CN1269790C - Clean production method for propylene glycol monomethyl ether acetate - Google Patents
Clean production method for propylene glycol monomethyl ether acetate Download PDFInfo
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- CN1269790C CN1269790C CN 200410065772 CN200410065772A CN1269790C CN 1269790 C CN1269790 C CN 1269790C CN 200410065772 CN200410065772 CN 200410065772 CN 200410065772 A CN200410065772 A CN 200410065772A CN 1269790 C CN1269790 C CN 1269790C
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- glycol monomethyl
- monomethyl ether
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Abstract
The present invention relates to a method for cleanly producing propylene glycol ether propionate. Propylene glycol ether and propionic acid serve as raw materials, and directly carry out esterification reaction under the functions of an acid catalyst and an azeotropic dehydrating agent. The present invention is characterized in that the azeotropic dehydrating agent is acetate or propionate. The present invention adopts the acetate or the propionate to serve as the azeotropic dehydrating agent, the toxicity is low, and the products are not polluted.
Description
Technical field:
The present invention relates to a kind of clean production method for propylene glycol monomethyl ether acetate.Propylene glycol monomethyl ether acetate has good solvability and relative high inclined to one side oiliness, except that being used for paint thinner, also can be used as synthetic resins with raw material, printing ink with solvent, substitute trichloroethane with electronic cleaning agent and used for cosmetic solvent.It is the ideal substitute of glycol ether acetic ester.
Background technology:
Propylene glycol monomethyl ether acetate (PMP) main component is propionic acid-1-methoxyl group-2-propyl diester, is (to contain a small amount of isomer 2-methoxyl group-1-propyl alcohol with alcohol in 1-methoxyl group-2-; Hereinafter to be referred as propylene glycol monomethyl ether, PM) and propionic acid (hereinafter to be referred as PA) be raw material, under acid catalyst and azeotropy dehydrant effect, carry out direct esterification reaction:
Propylene glycol monomethyl ether direct esterification legal system is equipped with propylene glycol monomethyl ether acetate, and its technological core is to select suitable catalyzer and azeotropy dehydrant for use, to improve activity, selectivity and the esterification yield of esterification.Traditional esterified acid catalyst all adopts liquid acid such as phosphoric acid, hydrochloric acid, the vitriol oil, chlorsulfonic acid, oxalic acid, tosic acid, methylsulfonic acid, the vitriol oil commonly used, tosic acid, but exist corrodibility strong, with the product separation difficulty, pollute shortcomings such as big; Thereby many solid acids are used for acid catalyzed reaction, and solid acid comprises heteropolyacid, super acids, mixed oxide, zeolite molecular sieve, ion exchange resin etc., and our company has developed solid super acid catalyst, separates easy (seeing CN1473815A) with product.
In the propylene glycol monomethyl ether acetate preparation process, move to the direction that helps generating ester, except the acid that makes one of reactant or alcohol are excessive, add azeotropy dehydrant and will react the by-product water that generates and constantly take out, with the transformation efficiency of raising reactant in order to make balance.
Select azeotropy dehydrant must follow following principle: the one, the azeotrope that azeotropic aqua and water form can not be too high, and boiling range is generally at 80～90 ℃; The 2nd, azeotropy dehydrant can not react with raw material, and promptly requiring solvent is non-polar solvent or the more weak solvent of polarity; The 3rd, the band aqua good with the water azeotropy under boiling state, at normal temperatures again can with the water natural layering, solubleness is little in water.Azeotropy dehydrant commonly used has benzene,toluene,xylene, hexane, hexanaphthene, ethylene dichloride, chlorine mill, tetracol phenixin etc.They and water azeotropic point are lower than 100 ℃, easy again and water stratification.The preparation of alcohol ether-ether is generally with benzene or toluene.
The dehydrating effect of benzene is good, but its toxicity is big, and is harmful to people's health; For toluene, dimethylbenzene, hexane, hexanaphthene, no matter how the condition of reaction process regulates, and all can carry about about 10% reactant propylene glycol monomethyl ether (seeing CN1092060A) secretly, and they are unfavorable azeotropy dehydrants.
Summary of the invention:
The objective of the invention is to overcome above-mentioned deficiency, provide a kind of toxicity lower, not the clean production method for propylene glycol monomethyl ether acetate of polluted product.
