CN102320962B - Method for catalytic synthesis of methyl propionate - Google Patents
Method for catalytic synthesis of methyl propionate Download PDFInfo
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- CN102320962B CN102320962B CN 201110200706 CN201110200706A CN102320962B CN 102320962 B CN102320962 B CN 102320962B CN 201110200706 CN201110200706 CN 201110200706 CN 201110200706 A CN201110200706 A CN 201110200706A CN 102320962 B CN102320962 B CN 102320962B
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Abstract
The invention discloses a method for catalytic synthesis of methyl propionate. The method comprises the steps of: uniformly mixing a catalyst and propanoic acid, adding to a reaction kettle, heating the reaction kettle in an oil bath, after the liquid in the kettle reaches a certain temperature, continuously adding a mixture of propanoic acid and methanol, beginning an esterification reaction, and rectifying with a rectifying tower to obtain methyl propionate, wherein the catalyst is selected from an ion liquid of pyridinium hydrogen sulfate, imidazolium hydrogen sulfate, pyridinium p-toluenesulfonate, imidazolium p-toluenesulfonate and imidazolium hydrogen phosphate or p-toluenesulfonic acid. The method has the advantages that the equipment corrosion caused by strong acidity when sulfuric acid is used as the catalyst is avoided, the industrial investment cost is lowered, the utilization rate of the catalyst is higher, and the yield of the esterification reaction can reach more than 93%.
Description
Technical field
The present invention relates to a kind of method that catalyzes and synthesizes methyl propionate.
Background technology
Methyl propionate generally is commonly used for the solvent of production of cellulose, coating and spicing product, also is used as the intermediate of multiple organic synthesis.In recent years, along with the development of MMA technology, having developed with the methyl propionate is raw material, with the technology of formaldehyde at the synthetic MMA of catalyzer condition, becomes a kind of new application of methyl propionate.
Traditional methyl propionate synthesis technique generally is catalyzer, propionic acid and the propionic acid synthesized methyl esters of methyl alcohol direct esterification with sulfuric acid.Sulfuric acid has very strong acidity and oxidisability, and material, the design requirements of equipment had very high requirement.The possessor is the stationary phase catalyzer by the acid ion resin to the greatest extent, and by the propionic acid synthesized methyl esters of gas-solid reaction, still, because it at first becomes reactant into gaseous state, energy consumption is higher, and gas-solid contact area is inhomogeneous, is subjected to the restriction of technology.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of method that catalyzes and synthesizes methyl propionate.
For solving the problems of the technologies described above, the present invention includes following steps:
(1) catalyst mix of getting 150-250 part propionic acid, 1.5-15 part by weight evenly places the reactor of rectifying tower, catalyzer is the ionic liquid of pyridine hydrosulfate, imidazole bisulfate, pyridine tosic acid, imidazoles tosic acid, imidazoles hydrophosphate, in the tosic acid more than one, and propionic acid is the technical grade propionic acid.
Catalyzer is one or more the mixture in above-mentioned ionic liquid or the tosic acid, and each component is pressed arbitrary proportion and mixed in the catalyst mixture.
(2) stir and heat described propionic acid and mixture of catalysts with oil bath, the temperature of thermal oil is 120-160 ℃, when treating that described propionic acid and mixture of catalysts temperature rise to 100-140 ℃, take by weighing 80-120 part methyl alcohol and 148-277 part propionic acid by weight, the mol ratio of methyl alcohol and propionic acid is 1:0.8-1, and the two is mixed, and regulates the charging flow velocity and be 0.4-0.8mL/min charging in the reactor continuously, methyl alcohol is the methyl alcohol of technical grade, keeps temperature in the kettle between 102-106 ℃.
(3) when the liquid level of reactor still liquid greater than the reactor height 3/4ths the time, stop to add propionic acid, only drip methyl alcohol continuously in still, the flow velocity of methyl alcohol is 0.1-0.3ml/min, be lower than 3/4ths of reactor height up to liquid level, continue to add described propionic acid and methanol mixture.
(4) treat that phlegma appears in cat head after, total reflux 20-40min.
(5) the control reflux ratio is 3-5, and the mixture of extraction methyl propionate places the water trap of cat head to leave standstill.
Optimum reflux ratio is 4.
(6) from water trap bottom extraction water layer, water trap top extraction methyl propionate.
