CN101906020B - Novel process for purifying 1,2-propylene glycol by ester exchange method - Google Patents
Novel process for purifying 1,2-propylene glycol by ester exchange method Download PDFInfo
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- CN101906020B CN101906020B CN2010102445849A CN201010244584A CN101906020B CN 101906020 B CN101906020 B CN 101906020B CN 2010102445849 A CN2010102445849 A CN 2010102445849A CN 201010244584 A CN201010244584 A CN 201010244584A CN 101906020 B CN101906020 B CN 101906020B
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Abstract
The invention relates to a novel process for purifying 1,2-propylene glycol by an ester exchange method. The technical scheme comprises two steps of: reactive distillation and propylene glycol refining, wherein in the reactive distillation, 1,2-propylene glycol co-produced by a dimethyl carbonate device and demineralized water added with a deodoring agent are introduced into a reactive rectifying tower, the obtained material on the tower top is recycled by a process spent water removing treatment device, and the residue of the reactive rectifying tower obtained at the tower bottom enters a subsequent step 2 for separation; in the propylene glycol refining, a bottom material from the reactive rectifying tower enters a propylene glycol refining tower, a water-containing propylene glycol crude product obtained from the tower top is recycled; a high-purity medical propylene glycol product can be obtained from the upper side stream; and the material obtained from the tower bottom can be recycled. The process has the advantages that: impurities in the 1,2-propylene glycol are reacted with the added deodoring agent, the reacted impurities are convenient to separate from the product, and the 1,2-propylene glycol of which color, smell, purity and other indexes meet medical requirement can be obtained finally.
Description
One, technical field:
The present invention relates to a kind of method of purification of 1,2-PD, particularly a kind of novel process for purifying of ester-interchange method 1,2-PD.
Two, background technology:
1,2-PD is very important industrial chemicals, and the production technique of 1,2-PD can be divided into " hydration method " and " ester-interchange method " two kinds at present." hydration method " process using propylene oxide and water are raw material, react under catalyst-free or an acidic catalyst effect, get 1,2-PD through refining the purification again." hydration method " method technique is succinct, flow process short, and the 1,2-PD quality product of production is better.At present, pharmaceutical grade 1,2-PD on sale mostly is " hydration method " explained hereafter and gets on the market.And " ester-interchange method " production technique, take propylene carbonate, methyl alcohol as raw material, sodium methylate is simultaneously coproduction of Catalyst Production methylcarbonate 1,2-PD.Because " ester-interchange method " is joint process, a covering device is produced methylcarbonate and two kinds of products of 1,2-PD simultaneously, has obvious cost advantage; Flow process is long, side reaction is more but exist, thereby " ester-interchange method " produce 1, the easy variable color of 2-propylene glycol product, irritating smell are large, the propylene glycol quality product is relatively poor, can not reach the requirement of pharmaceutical grade propylene glycol, can't be in sector applications such as medicine, food, essence, spices, makeup and high-grade resins.
Cause 1, the reason of 2-propylene glycol poor product quality, to contain 1-methoxy-2-propanol, 2-methoxy-1-propanol, 1-hydroxyl-2-acetone, 1-(2-propenyl oxygen base)-2-propyl alcohol, 3-(1 in the product, 3-dimethyl butoxy)-2-butanols, 1,2-Propanal dimethyl acetal, methoxyl group-vinyl acetic monomer, 1, the 1-dihydroxyl-trace impurities such as 2-propyl alcohol.Total foreign matter content is about 0.10%～0.30%, and the content of some impurity only is about 0.005%.Therefore, adopt the conventional rectification mode, can't obtain the qualified 1,2-PD product of colourity and smell.The document of notification number US5527973 adopts and adds organic acid or mineral acid in the aqueous solution of 1,3-PD and eliminate carbonyl material in the 1,3-PD; All adopt solid acid as catalyzer in the document of notification number US6235948 and notification number CN1345710, so that the impurity in the 1,3-PD reacts; Notification number CN1176054C is mixed with the aqueous solution with 1,3-PD first, then adds the compound of NH2-Y in the aqueous solution, reacts in reactor.In University Of Tianjin's Master's thesis " catalytic refining of 1,2-PD ", adopting solid acid is the catalytic refining that catalyzer carries out 1,2-PD.And the 1,2-PD that this patent is produced for ester-interchange method adopts reaction rectification technique, carries out in the reaction fractionating tower so that reaction and distillation operation coexist, and still has no relevant report both at home and abroad.