The object of the present invention is achieved like this: a kind of clean production method for propylene glycol monomethyl ether acetate, it is to be raw material with propylene glycol monomethyl ether and propionic acid, under acid catalyst and azeotropy dehydrant effect, carry out the direct esterification reaction, the azeotropy dehydrant that adopts in being characterized in reacting is acetic ester or propionic ester, propylene glycol monomethyl ether can 1-methoxyl group-2-propyl alcohol monomer, also can be the mixture of 1-methoxyl group-2-propyl alcohol and its isomer 2-methoxyl group-1-propyl alcohol, and its esterification formula is:
Or
Acetic ester comprises vinyl acetic monomer and N-BUTYL ACETATE, and propionic ester comprises methyl propionate, ethyl propionate, propyl propionate or isopropyl propionate, butyl propionate or isobutyl propionate etc., and its toxicity is lower, and polluted product is not safe in utilization; The reactant that the azeotrope that they and water form is taken out of is few, and its performance is better than toluene.
The rerum natura of reaction system is: the vinyl acetic monomer boiling point is 88 ℃, in the time of 20 ℃ in water solubleness be 8.7% (Wt); The N-BUTYL ACETATE boiling point is 126 ℃, in the time of 20 ℃ in water solubleness be 1% (Wt); The methyl propionate boiling point is 79.7 ℃, in the time of 20 ℃ in water solubleness be 0.5% (Wt); The ethyl propionate boiling point is 99.1 ℃, in the time of 20 ℃ in water solubleness be 2.4% (Wt); The propyl propionate boiling point is 122.5 ℃, in the time of 20 ℃ in water solubleness be 0.56% (Wt); The isopropyl propionate boiling point is 110 ℃ (100kPa), in the time of 20 ℃ in water solubleness be 0.6% (Wt); The butyl propionate boiling point is 146 ℃, and the utmost point is insoluble in water in the time of 20 ℃; The isobutyl propionate boiling point is 136.8 ℃, in the time of 20 ℃ in the water solubleness be 0.1% (Wt); The propylene glycol monomethyl ether boiling point is 120 ℃, and the boiling point of propionic acid is 144 ℃, and the boiling point of product propylene glycol monomethyl ether acetate is 160.5 ℃.
The binary azeotrope boiling point that N-BUTYL ACETATE and water are formed is 90.2 ℃, and azeotrope is formed: water 28.7% (Wt), N-BUTYL ACETATE 71.3% (Wt).The ternary azeotrope boiling point that N-BUTYL ACETATE, butanols and water are formed is 90.7 ℃, and azeotrope is formed: water 29% (Wt), butanols 8% (Wt), N-BUTYL ACETATE 63% (Wt).
71.4 ℃ of the binary azeotrope boiling points that methyl propionate and water are formed, azeotrope is formed: water 3.9% (Wt), ritalin 96.1% (Wt).The binary azeotrope boiling point that ethyl propionate and water are formed is 81.2 ℃, and azeotrope is formed: water 10% (Wt), ethyl propionate 90% (Wt).The binary azeotrope boiling point that propyl propionate and water are formed is 88.9 ℃, and azeotrope is formed: water 23% (Wt), propyl propionate 77% (Wt).The binary azeotrope boiling point that isobutyl propionate and water are formed is 92.8 ℃, and azeotrope is formed: water 32.2% (Wt), isobutyl propionate 67.8% (Wt).
Vinyl acetic monomer, N-BUTYL ACETATE can be hydrolyzed to pure and mild acetic acid, trace impurity meeting polluted product; Propyl propionate, butyl propionate and PM also can form azeotrope, and the propylene glycol monomethyl ether amount that causes carrying secretly in the by-product water is up to 15%, and they are not the ideal azeotropy dehydrants.The boiling point of isopropyl propionate is lower than propyl propionate, separate easily; Isobutyl propionate is lower than butyl propionate, separate easily.
The organism of carrying secretly in the methyl propionate by-product water is less, and dehydrating effect is good, but methyl propionate is difficult to directly be prepared by methyl alcohol and propionic acid in the propylene glycol monomethyl ether acetate reaction system.
Ethyl propionate and water stratification are good, do not form azeotrope substantially with PM yet, the organism of carrying secretly in the by-product water is less (to contain ethyl propionate 2.6% approximately, propionic acid 0.4%), ethyl propionate can directly be prepared by ethanol and propionic acid in the propylene glycol monomethyl ether acetate reaction system, easy to prepare, be the ideal azeotropy dehydrant.
The propionic ester preparation can add stoichiometric lower member ester fat alcohol (ethanol, propyl alcohol or butanols) and propionic acid in the propylene glycol monomethyl ether acetate reaction system, can generate corresponding propionic ester, and play the azeotropy dehydrant effect, propylene glycol monomethyl ether and acetic acid reaction are carried out smoothly.
