CN102603484A - Method for separating allyl alcohol and water by extractive distillation with N-methyl-pyrrolidone - Google Patents
Method for separating allyl alcohol and water by extractive distillation with N-methyl-pyrrolidone Download PDFInfo
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- CN102603484A CN102603484A CN2012100445557A CN201210044555A CN102603484A CN 102603484 A CN102603484 A CN 102603484A CN 2012100445557 A CN2012100445557 A CN 2012100445557A CN 201210044555 A CN201210044555 A CN 201210044555A CN 102603484 A CN102603484 A CN 102603484A
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Abstract
The invention discloses a method of separating allyl alcohol and water by extractive distillation with N-methyl-pyrrolidone, comprising the following steps: adding N-methyl-pyrrolidone used as an extractant and raw material liquid of allyl alcohol and water separately into an extractive distillation column according to a certain solvent ratio, removing water component at the top of the extractive distillation column, then obtaining more than 99.5% allyl alcohol product at the top of a solvent recovery column, and returning the extractant recycled at a column bottom into the extractive distillation column for recycling. The method provided by the invention adopts N-methyl-pyrrolidone as the extractant and separates allyl alcohol and water solution by the extractive distillation, and is an efficient and energy-saving separation process.
Description
Technical field
The invention belongs to the process method of chemical separation process, relate to a kind of method that adopts the N-Methyl pyrrolidone extracting rectifying to separate the allyl alcohol and water.
Background technology
Produce in the production technique of epoxy chloropropane in the allyl acetate method; Vinyl carbinol solution is the intermediates of allyl acetate hydrolysis system vinyl carbinol; Its composition is about the vinylcarbinol of 70wt%, water and a small amount of allyl aldehyde and the acetic acid of 30wt%; According to producing 50000 tons of epoxy chloropropane production equipments per year, the nearly 30,000 tons intermediates vinylcarbinol of annual production.
Vinyl carbinol has another name called vinylcarbinol; Colourless transparent liquid, boiling point are 97.1 ℃, and high-pure propylene alcohol is the midbody of medicine, agricultural chemicals and spices; Main verivate also is used to synthesize, glycerine, 1; 4-butyleneglycol and 3-bromopropylene or the like are still produced important organic synthesis raw materials such as softening agent and engineering plastics simultaneously, and its carbonate can be high-grade optical resin CR-39, TAC linking agent DAP.Along with the development in current market, to the increasing demand increase of high-purity vinyl carbinol.Because the allyl alcohol and water is an azeotropic system; Adopt conventional conventional distillation method can't obtain the highly purified allyl alcohol product; The refining purification separation processes of current high-purity vinyl carbinol has only the well-known chemical enterprise of external minority to grasp, but this technology is blocked always and on market, do not have open.
China's document (Jiangsu chemical industry; 1989 (4): 48～50) disclose a kind of benzene that adopts and carried out the research that intermittent azeotropic rectifying separates the allyl alcohol and water as entrainer; Can obtain the vinyl carbinol more than the 99.0w%t through the lab scale experiment; But its research only rests on the laboratory study stage, evaluation is not made in its industrialized enforcement.
USP (US 1279059) discloses a kind of The Dow Chemical Co. (US) 2030 Dow Center, Abbott Road, Midland, Michigan 48640, and has adopted benzene as entrainer extracting and separating allyl alcohol and water; Pass through operation conditions optimization; Obtain the above vinyl carbinol of 99.0w%t, this technology exists entrainer and consumes the more and bigger shortcoming of process energy consumption.
Chinese patent (CN86104244) discloses a kind of Japanese Showa Denko K. K and has adopted potassium phosphate salt the saltout vinyl carbinol and the aqueous solution; Separate through precise distillation then and can obtain the vinyl carbinol more than the 99.5w%t; This technology is industriallization at present, grows, invests shortcomings such as big and complicated operation but exist technical process.
Seeing that vinyl carbinol and water electrode difficulty are separated, the present situation of high energy consumption, develop a kind of separating technology efficiently such as methods such as extracting rectifying, membrane distillation or azeotropic distillation and enable to separate effectively, will have important economic benefit and social benefit.
Summary of the invention
The objective of the invention is to overcome the deficiency of prior art, a kind of method that adopts extracting rectifying to separate the allyl alcohol and water is provided, thereby can obtains the highly purified allyl alcohol product, the extraction agent N-Methyl pyrrolidone can be recycled simultaneously.
