CN102875326A - Method for preparing high-purity absolute methanol by azeotropic-adsorption method - Google Patents
Method for preparing high-purity absolute methanol by azeotropic-adsorption method Download PDFInfo
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- CN102875326A CN102875326A CN2012104213243A CN201210421324A CN102875326A CN 102875326 A CN102875326 A CN 102875326A CN 2012104213243 A CN2012104213243 A CN 2012104213243A CN 201210421324 A CN201210421324 A CN 201210421324A CN 102875326 A CN102875326 A CN 102875326A
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Abstract
The invention discloses a method for preparing high-purity absolute methanol by an azeotropic-adsorption method. The method comprises the following steps of: by taking methanol as a raw material, carrying out azeotropic rectification in the presence of entrainer ethyl acetate; and adsorbing prepared absolute methanol intermediate by an adsorption material ATBS copolymer to obtain high-purity absolute methanol product. By detection, the content of impurity metal ions in the high-purity absolute methanol product is less than 0.005% and the purity of the high-purity absolute methanol product reaches up to more than 99.95%, thus the high-purity absolute methanol product is in accordance with the SEMI-C1 standard in a micro-electronic industry. Compared with the prior art, the azeotropic-adsorption method effectively reduces the content of impurity metal ions, and the residual impurity metal ions can be further removed by utilizing strong adsorption capability of the ATBS copolymer on the impurity metal ions in absolute methanol intermediate; after the use efficiency of the ATBS copolymer is reduced, the ATBS copolymer can be eluted by eluent and treated by methods such as drying and dehydration, so that the copolymer can be recycled; and the product high-purity absolute methanol is stable in quality and high in purity, and is suitable for industrial production.
Description
Technical field
The present invention relates to the method that a kind of azeotropic-absorption method prepares high-pure anhydrous methyl alcohol.
Background technology
Methyl alcohol is a kind of important chemical industry basic material, is widely used in organic synthesis, medicine, agricultural chemicals, coating, dyestuff, automobile and the national defense industry.Can be used for making formaldehyde, agricultural chemicals (sterilant, desinsection mite), medicine (sulfamido, syntomycin class), dimethyl terephthalate (DMT), methyl methacrylate, methyl acrylate, acetic acid, methyl chloride, methylamine and methyl-sulfate, as the denaturing agent of organic extraction agent and alcohol, as the solvent of gas-chromatography and liquid-phase chromatographic analysis.Along with the development in epoch, the rise of electron trade is had higher requirement to the quality index of methyl alcohol, requires anhydrous methanol purity to reach more than 99.95%, and water content is lower than 0.05%, and the foreign metal ion content is less than 0.005% microelectronic industry standard.
In the prior art, organic synthesis reagent prepares handbook, and second edition (2005, p341) disclose a kind of methanol-water-ethyl acetate ternary azeotropic that adopts and carried out the method for rectifying, it is nearly 0.1% that the anhydrous methanol that obtains still contains, and fails to reach the desired value of industry standard." Journal of Membrane Science, the method for 1995,104 (1,2): 101-108 report is sulfonated phenylethylene (PSS) to be compounded on the microporous aluminum oxide supporter obtain PPSS/Al for Chen and Martin
2O
3Composite membrane, infiltration gas methanol concentration reaches 99.5% when charging methyl alcohol is 5.0-14.3%.Membrane sepn is comparatively effective to the improvement of the removal of ionic impurity and outward appearance colourity, but cost is high, is unsuitable for industrialization promotion.Above-mentioned two kinds of methods exist the product water content too high, the defective that product economy is not high.
Summary of the invention
Problem to be solved by this invention is to provide a kind of azeotropic-absorption method to prepare the method for high-pure anhydrous methyl alcohol, and is too high to overcome in the prior art product water content, the deficiency that quality stability is poor.
Technical conceive of the present invention is such:
Take methyl alcohol as raw material, in the presence of the entrainment agent ethyl acetate, carry out azeotropic distillation, the anhydrous methanol intermediate for preparing obtains high-pure anhydrous methyl alcohol through the absorption of sorbing material ATBS multipolymer adsorption column.