Three, summary of the invention:
Purpose of the present invention is exactly the problem for the 1,2-PD poor product quality of existing ester-interchange method production, and a kind of novel process for purifying of ester-interchange method 1,2-PD is provided.
A kind of novel process for purifying of ester-interchange method 1,2-PD, its technical scheme comprise reactive distillation and the refining two portions of propylene glycol:
Reactive distillation: the 1,2-PD of carbonate device coproduction and the de-mineralized water of interpolation deodorization agent are sent into reaction fractionating tower, and the mass ratio of control de-mineralized water and 1,2-PD is 0.2～10: 1; Control reaction fractionating tower temperature of reaction is at 60 ℃～190 ℃; Reaction pressure is controlled at 0.05MPa～0.20MPa; Control of reflux ratio is 0.30～2.0; Reaction time is controlled at 0.35～2.0 hour, and the cat head material that obtains is through going the process spent water treatment unit to recycle, and the still liquid of the reaction fractionating tower that tower reactor obtains enters in the subsequent step 2 and separates;
Propylene glycol is refining: the reaction fractionating tower tower reactor material from step 1 enters in the propylene glycol treating tower, controls this column overhead service temperature: 70 ℃～130 ℃; 120 ℃～140 ℃ of top side line propylene glycol drop temperatures; 140 ℃～170 ℃ of tower reactor service temperatures; Working pressure: 7KPa～20KPa; Control of reflux ratio: 0.50～2.0, the moisture propylene glycol crude product that cat head obtains returns carbonate device and reprocesses utilization; The top side line can obtain the propylene glycol product of purity more than 99.99%, enters pharmaceutical grade propylene glycol finished product tank field after cooling; Contain propylene glycol, dipropylene glycol in the material that tower reactor obtains, this partial material can be returned carbonate device and reprocess utilization.
Above-mentioned deodorization agent mixes with de-mineralized water first, enters together and carries out reactive distillation in the reaction fractionating tower; The deodorization agent structural formula is NH
2The mixture of one or several in the compound alkyl amine of-Y, azanol, hydrazine, the 2,4 dinitrophenyl hydrazine.
The addition of above-mentioned deodorization agent is the 1PPm～500PPm of 1,2-PD inventory.
Above-mentioned reaction fractionating tower is divided into rectifying section, conversion zone and stripping section, and wherein, rectifying section is gauze structured packing, and conversion zone is the guide float-valve tower tray, and stripping section is the guide float-valve tower tray.
Above-mentioned propylene glycol treating tower is divided into rectifying section and stripping section, and rectifying section is tower tray, several 50 of tower tray, and top side line propylene glycol is by 25,26,27 extraction; Stripping section is structured packing, 5 meters of packed heights; Propylene glycol treating tower tower body and inner column internals material are 304 stainless steels and make.
The invention has the beneficial effects as follows: take propylene carbonate and methyl alcohol as raw material production methylcarbonate coproduction 1, in the 2-propylene glycol process 1, the processing purifying technique of 2-propylene glycol, can adopt the mode of reactive distillation, react by the impurity that adds in deodorization agent and the 1,2-PD, reacted impurity is convenient to separate from product, finally obtain the indices such as colourity, smell, purity and all meet the 1,2-PD product that pharmaceutical grade requires.