(7) mixture for the treatment of the methyl propionate of extraction leaves standstill the back when not stratified in water trap, stop charging, improve the temperature of thermal oil simultaneously to 140-170 ℃, full extraction gets methyl propionate, when treating that the still liquid temp goes back up to 100-140 ℃, the thermal oil temperature is adjusted back to 120-160 ℃, continue charging, repeating step (5) and step (6), obtain methyl propionate, finish up to charging.
The beneficial effect that adopts technique scheme to produce is:
(1) strongly-acid has reduced the industrial investment cost to the corrodibility of equipment in the time of can avoiding making catalyzer with sulfuric acid.
(2) because the application's catalyzer is liquid, and reaction belongs to homogeneous reaction, and the utilization ratio of catalyzer is higher, the esterification yield can reach more than 93%.
Embodiment
Embodiment 1:
(1) the pyridine hydrosulfate ionic liquid that takes by weighing 200g technical grade propionic acid, 12g mixes the reactor that places rectifying tower.
(2) stir and heat above-mentioned propionic acid and mixture of catalysts with oil bath, the temperature of thermal oil is 130 ℃, when treating that above-mentioned propionic acid and mixture of catalysts temperature rise to 120 ℃, take by weighing 100g methyl alcohol and 231g propionic acid, with the two mixing, by regulating flow velocity in 0.8mL/min charging in the reactor continuously, keep temperature in the kettle at 104 ℃.
(3) when the liquid level of reactor still liquid greater than the reactor height 3/4ths the time, stop to add propionic acid, only drip above-mentioned methyl alcohol continuously in still, the flow velocity of methyl alcohol is 0.2ml/min, be lower than 3/4ths of reactor height up to liquid level, continue to add described propionic acid and methanol mixture.
(4) treat that phlegma appears in cat head after, total reflux 30min.
(5) the control reflux ratio is 4, and the mixture of extraction methyl propionate places the water trap of cat head to leave standstill.
(6) from water trap bottom extraction water layer, water trap top extraction methyl propionate.
(7) mixture for the treatment of the methyl propionate of extraction leaves standstill the back when not stratified in water trap, stop charging, improve the temperature to 150 ℃ of thermal oil simultaneously, full extraction gets methyl propionate, when treating that the still liquid temp goes back up to 120 ℃, the thermal oil temperature is adjusted back to 130 ℃, continue charging, repeating step (5) and step (6), obtain methyl propionate, finish up to charging.
The total recovery of methyl propionate is 94%.
Embodiment 2:
(1) tosic acid that takes by weighing 150g technical grade propionic acid, 1.5g mixes the reactor that places rectifying tower.
(2) stir and heat above-mentioned propionic acid and mixture of catalysts with oil bath, the temperature of thermal oil is 120 ℃, when treating that above-mentioned propionic acid and mixture of catalysts temperature rise to 100 ℃, take by weighing 80g methyl alcohol and 185g propionic acid, with the two mixing, by regulating flow velocity in 0.4mL/min charging in the reactor continuously, keep temperature in the kettle at 102 ℃.
(3) when the liquid level of reactor still liquid greater than the reactor height 3/4ths the time, stop to add propionic acid, only drip above-mentioned methyl alcohol continuously in still, the flow velocity of methyl alcohol is 0.1ml/min, be lower than 3/4ths of reactor height up to liquid level, continue to add described propionic acid and methanol mixture.
(4) treat that phlegma appears in cat head after, total reflux 20min.
(5) the control reflux ratio is 3, and the mixture of extraction methyl propionate places the water trap of cat head to leave standstill.
(6) from water trap bottom extraction water layer, water trap top extraction methyl propionate.
(7) mixture for the treatment of the methyl propionate of extraction leaves standstill the back when not stratified in water trap, stop charging, improve the temperature to 140 ℃ of thermal oil simultaneously, full extraction gets methyl propionate, when treating that the still liquid temp goes back up to 100 ℃, the thermal oil temperature is adjusted back to 120 ℃, continue charging, repeating step (5) and step (6), obtain methyl propionate, finish up to charging.
The total recovery of methyl propionate is 93.5%.
Embodiment 3:
(1) takes by weighing the reactor that 250g technical grade propionic acid, 10g imidazoles tosic acid ionic liquid and 5g pyridine tosic acid ionic liquid mix the rectifying tower that places 500ml.