Specifically, azeotropic-absorption method of the present invention prepares the method for high-pure anhydrous methyl alcohol, comprises the steps:
Moisture 4.5-5.5wt% methyl alcohol and entrainment agent ethyl acetate are added in the reactor, carry out azeotropic distillation, the anhydrous methanol intermediate heating of collecting enters the adsorption column absorption that sorbing material ATBS multipolymer medium is housed under 35-40 ℃, 0.4-0.6MPa condition, namely obtain high-pure anhydrous methyl alcohol.
Wherein, in the aforesaid method, the mass ratio of the methyl alcohol of described moisture 4.5-5.5wt% and entrainment agent ethyl acetate is 2-4: 1, g/g; The mass ratio of the methyl alcohol of described moisture 4.5-5.5wt% and ATBS multipolymer is 1: 0.05-0.10, g/g.
The monomer name of described ATBS multipolymer is called the 2-acrylamide-2-methylpro panesulfonic acid, has another name called AMBS, and this monomer and multipolymer thereof are commercially available technical grade product.And described ATBS multipolymer available 0.1mol/L sodium carbonate solution after using effectiveness to descend carries out the methods such as wash-out, drying and dehydrating to be processed as eluent, so that reuse.
The high-pure anhydrous methyl alcohol that adopts aforesaid method to make, wherein the foreign metal ion content is less than 0.005%, and purity reaches more than 99.95%, meets the standard of microelectronic industry SEMI-C1.
Compared with prior art:
Azeotropic distillation of the present invention is the content of impurity reduction metal ion effectively, and the strong adsorptive power of utilizing the ATBS multipolymer that the foreign metal ion in the anhydrous methanol intermediate is had can further be removed the residual impurity metal ion.ATBS multipolymer available 0.1mol/L sodium carbonate solution after using effectiveness to descend carries out the methods such as wash-out, drying and dehydrating to be processed as eluent, and multipolymer can be reused.Constant product quality, purity is high, is suitable for suitability for industrialized production.
Embodiment
The invention will be further described below in conjunction with embodiment, but embodiment does not limit protection scope of the present invention.
Embodiment 1
In the reactor that stirring, heating, spherical condensation tube, reflux, thermometer are housed, the methyl alcohol that adds respectively 1000g water content 4.8wt%, the 500g ethyl acetate, be warming up to 38 ℃ when stirring, azeotropic distillation steams the anhydrous methanol intermediate, water content 0.85% after testing, foreign metal ion content 0.08%.
Above-mentioned anhydrous methanol intermediate adding is equipped with in the reactor of temperature control unit, be heated to 40 ℃, under the pressure of 0.45MPa by the adsorption column of 50g ATBS multipolymer medium is housed, namely obtain the high-purity anhydrous methyl alcohol of target product, wherein water content adopts the karl Fischer volumetry to measure, and metal ion adopts ICP-MS to analyze.Detected result is: water content 0.17%, the foreign metal ion content is less than 0.005%.
Embodiment 2
In the reactor that stirring, heating, spherical condensation tube, reflux, thermometer are housed, the methyl alcohol that adds respectively 5000g water content 5.1wt%, the 1250g ethyl acetate, be warming up to 47 ℃ when stirring, azeotropic distillation steams the anhydrous methanol intermediate, water content 0.78% after testing, foreign metal ion content 0.069%.
Above-mentioned anhydrous methanol intermediate adding is equipped with in the reactor of temperature control unit, be heated to 35 ℃, under the pressure of 0.55MPa by the adsorption column of 500g ATBS multipolymer medium is housed, namely obtain the high-pure anhydrous methyl alcohol of target product, wherein water content adopts the karl Fischer volumetry to measure, and metal ion adopts ICP-MS to analyze.Detected result is: water content 0.14%, the foreign metal ion content is less than 0.005%.
Need to prove that above embodiment is only unrestricted in order to technical scheme of the present invention to be described.Although with reference to preferred embodiment the present invention is had been described in detail, those of ordinary skill in the art is to be understood that, can make amendment or be equal to replacement the technical scheme of invention, and not break away from the scope of technical solution of the present invention, it all should be encompassed in the claim scope of the present invention.