The invention provides a kind of separating technology of extracting rectifying allyl alcohol and water, mainly comprise abstraction distillation system, solvent recovering system and vacuum system.The key step of accomplishing technology of the present invention is following:
(1) extracting rectifying process: the liquid stock 2 of allyl alcohol and water from extractive distillation column 3 middle parts, extraction agent 1 adds from extractive distillation column top by certain solvent ratio; Overhead vapours obtains water 5 with certain reflux ratio extraction after condensing surface 4 condensations; The extraction agent solution 7 that is rich in vinyl carbinol gets into solvent recovery tower 8, for it heat power is provided through reboiler 6 in the tower;
(2) solvent recuperation process: the extraction agent solution 7 that is rich in vinyl carbinol gets into solvent recovery tower 8 middle parts; Overhead vapours after condensing surface 9 condensations with certain reflux ratio extraction vinylcarbinol product; The extraction agent that reclaims at the bottom of the tower is back to extractive distillation column and recycles, and for it heat power is provided through reboiler 11 in the tower.
Described extraction agent is a N-Methyl pyrrolidone, and its specification is more than the 99.0wt%.
Step (1) described " solvent ratio " is meant the volume ratio of extraction agent and allyl alcohol and water liquid stock, and solvent ratio is 2.5～4: 1.
In step (1), the number of theoretical plate of said extractive distillation column is preferably 40～45, and the cat head working pressure is preferably 100～105kPa, and solvent ratio is 2.5～4: 1, and reflux ratio is 1～5: 1, and tower top temperature is 100～105 ℃, and tower still temperature is 160～165 ℃.
In step (2), the number of theoretical plate of said solvent recovery tower is preferably 50～60, and the cat head working pressure is 10～20kPa, and reflux ratio is 2～4: 1, and tower top temperature is preferably 50～55 ℃, and tower still temperature is preferably 135～140 ℃.
The method of N-Methyl pyrrolidone SX rectifying separation allyl alcohol and water of the present invention has following characteristics:
(1) adopt extraction rectification technique can separate the vinyl carbinol and the aqueous solution effectively; The vinyl carbinol product that obtains is greater than 99.5wt%; The extraction agent price is lower, wide material sources, separation process scheme simple, process cost is lower, the process automation degree is high, has favorable economic benefit and social benefit.
(2) new separating technology has considered that the heat of internal process logistics is integrated, makes that the energy consumption of whole separating technology is lower, is a kind of energy-efficient separating technology.
Description of drawings
Fig. 1 is the extracting rectifying separation process scheme figure of allyl alcohol and water of the present invention.
The 1-extraction agent; The 2-liquid stock; The 3-extractive distillation column; 4-extractive distillation column condensing surface; The 5-fishery products; 6-extractive distillation column reboiler; 7-extracting rectifying tower bottoms; The 8-solvent recovery tower; 9-solvent recovery tower condensing surface; 10-vinylcarbinol product; 11-solvent recovery tower reboiler; 12-solvent recuperation tower bottoms (extraction agent of recovery).
Embodiment
Below in conjunction with embodiment, further specify the present invention, but the present invention is not limited to embodiment.
Certain enterprise's allyl acetate hydrolysis prepares the intermediates vinylcarbinol solution of epoxy chloropropane production process, sees table 1 through the vinylcarbinol and the water liquid stock composition that obtain after the initial gross separation.
Table 1 vinylcarbinol and water liquid stock are formed
| Component | Form (wt%) |
| Water | 30 |
| Vinyl carbinol | 70 |
Allyl alcohol and water liquid stock 2 is that 1000kg/hr gets into extractive distillation column 3 middle parts with the flow, and extraction agent N-Methyl pyrrolidone 1 gets into extractive distillation column 3 tops according to 2.5: 1 volume ratio, and this tower number of theoretical plate is 40; Tower top pressure is 100kPa, and tower top temperature is 100 ℃, and tower still temperature is 160 ℃; Overhead vapours is the water 5 that 1: 1 extraction product purity is 99.4wt% with reflux ratio after condensing surface 5 condensations; The extraction agent solution 7 that is rich in vinyl carbinol at the bottom of the tower gets into solvent recovery tower 8 middle parts, and this tower number of theoretical plate is 50, and tower top pressure is 10kPa; Tower top temperature is 50 ℃; Tower still temperature is 135 ℃, and overhead vapours is that 2: 1 extraction product purities are the vinyl carbinol product 10 more than the 99.0wt% with reflux ratio after condensing surface 9 condensations, and solvent recuperation tower bottoms 12 is the regenerated extraction agent and can be recycled.
