CN102134135A - Method for recovering and purifying tetra-alkylammonium hydroxide from waste liquor containing tetra-alkylammonium hydroxide - Google Patents
Method for recovering and purifying tetra-alkylammonium hydroxide from waste liquor containing tetra-alkylammonium hydroxide Download PDFInfo
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- CN102134135A CN102134135A CN2010101003846A CN201010100384A CN102134135A CN 102134135 A CN102134135 A CN 102134135A CN 2010101003846 A CN2010101003846 A CN 2010101003846A CN 201010100384 A CN201010100384 A CN 201010100384A CN 102134135 A CN102134135 A CN 102134135A
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Abstract
The invention relates to a method for recovering and purifying tetra-alkylammonium hydroxide from waste liquor containing the tetra-alkylammonium hydroxide, comprising the following steps of: transforming the tetra-alkylammonium hydroxide contained in the waste liquor into tetra-alkylammonium salt through acids; then filtering the transformed waste liquor through a nanofiltration membrane (NF membrane) separating device to remove impurities, i.e. high valent metals, photoresists, and the like so as to obtain penetrating fluids mainly containing the tetra-alkylammonium salt; also adding water to the concentration side of the nanofiltration membrane separating device, and increasing the speed of the tetra-alkylammonium salt passing through a nanofiltration membrane by utilizing Donnan effect generated on the surface of the nanofiltration membrane so as to further enhance the recovery rate and efficiency of the tetra-alkylammonium salt; and finally transforming the tetra-alkylammonium salt into the tetra-alkylammonium hydroxide through electrolysis, and recovering.
Description
Technical field
The present invention is about a kind of waste liquid recovery of tetraalkylammonium hydroxide and method of purifying tetraalkylammonium hydroxide of containing certainly.Especially, the present invention about a kind of hydrochlorate that tetraalkylammonium hydroxide in the development waste liquid is converted into tetra-allkylammonium after, the mat nano-filtration membrane is filtered purifying, and the hydrochlorate with the gained tetra-allkylammonium is electrolyzed to produce the autography waste liquid recovery of tetraalkylammonium hydroxide and the method for purifying tetraalkylammonium hydroxide subsequently.
Background technology
Tetraalkylammonium hydroxide is the electronic component industry, such as photoresistance photographic developer, particularly tetramethyl ammonium hydroxide commonly used such as semiconductor element industry, display panels industry and printed circuit board (PCB) industry.Tetraalkylammonium hydroxide is organic property highly basic, also can be used as acid-base neutralisation agent, interfacial agent, ionogen and rubber accelerator etc. and can be widely used in each field.
In the electronic component industry production process after coating eurymeric photoresist forms the photoresistance film on the base material, see through light shield (photo mask) irradiation and make photoresist produce chemical transformation, form resolvability photoresist zone and insolubility photoresist zone through irradiates light.The main photographic developer of eurymeric photoresist is a tetramethyl ammonium hydroxide, and the depleted aqueous solution is development waste liquid after developing, and it mainly consists of water, tetramethyl ammonium hydroxide and is dissolved in wherein photoresist.
The treatment process of this alkaline development waste liquid general with factory in spent acid carry out the adjustment of pH value and then degrade with active sludge, to remove ammonia nitrogen content in the waste water, but the biological degradability of tetramethyl ammonium hydroxide is poor, active sludge raise and train difficult, that treatment facility is provided with area is big, and therefore the method that develops many recovery and purifying tetramethyl ammonium hydroxide is arranged in the recent period.
U.S. Patent number 6083670 (be equivalent to TaiWan, China patent announcement number 464637) discloses a kind of regeneration treating method and device of photoresist video picture waste liquid, system utilizes nano-filtration membrane (NF film) to handle the photoresist development waste liquid that contains that contains tetramethyl ammonium and obtains concentrated solution and penetrating fluid, concentrated solution mainly contains impurity such as photoresist, and penetrating fluid mainly contains tetramethyl ammonium; Then use electrodialysis or electrolysis cells that penetrating fluid and/or concentrated solution are carried out concentrated and purified processing and carry out purifying and remove impurity with Zeo-karb and/or anionite-exchange resin.