Four, description of drawings:
Accompanying drawing 1 is process flow sheet of the present invention.
Five, embodiment:
Embodiment 1: a kind of novel process for purifying of ester-interchange method 1,2-PD, its technical scheme comprise reactive distillation and the refining two portions of propylene glycol:
1. reactive distillation: entered by first tower tray of reaction fractionating tower conversion zone by the 1,2-PD of fresh feed pump with the coproduction of methylcarbonate (DMC) device, the inventory of control propylene glycol is about 600Kg/h.First with deodorization agent NH
2-Y compound is squeezed in the static mixer with after de-mineralized water fully mixes by volume pump, enters with the 5th tower tray of de-mineralized water by the reaction fractionating tower conversion zone again.The add-on of control de-mineralized water is about 1200Kg/h.Deodorization agent adopts alkylamine, and addition is 0.12Kg/h; Certainly, also can adopt one or several the mixture in azanol, hydrazine, the 2,4 dinitrophenyl hydrazine, its addition is the 1PPm～500PPm of 1,2-PD inventory; Control reaction fractionating tower temperature of reaction about 130 ℃, tower top pressure 0.05MPa, reflux ratio 0.50, reaction time be controlled at 0.5 hour.The cat head material goes the process spent water treatment unit to recycle, and the tower reactor material goes to separate in the subsequent step 2.
The reaction fractionating tower rectifying section is the 5.0m gauze structured packing, and conversion zone is 20 guide float-valve tower trays, and stripping section is 20 guide float-valve tower trays.
2. propylene glycol is refining: the tower reactor material from reaction fractionating tower is entered by propylene glycol treating tower stripping section filler top, control cat head service temperature: 110 ℃, 135 ℃ of top side line propylene glycol drop temperatures, 170 ℃ of tower reactor service temperatures, cat head working pressure: 10KPa, control of reflux ratio: 2.0, full tower operation pressure drop: 5KPa.The amount of the moisture propylene glycol crude product that cat head obtains is: 92Kg/h, return the DMC device again and recycle.The top side line can obtain purity at the product more than 99.99%, about flow 500Kg/h, enters pharmaceutical grade propylene glycol finished product tank field again after cooling.The material 30Kg/h that contains " propylene glycol, dipropylene glycol " in the material that tower reactor obtains returns the DMC device and recycles.The propylene glycol treating tower is divided into and is rectifying section and stripping section.Rectifying section is tower tray, several 50 of tower tray, and top side line propylene glycol is by 25,26,27 extraction.Stripping section is structured packing, 5 meters of packed heights.Propylene glycol treating tower tower body and inner column internals material are 304 stainless steels.
Claims (2)
1. the novel process for purifying of an ester-interchange method 1,2-PD is characterized in that: comprise that reactive distillation and propylene glycol make with extra care two portions:
Reactive distillation: the 1,2-PD of carbonate device coproduction and the de-mineralized water of interpolation deodorization agent are sent into reaction fractionating tower, and the mass ratio of control de-mineralized water and 1,2-PD is 0.2～10: 1; Control reaction fractionating tower temperature of reaction is at 60 ℃～190 ℃; Reaction pressure is controlled at 0.05MPa～0.20MPa; Control of reflux ratio is 0.30～2.0; Reaction time is controlled at 0.35～2.0 hour, and the cat head material that obtains is through going the process spent water treatment unit to recycle, and the still liquid of the reaction fractionating tower that tower reactor obtains enters subsequent propylene glycol and separates in refining;
Propylene glycol is refining: the tower reactor material from the reaction fractionating tower of reactive distillation enters in the propylene glycol treating tower cat head service temperature of control propylene glycol treating tower: 70 ℃～130 ℃; 120 ℃～140 ℃ of top side line propylene glycol drop temperatures; 140 ℃～170 ℃ of tower reactor service temperatures; Working pressure: 7KPa～20KPa; Control of reflux ratio: 0.50～2.0, the moisture propylene glycol crude product that cat head obtains returns carbonate device and reprocesses utilization; The top side line can obtain the propylene glycol product of purity more than 99.99%, enters pharmaceutical grade propylene glycol finished product tank field after cooling; Contain propylene glycol, dipropylene glycol in the material that tower reactor obtains, this partial material can be returned carbonate device and reprocess utilization;
Described deodorization agent mixes with de-mineralized water first, enters together and carries out reactive distillation in the reaction fractionating tower; Deodorization agent is one or several the mixture in alkylamine, azanol, hydrazine, the 2,4 dinitrophenyl hydrazine;
Described reaction fractionating tower is divided into rectifying section, conversion zone and stripping section, and wherein, rectifying section is gauze structured packing, and conversion zone is the guide float-valve tower tray, and stripping section is the guide float-valve tower tray;
Described propylene glycol treating tower is divided into rectifying section and stripping section, and rectifying section is tower tray, several 50 of tower tray, and top side line propylene glycol is by 25,26,27 extraction; Stripping section is structured packing, 5 meters of packed heights; Propylene glycol treating tower tower body and inner column internals material are stainless steel and make.