The mass percent consumption that azeotropy dehydrant accounts for the total amount that feeds intake is 5～30% (are benchmark with the reaction mass), suitable mass percent consumption is 6～20% (are benchmark with the reaction mass), and best in quality per-cent consumption is 8～15% (are benchmark with the reaction mass).The dewatering agent consumption is lower than 5%, can not fully form azeotrope with reacting the water that forms, and causes dehydrating effect not good; The dewatering agent consumption is greater than 30%, and dehydrating effect can not increase, and also can cause the rectifying energy consumption to strengthen, and there is no need.Therefore, the dewatering agent consumption is controlled well, and dehydrating effect is good, and the rectifying energy consumption is again little.
Esterification main raw material propylene glycol monomethyl ether is a technical grade, and Yida Chemical Co., Ltd. Jiangyin produces, and carries out catalyzed reaction by propylene oxide and methyl alcohol, makes by rectifying, and product purity is greater than 99.0%.Propionic acid is a chemical pure, and Shanghai Ling Feng chemical reagent company limited produces, and content is greater than 99.0%.
Esterification adopts reaction rectification technique.Propylene glycol monomethyl ether, propionic acid and azeotropy dehydrant, acid catalyst added in the reactor that has rectifying tower, condenser and water trap react, constantly will react the moisture that generates at cat head goes out, and azeotropy dehydrant returns and heats up in a steamer to tower, and after drainage water reached theoretical value, reaction finished.Product is delivered to rectifying tower I, and dewatering agent, unreacting material are steamed, and returns to recycle, the thick product of tower still delivers to the settling vessel sedimentation, filter tell catalyzer after, thick product is delivered to rectifying tower II, steams product P MP.Fig. 1 is seen in the technical process of production process:
Esterification reaction temperature generally is controlled at 100～160 ℃, and suitable temperature of reaction is 120～160 ℃, and optimal reaction temperature is 130～155 ℃.The reaction system remains at boiling state, and the water of telling to reaction only reaches stoichiometric number.Temperature low reaction speed is slow, long reaction time, on the contrary the temperature height is then.But the too high quantity of reflux that causes of temperature is big, and the energy consumption height is unfavorable for operation again.
Acid catalyst mass percent consumption is 0.05～1% (is benchmark with the reaction-ure mixture), suitable mass percent consumption is 0.1～0.5% (is benchmark with the reaction-ure mixture), and best in quality per-cent consumption is 0.1～0.2% (is benchmark with the reaction-ure mixture).Catalyst levels is few, and speed of response is slow, too much also is no advantage to improving speed of response.
The solid super-strong acid consumption is 0.2～5% (is benchmark with the reaction-ure mixture), and suitable consumption is 0.6～3% (is benchmark with the reaction-ure mixture), and optimum amount is 1～2% (is benchmark with the reaction-ure mixture).
The mole proportioning of propylene glycol monomethyl ether and propionic acid is 0.8～1.3, and is too much or very few, except to react influential, the rectifying of product load is brought burden, energy consumption increases.The suitable propylene glycol monomethyl ether and the mole proportioning of propionic acid are 0.9～1.2, and the best propylene glycol monomethyl ether and the mole proportioning of propionic acid are 1.1～1.2, also are that excessive 10～20% (mol) of propylene glycol monomethyl ether are for best.Propionic acid feeds intake excessive, and is higher than 120 ℃ of propylene glycol monomethyl ether boiling points owing to 144 ℃ of propionic acid boiling points, brings difficulty for the reaction product rectifying separation; The propionic acid charging capacity is few, and reaction not exclusively.
Reaction product is at first carried out atmospheric distillation, and control still temperature is less than 165 ℃, and the top temperature is less than 150 ℃, and reflux ratio 1～8 steams foreshot and recycles.The thick product that removes front-end volatiles carries out rectifying, and control still temperature is collected reflux ratio 3～1 less than 175 ℃, 157～165 ℃ of fractions of top temperature, and product content is greater than 99.5%.
Description of drawings:
Fig. 1 is the process flow sheet of production process of the present invention.
Embodiment:
Example 1:
Having water trap, returning in the 500ml there-necked flask heat up in a steamer condenser ￠ 20 * 600 packing towers and add PM 180g respectively, PA 132g, tosic acid 0.3g, acetate butyl 47g, 130～145 ℃ of control reaction temperature keep reactant to be in boiling state all the time, reaction 4h, each fractional composition of reaction product gas chromatographic analysis is as follows: water 1.1%, assorted 0.3%, PA 11.6%, PM 14.9%, butyl propionate 10.9%, assorted 2.1%, mix 2.6%, PMP 56.3%.
