CN102206196A - Method for recovering morpholine from acidic waste water containing morpholine - Google Patents
Method for recovering morpholine from acidic waste water containing morpholine Download PDFInfo
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- CN102206196A CN102206196A CN2011100924491A CN201110092449A CN102206196A CN 102206196 A CN102206196 A CN 102206196A CN 2011100924491 A CN2011100924491 A CN 2011100924491A CN 201110092449 A CN201110092449 A CN 201110092449A CN 102206196 A CN102206196 A CN 102206196A
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- Prior art keywords
- morpholine
- waste water
- acid
- reclaims
- solution
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Abstract
The invention discloses a method for recovering morpholine from acidic waste water containing morpholine, which comprises: concentrating the acidic waste water containing morpholine, regulating pH value to precipitate a solid, filtering and distilling; adding adequate solid alkali; standing, dimixing to obtain a morpholine organic layer, adding drying agent into the morpholine organic layer, stirring, drying and standing overnight; and filtering again to obtain coarse morpholine, separating and purifying to obtain morpholine product. In the invention, equipment needed is less, investment is small, operation is simple, large-scale production is easy, and the reutilization rate of resources is improved; and the indexes of the recovered morpholine all reach quality standards of raw material morpholine, the morpholine can be recycled in production, the resource utilization rate in the production and use processes of morpholine are improved, production cost is lowered, and economic benefit and social benefit are created.
Description
Technical field
The invention belongs to chemical waste liquid recycling field, specially refer to the method that from the acid waste liquid that contains morpholine, reclaims morpholine.
Background technology
In the production process of relevant use morpholine, regular meeting produces some trade effluents that contain morpholine, if with these direct discharging of waste water, not only wastes resource and also can pollute environment.The method that reclaims morpholine at present mainly is an ion exchange method, it is that the trade effluent that will contain morpholine passes through Zeo-karb, with elutriant morpholine is eluted then, again the morpholine in the elutriant is separated, at last with behind the morpholine purifying again recovery set use.The weak point of this method is that operation steps is many, and the cycle is longer, and required equipment is many, and production capacity is restricted, the input cost height.
Summary of the invention
For solving above technical problem, the object of the present invention is to provide a kind of equipment simple, less investment, the method that from the acid waste water that contains morpholine, reclaims morpholine with low cost, workable.
The present invention seeks to realize like this:
A kind of method that from the acid waste water that contains morpholine, reclaims morpholine, carry out as follows:
A. earlier the acid waste water that contains morpholine is concentrated, remove most water, add concentration of lye again in the waste water after concentrating and be pH value to 8 ~ 14 that 1.0% ~ 40% alkali is regulated waste water, separate out a large amount of solids, then filtration;
B. the waste water after will filtering again distills;
C. under 25 ℃ ~ 65 ℃ condition, in step b distillate, add the solid alkali of capacity;
D. behind the standing demix, branch vibration layer obtains moisture 1.0%～10.0% morpholine organic layer, adds siccative and stir dried overnight in the morpholine organic layer;
E. filter once more, obtain moisture content, the crude product morpholine is separated purification promptly get the product morpholine at 0.1% ~ 10% crude product morpholine.
The content that step a contains morpholine in the waste water of morpholine is 0.5% ~ 90%; Contained acid is one or both in hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, formic acid, acetate, methylsulfonic acid, Phenylsulfonic acid, the oxalic acid in the acid waste liquid.
Alkali lye is Na among the above-mentioned steps a
2CO
3Solution, NaHCO
3Solution, K
2CO
3Solution, NaOH solution, KOH solution, Ca(OH)
2In solution, the ammoniacal liquor one or more.
Waste water after above-mentioned steps a concentrates adds alkali separate out solid after, naturally cool to 0 ℃ ~ 60 ℃, refilter.
Solid alkali is Na among the above-mentioned steps c
2CO
3, NaHCO
3, K
2CO
3, NaOH, KOH, Ca (OH)
2, Mg (OH)
2, Ba (OH)
2, sodium ethylate, a kind of in the potassium tert.-butoxide or more than 2 kinds.
