CN1699327A - Process for synthesizing propylene glycol monomethyl ether acetate (PMA) - Google Patents
Process for synthesizing propylene glycol monomethyl ether acetate (PMA) Download PDFInfo
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- CN1699327A CN1699327A CN 200510039023 CN200510039023A CN1699327A CN 1699327 A CN1699327 A CN 1699327A CN 200510039023 CN200510039023 CN 200510039023 CN 200510039023 A CN200510039023 A CN 200510039023A CN 1699327 A CN1699327 A CN 1699327A
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- propylene glycol
- glycol monomethyl
- monomethyl ether
- pma
- ether acetate
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Abstract
The invention relates to a process for synthesizing propylene glycol monomethyl ether acetate, which comprises subjecting propylene glycol methyl ether, acetic acid and toluene to esterification reaction at the presence of methyl benzene sulfonic acid catalyst, then reclaiming the excess propylene glycol methyl ether with dealkylation tower and rectifying, thus obtaining propylene glycol methyl ether acetic ester.
Description
Technical field
The present invention relates to the production technique of 1-Methoxy-2-propyl acetate.
Background technology
1-Methoxy-2-propyl acetate (PMA) is a kind of important senior solvent, and polarity and nonpolar material are all had very strong dissolving power.Its solubility property is higher than common solvent and propylene glycol ethers and glycol ethers solvent far away, and good with the compatibility of water.PMA can make the solvent of Mierocrystalline cellulose, superpolymer, rubber and natural macromolecular etc.Because characteristics such as 1-Methoxy-2-propyl acetate has solubility property height, good environmental protection, thermostability is excellent, the viscosity variation is little are widely used in fields such as coating, printing ink, printing and dyeing and agricultural chemicals, and are replacing bigger glycol ether of toxicity and esters solvent thereof.
Industrial main employing propylene glycol monomethyl ether (PM) is combined to PMA with acetic ester at present, uses traditional concentrated sulfuric acid catalyst in the building-up process.This technology exists the vitriol oil to equipment heavy corrosion, reactant last handling process complexity, and produces waste residue, waste liquor contamination environment, causes the problem that product yield is low, production cost is high, of poor benefits simultaneously.Cause the reason of these problems to be:
(1) must carry out the alkali neutralization to sulfuric acid after the concentrated sulfuric acid catalyst esterification, N-process has part acetic acid and alkali to produce acetate except that producing the sulfur waste hydrochlorate, causes the acetic acid loss;
(2) vitriol of Sheng Chenging and acetate must be discharged after sedimentation, and the waste residue of discharge is carried reaction product unavoidably secretly;
(3) in the reactant of sedimentation desalination, be dissolved with a small amount of vitriol and acetate, vitriol and acetate can accumulate in the filler of rectifying tower in the rectifying tower of product separation, cause rectification effect to worsen, product rectifying tower regularly (20-30 days) parking is washed tower, parking is washed tower and is not only had a strong impact on production efficiency, and produce waste water, loss product again.
(4) vitriol oil has very strong oxidisability, and the oxidized back of part material generates by product, makes product Tata still discharge black raffinate amount big (per 300 tons of products are discharged 3 tons of raffinates).
Enter 21 century, pollution and environmental problem are subjected to people's attention day by day, and Green Chemistry becomes the trend of chemical developer, and chemical reaction is in the requirement that all should consider Green Chemistry aspect technological design, operational condition and the catalyzer.
Summary of the invention
The object of the invention is can avoid above-mentioned defective, pollution-free, low consumed novel process for 1-Methoxy-2-propyl acetate (PMA) synthetic provides a kind of.
The present invention carries out esterification with propylene glycol monomethyl ether and acetic acid, toluene earlier under the p-methyl benzenesulfonic acid katalysis, carry out rectifying again after lightness-removing column reclaims excessive propylene glycol monomethyl ether, obtains 1-Methoxy-2-propyl acetate.
The present invention is directed to synthetic PMA uses traditional sulfuric acid catalyst to exist contaminate environment and the problem that influences product to carry out the development research of new catalyst.To synthetic PMA catalytic activity height, selectivity is good, the product yield height as catalyzer for p-methyl benzenesulfonic acid; To existing material is the PMA production unit non-corrosiveness of 316L; During reactant does not need and desalination, do not have waste residue, discharging of waste liquid, catalyzer can be recycled.This catalyst development successfully makes the production of PMA become advanced Green Chemistry, has simplified the last handling process that PMA produces greatly, has greatly improved the economic benefit that PMA produces.The present invention in the recycling of economy, the design of optimization reaction process, simplification last handling process and non-product component, has the irreplaceable advantage of traditional catalyst at the selectivity and the transformation efficiency that improve reaction process, demonstrates better industrial application prospect.
