CN102875326B - A kind of azeotropic-absorption method prepares the method for high-pure anhydrous methyl alcohol - Google Patents
A kind of azeotropic-absorption method prepares the method for high-pure anhydrous methyl alcohol Download PDFInfo
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- CN102875326B CN102875326B CN201210421324.3A CN201210421324A CN102875326B CN 102875326 B CN102875326 B CN 102875326B CN 201210421324 A CN201210421324 A CN 201210421324A CN 102875326 B CN102875326 B CN 102875326B
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Abstract
The invention discloses a kind of method that azeotropic-absorption method prepares high-pure anhydrous methyl alcohol, take methyl alcohol as raw material, azeotropic distillation is carried out under the existence of entrainment agent ethyl acetate, the anhydrous methanol intermediate prepared adsorbs through sorbing material ATBS multipolymer, namely obtain high-pure anhydrous methanol product, after testing, foreign metal ion content is less than 0.005%, purity reaches more than 99.95%, meets the standard of microelectronic industry SEMI-C1.Compared with prior art, azeotropic distillation of the present invention effectively can reduce the content of foreign metal ion, utilizes the strong adsorptive power that ATBS multipolymer has the foreign metal ion in anhydrous methanol intermediate, can remove residual impurity metal ion further; ATBS multipolymer available eluent after use effect declines carries out the method such as wash-out, drying and dehydrating and processes, and multipolymer can be reused; Constant product quality, purity is high, is suitable for suitability for industrialized production.
Description
Technical field
The present invention relates to a kind of method that 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 national defense industry.Can be used for manufacturing 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 quality index of rise to methyl alcohol of electron trade is had higher requirement, and requires that anhydrous methanol purity reaches more than 99.95%, water content lower than 0.05%, the microelectronic industry standard that foreign metal ion content is less than 0.005%.
In prior art, handbook prepared by organic synthesis reagent, and the second edition (2005, p341) discloses a kind of method adopting methanol-water-acetic acid ethyl ester ternary azeotropic to carry out rectifying, the anhydrous methanol obtained, still containing nearly 0.1%, fails to reach the desired value of industry standard." Journal of MembraneScience, to Chen and Martin the method that 1995,104 (1,2): 101-108 report be compounded on microporous alumina aluminium support body by sulfonated phenylethylene (PSS) to obtain PPSS/Al
2o
3composite membrane, permeates gas methanol concentration and reaches 99.5% when charging methyl alcohol is 5.0-14.3%.The improvement of membrane sepn to the removal of ionic impurity and outward appearance colourity is comparatively effective, but cost is high, is unsuitable for industrialization promotion.It is too high to there is product water content in above-mentioned two kinds of methods, the defect 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, too high to overcome product water content in prior art, the deficiency of quality stability difference.
Technical conceive of the present invention is such:
Take methyl alcohol as raw material, under the existence of entrainment agent ethyl acetate, carry out azeotropic distillation, the anhydrous methanol intermediate prepared, through the absorption of sorbing material ATBS multipolymer adsorption column, obtains high-pure anhydrous methyl alcohol.
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 reactor, carry out azeotropic distillation, the anhydrous methanol intermediate heating of collecting, 35-40 DEG C, enter the adsorption column absorption that sorbing material ATBS multipolymer medium is housed under 0.4-0.6MPa condition, namely obtain high-pure anhydrous methyl alcohol.
Wherein, in aforesaid method, the methyl alcohol of described moisture 4.5-5.5wt% and the mass ratio of entrainment agent ethyl acetate are 2-4: 1, g/g; The methyl alcohol of described moisture 4.5-5.5wt% and the mass ratio of ATBS multipolymer are 1: 0.05-0.10, g/g.
The monomer names of described ATBS multipolymer is 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 use effect declines carries out the method such as wash-out, drying and dehydrating as eluent and processes, so that reuse.