Leave standstill among the above-mentioned steps d nature cool to-5 ℃ ~ 50 ℃ after layering again.
Siccative described in the above-mentioned steps d is an anhydrous Na
2SO
4, anhydrous MgSO
4, anhydrous CaCl
2, a kind of among the solid NaOH, solid KOH, 4A molecular sieve or more than 2 kinds.
Separating and purifying method among the above-mentioned steps e is the method for rectifying.
Beneficial effect: equipment required for the present invention is few, invests for a short time, simple to operate, is easy to large-scale production, has improved resource utilization; The every index that reclaims morpholine all meets the quality standard of raw material morpholine, and recycling in can be used for producing and so forth, improved the resource utilization of morpholine in the production use, reduced production cost, has good economic benefit and social benefit.
Embodiment
Embodiment 1
To contain in the enamel reaction still of waste liquid 500kg suction 1000L of morpholine, and evenly stir down, normal pressure steams 280kg water, is cooled to 60 ℃ naturally, slowly drips 15% KOH solution 430kg, and the pH value of solution value is about 10 at this moment.When treating that temperature is reduced to 30 ℃, centrifugally get rid of filter, with the filtrate reconcentration, concentrated solution 190kg. treats to add 75kg solid Na after solution temperature is reduced to 50 ℃
2CO
3, be cooled to 10 ℃ again, divide to fall water layer to obtain moisture 5.8% morpholine 132kg.In above-mentioned morpholine, add 6 kilograms of anhydrous MgSO
4Dried overnight is filtered, and gets crude product morpholine 126kg.At last the crude product morpholine is carried out rectifying, collect main distillate fraction and obtain product morpholine 96kg, purity is 99.4%, and front-end volatiles and tailings collection are incorporated next batch into and applied mechanically.
Example 2
To contain in the enamel reaction still of waste liquid 2000kg suction 3000L of morpholine, and evenly stir and steam 1200kg water down, and be cooled to 50 ℃ naturally, and slowly drip 25% NaOH solution 1500kg, the pH value of solution value is about 11 at this moment.When treating that temperature is reduced to 25 ℃, centrifugally get rid of filter, with the filtrate reconcentration, concentrated solution 800kg.Add 300kg solid NaOH after being cooled to 60 ℃, be cooled to 5 ℃ again, divide to fall water layer to get moisture 5.6% morpholine 520kg.In above-mentioned morpholine, add 25 kilograms of anhydrous Na
2SO
4Dried overnight is filtered, and gets crude product morpholine 508kg.At last the crude product morpholine is carried out rectifying, collect main distillate fraction and obtain product morpholine 378kg, purity is 99.5%, and front-end volatiles and tailings are collected and entered next batch and apply mechanically.
Example 3
To contain in the enamel reaction still of waste liquid 2000kg suction 3000L of morpholine, and evenly stir and steam 1300kg water down, be cooled to 40 ℃ naturally, the slow KOH solution 1250kg of Dropwise 35 %, the pH value of solution is about 13 at this moment.When treating that temperature is reduced to 20 ℃, centrifugally get rid of filter, with the filtrate reconcentration, concentrated solution 828kg. adds the 315kg solid KOH after being cooled to 50 ℃, be cooled to 15 ℃ again, divide to fall water layer to obtain moisture 4.8% morpholine 518kg.In above-mentioned morpholine, add 25 kilograms of anhydrous CaCl
2Dried overnight is filtered, and gets crude product morpholine 503kg.At last the crude product morpholine is carried out rectifying, get product morpholine 369kg, purity is 99.6%, and front-end volatiles and tailings are collected and entered next batch and apply mechanically.