Example 2:
Having water trap, returning in the 1000ml there-necked flask heat up in a steamer condenser ￠ 20 * 1000 packing towers and add PM 270g respectively, PA 245g, tosic acid 1g, methyl propionate 42g, 130～160 ℃ of control reaction temperature keep reactant to be in boiling state all the time, reaction 6h divides water outlet 67g; Air distillation is collected boiling point less than 130 ℃ of fraction 50g, 130～150 ℃ of fraction 33g of boiling point; Get thick product 413g, each fractional composition of gas chromatographic analysis such as following table:
| Component | Analytical results |
| By-product water | Water 97.8%, methyl propionate 2.2% |
| Less than 130 ℃ of fractions | Water 4.0% mixes 0.3%, methyl propionate 79.5%, PM15.1%, assorted 0.2% |
| 130～150 ℃ of fractions | Water 1.2% mixes 0.6%, and PA 94.7%, mixes 0.1%, and PMP 2.6% |
| Thick product | Water 0.1%, PA 2.6%, and PMP 97.7% |
Example 3:
Having water trap, returning in the 1000ml there-necked flask heat up in a steamer condenser ￠ 20 * 1000 packing towers and add PM 270g respectively, PA 245g, tosic acid 1g, propyl propionate 42g, 130～156 ℃ of control reaction temperature keep reactant to be in boiling state all the time, reaction 5.5h divides water outlet 71g; Air distillation is collected boiling point less than 155 ℃ of fraction 109g, gets thick product 383g, each fractional composition of gas chromatographic analysis such as following table:
| Component | Analytical results |
| By-product water | Water 80.1%, propyl alcohol 1.0%, PM17.8%, methyl propionate 1.2% |
| Less than 150 ℃ of fractions | Water 6.4% mixes 0.6%, propyl alcohol 1.0%, and PA 12.6%, and PM 23.6%, propyl propionate 33.0%, PMP22.7% |
| Thick product | Water 0.06%, PA 0.9%, and PMP 99.0% |
Example 4:
Having water trap, returning in the 1000ml there-necked flask heat up in a steamer condenser ￠ 20 * 1000 packing towers and add PM 270g respectively, PA 245g, tosic acid 1g, butyl propionate 42g, 130～155 ℃ of control reaction temperature keep reactant to be in boiling state all the time, reaction 5h divides water outlet 57g; Air distillation is collected boiling point less than 152 ℃ of fraction 100g, gets thick product 405g, each fractional composition of gas chromatographic analysis such as following table:
| Component | Analytical results |
| By-product water | Water 88.2% mixes 0.2%, and PA 0.6%, and PM 10.9% |
| Less than 150 ℃ of fractions | Water 6.8% mixes 0.4%, and PA 15.6%, and PM 43.3%, butyl propionate 29.2%, and PMP 4.7% |
| Thick product | Water 0.06%, PA 2.0%, butyl propionate 2.7%, PMP 95.1% |
Example 5:
Having water trap, returning in the 1000ml there-necked flask heat up in a steamer condenser ￠ 20 * 1000 packing towers and add PM 270g respectively, PA 245g, tosic acid 1g, ethyl propionate (EP) 42g, 130～155 ℃ of control reaction temperature, keep reactant to be in boiling state all the time, reaction 5h divides water outlet 55g; Air distillation is collected boiling point less than 162 ℃ of fraction 74g, gets thick product 414g, each fractional composition of gas chromatographic analysis such as following table:
| Component | Analytical results |
| By-product water | Water 96.9%, PA 0.4%, and EP 2.6% |
| Less than 150 ℃ of fractions | Water 2.1% mixes 1.5%, and PA 29.7%, and EP 66.6% |
| Thick product | Water 0.05%, PA 1.6%, and PMP 98.3% |
Example 6:
Having water trap, returning in the 10000ml there-necked flask heat up in a steamer condenser ￠ 40 * 1000 packing towers and add PM 1452g respectively, PA 1110g, tosic acid 5g, EP 200g, 125～150 ℃ of control reaction temperature, keep reactant to be in boiling state all the time, the gas chromatographic analysis of reaction process and reaction product sees the following form:
Propylene glycol monomethyl ether acetate reaction and separating technology condition
| Step | The still temperature (℃) | The top temperature (℃) | Reflux ratio | Vacuum tightness (Mpa) | Remarks |
| Heating | ～124 | ～78 | Total reflux | 0 | Heat up, begin to reflux |
| Dehydration reaction | 124～149 | 78～82 | Total reflux | 0 | Return and heat up in a steamer 6h, divide water |
| Atmospheric distillation | ～148 | ～74 | 1∶1 | 0 | 10min, front-end volatiles |
| 149～150 | 78 | Total reflux | 0 | Divide water | |
| 151～163 | 92～130 | 3∶1 | 0 | Steam EP and unreacted reactant | |
| ～164 | 130～150 | 8∶1 | 0 | Steam unreacted reactant | |
| Cooling | Below 70 | 0 | Tell catalyzer |
The reaction process material analyzing
| Component | Analytical results | Remarks |
| By-product water | Water 90.3%, ethanol 5.9%, PM0.6%, EP1.9%, other is 1% years old | 277g |
| Foreshot | Ethanol 13.1% is not determined thing 13.5%, and PM 70.2%, and EP 1.2% | 11g |
| The dewatering agent fraction | PM 38.9％，EP 54.8％，PMP 4.2％ | 287g |
| The unreacted reactant fraction | PM 11.5％，EP 4.7％，PA 20.5％，PMP 60.4％ | 63g |
| Thick product | PMP 99.5％ | 2120g |
Claims (8)
1, a kind of clean production method for propylene glycol monomethyl ether acetate, it is to be raw material with propylene glycol monomethyl ether and propionic acid, under acid catalyst and azeotropy dehydrant effect, carries out the direct esterification reaction, it is characterized in that azeotropy dehydrant is an ethyl propionate.
