CN1180692A - Technology for preparing propylene-glycol monoalky lether carboxylic ester by catalytic distillation - Google Patents
Technology for preparing propylene-glycol monoalky lether carboxylic ester by catalytic distillation Download PDFInfo
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- CN1180692A CN1180692A CN96116543A CN96116543A CN1180692A CN 1180692 A CN1180692 A CN 1180692A CN 96116543 A CN96116543 A CN 96116543A CN 96116543 A CN96116543 A CN 96116543A CN 1180692 A CN1180692 A CN 1180692A
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Abstract
A catalyst distillation process for preparing propanediol monoalkylether carboxylate features that under the existance of acidic catalyst, propanediol monoalkylether and carboxylic acid take part in catalytic reaction and rectification at 80-160 deg.C and ordinary pressure-0.30 MPa in reaction-distilling tower at same time, where toluene is used as awzeotropic agent. The oil phase reflux is on the top of reaction-distilling tower. Its advantages include basically full reaction of raw materials, and no propanediol ether and carboxylic acid in aqueous phase on tower top, so greatly simplifying the recovery of sequential resultant.
Description
The present invention relates to the preparation technology of propylene-glycol monoalky lether carboxylic ester, especially about technology for preparing propylene-glycol monoalky lether carboxylic ester by catalytic distillation.
Propylene-glycol monoalky lether carboxylic ester is the senior industry solvent of going up of a kind of low toxicity of excellent property.Because its toxicity is low, solubility property is good, development abroad is very fast in recent years, is progressively substituting to be extensive use of at present but the higher glycol ether acetic ester of toxicity.It can be widely applicable for industries such as coating, printing, printing ink, clean-out system, textile dyestuff and leather retanning agent.The preparation of propylene-glycol monoalky lether carboxylic ester in the past is to be raw material with propylene glycol and carboxylic acid, is entrainer with toluene, generates propylene glycol ether carboxylate under an acidic catalyst effect.But this reaction is because esterification is subjected to the restriction of molecular balance, and reactant is converted at 80～95% o'clock, and esterification just stops.The aftertreatment trouble.It is raw material that patent No. US4544453 has just narrated with propylene-glycol monoalky lether and carboxylic acid, is entrainer with toluene, and entrainer refluxes, and injects water by cat head simultaneously, is removed by cat head with steam stripped method and anhydrates and unreacted propylene glycol and acetic acid.Raw material and an acidic catalyst p-methyl benzenesulfonic acid add from the tower still, have solved the loss problem of product ester.Yet slough water simultaneously by cat head, propylene glycol, acetic acid have brought the recovery problem of the propylene glycol and the acetic acid of aqueous phase, make aftertreatment need a lot of towers, especially the recovery of propylene glycol, bigger after propylene glycol monomethyl ether and the phase-splitting of water azeotropic in aqueous phase solubleness, be difficult to recovery with general distillating method and obtain water-free propylene glycol.
In order to overcome the shortcoming that conventional art exists, the purpose of this invention is to provide a kind of technology for preparing propylene-glycol monoalky lether carboxylic ester by catalytic distillation, propylene-glycol monoalky lether is carried out with separating simultaneously with the reaction of carboxylic acid, propylene glycol or acetic acid energy primitive reaction is complete simultaneously, and the cat head aqueous phase does not contain propylene glycol and acetic acid.Thereby simplify the subsequent reactions thing greatly and reclaim technology.
The objective of the invention is to realize: a kind of technology for preparing propylene-glycol monoalky lether carboxylic ester by catalytic distillation by following technical scheme, with propylene-glycol monoalky lether and carboxylic acid is reaction raw materials, toluene is entrainer, in the presence of an acidic catalyst, react, temperature of reaction is 80～160 ℃, reaction pressure is normal pressure～0.3MPa, wherein reaction raw materials catalyzed reaction and rectifying in catalytic distillation tower carries out simultaneously, the mol ratio of reaction raw materials carboxylic acid and propylene-glycol monoalky lether is 0.25～5: 1, the theoretical plate number of reactive distillation column is 30～50, the raw material feed entrance point is at reactive distillation column number of theoretical plate 1/4～2/3 place, and the quantity of reflux of cat head entrainer and the weight ratio of inlet amount are 0.03～0.4: 1.