Example 4
To contain in the enamel reaction still of waste liquid 2000kg suction 3000L of morpholine, and evenly stir and steam 1400kg water down, and be cooled to 30 ℃ naturally, and slowly drip 40% NaOH solution 950kg, the pH value of solution value is about 14 at this moment.When being cooled to 15 ℃, centrifugally get rid of filter, with the filtrate reconcentration, concentrated solution 832kg. treats to add 320kg solid NaOH behind the liquid temperature drop to 50 ℃, be cooled to 10 ℃ again, divide to fall water layer to obtain moisture 4.1% morpholine 523kg.In above-mentioned morpholine, add 25 kilograms of solid NaOH dried overnight, filter, get crude product morpholine 510kg.With the rectifying of crude product morpholine, get main distillate fraction 385kg, morpholine purity is 99.5%, front-end volatiles and tailings are collected and are entered next batch and apply mechanically.
Example 5
To contain in the enamel reaction still of waste liquid 2000kg suction 3000L of morpholine, and evenly stir and steam 1000kg water down, and be cooled to 20 ℃ naturally, and slowly drip 30% KOH solution 1270kg, the pH value of solution value is about 12 at this moment.When waiting to be cooled to 10 ℃, centrifugally get rid of filter, with the filtrate reconcentration, concentrated solution 829kg. treats to add the 320kg solid KOH when solution temperature is reduced to 35 ℃, be cooled to 25 ℃ again, divide to fall water layer to obtain moisture 3.9% morpholine 518kg.In above-mentioned morpholine, add 25 kilograms of KOH dried overnight, filter, get crude product morpholine 508kg.With the rectifying of crude product morpholine, get product morpholine 376kg, purity is 99.6%, front-end volatiles and tailings are collected and are entered next batch and apply mechanically.
Claims (8)
1. method that from the acid waste water that contains morpholine, reclaims morpholine, carry out as follows:
A. earlier the acid waste water that contains morpholine is concentrated, add pH value to 8 ~ 14 that alkali is regulated waste water in the waste water after concentrating again, separate out solid, filter then;
B. the waste water after will filtering again distills;
C. under 25 ℃ ~ 65 ℃ condition, in step b distillate, add the solid alkali of capacity;
D. standing demix obtains the morpholine organic layer, adds siccative and stir dried overnight in the morpholine organic layer;
E. filter once more, obtain the crude product morpholine, the crude product morpholine is separated purification promptly get the product morpholine.
2. according to the described method that reclaims morpholine from the acid waste water that contains morpholine of claim 1, it is characterized in that: the content that described step a contains morpholine in the waste water of morpholine is 0.5% ~ 90%; Contained acid is one or both in hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, formic acid, acetate, methylsulfonic acid, Phenylsulfonic acid, the oxalic acid in the acid waste liquid.
3. according to the described method that reclaims morpholine from the acid waste water that contains morpholine of claim 1, it is characterized in that: described step a alkali lye is Na
2CO
3Solution, NaHCO
3Solution, K
2CO
3Solution, NaOH solution, KOH solution, Ca(OH)
2In solution, the ammoniacal liquor one or more.
4. according to the described method that from the acid waste water that contains morpholine, reclaims morpholine of claim 1, it is characterized in that: the waste water after step a concentrates adds alkali separate out solid after, naturally cool to 0 ℃ ~ 60 ℃, refilter.
5. according to the described method that reclaims morpholine from the acid waste water that contains morpholine of claim 1, it is characterized in that: the solid alkali of described step c is Na
2CO
3, NaHCO
3, K
2CO
3, NaOH, KOH, Ca (OH)
2, Mg (OH)
2, Ba (OH)
2, sodium ethylate, a kind of in the potassium tert.-butoxide or more than 2 kinds.
6. according to the described method that from the acid waste water that contains morpholine, reclaims morpholine of claim 1, it is characterized in that: leave standstill in the steps d nature cool to-5 ℃ ~ 50 ℃ after layering again.
7. according to the described method that reclaims morpholine from the acid waste water that contains morpholine of claim 1, it is characterized in that: siccative is an anhydrous Na in the described steps d
2SO
4, anhydrous MgSO
4, anhydrous CaCl
2, a kind of among the solid NaOH, solid KOH, 4A molecular sieve or more than 2 kinds.
