine production process by product N-methylmorpholine boiling points and purpose product morpholine boiling points, simultaneously because ethylene glycol monomethyl ether has can form minimum azeotropic mixture, form the characteristic of maximum azeotrope thing with morpholine with water, cause that ethylene glycol monomethyl ether impurity is difficult to remove in the morpholine product, the high purity morpholine is difficult to obtain, and has influenced the range of application of morpholine product.
Summary of the invention
The objective of the invention is to overcome the deficiency of prior art, a kind of method that removes ethylene glycol monomethyl ether impurity in the thick product of morpholine device is provided.
Technical solution of the present invention is to utilize ethylene glycol monomethyl ether to have the advantages that to form minimum azeotropic mixture with water, morpholine device first lightness-removing column is improved, introduce direct superheated vapo(u)r at stripping section, suppress ethylene glycol monomethyl ether and morpholine formation maximum azeotrope thing and enter the tower still, make ethylene glycol monomethyl ether impurity, N-methylmorpholine and N-ethylmorpholine by product and most of water enter postprocessing working procedures as front-end volatiles in the cat head extraction, reduce or avoid ethylene glycol monomethyl ether to enter the tower still, cause that the morpholine quality product descends.
A kind of method that removes ethylene glycol monomethyl ether impurity in the thick product of morpholine device is characterized in that, is provided with rectifying tower, establishes reboiler under the tower, and cat head is established condensate cooler, the front-end volatiles jar; The deammoniation tower tower bottoms is through charging pumping preheater in the morpholine device, be heated to 110 ℃～120 ℃ after, enter the rectifying tower middle part, deionized water send the vaporizer gasification through water pump, again through superheater, is heated to 115 ℃～125 ℃, enters the rectifying tower bottom; 118 ℃～127 ℃ of rectifying tower column bottom temperatures; The rectifying tower tower top pressure is a normal atmosphere, 97 ℃～99 ℃ of temperature, overhead vapours is advanced the condensate cooler condensation and is cooled off laggard phlegma storage tank, a phlegma part is back to rectifying tower, reflux ratio is (2.0～4.0): 1, the gold-plating branch advances next process before the cat head, and the discharging of rectifying Tata still is to finish the raw morpholine product that removes ethylene glycol monomethyl ether, as the raw material of later separation operation.
The described method that removes ethylene glycol monomethyl ether impurity in the thick product of morpholine device, its process is that rectifying tower is carried the direct superheated vapo(u)r of introducing in the gold-plating section, adopt the operate continuously mode, finish N-methylmorpholine in the morpholine device deamination tower bottoms, removing of N-ethylmorpholine by product and ethylene glycol monomethyl ether impurity, the tower still takes off the thick product of ether and does not contain or contain micro-N-methylmorpholine, N-ethylmorpholine by product and ethylene glycol monomethyl ether component, it is characterized in that the mass flux ratio of ethylene glycol monomethyl ether impurity is (90～180) in the mass rate of the superheated vapo(u)r that is taken place by deionized water and the deammoniation tower supplied materials: 1.
Advantage of the present invention, exactly in that technical process is improved to morpholine device separation circuit, under the condition that does not increase other processing units, by in first lightness-removing column, introducing direct superheated vapo(u)r, with the ethylene glycol monomethyl ether impurity removal, avoid it to enter follow-up equipment, improve the morpholine quality product of morpholine device.
Description of drawings
Fig. 1 is a general flow chart of the present invention.
Embodiment
Below in conjunction with specific embodiment, the present invention is described further.
The deammoniation tower tower bottoms that adopts XX chemical industry company limited morpholine device is as raw material (abbreviation raw material), and raw material consists of: water 29.87%, N-methylmorpholine 1.46%, N-ethylmorpholine 3.92%, ethylene glycol monomethyl ether 0.46%, morpholine 60.31%, all the other are high boiling material.
The glass continuous rectification apparatus is adopted in test, rectifying tower 1 internal diameter 25mm, adopt the Dixon ring filler of Φ 3, rectifying section packed height 500mm, stripping section are two sections, the upper end highly is 400mm, the lower end is 200mm, and the electrically heated glass bilayer sleeve is adopted in the insulation of tower joint, and the tower still is the outer circulation heating kettle, reflux ratio adopts electro-magnet and rly. control, and technical process is referring to accompanying drawing.Raw material and superheated vapo(u)r generation water all adopt constant-flux pump to carry.
Connect the water coolant of overhead condensation water cooler (3), make condenser enter working order.Deionized water is vaporized in water pump (5) will be squeezed into vaporizer (6), water vapour after the vaporization enters into the stripping section of glass rectifying tower (1) again through superheater (7) heating, when the vapour condensation phenomenon appears in cat head, start raw material fresh feed pump (8), after preheater (9) preheating, enter in the glass rectifying tower (1), the cat head mixed vapour is after condensate cooler (3) condensation, and the part extraction enters in the front-end volatiles jar (4), partial reflux.When the tower bottoms position reaches 35% left and right sides, start tower still reboiler (2).The extraction that the tower still takes off the thick product of ether utilizes the overflow mode.
