CN103012149A - Esterification reaction-pervaporation membrane separation integrated method for producing methyl 3-hydroxypropionate - Google Patents
Esterification reaction-pervaporation membrane separation integrated method for producing methyl 3-hydroxypropionate Download PDFInfo
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- CN103012149A CN103012149A CN2012105172880A CN201210517288A CN103012149A CN 103012149 A CN103012149 A CN 103012149A CN 2012105172880 A CN2012105172880 A CN 2012105172880A CN 201210517288 A CN201210517288 A CN 201210517288A CN 103012149 A CN103012149 A CN 103012149A
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Abstract
The invention relates to an esterification reaction-pervaporation membrane separation integrated method for producing methyl 3-hydroxypropionate. The method comprises a process of performing esterification reaction between methanol and 3-hydroxypropionic acid to generate methyl 3-hydroxypropionate, wherein the process comprises the following steps: (1) mixing 3-hydroxypropionic acid and methanol in an esterification reactor, heating, then adding a catalyst, and reacting; and (2) pumping the obtained reaction solution into a pervaporation membrane separation device, dewatering the reaction liquid through the membrane, circularly returning the reaction solution into the esterification reactor, and further performing esterification reaction, thus obtaining the high-purity methyl 3-hydroxypropionate product after the esterification reaction is completed. According to the method provided by the invention, the area of the used membrane is small, the raw material solution/catalyst mass ratio and the reaction temperature are low, the purity and yield of methyl 3-hydroxypropionate can be greatly increased, the process is simple, and the course is stable. Thus, the invention can be easily used in the large-scale production of methyl 3-hydroxypropionate.
Description
Technical field
The present invention relates to the application of infiltration evaporation membrane technique in the esterification industry, relating in particular to is to adopt esterification reaction-infiltration evaporation barrier separation integral process to produce the method for 3-hydroxy methyl propionate.
Background technology
3-hydroxy-propionic acid (chemical call number (CAS) 503-66-2, molecular formula C
3H
6O
3, chemical structural formula HOCH
2CH
2COOH, molecular weight 90.08), be three carbon without chiral organic acid, with lactic acid isomers each other, be a kind of Important Platform compound that in recent years rises.It is colourless, tasteless, be oily liquids under the room temperature, dissolves each other with multi-solvents such as water, alcohol, ethers, can be widely used in the production of coating, tackiness agent, Water Treatment Chemicals and personal care articles; Also can dewater and generate vinylformic acid, oxidation generation propanedioic acid, esterification generation ester, reduction generation 1,3-PD and synthesizing new polyester.
One of important step of fermentation method 3-hydroxy-propionic acid production process is that methyl alcohol and the reaction of 3-hydroxy methyl propionate generate the 3-hydroxy methyl propionate.At present, mostly all to maintain the weight ratio of methyl alcohol and 3-hydroxy-propionic acid be in 1.5:1 or the higher liquid system to this esterification.The 3-hydroxy methyl propionate that esterification reaction of organic acid obtains and reaction of sodium bicarbonate generate the 3-Sodium Lactate, the 3-Sodium Lactate can be converted into the 3-hydroxy-propionic acid by h type resin again.Generally speaking, conversion rate of esterification can be subject to the inhibition of water byproduct usually, makes reaction yield be difficult to improve, and affects 3-hydroxy-propionic acid technique and productive rate thereof.
O.L. Liu, H.F. Chen is at article " Modelling of esterification of acetic acid with n-butanol in the presence of Zr (SO4) 2-4H2O coupled pervaporation " (" Journal of Membrane Science " 2002,196, studied the impact of esterification reaction-infiltration evaporation integrated technology on acetic acid and propyl carbinol esterification 171-178), show that propyl carbinol/the quality of acetic acid ratio is 1.98 initial, the ratio 0.23cm of membrane area and reaction solution volume
-1, under 80 ° of C conditions, adopt the esterification yied of integrated technology to be promoted to about 90% from original about 75%.
Wang Lefu, " impact that esterification coupling infiltration evaporation membrane process moves balance " (" chemical reaction engineering and technique " 1999 of Li Xuehui, 15(4): 443-449), adopt the PVA/PAN composite membrane, investigated the building-up process factor of n-butyl acetate in infiltration evaporation-esterification coupling composite film reactor to the impact of esterification chemical balance shifting, the result shows, alcohol/sour mass ratio (greater than 1.24) and high membrane area and reaction solution volume are than (0.5cm in higher temperature of reaction (80 ° of C) and higher initial reaction liquid
-1) condition under, the high yield that reaction 9 as a child reached ester.