Among the present invention, the add-on of p-methyl benzenesulfonic acid is 0.4～0.5% of a total reaction amount.When catalyst levels was 0.4～0.5%, conversion rate of esterification had reached the highest by 100%.
Add in the reaction kettle of the esterification of the present invention after 500 kilograms of 18 tons of the propylene glycol monomethyl ethers, 12.1 tons of acetic acid, entrainer toluene, add p-methyl benzenesulfonic acid.
During esterification, be warming up to 100 °～105 ° earlier, dewater simultaneously, react after 16～20 hours, temperature of reaction rises to 150 ° again.
Embodiment:
(1) in reaction kettle of the esterification, adds after 500 kilograms of 18 tons of the propylene glycol monomethyl ethers (PM), 12.1 tons of acetic acid, entrainer toluene, add 122 kilograms of p-methyl benzenesulfonic acids.
(2) heat temperature raising to 103 degree reacts, and dewaters simultaneously, and water is separated with toluene.After the esterification 16～20 hours, temperature of reaction rises to 150 degree again.Treat that esterification finishes, reaction mass input lightness-removing column.Reclaim excessive propylene glycol monomethyl ether, simultaneously with the reactant pump to rectifying tower.
(3) with after the reactant rectifying, the rectifying tower bottom product is collected the barrelling metering, (the residual quantity discharged 56+4+6+6 of still, it is residual that 300 tons of products are discharged 3 tons of stills approximately), when initial 5 batches of esterifications feed intake, use new catalyst for esterification, collected product tower still residual (containing new catalyst for esterification) returns reaction kettle of the esterification when obtaining 20-30 ton PMA product, recycle repeatedly in the process,, then can suitably add a small amount of raw catalyst (10 kilograms of additional amounts) if reaction time of esterification prolongs to some extent.
(4) view apparatus working order, 300 tons of products of every production are the discharge section raffinate in right amount.
P-methyl benzenesulfonic acid (English name: P-Toluene Sulfonic acid)
Structural formula:
Molecular formula: C
7H
8SO
3
Molecular weight: 172.20
Proterties: this product is for singly chatting plate crystal or powder, and soluble in water, pure, ether are dissolved in hot benzene.This product exists with one or four crystallizations sometimes, and fusing point is 107 ℃ when anhydrous, 36 ℃ of crystal water fusing points, 140 ℃/20mmHg of boiling point.
New catalyst p-methyl benzenesulfonic acid and concentrated sulfuric acid catalyst esterification property comparison, as following table:
Test conditions: propylene glycol monomethyl ether 1.15mol (104g); Acetic acid 1.0mol (60g); Band aqua toluene 20ml
| Catalyzer | The vitriol oil | P-methyl benzenesulfonic acid |
| Catalyst levels (accounting for the ratio WT% of reinforced total amount) | ??0.2 | ??0.4 |
| Dehydrating amount (ml) | ??20 | ??20 |
| Dewatering time (min) | ??35 | ??35 |
| Reaction conversion ratio | ??100 | ??100 |
| Reaction preference | ??97 | ??100 |
| Reaction yield | ??97 | ??100 |
From above result as can be known, under suitable catalyst levels, when adopting new catalyst as the alcohol ether esterifying catalyst, has the best suitable esterification reaction rate of reaction conversion ratio, selectivity, yield and the vitriol oil, the catalysis excellent combination property can substitute the vitriol oil fully as third (second) glycol ethers acetic ester synthetic catalyzer.
The catalyst recirculation use-testing
In reaction system, do not have very big solvability because new catalyst does not produce burn into to production unit and pipeline, can consider that in actual production catalyst recirculation uses with the raising market competitiveness that reduces production costs.
Test conditions:
Propylene glycol monomethyl ether 1.15mlo (104g); Acetic acid 1.0mol (60g); Band aqua toluene 20ml; Dewatering time 40min.
Testing sequence:
Utilize the method for underpressure distillation to remove the band aqua in the reaction solution of first set reaction, excessive propylene glycol and most ester, keep and contain about the still liquid 30-40ml of catalyzer, in reactor, add fresh propylene glycol, acetic acid and band aqua again and under identical reaction conditions, carry out the catalyst recirculation use-testing, the results are shown in following table.