The reaction raw materials propylene-glycol monoalky lether is propylene glycol monomethyl ether, propylene-glycol ethyl ether in the technique scheme; Carboxylic acid is an acetic acid.An acidic catalyst is p-methyl benzenesulfonic acid, Phenylsulfonic acid resin; The temperature of reaction preferable range is 100～150 ℃, and the mol ratio of reaction raw materials carboxylic acid and propylene-glycol monoalky lether is 0.5～4: 1; The theoretical plate number preferable range of catalytic distillation tower is 40～50, and the weight ratio preferable range of the quantity of reflux of cat head entrainer and inlet amount is 0.06～0.2: 1.
The present invention selects suitable process conditions owing to adopted catalytic distillation technology, and propylene glycol and carboxylic acid are when constantly reacting in the reactive distillation column, product ester and water are constantly separated, steamed by tower still and cat head respectively, under the catalytic distillation condition, reaction trends towards fully.Thereby make the cat head aqueous phase not contain propylene glycol, acetic acid.Steam at the bottom of the tower that propylene-glycol monoalky lether carboxylic ester content is 30～97% (weight) in the material, acetic acid 0.1～70% (weight), propylene-glycol monoalky lether 1～3% (weight) is below the water 0.5% (weight).This bottoms material advances the product purification tower, removes a spot of acetic acid, propylene-glycol monoalky lether with general distillation, and minor amount of water is with regard to recyclable smart product propylene-glycol monoalky lether carboxylic ester.Propylene glycol and the acetic acid told return reactive distillation column, have simplified the subsequent reactions thing greatly and have reclaimed technology, have obtained reaction effect preferably.
Accompanying drawing 1 is a technology for preparing propylene-glycol monoalky lether carboxylic ester by catalytic distillation.
1 is catalytic distillation tower in accompanying drawing 1, and 2 is the catalytic distillation section, and 3 is the raw material feed entrance point, and 4 is water-and-oil separator, and 5 is condenser, and 6 is the discharging of catalytic distillation Tata still, and 7 is the water discharging.
Raw material propylene-glycol monoalky lether and carboxylic acid are in 1/4～2/3 place, the conversion zone middle and upper part position charging of catalytic distillation tower, and be anti-Answer material under the acidic catalyst effect, constantly reaction, water generation reaction forms azeotropic mixture and not in the presence of the methylbenzene azeotropic agent Disconnectedly separated, cat head steams thing after condenser 5 condensations, enters oil water separator 4, is divided in oil water separator 4 Become oil phase and water, the water that does not contain propylene-glycol monoalky lether and acetic acid is drawn. Contain a small amount of propylene-glycol monoalky lether and first The oil phase of benzene azeotropic agent refluxes, and the weight ratio of the capacity of returns of cat head entrainer and catalytic distillation tower raw material inlet amount is 0.03～0.4: 1, the propylene-glycol monoalky lether carboxylic ester of unreacted carboxylic acid, a small amount of propylene-glycol monoalky lether and generation steams by reaction Heat up in a steamer Tata still discharging 6, this tower reactor material is removed carboxylic acid, propanediol monoalkyl again through the product treating column with general distillation method Ether and minor amount of water get pure propylene-glycol monoalky lether carboxylic ester product.
[embodiment 1]
The successive reaction distillation tower, rectifying section is that the filled section has 27 theoretical stages, stripping section has 16 theoretical stages, under the normal pressure, with toluene is entrainer, and the Phenylsulfonic acid resin is that catalyzer carries out catalytic distillation, and the weight ratio of charging acetic acid and propylene glycol monomethyl ether is 25: 75, the weight ratio of entrainer refluxing toluene amount and inlet amount is 0.10, the reactive distillation column tower top temperature is 84 ℃, and tower still temperature is 136 ℃, and the raw material feeding temperature is 80 ℃, the overhead water phase composite is water 99.6% by weight percentage by analysis, toluene 0.05%, other impurity 0.35% consists of propylene glycol monomethyl ether 0.29% by weight percentage in the cat head oil phase, water 0.40%, toluene 99.32%.It is acetic acid 0.1% by weight percentage that the discharging of tower still is formed, propylene glycol monomethyl ether 40.9%, water 0.20%, 1-Methoxy-2-propyl acetate 58.8%.[embodiment 2]