2, a kind of clean production method for propylene glycol monomethyl ether acetate according to claim 1, it is characterized in that propylene glycol monomethyl ether is the mixture of 1-methoxyl group-2-propyl alcohol monomer or 1-methoxyl group-2-propyl alcohol and its isomer 2-methoxyl group-1-propyl alcohol, its esterification formula is:
3, a kind of clean production method for propylene glycol monomethyl ether acetate according to claim 1 and 2 is characterized in that the mass percent consumption that the azeotropy dehydrant ethyl propionate accounts for the total amount that feeds intake is 6～20%.
4, a kind of clean production method for propylene glycol monomethyl ether acetate according to claim 1 and 2 is characterized in that the mass percent consumption that the azeotropy dehydrant ethyl propionate accounts for the total amount that feeds intake is 8～15%.
5, a kind of clean production method for propylene glycol monomethyl ether acetate according to claim 1 and 2, it is characterized in that esterification adopts reaction rectification technique: with propylene glycol monomethyl ether, propionic acid and azeotropy dehydrant, acid catalyst adds and has rectifying tower, react in the reactor of condenser and water trap, constantly will react the moisture that generates at cat head goes out, and azeotropy dehydrant returns and heats up in a steamer to tower, after the drainage water, reaction finishes, product is delivered to rectifying tower I, with dewatering agent, unreacting material steams, return and recycle, the thick product of tower still is delivered to the settling vessel sedimentation, after catalyzer was told in filtration, thick product was delivered to rectifying tower II, steams the propylene glycol monomethyl ether acetate elaboration.
6, a kind of clean production method for propylene glycol monomethyl ether acetate according to claim 5 is characterized in that the esterification temperature is 120～160 ℃.
7, a kind of clean production method for propylene glycol monomethyl ether acetate according to claim 6 is characterized in that the esterification temperature is 130～155 ℃.
8, a kind of clean production method for propylene glycol monomethyl ether acetate according to claim 7 is characterized in that mole proportioning that feeds intake of propylene glycol monomethyl ether and propionic acid is 0.9～1.2.
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| CN101921179B (en) * | 2010-08-11 | 2013-03-27 | 安徽立兴化工有限公司 | Preparation method of dipropylene glycol methyl propyl ether |
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Address after: Zhuangqiu Li Gang Zhen Xi Shi Qiao Bei Guo Zhuang 214444 of Jiangsu Province, Jiangyin City No. 1 Patentee after: JIANGSU YIDA CHEMICAL Co.,Ltd. Patentee after: NANJING FORESTRY University Address before: Zhuangqiu Li Gang Zhen Xi Shi Qiao Bei Guo Zhuang 214444 of Jiangsu Province, Jiangyin City No. 1 Patentee before: Jiangsu Yida Chemical Co.,Ltd. Patentee before: Nanjing Forestry University Address after: Zhuangqiu Li Gang Zhen Xi Shi Qiao Bei Guo Zhuang 214444 of Jiangsu Province, Jiangyin City No. 1 Patentee after: Jiangsu Yida Chemical Co.,Ltd. Patentee after: NANJING FORESTRY University Address before: Zhuangqiu Li Gang Zhen Xi Shi Qiao Bei Guo Zhuang 214444 of Jiangsu Province, Jiangyin City No. 1 Patentee before: Jiangyin Yida Chemical Co.,Ltd. Patentee before: Nanjing Forestry University |