CN1275974A - Continuous process for the production of carboxylic acid esters of alkylene glycol monoalkyl ethers - Google Patents
Continuous process for the production of carboxylic acid esters of alkylene glycol monoalkyl ethers Download PDFInfo
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- CN1275974A CN1275974A CN 97182427 CN97182427A CN1275974A CN 1275974 A CN1275974 A CN 1275974A CN 97182427 CN97182427 CN 97182427 CN 97182427 A CN97182427 A CN 97182427A CN 1275974 A CN1275974 A CN 1275974A
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Abstract
The present invention provides an improved method for the preparation of carboxylic acid esters of alkylene glycol monoalkyl ethers by the acid catalyzed esterification of the monoalkyl ether with a carboxylic acid. In a preferred embodiment of the invention, the carboxylic acid and alcohol are reacted in a reactor/column and the resulting ester product is distilled into an overhead decanter/extractor as a single phase. A small amount of solvent, preferably a hydrocarbon is aded to the mixture causing the resulting distillate to separate into two phases, one phase containing the desired product, the other containing primarily water. The process described is applicable to both batch and containuous operation and is not constrained by the difficulty of separating closely boiling azeotropes and results in substantially higher production rates than achieved by current processes.
Description
Invention field
The present invention relates to the production method of the production method of carboxylicesters, particularly alkoxy alkyl.
Background of invention
The present invention relates to the method for the alkoxy alkyl of the production method of carboxylicesters, particularly production alkylene glycol monoalkyl ethers in a continuous manner.Except that unreacted reactant, the water that reaction is emitted also can cause operation and issues of purification.
In the method that makes alcohol and carboxylic acid reaction continuous production ester, removing the water that produces in the reaction process can increase transformation efficiency.Usually, reaction process is carried out in the reactor of the mixture that comprises alcohol, carboxylic acid, ester, water and acid catalyst.The reactor heating is obtained the equilibrated mixture, and product distills in separation column.When product is distilled, alcohol and carboxylic acid is added in the reactor.For simple ester such as ethyl acetate and butylacetate, water can be removed with azeotrope with ester and unconverted alcohol.Overhead product is separable into two kinds of liquid phases.The upper strata also is referred to as " oil phase ", mainly comprises ester and a spot of pureer and milder water.And lower floor is referred to as " water ", mainly comprises water and some esters and alcohol.Water is transferred in the distillation tower, water is discharged with waste material, overhead product is circulated from the bottom of tower.Oil phase distills with the basic emission product of producing pure ester in scavenging tower and is circulated to the overhead product that reacts in the product.In recent years this process has been carried out optimizing to allow producing these simple esters with high yield.
When people attempt to adopt this method to come esterification alkylene glycol monoalkyl ethers such as 1-methoxyl group-2-propyl alcohol, find that this method is infeasible fully or almost be infeasible.From the overhead product of reaction tower and be not easy to be separated into two-phase, this makes and is difficult to remove water in the dereaction by aforesaid method.The reason that can not take place that is separated is that these pure and mild esters are more stable in water compared with simple ester.Also find in addition, can operate reaction tower/distillation tower in such a way, thereby be separated into the very near azeotrope of two kinds of boiling points (a kind of alkylene glycol monoalkyl ethers that is rich in, and another kind is rich in corresponding ester).Though this point can realize by distillation tower is operated under high reflux ratio, operate distillation tower by this way and will reduce its capacity greatly.Although this process also can be produced the overhead product that can be separated into oil phase and water, separation degree is very difficult.And then reaction tower/distillation tower must be operated under very low speed, causes the integral production process non-remunerative from saying so economically.
Owing to exist above-mentioned solubility problem, alkylene glycol monoalkyl ethers ester to adopt the described method of EP0119833B1 to produce usually.To add to such as the compound of toluene in the reactor, and by still-process water and toluene be distilled with azeotrope and remove.This makes reaction be tending towards finishing.Azeotrope is separated into two-phase; Water is removed with water, and oil phase is recycled in the reactor.In the method, only be water as azeotrope, and ester, unreacted alcohol or carboxylic acid and catalyzer are stayed in the reactor.This method need be removed catalyzer by neutralization or other method from product before purifying.Another defective is that these methods normally move with intermittence by discrete mode, causes the low and catalyst loss of raw material efficient.In addition, the ester that makes by this way also exists acidity and stability problem.
