CN101314573B - Method for treating tetramethyl ammonium carbonate with ion exchange resin - Google Patents
Method for treating tetramethyl ammonium carbonate with ion exchange resin Download PDFInfo
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- CN101314573B CN101314573B CN2008100629624A CN200810062962A CN101314573B CN 101314573 B CN101314573 B CN 101314573B CN 2008100629624 A CN2008100629624 A CN 2008100629624A CN 200810062962 A CN200810062962 A CN 200810062962A CN 101314573 B CN101314573 B CN 101314573B
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Abstract
The invention discloses a method for using ion exchange resins to process tetramethylammonium carbonate. The method comprises the following steps that: after the resins are activated by acids, acid and alkali resistant resins which are not dissolved in water are used for processing a tetramethylammonium carbonate water solution, and the content of a single metallic ion in the tetramethylammonium carbonate water solution is reduced to ppm level through ion exchange and absorption of metallic irons in the solution; and the processed resins are regenerated through acid treatment and can be recycled. The method can realize high-efficiency and energy-saving removal of the metallic ions, with high absorption rate; and the ion exchange resins are easy to regenerate and are recycled, thereby the cost is saved.
Description
Technical field
The present invention relates to a kind of ion-exchange purification techniques, a kind of specifically spent ion exchange resin is handled the method for tetramethyl-volatile salt.
Background technology
Electronic-grade Tetramethylammonium hydroxide (Tetramethyl Ammonium Hydroxide is called for short TMAH) as the developing solution in liquid crystal and the semi-conductor chip production process, is one of electronic chemical product of consumption maximum.The main preparation methods of electronic-grade Tetramethylammonium hydroxide is to make by electrolysis tetramethyl-volatile salt (Tetramethyl Ammonium Carbonate is called for short TMAC).Because the electronic-grade Tetramethylammonium hydroxide requires the single metal ion content less than 10ppb, therefore, can't realize by electrolysis with ion-exchange film control concentration of metal ions fully, must carry out removing and controlling of metal ion with TMAC to the electrolysis raw material.
Ion exchange resin is a kind of relatively method of gentle, energy-conservation removal metal ion.
Chinese invention patent application CN1446755 discloses a kind of weak base anion-exchange resin absorption heavy metal method that belongs in the water technology.This method is that what to adopt is not traditional ion-exchange theory, but form the coordination chemistry theory of complex compound based on the ammonia atom on the resin amidine functional group and heavy metal ion, water can be achieved the goal under normal temperature, normal pressure by weak base anion-exchange resin.Solved the purifying treatment problem of micro heavy pollution natural water body.
MD Ramans etc. propose a plurality of applications for a patent for invention, as Chinese invention patent CN1155889, CN1171847 etc., utilize ion exchange resin to make semi-conductor institute with photoresist.But the ion exchange resin of propositions such as MD Raman is water insoluble, but is dissolved in the resin of alkali aqueous solution.
Summary of the invention
The invention provides a kind of method for the treatment of tetramethyl ammonium carbonate with ion exchange resin, the plastic resin treatment TMAC aqueous solution with a kind of water insoluble and acid and alkali-resistance, by ion-exchange absorption solution metal ion, make that the single metal ion content is reduced to the ppm level in the TMAC aqueous solution.
A kind of method for the treatment of tetramethyl ammonium carbonate with ion exchange resin may further comprise the steps:
(1) resin activation: resin is added washed with de-ionized water to neutral, elimination water, adding the quality percentage composition is the mineral acid of 2-10%, and the sour volume of adding is 3-8 a times of resin volume, stirs 2-8 hour, and to neutral, elimination water is standby with washed with de-ionized water;
(2) plastic resin treatment tetramethyl-volatile salt: adding the quality percentage composition with the good resin of activation is 30-65% tetramethyl-ammonium carbonate solution, stirs after-filtration;
(3) resin regeneration: will adsorb the resin after saturated of metal ion in the tetramethyl-volatile salt and add deionized water, clean to neutral, elimination water, adding the quality percentage composition is the mineral acid of 2-10%, the sour volume that adds is 3-8 a times of resin volume, stirs to take off in 2-8 hour and inhales regeneration, and is extremely neutral with washed with de-ionized water, elimination water, standby.
In the described step (2), the TMAC aqueous solution that adds resin stirred for 20-65 ℃ reached that metal ion is adsorbed balance in the tetramethyl-volatile salt in 2-8 hour.
Described mineral acid adopts hydrochloric acid usually.
Resin of the present invention adopts chelating ion exchange resin, can select for use and float the special C100 of Lay, C100E, Baeyer TP208, chelating ion exchange resin such as TP2000, its active group is many polymerization of olefin using catalyst body, contain two or more bonded atoms, as N.O.S etc., and between bonded atom preferably across two or three nonbonding atoms, such resin is being fit under the condition, forms the inner complex-inner complex with ring texture with the ion of the electron pair that can accept bonded atom.