The successive reaction distillation tower, rectifying section is the filled section, and 32 theoretical stages are arranged, and stripping section has 18 theoretical stages, and pressure is under the 0.1MPa, is entrainer with toluene, is that catalyzer carries out reaction distillation to the toluene Phenylsulfonic acid.Charging acetic acid and propylene glycol monomethyl ether are 72.7: 27.3 with weight ratio, entrainer refluxing toluene amount and inlet amount are 0.06 with weight ratio, the reactive distillation column tower top temperature is 94 ℃, and tower still temperature is 149 ℃, and the raw material feeding temperature is 90 ℃, the overhead water phase composite is water 99.7% by weight percentage by analysis, toluene 0.04%, other impurity 0.26% consists of propylene glycol monomethyl ether 0.30% by weight percentage in the cat head oil phase, water 0.45%, toluene 99.25%.It is acetic acid 57.56% by weight percentage that the discharging of tower still is formed, propylene glycol monomethyl ether 0.23%, water 0.21%, 1-Methoxy-2-propyl acetate 42.0%.[embodiment 3]
The successive reaction distillation tower, rectifying section is the filled section, and 22 theoretical stages are arranged, and stripping section has 8 theoretical stages, and pressure is under the 0.30MPa, is entrainer with toluene, and the Phenylsulfonic acid resin is that catalyzer carries out reaction distillation.Charging acetic acid and propylene glycol monomethyl ether are 76.9: 23.1 with weight ratio, the weight ratio of entrainer refluxing toluene amount and inlet amount is 0.40, the reactive distillation column tower top temperature is 104 ℃, tower still temperature is 169 ℃, the raw material feeding temperature is 100 ℃, the overhead water phase composite is water 99.3% by weight percentage by analysis, toluene 0.05%, other impurity 0.65%.Forming in the cat head oil phase toluene is propylene glycol monomethyl ether 0.78% by weight percentage, water 0.70%, toluene 98.52%.It is acetic acid 64.45% by weight percentage that the discharging of tower still is formed, propylene glycol monomethyl ether 0.20%, water 0.25%, propylene-glycol ether acetate 35.1%.[embodiment 4]
The successive reaction distillation tower, rectifying section is the filled section, and 18 theoretical stages are arranged, and stripping section has 30 theoretical stages, under the normal pressure, is entrainer with toluene, and the Phenylsulfonic acid resin is that catalyzer carries out reaction distillation.The weight ratio of charging acetic acid and propylene-glycol ethyl ether is 48.1: 51.9, the weight ratio of entrainer refluxing toluene amount and inlet amount is 0.20, the reactive distillation column tower top temperature is 84 ℃, and tower still temperature is 144 ℃, and the raw material feeding temperature is 80 ℃, the overhead water phase composite is water 99.81% by weight percentage by analysis, toluene 0.05%, other impurity 0.14% consists of propylene-glycol ethyl ether 0.19% by weight percentage in the cat head oil phase, water 0.37%, toluene 99.44%.It is acetic acid 15.23% by weight percentage that the discharging of tower still is formed, propylene-glycol ethyl ether 0.58%, water 0.19%, propylene-glycol ethyl ether acetic ester 84.0%.
Claims (8)
1, a kind of technology for preparing propylene-glycol monoalky lether carboxylic ester by catalytic distillation, with propylene-glycol monoalky lether and carboxylic acid is reaction raw materials, toluene is entrainer, in the presence of an acidic catalyst, react, temperature of reaction is 80～160 ℃, reaction pressure is to react under normal pressure～0.3MPa condition, it is characterized in that reaction raw materials catalyzed reaction and rectifying in catalytic distillation tower carry out simultaneously, the mol ratio of reaction raw materials carboxylic acid and propylene-glycol monoalky lether is 0.25～5: 1, the theoretical plate number of reactive distillation column is 30～50, the raw material feed entrance point is at reactive distillation column number of theoretical plate 1/4～2/3 place, and the quantity of reflux of cat head entrainer and the weight ratio of inlet amount are 0.03～0.4: 1.
2,, it is characterized in that the reaction raw materials propylene-glycol monoalky lether is propylene glycol monomethyl ether, propylene-glycol ethyl ether according to the described technology for preparing propylene-glycol monoalky lether carboxylic ester by catalytic distillation of claim 1.
3,, it is characterized in that the reaction raw materials carboxylic acid is an acetic acid according to the described technology for preparing propylene-glycol monoalky lether carboxylic ester by catalytic distillation of claim 1.
4,, it is characterized in that an acidic catalyst is p-methyl benzenesulfonic acid, Phenylsulfonic acid resin according to the described technology for preparing propylene-glycol monoalky lether carboxylic ester by catalytic distillation of claim 1.
5,, it is characterized in that temperature of reaction is 100～150 ℃ according to the described technology for preparing propylene-glycol monoalky lether carboxylic ester by catalytic distillation of claim 1.