Summary of the invention
The objective of the invention is to overcome an above-mentioned difficult problem.Have found that the production process of alkylene glycol monoalkyl ethers ester such as acetate 1-methoxyl group-2-propyl ester can be carried out in successive processes, and realize high yield, reach superior product quality and catalyzer at a high speed and do not lose etc.The object of the present invention is achieved like this: adopt water as entrainer, the azeotrope with water, carboxylicesters and some unreacted glycol ether alcohol from reactor enters the product distillation in overhead product decantor/extractor.A spot of inert solvent is added in decantor/extractor, so that overhead product is separated into oil phase and water.Oil phase mainly comprises solvent, ester and a spot of water and unreacted alcohol.Water mainly comprises water and unreacted alcohol and some ester.Unreacted carboxylic acid and catalyzer are still in reactor.This method needn't be handled the separation difficult problem of very near azeotrope of boiling point or high boiling ester product, and with higher in fact productivity operation.And then carboxylic acid can not be distilled in the overhead product, can not pollute product.
The accompanying drawing summary
Fig. 1 has illustrated the preferred embodiments of the invention, and the esterification process of employing reactor/reboiler, distillation tower and decantor/separator has been described.
Detailed Description Of The Invention
The invention provides a kind of side by making carboxylic acid and alcohol reaction produce alkoxy alkyl Method. In a preferred embodiment of the invention, carboxylic acid carries out anti-in reactor/reboiler with alcohol Should, the ester products of generation with single-phase by water boil distill permanently enter the overhead decanter/ In the extractor. A small amount of extractant is added in the mixture so that the distillate that forms is separated into Two-phase, one comprises required product mutually, and another mainly comprises water mutually. Method of the present invention Needn't process the separation difficult problem of the very near azeotropic mixture of boiling point or high boiling ester product, thereby than conventional The productivity ratio that the easier realization of method is higher.
According to the present invention, a kind of production method of carboxylicesters of alkylene glycol monoalkyl ethers is provided, it comprises:
A) in the presence of a kind of acid catalyst, make to have 1 to the monocarboxylic acid or the halogenated monocarboxylic acid of about 10 carbon atoms and have the alkylene glycol monoalkyl ethers reaction of following formula:
Wherein, n=0-6; R
1, R
2=H, CH
3--(CH
2)
n-, X=Cl, arbitrary position that Br, FX group can be on chains;
B) in distillation tower, mixture is distilled, adopt water and carboxylicesters and unreacted alkylene glycol monoalkyl ethers to form azeotrope simultaneously;
C) will cause in the overhead product extractor from the overhead product of (b) and contact with the inert solvent (being also referred to as phase separation agent) of significant quantity to form at least two liquid phases;
D) two-phase (water and oil (product) are mutually) of the mixture that forms is separated;
E) oil phase is distilled to reclaim (pure basically) monocarboxylic acid ester products and inert solvent (being used to recycle); With
F) water is distilled (being used for the water of waste treatment and the pure and mild ester that is used to recycle with recovery).
Aforesaid method can be used for continuous reaction apparatus or rhythmic reaction device.Be preferred for comprising the continuous reaction apparatus of reaction tower, distillation tower and overhead product decantor/extractor.
C
1-10The example of acid includes but not limited to: acetate, formic acid, propionic acid, isopropylformic acid and butanic acid.The example of the diol ester of the inventive method product includes but not limited to: acetate 1-oxyethyl group-2-ethyl ester, acetate 1-methoxyl group-2-propyl ester and propionic acid 1-methoxyl group-2-propyl ester.The embodiment of useful ether is 1-oxyethyl group-2-ethanol and 1-methoxyl group-2-propyl alcohol etc.
Reaction adopts acid as catalyzer, and mineral acid for example is as the vitriol oil, hydrochloric acid, nitric acid etc.Also can adopt Lewis acid such as boron trifluoride, antimony pentafluoride etc.Can also adopt organic sulfonic acid and halogenosulfonic acid, as methylsulfonic acid, ethyl sulfonic acid and fourth sulfonic acid, trifluoromethanesulfonic acid, trichlorine methylsulfonic acid, neighbour-or right-toluenesulphonic acids, Phenylsulfonic acid etc., and strongly-acid sulfonated aromatic ion exchange resin and perfluoro alkyl sulfonic acid resin.In the reaction mixture gross weight, the consumption of acid catalyst is generally about 0.01 to about 10wt%, and preferred about 0.1 to about 2.0wt%, and this content can change according to the acid of concrete employing.
Below explain the difference between the method that adopts phase separation agent (extraction agent) among the present azeotropic method that adopts and the present invention.For example, when hydrocarbon was used as entrainer, it can add to or be present in reactor/reboiler.Stablize the boiling point mixture and distill the overhead product that comprises hydrocarbon and other component with generation by distillation tower, in this case, described other component mainly is a water.Purpose product, unreacted alcohol and/or carboxylic acid and catalyzer are then stayed in reactor/reboiler.When hydrocarbon during as the phase separation agent (extraction agent) in the inventive method, it can add in overhead product decantor/separator, makes product be separated into two-phase.Operate in this way, can not distill out carboxylic acid, greatly simplified the purge process of product.