(2) stir and heat above-mentioned propionic acid and mixture of catalysts with oil bath, the temperature of thermal oil is 160 ℃, when treating that above-mentioned propionic acid and mixture of catalysts temperature rise to 140 ℃, take by weighing 120g methyl alcohol and 277g propionic acid, with the two mixing, by regulating flow velocity in 0.6mL/min charging in the reactor continuously, keep temperature in the kettle at 102 ℃.
(3) when the liquid level of reactor still liquid greater than the reactor height 3/4ths the time, stop to add propionic acid, only drip above-mentioned methyl alcohol continuously in still, the flow velocity of methyl alcohol is 0.3ml/min, be lower than 3/4ths of reactor height up to liquid level, continue to add described propionic acid and methanol mixture.
(4) treat that phlegma appears in cat head after, total reflux 40min.
(5) the control reflux ratio is 5, and the mixture of extraction methyl propionate places the water trap of cat head to leave standstill.
(6) from water trap bottom extraction water layer, water trap top extraction methyl propionate.
(7) mixture for the treatment of the methyl propionate of extraction leaves standstill the back when not stratified in water trap, stop charging, improve the temperature to 160 ℃ of thermal oil simultaneously, full extraction gets methyl propionate, when treating that the still liquid temp goes back up to 170 ℃, the thermal oil temperature is adjusted back to 160 ℃, continue charging, repeating step (5) and step (6), obtain methyl propionate, finish up to charging.
The total recovery of methyl propionate is 94.5%.
Embodiment 4:
(1) tosic acid that takes by weighing 150g technical grade propionic acid, 1.5g mixes the reactor of the rectifying tower that places 500ml.
(2) stir and heat above-mentioned propionic acid and mixture of catalysts with oil bath, the temperature of thermal oil is 120 ℃, when treating that above-mentioned propionic acid and mixture of catalysts temperature rise to 100 ℃, take by weighing 80g methyl alcohol and 148g propionic acid, with the two mixing, by regulating flow velocity in 0.4mL/min charging in the reactor continuously, keep temperature in the kettle at 102 ℃.
(3) when the liquid level of reactor still liquid greater than the reactor height 3/4ths the time, stop to add propionic acid, only drip above-mentioned methyl alcohol continuously in still, the flow velocity of methyl alcohol is 0.1ml/min, be lower than 3/4ths of reactor height up to liquid level, continue to add described propionic acid and methanol mixture.
(4) treat that phlegma appears in cat head after, total reflux 20min.
(5) the control reflux ratio is 3, and the mixture of extraction methyl propionate places the water trap of cat head to leave standstill.
(6) from water trap bottom extraction water layer, water trap top extraction methyl propionate.
(7) mixture for the treatment of the methyl propionate of extraction leaves standstill the back when not stratified in water trap, stop charging, improve the temperature to 140 ℃ of thermal oil simultaneously, full extraction gets methyl propionate, when treating that the still liquid temp goes back up to 100 ℃, the thermal oil temperature is adjusted back to 120 ℃, continue charging, repeating step (5) and step (6), obtain methyl propionate, finish up to charging.
The total recovery of methyl propionate is 93%.
Embodiment 5:
Catalyzer is tosic acid, 3g pyridine hydrosulfate, 1g imidazole bisulfate, the 2g pyridine tosic acid of 2g.Other steps are with embodiment 1, and the total recovery of last methyl propionate is 93.2%
Embodiment 6:
Catalyzer is the ion of 2g imidazoles tosic acid and 3g pyridine hydrosulfate, 5g imidazoles hydrophosphate.Other steps are with embodiment 1, and the total recovery of last methyl propionate is 94.1%
Embodiment 7:
Catalyzer is ionic liquid and the 2.5g tosic acid of 1g pyridine hydrosulfate, 0.5g imidazole bisulfate, 2g pyridine tosic acid, 1.5g imidazoles tosic acid, 1g imidazoles hydrophosphate.Other steps are with embodiment 1, and the total recovery of last methyl propionate is 93.8%.
Embodiment 8:
Catalyzer is 3g pyridine hydrosulfate, 4.5g imidazole bisulfate, 0.5g pyridine tosic acid.Other steps are with embodiment 2, and the total recovery of last methyl propionate is 93%.
Embodiment 9:
Catalyzer is the 6.5g imidazole bisulfate.Other steps are with embodiment 3, and the total recovery of last methyl propionate is 94.1%.