Yet, with nano-filtration membrane (NF film) handle contain tetramethyl ammonium contain the photoresist development waste liquid time, the filtration velocity of nano-filtration membrane is fast under the lower concentration situation, but there is a certain proportion of tetramethyl ammonium can residue in the concentrated solution, photoresist concentration higher (because of down) in this part concentrated solution by the interception of NF film.Also strengthen along with concentrated solution concentration increases osmotic pressure, cause the filtration velocity of filtering membrane slack-off or increase pressure, and the problem of filtration velocity and deterioration of efficiency is arranged.And make penetrating fluid can cause the rate of recovery low excessively merely through electrodialysis or electrolytic recovery tetramethyl ammonium hydroxide, if make the NF concentrated solution by electrodialysis or electrolytic desalting groove during with the tetramethyl ammonium in the further recovery enriched material, will be because of photoresist impact the work-ing life to electrodialysis or electrolytic film, and because therefore electrodialysis or electrolytic film fetch long price have also influenced recovery price and industrial utilization.
Summary of the invention
Therefore, the objective of the invention is to, provide a kind of from the waste liquid that contains tetraalkylammonium hydroxide, especially the method for recovery of autography waste liquid and purifying tetraalkylammonium hydroxide can overcome the known techniques shortcoming and improve the rate of recovery and reduce cost recovery.
According to the present invention, a kind of waste liquid recovery of tetraalkylammonium hydroxide and method of purifying tetraalkylammonium hydroxide of containing certainly is provided, this waste liquid comprises impurity such as hydroxide four alkane ammoniums and photoresist at least, and this method comprises the following steps: at least
(1) makes hydroxide four alkane ammoniums in this waste liquid convert the hydrochlorate of tetra-allkylammonium to by acid, form the waste liquid of the hydrochlorate that contains tetra-allkylammonium;
(2) waste liquid that makes this hydrochlorate that contains tetra-allkylammonium is by having the tripping device of nano-filtration membrane, the penetrating fluid that obtains to contain the concentrated solution of photoresist and other impurity and contain the hydrochlorate of tetra-allkylammonium in the per-meate side of this nano-filtration membrane in the concentration side of this nano-filtration membrane;
(3) continue to carry out this filtering separation step of step (2), when the concentrated solution conductivity value of concentration side is above greater than 20000 μ s/cm, adds the penetrating fluid volume that pure water proceeds to filter until permeate side in the filtering membrane concentration side of this tripping device and reach more than the 90 volume % of the volume that disposes waste liquid at first; And
(4) collect penetrating fluid and carry out electrolysis, make the hydrochlorate of tetra-allkylammonium contained in this penetrating fluid convert tetraalkylammonium hydroxide to and reclaimed.
In the aforesaid method step of the present invention (1), this waste liquid that contains tetraalkylammonium hydroxide is preferably development waste liquid, in this step (1), by acid make all or part of conversion method that is converted to the hydrochlorate of tetra-allkylammonium of tetraalkylammonium hydroxide in the development waste liquid can use this skill to know to know in order to hydroxide four alkane ammoniums are directly or indirectly converted to any method of the hydrochlorate of four alkane ammoniums, in the present invention, do not limited, but for example following several methods can be arranged for example: (one) with tetraalkylammonium hydroxide with batch or the tubing string mode by strongly acidic cation-exchange or weak-type Zeo-karb, tetraalkyl ammonium ion is adsorbed on the Zeo-karb, again with organic acid or mineral acid hydrochloric acid for example, nitric acid, sulfuric acid, carbonic acid etc. dash the hydrochlorate of carrying the tetra-allkylammonium of regenerating.(2) organic acid or mineral acid for example are neutralized to pH 12～3 with it in direct adding such as hydrochloric acid, nitric acid, sulfuric acid, the carbonic acid tetraalkylammonium hydroxide solution.