Useful phase separation agent comprises those inert, compatible with reactive component chemistry and make the purpose product be separated into the biphase material.Solvent can be straight chain, side chain, aromatics or cyclic hydrocarbon, ester, ether, ketone or fluorine chlorine compound.Usually, these compounds have about 5 to 12 carbon atoms.The example of The suitable solvent includes but not limited to: pentane, pentamethylene, hexane, hexanaphthene, toluene, benzene, dimethylbenzene, alkene, butylacetate, propyl acetate, ethyl acetate, methyl tertiary butyl ether, Di Iso Propyl Ether, methylethylketone, methyl propyl ketone, methyl butyl ketone, and corresponding compounds, fluorine chlorine compound, chloroform, tetracol phenixin, methylene dichloride and Freons
Preferred phase separation agent is C
5-C
12Hydrocarbon is particularly when operating under atmospheric condition.Generally be not preferably greater than C
12Hydrocarbon.If hydrocarbon has too high boiling point, then hydrocarbon can be stayed in the reactor and can not enter in the overhead product susceptor/decantor of distillation tower.If hydrocarbon has too low boiling point, it is infeasible then adopting this type of hydrocarbon under atmospheric condition.Can adopt alkene, but because their meeting polymerizations in reactor, making it is not preferred solvent.
Phase separation agent should use can form two liquid phases in decantor/extractor operating temperature range with significant quantity.Suitable consumption is about 5 to about 70wt%, and preferred 10 to about 50wt%, and first-selection about 20 is to about 40wt%.Phase separation agent can not carry out phase-splitting very little, and it is too many, with undue equipment size of needs and too much energy consumption.
Acid catalyzed esterification can be carried out in any suitable reactor, and described reactor has the device that makes reactant blended device, conditioned reaction actuator temperature and isolate the device of the water that produces in purpose ester products and the reaction process from unreacted component.In preferred embodiments, except adopting said apparatus, also adopt distillation tower, condenser and be used for removing the desolvate phase separator or the decantor/extractor of (comprising product)-water, and be used for returning solvent and water device to distillation tower.
The general process of reaction is that glycol ethers, carboxylic acid and acid catalyst are added in reactor or the reaction tower.With mixture heating up and remain on the required suitable period of next section of temperature of reaction, then, the distillatory product mixtures is transferred in the overhead product phase separator.In phase separator, mixture is contacted with phase separation solvent, thereby be separated.Carry out the product sepn process then, comprise that the mixture phase (water and oily (containing product) are mutually) that will form separates, two-phase is distilled, reclaim required monocarboxylic ester.
Referring to accompanying drawing 1, this description of drawings reactor/reboiler, wherein, adopt the standard reaction engineering method reactant to be contacted together and thorough mixing.If operate in a continuous manner, the input speed of reactant is adjusted to the suitable residence time of protection under temperature of reaction.Mixture is added to the bottom of distillation tower, in distillation tower, distill ester products, water and unreacted reactant.The product logistics that comprises after the distillation of required ester products adds in decantor/separator, at this, adds phase separation agent in mixture, thereby mixture is divided at least two kinds of liquid phases.Oil phase or product and aqueous phase separation are opened.Then, product is distilled mutually so that its purity is higher.The water that comprises most of water, some esters and some unreacted alcohol is delivered in the organism recovery tower.
The general reaction conditions of esterification of the present invention comprises: the temperature range in reactor/tower is 80 to about 160 ℃, and pressure is about 0.1 to 10 normal atmosphere, and reactor residence time is about 0.3 to about 5 hours.Three parameters can be regulated to optimize reaction process, these three parameters can there are differences concerning producing different esters.Consider that from economic angle preferred condition is to operate under near 1 normal atmosphere, reactor residence time is about 0.5-2 hour.
Though method of the present invention relates to production alkylene glycol monoalkyl ethers ester, this process also can be used to carry out general esterification process.It will be appreciated by those skilled in the art that adopting suitable glycol ethers and monocarboxylic acid, method of the present invention can be widely used in produces other ester, as acetate propylene glycol mono, butyric acid dipropylene glycol mono octyl ester, formic acid glycol monomethyl ethyl ester etc.