Benedict D. J, Parulekar S.J, Tsai S.-P. is at article " Pervaproation-assisted esterfication of lacitic and succinic acids with downstream ester recovery " (" Journal of Membrane Science " 2006, adopt the experimental study of esterification reaction-infiltration evaporation integrated technology in the ethyl lactate building-up reactions of GFT-1005 film 281:435-445), the result shows, at the wallpaper 0.091cm of membrane area and reaction solution volume
-1, it is initial that ethanol/the lactic acid mass ratio is under the condition of 0.64,95 ° of C, after 8 hours, the ethyl lactate productive rate is about 85%.
M.T. Sanz and Jurgen Gmehling are successively at " Esterification of acetic acid with isopropanol coupled with pervaproation part I:Kinetics and pervaproation studies " (" Chemical Engineering Journal " 2006,123,1-8) with " Esterification of acetic acid with isopropanol coupled with pervaporation part II:Study of a pervaproation reactor " (" Chemical Engineering Journal " 2006,123, report 9-14), use PERVAP 2201 film alternatives to remove the water that generates in Virahol/esterification reaction, along with Virahol/acetic acid molar ratio, the ratio of membrane area and reaction solution volume, the increase of the addition of service temperature and catalyzer, esterification yield all has raising in various degree, but the reaction times is long, adopts after 10 hours to reach the esterification balance.
Patent " esterification reaction-infiltration evaporation barrier separation integral process is produced ascorbic method " (application number: 200710071145.0) adopt the esterification reaction-infiltration evaporation membrane integrating technique that production of vitamin C technique is improved, obtained equally preferably result.
The esterification reaction-infiltration evaporation membrane integrating technique that above-mentioned document relates to, or under higher temperature of reaction or the ratio condition at higher membrane area and reaction solution volume, be respectively applied to or the esterification of the liquid starting material of butylacetate or ethyl lactate or Iso Butyl Acetate etc., not yet relate to the application of the esterification combined films technology of 3-hydroxy-propionic acid production process.
Summary of the invention
The present invention is according to the deficiencies in the prior art, provides a kind of employing esterification reaction-infiltration evaporation barrier separation integral process to promote the reaction of 3-hydroxy methyl propionate, improves the purity of 3-hydroxy-propionic acid.
Processing step of the present invention is as follows:
(1) in reactor is to be warming up to 60-80 ° of C after the 3-hydroxy-propionic acid solution of 70%-95% and the methanol mixed with purity under 30-45 ° of C, adds the vitriol oil;
Described methyl alcohol and 3-hydroxy-propionic acid mass ratio are 0.8-1.2; The catalyzer vitriol oil and 3-hydroxy-propionic acid mass ratio are 0.014-0.032;
(2) reaction solution that step (1) is obtained passes into the infiltration evaporation membrane separation unit continuously, returns step (1) reactor through membrane sepn except the circulation of the reaction solution after anhydrating, and reaction conditions is constant, proceeds esterification reaction of organic acid;
Described infiltrating and vaporizing membrane is PERVAP 2201 type osmotic, evaporating and dewatering membranes; The effective film area of infiltration evaporation film device is 0.08-0.12cm with the ratio of reaction solution volume
-1The reaction solution circular flow of infiltration evaporation membrane separation unit is that the film downstream side vacuum tightness of 30-105 L/h. infiltration evaporation membrane separation unit is 450-700Pa;
(3) the reaction solution cooling is obtained high purity 3-hydroxy methyl propionate reaction solution, its purity is more than 98%.
The invention has the beneficial effects as follows: invention is used for 3-hydroxy methyl propionate process with infiltrating and vaporizing membrane, form esterification-barrier separation integral process, make the water byproduct in the reaction product see through film in time to remove, make esterification break through the restriction of conventional esterification balance, high conversion obtains 3-hydroxy methyl propionate liquid and enters follow-up producing process, thereby obviously improve the production technique of 3-hydroxy-propionic acid, improve the productive rate of 3-hydroxy-propionic acid.The membrane area of process using of the present invention is little, and when temperature of reaction is all lower for alcohol/sour quality in the initial reaction liquid, can increase substantially the yield of 3-hydroxy methyl propionate.Technique of the present invention can be implemented at the esterification production line of existing 3-hydroxy-propionic acid explained hereafter, membrane separation unit and esterifier is connected and installed get final product, and technique is simple and easy to operation.