Allyl alcohol and water liquid stock 2 is that 1000kg/hr gets into extractive distillation column 3 middle parts with the flow, and extraction agent N-Methyl pyrrolidone 1 gets into extractive distillation column 3 tops according to 3: 1 volume ratio, and this tower number of theoretical plate is 42; Tower top pressure is 103kPa, and tower top temperature is 102 ℃, and tower still temperature is 162.6 ℃; Overhead vapours is the water 5 that 3: 1 extraction product purities are 99.4wt% with reflux ratio after condensing surface 5 condensations; The extraction agent solution 7 that is rich in vinyl carbinol at the bottom of the tower gets into solvent recovery tower 8 middle parts, and this tower number of theoretical plate is 55, and tower top pressure is 15kPa; Tower top temperature is 52 ℃; Tower still temperature is 138 ℃, and overhead vapours is that 3: 1 extraction product purities are the vinylcarbinol product 10 more than the 99.5wt% with reflux ratio after condensing surface 9 condensations, and solvent recuperation tower bottoms 12 is the regenerated extraction agent and can be recycled.
Allyl alcohol and water liquid stock 2 is that 1000kg/hr gets into extractive distillation column 3 middle parts with the flow, and extraction agent N-Methyl pyrrolidone 1 gets into extractive distillation column 3 tops according to 4: 1 volume ratio, and this tower number of theoretical plate is 45; Tower top pressure is 105kPa, and tower top temperature is 105 ℃, and tower still temperature is 165 ℃; Overhead vapours is the water 5 that 5: 1 extraction product purities are 99.4wt% with reflux ratio after condensing surface 5 condensations; The extraction agent solution 7 that is rich in vinyl carbinol at the bottom of the tower gets into solvent recovery tower 8 middle parts, and this tower number of theoretical plate is 60, and tower top pressure is 20kPa; Tower top temperature is 55 ℃; Tower still temperature is 140 ℃, and overhead vapours is that 4: 1 extraction product purities are the vinylcarbinol product 10 more than the 99.5wt% with reflux ratio after condensing surface 9 condensations, and solvent recuperation tower bottoms 12 is the regenerated extraction agent and can be recycled.
A kind of method that adopts the N-Methyl pyrrolidone extracting rectifying to separate the allyl alcohol and water that the present invention proposes; Be described through preferred embodiment; Person skilled obviously can be in not breaking away from content of the present invention, spirit and scope to equipment as herein described with the preparation method changes or suitably change and combination, realize the present invention's technology.Special needs to be pointed out is, the replacement that all are similar and change apparent to those skilled in the artly, they are regarded as and are included in spirit of the present invention, scope and the content.
Claims (5)
1. method that adopts extracting rectifying to separate the allyl alcohol and water, its step is following:
(1) extracting rectifying unit: extraction agent (1) gets in the tower from extractive distillation column (3) top and middle part respectively by certain solvent ratio with the liquid stock (3) of allyl alcohol and water; Cat head obtains the above aqueous distillate (5) of 99.9wt%, obtains being rich in the extraction agent solution (7) of vinyl carbinol at the bottom of the tower;
(2) solvent recovery unit: the extraction agent solution (7) that is rich in vinyl carbinol is discharged entering solvent recovery tower (8) middle part at the bottom of extractive distillation column; Cat head obtains the above vinyl carbinol product (10) of 99.5wt%; The tower still is the recovery extraction agent (11) of discharge, returns in the extractive distillation column (3) to recycle.
2. according to the described method of claim 1, it is characterized in that said extraction agent is a N-Methyl pyrrolidone, the product specification of N-Methyl pyrrolidone is greater than 99.0wt%.
3. method according to claim 1 and 2, the volume ratio that it is characterized in that extraction agent and liquid stock is 2.5～4: 1.