Following embodiment is used to illustrate the present invention, but they are not limiting the scope of the invention.EXAMPLE Example 1
Conversion unit is assembled by following apparatus: 30 column plates, 2 " the Oldershaw distillation tower of diameter, reflux cooler, overhead product receptor (decantor) and reboiler/reactors.Pump be used for transmitting fresh material to reboiler and transfer ring hexane to the overhead product receptor.The acetate 1-methoxyl group-2-propyl ester, 1-methoxyl group-2-propyl group alcohol of 66.0g, the Glacial acetic acid of 132.1g, the water of 67.1g and the methanesulfonic acid catalyzed agent of 17.9g that in reboiler/reactor, add 62.8g.Distillation tower is under atmospheric pressure operated, and reflux ratio is 1.0.The 1-methoxyl group of consisting of of fresh material: 44.0wt%-2-propyl group alcohol, the Glacial acetic acid of 14.0wt% and the water of 42.0wt% add to this fresh material in the reboiler, and feed rate is 5.28g/min.Hexanaphthene is added in the overhead product receptor, and feed rate is 1.07g/min.The temperature of reboiler remains on 112 ℃ in the operating process, and the temperature at distillation tower top tray place is 94 ℃; This assurance does not have or does not almost have hexanaphthene to be present in distillation tower or the reactor/reboiler.Comprising cyclohexane feed, is 6.36g/min by the total output of overhead product decantor.The overhead product of condensation is separated into the oil phase that mainly comprises hexanaphthene and acetate 1-methoxyl group-2-propyl ester immediately, and the water that mainly comprises water and the pure and mild acetate 1-methoxyl group of part 1-methoxyl group-2-propyl group-2-propyl ester.Only with aqueous-phase reflux to distillation tower.These operational conditions kept 5 hours.
With the composition that adds the overhead product before the hexanaphthene through being measured as: the water of acetate 1-methoxyl group-2-propyl ester of 33.1wt%, the 1-methoxyl group of 21.2wt%-pure and mild 45.7wt% of 2-propyl group.Determine that from this measurement under these reaction conditionss, this mixture can not be separated into two-phase.After adding hexanaphthene, be separated, oil phase comprise hexanaphthene, the 46.6wt% of 44.1wt% acetate 1-methoxyl group-2-propyl ester, 7.7wt% the water of 1-methoxyl group-pure and mild 1.6wt% of 2-propyl group.Hexanaphthene with about 10wt% is also observed into phase.Embodiment 2
After the process of embodiment 1, distillation tower is in 0.68 time operation of reflux ratio, the 1-methoxyl group of consisting of of fresh material: 47.7wt%-2-propyl group alcohol, the Glacial acetic acid of 18.2wt% and the water of 34.0wt% add to this fresh material in the reboiler, and feed rate is 5.85g/min.Hexanaphthene is added in the overhead product receptor, and feed rate is 2.01g/min.The temperature of reboiler is maintained at about 115 ℃ in the operating process, and the temperature at distillation tower top tray place is about 93 ℃.Comprising cyclohexane feed, is 7.78g/min by the total output of overhead product decantor.As in the foregoing embodiment, oil phase and water have been separated into.These operational conditions kept 4 hours.
In the overhead product receptor, to add consisting of of overhead product before the hexanaphthene: the water of acetate 1-methoxyl group-2-propyl ester of 32.5wt%, the 1-methoxyl group of 19.3wt%-pure and mild 48.2wt% of 2-propyl group.Determine that from this experiment this mixture can not be separated into two-phase.
After adding hexanaphthene and being separated, the consisting of of product phase: acetate 1-methoxyl group-2-propyl ester of the hexanaphthene of 50.8wt%, 43.5wt%, 5.7wt% the water of 1-methoxyl group-pure and mild 0.0wt% of 2-propyl group.Comparative example
The many experiments that do not add hexanaphthene show, can not be separated in the overhead product receptor, unless the reflux ratio in the tower is at least 3.0, are preferably greater than 5.0 when adopting the tower of 30 column plates.But under these operational conditions, the charging of reboiler may only be maintained at about the speed of 1.0g/min.In fact, also be impossible even under this speed, work as circulation unreacted 1-methoxyl group-2-propyl ether, must consider the operation dehydration tower.
These embodiment show, compare with the situation of not using phase-separating agent, and the speed that required ester products can be high 5 times is discharged.The result shows that also the distillable product that obtains comprises needed ester, and it does not comprise the carboxylic acid reaction thing.The result shows that also actual mechanical process need not acid catalyst is neutralized to reclaim pure products.