Resin after initial activation is through absorption and take off suction reprocessing cycle processing TMAC.
The inventive method is with a kind of plastic resin treatment TMAC aqueous solution of water insoluble and acid and alkali-resistance, by ion-exchange absorption solution metal ion, make that the single metal ion content is reduced to the ppm level in the TMAC aqueous solution, can remove metal ion efficient, energy-conservationly, the adsorption rate height, and ion exchange resin is regenerated easily, and cost is saved in recycle.
Description of drawings
Fig. 1 is the inventive method schema.
Embodiment
Resin activation: the 300ml resin is added in the 4L plastic tank, add to stir behind the deionized water 2000ml and cleaned to neutral elimination water in 2 hours; Stirred 4 hours after adding 2-10% high purity hydrochloric acid 2000ml, clean to neutral with high purity water, elimination water is standby.
The resin that resin regeneration: 300ml handles behind the TMAC is put into the 4L plastic tank, adds deionized water 2000ml, stirs 1-2 hour, cleans to neutral elimination water; Add 2-10% high purity hydrochloric acid 2000ml, stirred 6 hours, extremely neutral with washed with de-ionized water, elimination water; Standby.
Embodiment 1
40 ℃ of temperature with 20kg concentration 50%TMAC, add the C100 resin 10kg after activating, circular treatment 2 hours.
Metal ion content before handling (unit: ppb) be: Li＜0.05, Na 0.53, and Mg 0.38, Al 0.25, and K 0.95, and Ca 0.72, Cr 61.3, and Mn 4.35, and Fe 220.5, Ni 38.0, and Co 1.07, and Cu 1.36, Zn 1.89, and Mo 4.98, Cd＜0.05, Pb＜0.5, Ag 0.07, and Ti 0.87;
(unit: ppb) be: Li 0.07, and Na 0.5, and Mg 0.21, and Al 0.44, and K 0.9, and Ca 0.9 to handle the back metal ion content, Cr 40.9, and Mn 2.35, and Fe 180.5, and Ni 1.87, and Co 1.62, and Cu 0.53, Zn 1.92, and Mo 2.21, Cd＜0.05, and Pb＜0.5, Ag 0.05, and Ti 0.56.
Resin regeneration.
Embodiment 2
50 ℃ of temperature with 20kg concentration 50%TMAC, add the C100E resin 10kg after activating, circular treatment 6 hours.
Metal ion content before handling (unit: ppb) be: Li＜0.05, Na 0.53, and Mg 0.38, Al 0.25, and K 0.95, and Ca 0.72, Cr 61.3, and Mn 4.35, and Fe 220.5, Ni 38.0, and Co 1.07, and Cu 1.36, Zn 1.89, and Mo 4.98, Cd＜0.05, Pb＜0.5, Ag 0.07, and Ti 0.87;
Metal ion content after handling (unit: ppb) be: Li＜0.05, Na 0.54, and Mg 0.16, and Al 0.14, and K 1.02, and Ca 0.32, Cr 50.9, and Mn 0.98, and Fe 7.8, and Ni 1.5, and Co 1.45, Cu0.34, Zn 1.87, and Mo 2.11, Cd＜0.05, and Pb＜0.5, Ag 0.05, and Ti 0.44.
Resin regeneration.
Embodiment 3
65 ℃ of temperature with 20kg concentration 30%TMAC, add activation back TP208 resin 10kg, circular treatment 8 hours.
Metal ion content before handling (unit: ppb) be: Li＜0.05, Na 0.53, and Mg 0.38, Al 0.25, and K 0.95, and Ca 0.72, Cr 61.3, and Mn 3.35, and Fe 165.5, Ni 38.0, and Co 0.98, and Cu 1.36, Zn 1.89, and Mo 2.98, Cd＜0.05, Pb＜0.5, Ag 0.07, and Ti 0.67;
Metal ion content after handling (unit: ppb) be: Li＜0.05, Na 0.54, and Mg 0.18, Al 0.11, and K 1.02, and Ca 0.32, Cr 40.9, and Mn 0.98, and Fe 117.8, Ni 1.5, and Co 1.45, and Cu 0.34, Zn 1.27, and Mo 2.11, Cd＜0.05, Pb＜0.5, Ag 0.05, and Ti 0.34.
Resin regeneration.
Embodiment 4
20 ℃ of temperature with 20kg concentration 65%TMAC, add the TP2000 resin 10kg after activating, circular treatment 6 hours.