8. according to the described method that reclaims morpholine from the acid waste water that contains morpholine of claim 1, it is characterized in that: the separating and purifying method among the described step e is the method for rectifying.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110092449 CN102206196B (en) | 2011-04-13 | 2011-04-13 | Method for recovering morpholine from acidic waste water containing morpholine |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110092449 CN102206196B (en) | 2011-04-13 | 2011-04-13 | Method for recovering morpholine from acidic waste water containing morpholine |
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|---|---|
| CN102206196A true CN102206196A (en) | 2011-10-05 |
| CN102206196B CN102206196B (en) | 2013-03-13 |
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|---|---|---|---|
| CN 201110092449 Active CN102206196B (en) | 2011-04-13 | 2011-04-13 | Method for recovering morpholine from acidic waste water containing morpholine |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103936214A (en) * | 2013-08-02 | 2014-07-23 | 浙江赛特膜技术有限公司 | Method for bipolar membrane electrodialysis treatment of 3-aminopyrazole-4-carboxamide hemisulfate production wastewater and recycling of sulfuric acid |
| CN106746127A (en) * | 2016-08-19 | 2017-05-31 | 江苏好收成韦恩农化股份有限公司 | A kind of ethofumesate produces waste water reclaiming recovery process |
| CN108047164A (en) * | 2018-02-01 | 2018-05-18 | 山东瑞博龙化工科技股份有限公司 | The Application way of morpholine is recycled in a kind of acryloyl morpholine production technology |
| 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 |
| CN112479459A (en) * | 2020-11-19 | 2021-03-12 | 万华化学集团股份有限公司 | Preparation method of preferential water permeable membrane, morpholine wastewater treatment method and morpholine substance recovery method |
| 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) |
| 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) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2776972A (en) * | 1954-09-27 | 1957-01-08 | Jefferson Chem Co Inc | Recovery of morpholine from aqueous solutions thereof |
| CN101538240A (en) * | 2009-03-12 | 2009-09-23 | 浙江升华拜克生物股份有限公司 | Method for recycling solid wastes in carbonate production |
-
2011
- 2011-04-13 CN CN 201110092449 patent/CN102206196B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2776972A (en) * | 1954-09-27 | 1957-01-08 | Jefferson Chem Co Inc | Recovery of morpholine from aqueous solutions thereof |
| CN101538240A (en) * | 2009-03-12 | 2009-09-23 | 浙江升华拜克生物股份有限公司 | Method for recycling solid wastes in carbonate production |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103936214A (en) * | 2013-08-02 | 2014-07-23 | 浙江赛特膜技术有限公司 | Method for bipolar membrane electrodialysis treatment of 3-aminopyrazole-4-carboxamide hemisulfate production wastewater and recycling of sulfuric acid |
| CN106746127A (en) * | 2016-08-19 | 2017-05-31 | 江苏好收成韦恩农化股份有限公司 | A kind of ethofumesate produces waste water reclaiming recovery process |
| CN108047164A (en) * | 2018-02-01 | 2018-05-18 | 山东瑞博龙化工科技股份有限公司 | The Application way of morpholine is recycled in a kind of acryloyl morpholine production technology |
| 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) |
| 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) |
| 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 |
| CN112479459A (en) * | 2020-11-19 | 2021-03-12 | 万华化学集团股份有限公司 | Preparation method of preferential water permeable membrane, morpholine wastewater treatment method and morpholine substance recovery method |
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|---|---|
| CN102206196B (en) | 2013-03-13 |
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Effective date of registration: 20220414 Address after: 442500 No.1 Tiansheng Road, Yunxian Economic Development Zone, Shiyan City, Hubei Province Patentee after: HUBEI TIANSHENG PHARMACEUTICAL Co.,Ltd. Address before: 408302 No. 138, Yuwu Road, Xinmin Town, Dianjiang County, Chongqing Patentee before: CHONGQING WAYCOME PHARMACEUTICAL Co.,Ltd. |
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