Among the present invention, so-called " hydrochlorate of tetra-allkylammonium " means by acid and makes the alkali salt of tetraalkylammonium hydroxide be transformed into the salt that hydrochlorate becomes.The hydrochlorate that is become will be on decide in order to neutral acid kind, and when for example using hydrochloric acid as neutralizing acid, the hydrochlorate of this tetra-allkylammonium means the chlorination tetra-allkylammonium, and during use sulfuric acid, then refer to sulfuric acid tetra-allkylammonium etc.Also same when using other acid.
The nanofiltration film device that has that uses in the aforesaid method step of the present invention (2) comprises a thickener at least, in order to hold the waste liquid behind wherein contained tetraalkylammonium hydroxide becomes tetra-allkylammonium through conversion process the hydrochlorate; One filtrate receiver is in order to hold the penetrating fluid by the hydrochlorate that contains tetra-allkylammonium of nano-filtration membrane; One nano-filtration membrane pipe, in order to the hydrochlorate of tetra-allkylammonium and photoresist and high-valency metal as: Fe, Al etc. separates; One pure water cylinder is used to thickener and supplies with pure water; And a pumping, in order to pure water is pumped in the thickener from pure water cylinder.Through the nano-filtration membrane pipe and separate, its pressure better is set at 5～25kg/cm to the liquid of the hydrochlorate that contains photoresist, high-valency metal and tetra-allkylammonium that will be in thickener via group's Pu pressurization
2, the main component that can in filtrate receiver, obtain to have removed impurity such as photoresist and high-valency metal be tetra-allkylammonium hydrochlorate penetrating fluid and obtain to be mainly the concentrated solution of impurity such as containing photoresist and high-valency metal in thickener.
In the above-mentioned steps (2) of the inventive method, used nano-filtration membrane can be used, and can to distinguish molecular weight be 100～1000 nano-filtration membrane pipe, and can use one or more filtering membrane tube, when using a plurality of filtering membrane tube, can connect and arbitrary combination in parallel use.
In the above-mentioned steps (2) of the inventive method, the pure water that makes an addition in the thickener can use former water, ultrapure water or deionized water.
In the above-mentioned steps (3) of the inventive method, when the concentrated solution conductivity value of concentration side is above greater than 20000 μ s/cm, adds the penetrating fluid volume that pure water proceeds to filter until permeate side in the filtering membrane concentration side of this tripping device and reach more than the 90 volume % of the volume that disposes waste liquid at first.In nanofiltration membrane (NF film) tripping device, along with the filtration time increase, to rise gradually owing to concentrate the concentration of end tetraalkylammonium salt, concentrated end osmotic pressure also raise gradually and caused filtration velocity to descend this moment.Because of nano-filtration membrane (NF film) surface is electronegative, the film surface produces the Donnan effect in the filtration procedure, being equivalent to the spissated effect of reverse osmosis membrane when filtering dilute solution rises concentration side conductivity value gradually, when the conductivity value is promoted to 20000 μ s/cm when above, add water gradually in thickener, the Donnan effect of utilizing film surface to produce will help hydrochlorate extraction with tetra-allkylammonium in the thickener by nano-filtration membrane to filtrate receiver, and then make the concentrated solution conductivity descend, make the penetrating fluid conductivity to increase and increase the rate of recovery.
At last, in the step (4) of method of the present invention, collected penetrating fluid is carried out electrolysis, make the hydrochlorate of tetra-allkylammonium contained in this penetrating fluid convert hydroxide four alkane ammoniums to and reclaimed.Any electrolysis/electrodialysis technology that the method that converts the hydrochlorate electrolysis/electrodialysis of tetra-allkylammonium to tetraalkylammonium hydroxide can be used this skill to know to know, for example utilize one electrolysis/electrodialysis device to carry out, this electrolyzer comprises a cationic exchange membrane, in order to electrolyzer is divided into anolyte compartment and cathode compartment, in the anolyte compartment, comprise an anode and contain the solution of the hydrochlorate of tetra-allkylammonium, in cathode compartment, comprise a negative electrode and water, between two electrodes, supply direct current, thereby obtain the tetraalkylammonium hydroxide of purifying and reclaimed from cathode side.But these hydrochlorates with tetra-allkylammonium convert the electrolysis process reference example of hydroxide four alkane ammoniums such as the method described in Japanese kokai publication sho 57-181385 and the U.S. Patent number the 5968338th to, and it is for reference that these patent document contents are incorporated this paper into.