6, according to the described technology for preparing propylene-glycol monoalky lether carboxylic ester by catalytic distillation of claim 1, tool is characterised in that the mol ratio of reaction raw materials carboxylic acid and propylene-glycol monoalky lether is 0.5～4: 1.
7, according to the described technology for preparing propylene-glycol monoalky lether carboxylic ester by catalytic distillation of claim 1, the number of theoretical plate that it is characterized in that catalytic distillation tower is 40～50.
8,, it is characterized in that the quantity of reflux of cat head entrainer and the weight ratio of inlet amount are 0.06～0.2 according to the described technology for preparing propylene-glycol monoalky lether carboxylic ester by catalytic distillation of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96116543A CN1063427C (en) | 1996-10-22 | 1996-10-22 | Technology for preparing propylene-glycol monoalky lether carboxylic ester by catalytic distillation |
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| CN96116543A CN1063427C (en) | 1996-10-22 | 1996-10-22 | Technology for preparing propylene-glycol monoalky lether carboxylic ester by catalytic distillation |
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| CN1180692A true CN1180692A (en) | 1998-05-06 |
| CN1063427C CN1063427C (en) | 2001-03-21 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1304359C (en) * | 2005-04-22 | 2007-03-14 | 江苏华伦化工有限公司 | Process for synthesizing propylene glycol methyl ether acetate |
| CN101337884B (en) * | 2008-08-08 | 2011-05-11 | 德纳（南京）化工有限公司 | Method for preparing 2-Butoxyethyl acetate by continuous esterification reaction |
| CN101337885B (en) * | 2008-08-08 | 2011-07-20 | 德纳（南京）化工有限公司 | Method for preparing 1-Methoxy-2-propyl acetate by continuous esterification reaction |
| CN106478417A (en) * | 2016-09-28 | 2017-03-08 | 南京工业大学 | Method for preparing propylene glycol monomethyl ether acetate by continuous reactive distillation |
| CN107986948A (en) * | 2017-12-25 | 2018-05-04 | 福州大学 | Reaction unit and its application of electronic grade propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate are synthesized for propylene oxide two-step reaction |
| CN109456190A (en) * | 2018-10-18 | 2019-03-12 | 天津大学 | A kind of method of the continuous synthesizing propylene glycol monomethyl ether acetate of the highly selective catalytic distillation of low temperature |
| CN115872868A (en) * | 2021-09-27 | 2023-03-31 | 载元产业株式会社 | Method for purifying high-purity alkylene glycol monoalkyl ether carboxylate for photoresist process |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3475188D1 (en) * | 1983-03-17 | 1988-12-22 | Atlantic Richfield Company | |
| FR2729389A1 (en) * | 1995-01-13 | 1996-07-19 | Shiny Chemical Ind Co Ltd | Propylene glycol mono:alkyl:ether ester(s) |
-
1996
- 1996-10-22 CN CN96116543A patent/CN1063427C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1304359C (en) * | 2005-04-22 | 2007-03-14 | 江苏华伦化工有限公司 | Process for synthesizing propylene glycol methyl ether acetate |
| CN101337884B (en) * | 2008-08-08 | 2011-05-11 | 德纳（南京）化工有限公司 | Method for preparing 2-Butoxyethyl acetate by continuous esterification reaction |
| CN101337885B (en) * | 2008-08-08 | 2011-07-20 | 德纳（南京）化工有限公司 | Method for preparing 1-Methoxy-2-propyl acetate by continuous esterification reaction |
| CN106478417A (en) * | 2016-09-28 | 2017-03-08 | 南京工业大学 | Method for preparing propylene glycol monomethyl ether acetate by continuous reactive distillation |
| CN107986948A (en) * | 2017-12-25 | 2018-05-04 | 福州大学 | Reaction unit and its application of electronic grade propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate are synthesized for propylene oxide two-step reaction |
| CN107986948B (en) * | 2017-12-25 | 2020-10-09 | 福州大学 | Reaction device for synthesizing electronic-grade propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate through two-step reaction of propylene oxide and application of reaction device |
| CN109456190A (en) * | 2018-10-18 | 2019-03-12 | 天津大学 | A kind of method of the continuous synthesizing propylene glycol monomethyl ether acetate of the highly selective catalytic distillation of low temperature |
| CN115872868A (en) * | 2021-09-27 | 2023-03-31 | 载元产业株式会社 | Method for purifying high-purity alkylene glycol monoalkyl ether carboxylate for photoresist process |
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