Metal ion content before handling (unit: ppb) be: Li＜0.05, Na 0.53, and Mg 0.38, Al 0.25, and K 0.95, and Ca 0.72, Cr 61.3, and Mn 3.35, and Fe 165.5, Ni 38.0, and Co 0.98, and Cu 1.36, Zn 1.89, and Mo 2.98, Cd＜0.05, Pb＜0.5, Ag 0.07, and Ti 0.67;
Metal ion content after handling (unit: ppb) be: Li＜0.05, Na 0.54, and Mg 0.18, and Al 0.11, and K 1.02, and Ca 0.32, Cr 40.9, and Mn 0.98, and Fe 37.8, and Ni 1.5, and Co 1.23, and Cu 0.24, Zn 1.27, and Mo 2.11, Cd＜0.05, and Pb＜0.5, Ag 0.05, and Ti 0.32.
Resin regeneration.
Claims (1)
1. the method for a treating tetramethyl ammonium carbonate with ion exchange resin may further comprise the steps:
(1) resin activation: resin is added washed with de-ionized water to neutral, elimination water, adding the quality percentage composition is the hydrochloric acid of 2-10%, and the sour volume of adding is 3-8 a times of resin volume, stirs 2-8 hour, and to neutral, elimination water is standby with washed with de-ionized water;
(2) plastic resin treatment tetramethyl-volatile salt: adding the quality percentage composition with the good resin of activation is 30-65% tetramethyl-ammonium carbonate solution, stirs 2-8 hour after-filtration down at 20-65 ℃;
(3) resin regeneration: will adsorb the resin after saturated of metal ion in the tetramethyl-volatile salt and add deionized water, clean to neutral, elimination water, adding the quality percentage composition is the mineral acid of 2-10%, the sour volume that adds is 3-8 a times of resin volume, stirs to take off in 2-8 hour and inhales regeneration, and is extremely neutral with washed with de-ionized water, elimination water, standby;
Described resin is C100 resin, C100E resin, TP208 resin or TP2000 resin.
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| CN101993380B (en) * | 2009-08-11 | 2013-05-01 | 兆联实业股份有限公司 | Equipment and method for recovering tetramethylammonium hydroxide |
| CN114920658B (en) * | 2022-06-28 | 2024-05-03 | 大连理工大学盘锦产业技术研究院 | Method for purifying choline hydroxide by ion exchange resin |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4714530A (en) * | 1986-07-11 | 1987-12-22 | Southwestern Analytical Chemicals, Inc. | Method for producing high purity quaternary ammonium hydroxides |
| WO1990006382A1 (en) * | 1988-11-28 | 1990-06-14 | Southwestern Analytical Chemicals, Inc. | Method for purifying quaternary ammonium hydroxides |
| CN1074425C (en) * | 1994-08-23 | 2001-11-07 | 科莱恩金融(Bvi)有限公司 | Metal ion reduction in novolak resin solution using an anion exchange resin |
| CN1082677C (en) * | 1994-12-30 | 2002-04-10 | 科莱恩金融(Bvi)有限公司 | Metal ion reduction using ion exchange resin in polar solvent |
| CN1446755A (en) * | 2003-04-10 | 2003-10-08 | 清华大学 | Method for adsorbing heavy metal by using weak anion resin |
-
2008
- 2008-07-08 CN CN2008100629624A patent/CN101314573B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4714530A (en) * | 1986-07-11 | 1987-12-22 | Southwestern Analytical Chemicals, Inc. | Method for producing high purity quaternary ammonium hydroxides |
| WO1990006382A1 (en) * | 1988-11-28 | 1990-06-14 | Southwestern Analytical Chemicals, Inc. | Method for purifying quaternary ammonium hydroxides |
| CN1074425C (en) * | 1994-08-23 | 2001-11-07 | 科莱恩金融(Bvi)有限公司 | Metal ion reduction in novolak resin solution using an anion exchange resin |
| CN1082677C (en) * | 1994-12-30 | 2002-04-10 | 科莱恩金融(Bvi)有限公司 | Metal ion reduction using ion exchange resin in polar solvent |
| CN1446755A (en) * | 2003-04-10 | 2003-10-08 | 清华大学 | Method for adsorbing heavy metal by using weak anion resin |
Non-Patent Citations (4)
| Title |
|---|
| 朱小晶等.四甲基氢氧化铵的制备与提纯综述.江苏化工31 5.2003,31(5),20-23. |
| 朱小晶等.四甲基氢氧化铵的制备与提纯综述.江苏化工31 5.2003,31(5),20-23. * |
| 蒋翔等.氨基硫脲-甲醛螯合树脂的合成及吸附性能.离子交换与吸附24 2.2008,24(2),119-122. |
| 蒋翔等.氨基硫脲-甲醛螯合树脂的合成及吸附性能.离子交换与吸附24 2.2008,24(2),119-122. * |
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Address after: Hangzhou Xiaoshan Linjiang Industrial Park Red fifteen road Xiaoshan District Hangzhou 310000 Zhejiang province No. 9936 Patentee after: Hangzhou gelinda electronic materials Limited by Share Ltd Address before: Room 102, room B, No. 2, No. 4028, Binjiang District South Ring Road, Hangzhou, Zhejiang Patentee before: Hangzhou Greenda Chemical Co., Ltd. |