Claims (8)
1, a kind of production method of carboxylicesters of alkylene glycol monoalkyl ethers comprises:
A) in a reaction tower, in the presence of a kind of acid catalyst, make the reaction of monocarboxylic acid or halogenated monocarboxylic acid with 1-10 carbon atom and alkylene glycol monoalkyl ethers with following formula:
Wherein, n=0-6; R
1, R
2=H, CH
3-(CH
2)
n-, X=Cl, Br, F
B) in distillation tower, mixture is distilled, utilize reaction water and carboxylicesters and unreacted alkylene glycol monoalkyl ethers to form azeotrope simultaneously;
C) will cause from the overhead product of (b) in overhead product extractor/separator and with the inert solvent contact of significant quantity to form at least two mutually;
D) with the two-phase of the mixture that forms separately to form water and oil phase (product mutually);
E) oil phase is distilled to reclaim monocarboxylic acid ester products and inert solvent.
2, according to the method for claim 1, wherein, acid catalyst is selected from: the vitriol oil, hydrochloric acid, nitric acid, boron trifluoride, antimony pentafluoride, sulfonic acid such as methylsulfonic acid, ethyl sulfonic acid and fourth sulfonic acid, trifluoromethanesulfonic acid, trichlorine methylsulfonic acid, neighbour-or right-toluenesulphonic acids, Phenylsulfonic acid and sulfonated aromatic ion exchange resin and perfluoro alkyl sulfonic acid resin.
3, according to the process of claim 1 wherein that ether is 1-methoxyl group-2-propyl alcohol, 1-oxyethyl group-2-ethanol.
4, according to the process of claim 1 wherein that inert solvent is straight chain, side chain, aromatics, cyclophane family (cycloaromatic) hydrocarbon, ester, ether, ketone and fluorine chlorine compound.
5, according to the method for claim 4, wherein, solvent is selected from C
5-C
12, pentane, pentamethylene, hexane, hexanaphthene, toluene, benzene, dimethylbenzene; Butylacetate, propyl acetate, ethyl acetate, MTBE, Di Iso Propyl Ether, MEK, MPK, MBK and corresponding hyperbranched compounds, methylene dichloride, tetracol phenixin.
6, according to the method for claim 5, wherein, the consumption of solvent is about 5-70wt%.
7, according to the method for claim 6, wherein, the consumption of solvent is about 10-50wt%.
8, according to the method for claim 7, wherein, the consumption of solvent is about 20-40wt%.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97182427A CN1107048C (en) | 1997-10-31 | 1997-10-31 | Continuous process for the production of carboxylic acid esters of alkylene glycol monoalkyl ethers |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97182427A CN1107048C (en) | 1997-10-31 | 1997-10-31 | Continuous process for the production of carboxylic acid esters of alkylene glycol monoalkyl ethers |
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| CN1275974A true CN1275974A (en) | 2000-12-06 |
| CN1107048C CN1107048C (en) | 2003-04-30 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101475478B (en) * | 2009-01-20 | 2012-05-23 | 江苏怡达化工有限公司 | Method for synthesizing ethylene glycol monobutyl ether acetate |
| CN108997118A (en) * | 2018-08-07 | 2018-12-14 | 安庆市鑫祥瑞环保科技有限公司 | A method of compounding extractant and the industrial wastewater using compounding extracting rectifying processing propylene glycol methyl ether acetate |
| CN109265340A (en) * | 2018-11-19 | 2019-01-25 | 深圳市前海博扬研究院有限公司 | A kind of glycol ChanShuDing ether carboxylate and preparation method thereof |
| CN113636932A (en) * | 2014-06-24 | 2021-11-12 | 陶氏环球技术有限责任公司 | Method for manufacturing low VOC coalescing aids |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5618973A (en) * | 1994-11-10 | 1997-04-08 | Union Carbide Chemicals & Plastics Technology Corporation | Esterification process |
-
1997
- 1997-10-31 CN CN97182427A patent/CN1107048C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101475478B (en) * | 2009-01-20 | 2012-05-23 | 江苏怡达化工有限公司 | Method for synthesizing ethylene glycol monobutyl ether acetate |
| CN113636932A (en) * | 2014-06-24 | 2021-11-12 | 陶氏环球技术有限责任公司 | Method for manufacturing low VOC coalescing aids |
| CN108997118A (en) * | 2018-08-07 | 2018-12-14 | 安庆市鑫祥瑞环保科技有限公司 | A method of compounding extractant and the industrial wastewater using compounding extracting rectifying processing propylene glycol methyl ether acetate |
| CN109265340A (en) * | 2018-11-19 | 2019-01-25 | 深圳市前海博扬研究院有限公司 | A kind of glycol ChanShuDing ether carboxylate and preparation method thereof |
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