The underlying condition of this operation is: the cat head working pressure is a normal atmosphere, 97～99 ℃ of cat head service temperatures, and tower still service temperature is 118～127 ℃.The raw material inlet amount is 1.0ml/min, be 1.03g/min, the flow of steam water is 0.43～0.86ml/min, the mass rate ratio that is the direct heating vapor quality flow and the first lightness-removing column charging ethylene glycol monomethyl ether impurity is (90～180): 1, temperature is 115～125 ℃, and reflux ratio is (2.0～4.0): 1.
Embodiment 1
The cat head working pressure is a normal atmosphere, 98 ℃ of cat head service temperatures, and tower still service temperature is 115 ℃.The thick product inlet amount of morpholine is 1.0ml/min, be 1.03g/min, the de-ionized water flow rate that the generation steam is used is 0.43ml/min, and reflux ratio is 3: 1, the mass rate ratio of direct heating vapor quality flow and rectifying tower 1 charging ethylene glycol monomethyl ether impurity is 90: 1, and temperature is 120 ℃.
Tower bottoms reaction result composed as follows is as follows: water 3.68%, and N-methylmorpholine 0.01%, N-ethylmorpholine 0.01%, ethylene glycol monomethyl ether 0.06%, morpholine 90.27%, all the other are high boiling material.Reaction result composed as follows is as follows: water 3.68%, and N-methylmorpholine 0.01%, N-ethylmorpholine 0.01%, ethylene glycol monomethyl ether 0.06%, morpholine 90.27%, all the other are high boiling material.
Table 1 provides the data of embodiment 2～embodiment 11, and tower bottoms promptly takes off N-methylmorpholine in the thick product of ether, N-ethylmorpholine, and ethylene glycol monomethyl ether greatly reduces, and the purity of morpholine significantly improves.
Claims (2)
1. a method that removes ethylene glycol monomethyl ether impurity in the thick product of morpholine device is characterized in that, is provided with rectifying tower (1), establishes reboiler (2) under the tower, and cat head is established condensate cooler (3), front-end volatiles jar (4); The deammoniation tower tower bottoms is after fresh feed pump (8) send preheater (9) to be heated to 110 ℃～120 ℃ in the morpholine device, enter rectifying tower (1) middle part, deionized water send vaporizer (6) gasification through water pump (5), again through superheater (7), be heated to 115 ℃～125 ℃, enter rectifying tower (1) bottom; Temperature at the bottom of rectifying tower (1) tower is 118 ℃～127 ℃; Rectifying tower (1) tower top pressure is a normal atmosphere, 97 ℃～99 ℃ of temperature, overhead vapours is advanced condensate cooler (3) condensation and is cooled off laggard phlegma storage tank (4), a phlegma part is back to rectifying tower (1), reflux ratio is (2.0～4.0): 1, the gold-plating branch advances next process before the cat head, and the discharging of rectifying tower (1) tower still is to finish the raw morpholine product that removes ethylene glycol monomethyl ether, as the raw material of later separation operation.
2. according to the described method that removes ethylene glycol monomethyl ether impurity in the thick product of morpholine device of claim 1, its process is that rectifying tower (1) is carried the direct superheated vapour of introducing in the gold-plating section, the continuous rectification operation, finish N-methylmorpholine in the morpholine device deamination tower bottoms, removing of N-ethylmorpholine by product and ethylene glycol monomethyl ether impurity, and at cat head as the front-end volatiles extraction, take off the thick product of ether in the tower still and do not contain or contain micro-N-methylmorpholine, N-ethylmorpholine by product and ethylene glycol monomethyl ether component, it is characterized in that, the mass flux ratio of ethylene glycol monomethyl ether impurity is (90～180) in the mass rate of superheated vapour and the deammoniation tower supplied materials: 1, and the temperature of superheated vapour is 115 ℃～125 ℃.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 201010516869 CN102002019A (en) | 2010-10-18 | 2010-10-18 | Method for removing ethylene glycol monomethyl ether impurity in coarse product of morpholine device |
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| Application Number | Priority Date | Filing Date | Title |