2. the novel process for purifying of ester-interchange method 1,2-PD according to claim 1, it is characterized in that: the addition of described deodorization agent is the 1PPm～500PPm of 1,2-PD inventory.
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| CN2010102445849A CN101906020B (en) | 2010-07-30 | 2010-07-30 | Novel process for purifying 1,2-propylene glycol by ester exchange method |
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| CN2010102445849A CN101906020B (en) | 2010-07-30 | 2010-07-30 | Novel process for purifying 1,2-propylene glycol by ester exchange method |
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| CN101906020B true CN101906020B (en) | 2013-03-13 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103193594B (en) * | 2012-01-10 | 2015-01-07 | 中国石油化工股份有限公司 | Method for separating ethylene glycol and 1, 2-butanediol |
| CN110724035B (en) * | 2018-07-16 | 2022-12-20 | 东营市海科新源化工有限责任公司 | Purification method and purification system of vicinal diol compound |
| CN115400706A (en) * | 2022-08-29 | 2022-11-29 | 山东海科新源材料科技股份有限公司 | Device and method for purifying and deodorizing cosmetics grade 1,3-butanediol |
| CN116589342B (en) * | 2023-07-17 | 2023-10-17 | 万华化学集团股份有限公司 | Method for catalytic removal of odor impurities from crude 1, 2-propylene glycol |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5527973A (en) * | 1994-12-16 | 1996-06-18 | Kelsey; Donald R. | Purification of 1,3-propanediol |
| CN1413971A (en) * | 2002-09-25 | 2003-04-30 | 黑龙江省石油化学研究院 | Method for removing carbonyl material from 1,3-propylene-glycol |
| CN101774888A (en) * | 2009-12-24 | 2010-07-14 | 山东海科化工集团有限公司 | Novel technique for purifying high-quality propylene glycol in production process of dimethyl carbonate |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5527973A (en) * | 1994-12-16 | 1996-06-18 | Kelsey; Donald R. | Purification of 1,3-propanediol |
| CN1413971A (en) * | 2002-09-25 | 2003-04-30 | 黑龙江省石油化学研究院 | Method for removing carbonyl material from 1,3-propylene-glycol |
| CN101774888A (en) * | 2009-12-24 | 2010-07-14 | 山东海科化工集团有限公司 | Novel technique for purifying high-quality propylene glycol in production process of dimethyl carbonate |
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Address after: 257000 23 Zoucheng Road, Shengli Industrial Park, Dongying District, Dongying City, Shandong Province Patentee after: Shandong Haike Xinyuan material technology Co., Ltd Address before: 257000 Shengli Industrial Zone, Dongying, Shandong Patentee before: DONGYING HI-TECH SPRING CHEMICAL INDUSTRY Co.,Ltd. |