Claims (3)
1. an azeotropic-absorption method prepares the method for high-pure anhydrous methyl alcohol, it is characterized in that, comprises the steps:
Methyl alcohol and the entrainment agent ethyl acetate of moisture 4.5-5.5wt% are added in the reactor, carry out azeotropic distillation, to the anhydrous methanol intermediate heating of collecting, under 35-40 ℃, 0.4-0.6MPa condition, enter the adsorption column absorption that sorbing material ATBS multipolymer medium is housed, namely obtain high-pure anhydrous methyl alcohol.
2. method according to claim 1 is characterized in that, the mass ratio of the methyl alcohol of described moisture 4.5-5.5wt% and entrainment agent ethyl acetate is 2-4: 1, g/g.
3. method according to claim 1 is characterized in that, the mass ratio of the methyl alcohol of described moisture 4.5-5.5wt% and ATBS multipolymer is 1: 0.05-0.10, g/g.
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| CN201210421324.3A CN102875326B (en) | 2012-10-29 | 2012-10-29 | A kind of azeotropic-absorption method prepares the method for high-pure anhydrous methyl alcohol |
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| CN201210421324.3A CN102875326B (en) | 2012-10-29 | 2012-10-29 | A kind of azeotropic-absorption method prepares the method for high-pure anhydrous methyl alcohol |
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| CN102875326B CN102875326B (en) | 2015-08-26 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103601233A (en) * | 2013-12-02 | 2014-02-26 | 国药集团化学试剂有限公司 | Method for improving quality of silver nitrate |
| CN110330640A (en) * | 2019-07-15 | 2019-10-15 | 万华化学集团股份有限公司 | A kind of refining methd of high molecular weight alkyl end capped polyether |
Citations (3)
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| EP0629421A1 (en) * | 1993-06-18 | 1994-12-21 | The M.W. Kellogg Company | Intermediate reboiler for a methanol plant |
| CN101367725A (en) * | 2008-09-26 | 2009-02-18 | 天津大学 | Process for separation of methanol and ethyl acetate with double-column in series |
| CN102188956A (en) * | 2011-04-13 | 2011-09-21 | 南京大学 | Heavy metal adsorption copolymer with sulfonic acid group and preparation method thereof, and application of heavy metal adsorption copolymer to water treatment |
-
2012
- 2012-10-29 CN CN201210421324.3A patent/CN102875326B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0629421A1 (en) * | 1993-06-18 | 1994-12-21 | The M.W. Kellogg Company | Intermediate reboiler for a methanol plant |
| CN101367725A (en) * | 2008-09-26 | 2009-02-18 | 天津大学 | Process for separation of methanol and ethyl acetate with double-column in series |
| CN102188956A (en) * | 2011-04-13 | 2011-09-21 | 南京大学 | Heavy metal adsorption copolymer with sulfonic acid group and preparation method thereof, and application of heavy metal adsorption copolymer to water treatment |
Non-Patent Citations (3)
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| 刘范嘉等: "我国工业甲醇提纯制备高纯甲醇的研究进展", 《化工进展》 * |
| 蒋磊等: "聚丙烯酸系吸附性树脂材料的合成及应用研究进展", 《当代化工》 * |
| 谢建军等: "聚2-丙烯酰胺-2-甲基丙磺酸高吸水性树脂等温吸附重金属离子", 《化学工程》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103601233A (en) * | 2013-12-02 | 2014-02-26 | 国药集团化学试剂有限公司 | Method for improving quality of silver nitrate |
| CN103601233B (en) * | 2013-12-02 | 2015-10-21 | 国药集团化学试剂有限公司 | A kind of method promoting quality of silver nitrate |
| CN110330640A (en) * | 2019-07-15 | 2019-10-15 | 万华化学集团股份有限公司 | A kind of refining methd of high molecular weight alkyl end capped polyether |
| CN110330640B (en) * | 2019-07-15 | 2022-02-18 | 万华化学集团股份有限公司 | Refining method of high molecular weight alkyl terminated polyether |
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| CN102875326B (en) | 2015-08-26 |
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