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| CN 201010516869 CN102002019A (en) | 2010-10-18 | 2010-10-18 | Method for removing ethylene glycol monomethyl ether impurity in coarse product of morpholine device |
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| CN 201010516869 Pending CN102002019A (en) | 2010-10-18 | 2010-10-18 | Method for removing ethylene glycol monomethyl ether impurity in coarse product of morpholine device |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019162120A1 (en) | 2018-02-22 | 2019-08-29 | Basf Se | Method for depleting 2-methoxyethanol (moe) |
| WO2019162121A1 (en) | 2018-02-22 | 2019-08-29 | Basf Se | Method for the continuous separation by distillation of mixtures that contain morpholine (mo), monoaminodiglycol (adg), ammonia, water and methoxyethanol (moe) |
| CN110563669A (en) * | 2019-10-09 | 2019-12-13 | 四川鸿鹏新材料有限公司 | Method and device for improving morpholine purity |
| JP2021518334A (en) * | 2018-03-15 | 2021-08-02 | ビーエイエスエフ・ソシエタス・エウロパエアＢａｓｆ Ｓｅ | Method for removing methoxyethanol from a mixture containing methoxyethanol and morpholine |
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| CN1308023A (en) * | 2001-02-13 | 2001-08-15 | 安徽阜阳化工总厂 | Heat-containing effuent recovering and utilizing process and equipment for morpholine preparation |
| CN1830971A (en) * | 2006-04-26 | 2006-09-13 | 吉林化工学院 | Method for producing marpholine and monoethylamine using by-products N-ethylamine from morpholine prodn. installation as raw material |
| CN101613327A (en) * | 2009-07-25 | 2009-12-30 | 安徽昊源化工集团有限公司 | A kind of device and production technique thereof of protecting morpholine catalyst |
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2010
- 2010-10-18 CN CN 201010516869 patent/CN102002019A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1308023A (en) * | 2001-02-13 | 2001-08-15 | 安徽阜阳化工总厂 | Heat-containing effuent recovering and utilizing process and equipment for morpholine preparation |
| CN1830971A (en) * | 2006-04-26 | 2006-09-13 | 吉林化工学院 | Method for producing marpholine and monoethylamine using by-products N-ethylamine from morpholine prodn. installation as raw material |
| CN101613327A (en) * | 2009-07-25 | 2009-12-30 | 安徽昊源化工集团有限公司 | A kind of device and production technique thereof of protecting morpholine catalyst |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019162120A1 (en) | 2018-02-22 | 2019-08-29 | Basf Se | Method for depleting 2-methoxyethanol (moe) |
| WO2019162121A1 (en) | 2018-02-22 | 2019-08-29 | Basf Se | Method for the continuous separation by distillation of mixtures that contain morpholine (mo), monoaminodiglycol (adg), ammonia, water and methoxyethanol (moe) |
| CN111741949A (en) * | 2018-02-22 | 2020-10-02 | 巴斯夫欧洲公司 | Method for the continuous separation by distillation of a mixture comprising Morpholine (MO), monoaminodiglycol (ADG), ammonia, water and Methoxyethanol (MOE) |
| JP2021514376A (en) * | 2018-02-22 | 2021-06-10 | ビーエイエスエフ・ソシエタス・エウロパエアＢａｓｆ Ｓｅ | 2-Method for reducing methoxyethanol (MOE) |
| JP2021514378A (en) * | 2018-02-22 | 2021-06-10 | ビーエイエスエフ・ソシエタス・エウロパエアＢａｓｆ Ｓｅ | A method for continuously distilling a mixture containing morpholine (MO), monoaminodiglycol (ADG), ammonia, water and methoxyethanol (MOE). |
| US11214555B2 (en) | 2018-02-22 | 2022-01-04 | Basf Se | Method for depleting 2-methoxyethanol (MOE) |
| US11518749B2 (en) | 2018-02-22 | 2022-12-06 | Basf Se | Method for the continuous separation by distillation of mixtures that contain morpholine (MO), monoaminodiglycol (ADG), ammonia, water and methoxyethanol (MOE) |
| JP7237081B2 (en) | 2018-02-22 | 2023-03-10 | ビーエーエスエフ ソシエタス・ヨーロピア | Method for reducing 2-methoxyethanol (MOE) |
| JP7305661B2 (en) | 2018-02-22 | 2023-07-10 | ビーエーエスエフ ソシエタス・ヨーロピア | Process for continuously distillative separation of a mixture containing morpholine (MO), monoaminodiglycol (ADG), ammonia, water and methoxyethanol (MOE) |
| CN111741949B (en) * | 2018-02-22 | 2024-03-15 | 巴斯夫欧洲公司 | Method for continuously separating a mixture comprising Morpholine (MO), monoaminodiglycol (ADG), ammonia, water and Methoxyethanol (MOE) by distillation |
| JP2021518334A (en) * | 2018-03-15 | 2021-08-02 | ビーエイエスエフ・ソシエタス・エウロパエアＢａｓｆ Ｓｅ | Method for removing methoxyethanol from a mixture containing methoxyethanol and morpholine |
| CN110563669A (en) * | 2019-10-09 | 2019-12-13 | 四川鸿鹏新材料有限公司 | Method and device for improving morpholine purity |
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