Description of drawings
Fig. 1 is the process flow sheet of the method for the invention;
Fig. 2 is the using appts schematic diagram of esterification reaction-infiltration evaporation barrier separation integral process of the present invention;
Among the figure: 1-esterification liquid, 2-feed pump, 3-infiltration evaporation membrane separation apparatus, 4-infiltrating and vaporizing membrane, 5-sampling jug, 4-cold-trap, 6-vacuum pump, 8-condensing reflux pipe, 9-there-necked flask, 10-constant speed electronic stirrer, 11-thermostat water bath.
Embodiment
The present embodiment 1
Referring to Fig. 1,3-hydroxy methyl propionate reaction-infiltration evaporation barrier separation integral process flow process is:
Binary reaction liquid → the esterification of preparation 3-hydroxy-propionic acid and methyl alcohol → infiltration evaporation membrane sepn → esterification reaction of organic acid stops.The inventive method through esterification reaction-infiltration evaporation membrane sepn integrating process, obtains to be used for the highly purified 3-hydroxy methyl propionate liquid that the 3-hydroxy-propionic acid is produced at last from 3-hydroxy-propionic acid raw material.
In the experimental installation of integrated technique shown in Figure 2, carry out the esterification reaction-infiltration evaporation membrane sepn.Get 80 mL methyl alcohol (density 0.792 g/mL), inject belt stirrer, in the there-necked flask of reflux exchanger, open agitator, then inject 82 g purity and be 91% 3-hydroxy-propionic acid (methyl alcohol and 3-hydroxy-propionic acid mass ratio are 0.852), the control homo(io)thermism is in 55 ° of C, then add the 1mL vitriol oil (density 1.84g/mL, the vitriol oil and 3-hydroxy-propionic acid mass ratio are 0.0245), open condensate water circulatory, open simultaneously the fresh feed pump of infiltration evaporation membrane separation unit, the esterification reaction-infiltration evaporation integration technique of membrane begins timing, and the model that much used SULZER company produces is that the effective film area of the infiltrating and vaporizing membrane of PERVAP 2201 is 15 cm
2(the effective film area is 0.09375cm with the ratio of reaction solution volume
-1), the feed liquid flow of fresh feed pump is 40L/h, film downstream side vacuum tightness is 650 Pa, detects a component and content thereof in each moment reaction liquid by high performance liquid chromatograph (HPLC).After esterification reaction-infiltration evaporation membrane sepn integrated system reacts 8-9 hour, HPLC the analysis showed that, the 3-hydroxy-propionic acid of 98.4% in the reaction solution has been converted to the 3-hydroxy methyl propionate, stop esterification reaction of organic acid this moment, obtain the faint yellow 3-hydroxy methyl propionate of 146 ml liquid, it is moved into subsequent handling, be used for the production of 3-hydroxy-propionic acid.
The operation condition of chromatogram of HPLC is as shown in table 1.Table 1 operational condition is applied to other embodiment of this reverse side equally.
Table 1 HPLC and operation condition of chromatogram thereof
Embodiment 2
According to the operation of embodiment 1, wherein, the effective film area that only changes infiltrating and vaporizing membrane is 0.063cm with reaction solution volume ratio
-1, film downstream side vacuum tightness is 600pa, and when esterification reaction of organic acid finished, HPLC the analysis showed that, and the 3-hydroxy-propionic acid of 93.86% in the reaction solution is converted into the 3-hydroxy methyl propionate, obtains the flaxen 3-hydroxy methyl propionate of 152mL liquid.
According to the operation of embodiment 1, wherein only change methyl alcohol and 3-hydroxy-propionic acid mass ratio is 1.04, film downstream vacuum tightness is 650pa, and the HPLC experiment shows, and 97.2% 3-hydroxy-propionic acid changes the 3-hydroxy methyl propionate in the reaction solution.Obtain the flaxen 3-hydroxy methyl propionate of 149ml solution.
Operation according to embodiment 1, wherein change respectively methyl alcohol and 3-hydroxy-propionic acid mass ratio is 1, film downstream side vacuum tightness is 600pa, and HPLC the analysis showed that, the 3-hydroxy-propionic acid of 98.73% in the reaction solution is converted into the 3-hydroxy methyl propionate, obtains the flaxen 3-hydroxy methyl propionate of 150 ml liquid.