4. method according to claim 1 and 2; The operational condition that it is characterized in that extractive distillation column is: number of theoretical plate is 40～45, and the cat head working pressure is 100～105kPa, and solvent ratio is 2.5～4: 1; Reflux ratio is 1～5: 1; Tower top temperature is 100～105 ℃, and tower still temperature is 160～165 ℃, and the extraction agent inlet temperature of stabilizer is 100～105 ℃.
5. method according to claim 1 and 2, it is characterized in that the operational condition of solvent recovery tower is: number of theoretical plate is 50～60, the cat head working pressure is 10～20kPa; Reflux ratio is 2～4: 1; More preferably 3: 1, tower top temperature was 50～55 ℃, and tower still temperature is 135～140 ℃.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201210044555.7A CN102603484B (en) | 2012-02-23 | 2012-02-23 | Method for separating allyl alcohol and water by extractive distillation with N-methyl-pyrrolidone |
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| CN201210044555.7A CN102603484B (en) | 2012-02-23 | 2012-02-23 | Method for separating allyl alcohol and water by extractive distillation with N-methyl-pyrrolidone |
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| CN102603484A true CN102603484A (en) | 2012-07-25 |
| CN102603484B CN102603484B (en) | 2014-07-02 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106431841A (en) * | 2016-09-19 | 2017-02-22 | 青岛科技大学 | Method for separating isobutanol and n-heptane mixture through heat integration extractive distillation |
| CN107698428A (en) * | 2017-09-27 | 2018-02-16 | 湖北绿色家园材料技术股份有限公司 | A kind of method of moisture in separation allyl alcohol |
| CN109134198A (en) * | 2018-11-08 | 2019-01-04 | 山东科技大学 | A kind of method of separation of extractive distillation tetrafluoropropanol and water azeotropic mixture |
| CN114262261A (en) * | 2022-01-06 | 2022-04-01 | 万华化学集团股份有限公司 | Separation method of 2-methyl-3-butyne-2-ol crude product |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2605216A (en) * | 1944-04-15 | 1952-07-29 | Shell Dev | Process for separating the azeotropic mixture of allyl alcohol and allyl acetate |
| JPS62149638A (en) * | 1985-12-24 | 1987-07-03 | Showa Denko Kk | Purification of allyl alcohol |
| CN1325373A (en) * | 1998-11-09 | 2001-12-05 | 阿科化学技术公司 | Allyl alcohol purification |
| CN1560008A (en) * | 2004-03-09 | 2005-01-05 | 南京师范大学 | Process for separating ethandiol, mono methyl ether, isopropyl alcohol and water combined by extracting and axeotropy |
-
2012
- 2012-02-23 CN CN201210044555.7A patent/CN102603484B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2605216A (en) * | 1944-04-15 | 1952-07-29 | Shell Dev | Process for separating the azeotropic mixture of allyl alcohol and allyl acetate |
| JPS62149638A (en) * | 1985-12-24 | 1987-07-03 | Showa Denko Kk | Purification of allyl alcohol |
| CN1325373A (en) * | 1998-11-09 | 2001-12-05 | 阿科化学技术公司 | Allyl alcohol purification |
| CN1560008A (en) * | 2004-03-09 | 2005-01-05 | 南京师范大学 | Process for separating ethandiol, mono methyl ether, isopropyl alcohol and water combined by extracting and axeotropy |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106431841A (en) * | 2016-09-19 | 2017-02-22 | 青岛科技大学 | Method for separating isobutanol and n-heptane mixture through heat integration extractive distillation |
| CN106431841B (en) * | 2016-09-19 | 2019-01-08 | 青岛科技大学 | A method of being thermally integrated separation of extractive distillation isobutanol and normal heptane mixture |
| CN107698428A (en) * | 2017-09-27 | 2018-02-16 | 湖北绿色家园材料技术股份有限公司 | A kind of method of moisture in separation allyl alcohol |
| CN107698428B (en) * | 2017-09-27 | 2022-09-20 | 湖北绿色家园材料技术股份有限公司 | Method for separating water in allyl alcohol |
| CN109134198A (en) * | 2018-11-08 | 2019-01-04 | 山东科技大学 | A kind of method of separation of extractive distillation tetrafluoropropanol and water azeotropic mixture |
| CN114262261A (en) * | 2022-01-06 | 2022-04-01 | 万华化学集团股份有限公司 | Separation method of 2-methyl-3-butyne-2-ol crude product |
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| CN102603484B (en) | 2014-07-02 |
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