Catalyst recirculation is used the result
| Cycle index | Dewatering time (min) | Transformation efficiency (%) | Selectivity (%) |
| ??1 | ??40 | ??100 | ??100 |
| ??2 | ??40 | ??100 | ??100 |
| ??3 | ??40 | ??100 | ??100 |
| ??4 | ??40 | ??100 | ??100 |
| ??5 | ??40 | ??100 | ??100 |
By last table result as can be known, catalyzer catalytic activity after recycling 5 times does not descend, so think that this catalyzer is at the stable reaction conditions that suits and do not have to can be recycled under the situation of loss.
Claims (4)
1, the technology of synthesizing propylene glycol monomethyl ether acetate (PMA), it is characterized in that may further comprise the steps: earlier propylene glycol monomethyl ether and acetic acid, toluene are carried out esterification under the p-methyl benzenesulfonic acid katalysis, after lightness-removing column reclaims excessive propylene glycol monomethyl ether, carry out rectifying again, obtain 1-Methoxy-2-propyl acetate.
2, according to the technology of the described synthesizing propylene glycol monomethyl ether acetate of claim 1 (PMA), it is characterized in that: the add-on of p-methyl benzenesulfonic acid is 0.4～0.5% of a total reaction amount.
3, according to the technology of the described synthesizing propylene glycol monomethyl ether acetate of claim 2 (PMA), it is characterized in that: add in the reaction kettle of the esterification after 500 kilograms of 18 tons of the propylene glycol monomethyl ethers, 12.1 tons of acetic acid, entrainer toluene, add p-methyl benzenesulfonic acid.
4, according to the technology of the described synthesizing propylene glycol monomethyl ether acetate of claim 2 (PMA), it is characterized in that: be warming up to 100 °～105 ° during esterification, dewater simultaneously, react after 16～20 hours, temperature of reaction rises to 150 ° again.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100390234A CN1304359C (en) | 2005-04-22 | 2005-04-22 | Process for synthesizing propylene glycol monomethyl ether acetate (PMA) |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100390234A CN1304359C (en) | 2005-04-22 | 2005-04-22 | Process for synthesizing propylene glycol monomethyl ether acetate (PMA) |
Publications (2)
| Publication Number | Publication Date |
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| CN1699327A true CN1699327A (en) | 2005-11-23 |
| CN1304359C CN1304359C (en) | 2007-03-14 |
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| Application Number | Title | Priority Date | Filing Date |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101693661B (en) * | 2009-10-15 | 2012-09-05 | 无锡百川化工股份有限公司 | Method for producing propylene glycol methyl ether acetate |
| CN103433069A (en) * | 2013-09-05 | 2013-12-11 | 上海多纶化工有限公司 | Catalyst used for synthesizing methoxy-polyoxyethylene ether (methyl) acrylate |
| WO2018192195A1 (en) * | 2017-04-20 | 2018-10-25 | 江苏华伦化工有限公司 | Method for preparing semiconductor-grade propylene glycol methyl ether acetate |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5239111A (en) * | 1992-10-14 | 1993-08-24 | Shiny Chemical Industrial Co., Ltd. | Propylene glycol monomethyl ether propionate compound and the process for the preparation thereof |
| CN1128749A (en) * | 1995-02-07 | 1996-08-14 | 胜一化工股份有限公司 | Propanediol monoalkyl ether ester compound and prepn. method thereof |
| CN1063427C (en) * | 1996-10-22 | 2001-03-21 | 中国石油化工总公司上海石油化工研究院 | Technology for preparing propylene-glycol monoalky lether carboxylic ester by catalytic distillation |
-
2005
- 2005-04-22 CN CNB2005100390234A patent/CN1304359C/en active Active
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101693661B (en) * | 2009-10-15 | 2012-09-05 | 无锡百川化工股份有限公司 | Method for producing propylene glycol methyl ether acetate |
| CN103433069A (en) * | 2013-09-05 | 2013-12-11 | 上海多纶化工有限公司 | Catalyst used for synthesizing methoxy-polyoxyethylene ether (methyl) acrylate |
| WO2018192195A1 (en) * | 2017-04-20 | 2018-10-25 | 江苏华伦化工有限公司 | Method for preparing semiconductor-grade propylene glycol methyl ether acetate |
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| Publication number | Publication date |
|---|---|
| CN1304359C (en) | 2007-03-14 |
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