Operation according to embodiment 1, the feeding liquid flow that wherein changes the infiltration evaporation film separating system is that 60L/h and the vitriol oil and 3-hydroxy-propionic acid mass ratio are 0.0314, film downstream side vacuum tightness is 620pa, HPLC the analysis showed that, the 3-hydroxy-propionic acid of 99.08% in the reaction solution is converted into the 3-hydroxy methyl propionate, obtains the flaxen 3-hydroxy methyl propionate of 147ml liquid.
Operation according to embodiment 1, the feeding liquid flow that wherein changes the infiltration evaporation film separating system is that 100L/h and the vitriol oil and 3-hydroxy-propionic acid mass ratio are 0.0142, film downstream side vacuum tightness is 670pa, HPLC the analysis showed that, the 3-hydroxy-propionic acid of 98.2% in the reaction solution is converted into the 3-hydroxy methyl propionate, obtains the flaxen 3-hydroxy methyl propionate of 150ml liquid.
Claims (1)
1. the method for the integrated production 3-of an esterification reaction-infiltration evaporation membrane sepn hydroxy-propionic acid is characterized in that:
(1) in reactor is to be warming up to 60-80 ° of C after the 3-hydroxy-propionic acid solution of 70%-95% and the methanol mixed with purity under 30-45 ° of C, adds the vitriol oil;
Described methyl alcohol and 3-hydroxy-propionic acid mass ratio are 0.8-1.2; The catalyzer vitriol oil and 3-hydroxy-propionic acid mass ratio are 0.014-0.032;
(2) reaction solution that step (1) is obtained passes into the infiltration evaporation membrane separation unit continuously, returns step (1) reactor through membrane sepn except the circulation of the reaction solution after anhydrating, and reaction conditions is constant, proceeds esterification reaction of organic acid;
Described infiltrating and vaporizing membrane is PERVAP 2201 type osmotic, evaporating and dewatering membranes; The effective film area of infiltration evaporation film device is 0.08-0.12cm with the ratio of reaction solution volume
-1The reaction solution circular flow of infiltration evaporation membrane separation unit is 30-105 L/h, and the film downstream side vacuum tightness of infiltration evaporation membrane separation unit is 450-700Pa;
(3) the reaction solution cooling is obtained high purity 3-hydroxy methyl propionate reaction solution, its purity is more than 98%.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103508916A (en) * | 2013-10-25 | 2014-01-15 | 山东新华制药股份有限公司 | Preparation technology for paracetamol |
| CN109776314A (en) * | 2019-01-31 | 2019-05-21 | 新昌县泰如科技有限公司 | A kind of preparation method of cinnamate |
Citations (2)
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| CN1800135A (en) * | 2002-03-25 | 2006-07-12 | 嘉吉有限公司 | Methods of manufacturing derivatives of beta-hydroxycarboxylic acids |
| CN101139290A (en) * | 2007-09-14 | 2008-03-12 | 浙江工商大学 | Method for producing vitamin C by esterification reaction-infiltration evaporation barrier separation integral process |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1800135A (en) * | 2002-03-25 | 2006-07-12 | 嘉吉有限公司 | Methods of manufacturing derivatives of beta-hydroxycarboxylic acids |
| CN101139290A (en) * | 2007-09-14 | 2008-03-12 | 浙江工商大学 | Method for producing vitamin C by esterification reaction-infiltration evaporation barrier separation integral process |
Non-Patent Citations (3)
| Title |
|---|
| PATRICIA DELGADO ET AL.: "Ethyl lactate production via esterification of lactic acid with ethanol combined with pervaporation", 《CHEMICAL ENGINEERING JOURNAL》, vol. 165, 31 December 2010 (2010-12-31), pages 693 - 700, XP027492664, DOI: doi:10.1016/j.cej.2010.10.009 * |
| 蔡邦肖等: "VC生产中集成工艺对酯化反应和膜分离性能的影响", 《中国食品学报》, vol. 9, no. 5, 31 October 2009 (2009-10-31), pages 93 - 99 * |
| 阎建民等: "渗透汽化脱水技术及其在酯化工业中的应用", 《现代化工》, vol. 21, no. 8, 31 August 2001 (2001-08-31), pages 12 - 17 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103508916A (en) * | 2013-10-25 | 2014-01-15 | 山东新华制药股份有限公司 | Preparation technology for paracetamol |
| CN109776314A (en) * | 2019-01-31 | 2019-05-21 | 新昌县泰如科技有限公司 | A kind of preparation method of cinnamate |
| CN109776314B (en) * | 2019-01-31 | 2021-11-12 | 新昌县泰如科技有限公司 | Preparation method of cinnamate |
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Application publication date: 20130403 |