Adopt the high-pure anhydrous methyl alcohol that aforesaid method is obtained, wherein 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 effectively can reduce the content of foreign metal ion, utilizes the strong adsorptive power that ATBS multipolymer has the foreign metal ion in anhydrous methanol intermediate, can remove residual impurity metal ion further.ATBS multipolymer available 0.1mol/L sodium carbonate solution after use effect declines carries out the method such as wash-out, drying and dehydrating as eluent and processes, and multipolymer can be reused.Constant product quality, purity is high, is suitable for suitability for industrialized production.
Embodiment
Below in conjunction with embodiment, the invention will be further described, but embodiment does not limit the scope of the invention.
Embodiment 1
In the reactor that stirring, heating, spherical condensation tube, reflux, thermometer are housed, add the methyl alcohol of 1000g water content 4.8wt% respectively, 500g ethyl acetate, 38 DEG C are warming up to while stirring, azeotropic distillation steams anhydrous methanol intermediate, water content 0.85% after testing, foreign metal ion content 0.08%.
Being added by above-mentioned anhydrous methanol intermediate is equipped with in the reactor of temperature control unit, be heated to 40 DEG C, by being equipped with the adsorption column of 50g ATBS multipolymer medium under the pressure of 0.45MPa, namely the high-purity anhydrous methyl alcohol of target product is obtained, wherein water content adopts karl Fischer volumetry to measure, and metal ion adopts ICP-MS to analyze.Detected result is: water content 0.17%, and foreign metal ion content is less than 0.005%.
Embodiment 2
In the reactor that stirring, heating, spherical condensation tube, reflux, thermometer are housed, add the methyl alcohol of 5000g water content 5.1wt% respectively, 1250g ethyl acetate, 47 DEG C are warming up to while stirring, azeotropic distillation steams anhydrous methanol intermediate, water content 0.78% after testing, foreign metal ion content 0.069%.
Being added by above-mentioned anhydrous methanol intermediate is equipped with in the reactor of temperature control unit, be heated to 35 DEG C, by being equipped with the adsorption column of 500g ATBS multipolymer medium under the pressure of 0.55MPa, namely the high-pure anhydrous methyl alcohol of target product is obtained, wherein water content adopts karl Fischer volumetry to measure, and metal ion adopts ICP-MS to analyze.Detected result is: water content 0.14%, and foreign metal ion content is less than 0.005%.
It should be noted that, above embodiment is only in order to illustrate technical scheme of the present invention and unrestricted.Although with reference to preferred embodiment to invention has been detailed description, those of ordinary skill in the art is to be understood that, can modify to the technical scheme of invention or equivalent replacement, and not depart from the scope of technical solution of the present invention, it all should be encompassed in right of the present invention.
Claims (1)
1. azeotropic-absorption method prepares a method for high-pure anhydrous methyl alcohol, it is characterized in that, comprises the steps:
The methyl alcohol of moisture 4.5-5.5wt% and entrainment agent ethyl acetate are added in reactor, carry out azeotropic distillation, to the anhydrous methanol intermediate heating of collecting, 35-40 DEG C, enter the adsorption column absorption that sorbing material ATBS multipolymer medium is housed under 0.4-0.6MPa condition, namely obtain high-pure anhydrous methyl alcohol;
The methyl alcohol of described moisture 4.5-5.5wt% and the mass ratio of ATBS multipolymer are 1:0.05-0.10, g/g;
The methyl alcohol of described moisture 4.5-5.5wt% and the mass ratio of entrainment agent ethyl acetate are 2-4:1, 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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| CN102875326B true CN102875326B (en) | 2015-08-26 |
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| 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 |
| 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 |
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 |
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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)
| Title |
|---|
| 我国工业甲醇提纯制备高纯甲醇的研究进展;刘范嘉等;《化工进展》;20070525;第26卷(第05期);664-667 * |
| 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;谢建军等;《化学工程》;20080515;第36卷(第05期);5-8 * |
| 聚丙烯酸系吸附性树脂材料的合成及应用研究进展;蒋磊等;《当代化工》;20110831;第40卷(第08期);827-830,834 * |
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