Claims (1)
1. method that catalyzes and synthesizes methyl propionate is characterized in that may further comprise the steps:
(1) catalyst mix of getting 150-250 part propionic acid, 1.5-15 part by weight evenly places the reactor of rectifying tower, catalyzer is more than one in pyridine hydrosulfate, imidazole bisulfate, pyridine tosic acid, imidazoles tosic acid, the tosic acid, and propionic acid is the technical grade propionic acid;
(2) stir and heat described propionic acid and mixture of catalysts with oil bath, the temperature of thermal oil is 120-160 ℃, when treating that described propionic acid and mixture of catalysts temperature rise to 100-140 ℃, take by weighing 80-120 part methyl alcohol and 148-277 part propionic acid by weight, the mol ratio of methyl alcohol and propionic acid is 1:0.8-1, and the two is mixed, and regulates the charging flow velocity and be 0.4-0.8mL/min charging in the reactor continuously, methyl alcohol is the methyl alcohol of technical grade, keeps temperature in the kettle between 102-106 ℃;
(3) when the liquid level of reactor still liquid greater than the reactor height 3/4ths the time, stop to add propionic acid, only drip methyl alcohol continuously in still, the flow velocity of methyl alcohol is 0.1-0.3ml/min, be lower than 3/4ths of reactor height up to liquid level, continue to add described propionic acid and methanol mixture;
(4) treat that phlegma appears in cat head after, total reflux 20-40min;
(5) the control reflux ratio is 4, and the mixture of extraction methyl propionate places the water trap of cat head to leave standstill;
(6) from water trap bottom extraction water layer, water trap top extraction methyl propionate;
(7) mixture for the treatment of the methyl propionate of extraction leaves standstill the back when not stratified in water trap, stop charging, improve the temperature of thermal oil simultaneously to 140-170 ℃, full extraction gets methyl propionate, when treating that the still liquid temp goes back up to 100-140 ℃, the thermal oil temperature is adjusted back to 120-160 ℃, continue charging, repeating step (5) and step (6), obtain methyl propionate, finish up to charging.
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| CN102336661A (en) * | 2011-07-21 | 2012-02-01 | 北京旭阳化工技术研究院有限公司 | Preparation method of methyl propionate |
| CN104761450B (en) * | 2012-12-20 | 2016-08-24 | 常州市松盛香料有限公司 | The preparation method of ethyl propionate |
| CN109020811A (en) * | 2018-09-19 | 2018-12-18 | 张家港瀚康化工有限公司 | The method for preparing propionic ester using microreactor |
| CN109942420A (en) * | 2019-04-16 | 2019-06-28 | 张家港瀚康化工有限公司 | A kind of method of reaction rectification method preparation high-purity propionic ester |
| CN112851507A (en) * | 2021-01-25 | 2021-05-28 | 西南化工研究设计院有限公司 | Process for synthesizing methyl methacrylate by ethanol |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101560151A (en) * | 2009-05-22 | 2009-10-21 | 南京大学 | Process for continuously generating methyl acetate by reactive distillation taking ionic liquid as catalyst |
| CN101033210B (en) * | 2007-04-06 | 2010-08-11 | 中国科学院新疆理化技术研究所 | Functionalized acidic ionic liquid based on pyridine cation and its synthetic method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101033210B (en) * | 2007-04-06 | 2010-08-11 | 中国科学院新疆理化技术研究所 | Functionalized acidic ionic liquid based on pyridine cation and its synthetic method and application |
| CN101560151A (en) * | 2009-05-22 | 2009-10-21 | 南京大学 | Process for continuously generating methyl acetate by reactive distillation taking ionic liquid as catalyst |
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Inventor after: Yang Xuegang Inventor after: Li Hui Inventor after: Zhang Minsheng Inventor after: Zhang Xinzhi Inventor after: Zhang Yingwei Inventor after: Wang Lingqing Inventor after: Yang Hongqing Inventor after: Yin Zujian Inventor after: Huang Maohui Inventor after: Yun Zhiqiang Inventor after: Chen Xibo Inventor before: Yang Xuegang Inventor before: Zhang Minsheng Inventor before: Zhang Xinzhi Inventor before: Zhang Yingwei Inventor before: Wang Lingqing Inventor before: Yang Hongqing Inventor before: Yin Zujian Inventor before: Huang Maohui Inventor before: Yun Zhiqiang Inventor before: Li Hui |
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