In the method for the present invention, make hydroxide four alkane ammoniums in this development waste liquid convert the hydrochlorate of tetra-allkylammonium to by acid in step (1), formation contains before or after the development waste liquid of hydrochlorate of tetra-allkylammonium, also can make this development waste liquid carry out pre-treatment earlier, and before the electrolysis of step (4), make penetrating fluid carry out pre-treatment, these pre-treatment are exemplified as for example to concentrate and reach purifying in advance, these concentrate and for example can be exemplified as that evaporation concentration, reverse osmosis membrane concentrate, membrane distillation concentrates etc., to reach proper concn.Purifying can be exemplified as and for example utilize activated carbon treatment, Zeo-karb and/or anionite-exchange resin etc. to remove the micro-impurity such as the purifying in advance of trace impurities such as photoresist, positively charged ion and/or negatively charged ion in advance, is the purification step of purpose to reach each industrial electronic purity.
Embodiment
Embodiment
Below will offer some clarification on the present invention with embodiment, but the scope that it should be construed as limiting the invention.Tetramethyl ammonium hydroxide concentration is by Acid and Alkali Titration Analysis, and the hydrochlorate rate of recovery of tetramethyl-ammonium is by formula:
With (penetrating fluid conductivity * penetrating fluid volume)/(conductivity of the hydrochlorate of tetramethyl-ammonium after the acid neutralization * initial treatment solution volume) * 100%
Calculate and get, the residual system of photoresist is that 280nm detects its absorbancy and gives qualitatively by UV-light-visible light absorptiometer in wavelength set, and the high more expression photoresist of absorbance concentration is big more.
Embodiment 1
Sample solution system by A company of liquid-crystal display (LCD) factory in manufacturing processed, by the development waste liquid of developing manufacture process discard solution discharge port direct sampling.The contained by analysis tetramethyl ammonium hydroxide concentration of this development waste liquid is 0.66 weight %, and is that to detect its absorbancy be 0.602 to 280nm with UV-light-visible light absorptiometer in wavelength set.Getting this development waste liquid of 50.30L, through 32%HCl its pH to be adjusted to the pH that is suitable for the nanofiltration membrane separation unit be 6.991, be sample solution, convert tetramethyl ammonium hydroxide contained in it to Tetramethylammonium chloride this moment, and the Tetramethylammonium chloride conductivity EC that records with conductoscope is 7170 μ s/cm.
This sample solution is comprised nano-filtration membrane (NF film) tripping device (stepping the objective goods of first company design for Taiwan) by one, the nano-filtration membrane (NF film) that this device uses is the NF90-2540 of FILMTEC company manufacturing, and this tripping device possesses a thickener, in order to hold the development waste liquid of wherein contained tetramethyl ammonium hydroxide after conversion process becomes Tetramethylammonium chloride; One filtrate receiver is in order to hold the penetrating fluid that contains the chlorination tetramethyl-ammonium by nano-filtration membrane; One nano-filtration membrane pipe, in order to Tetramethylammonium chloride and photoresist and high-valency metal as: Fe, Al etc. separates; One pure water cylinder is used to thickener and supplies with pure water; And a pumping, utilize so that pure water is pumped in the thickener from pure water cylinder.The initial flow of the tripping device of nano-filtration membrane is that 0.1L/min, original pressure are 8.5kg/cm
2, sample solution begins to be concentrated in thickener and flow reduces gradually along with tripping device starts, and is adjusted for keep the flow certain pressure to increase thereupon.
Detect the conductivity value when the concentrated solution side and be promoted to 20000 μ s/cm when above; This moment, flow was that 0.1L/min, pressure are 15.5kg/cm
2, starting the pure water pumping, beginning is added pure water (being preferably deionized water) in thickener with the speed of 0.1L/min, and liquor capacity stops to test to 49.5L in permeable tank.
In the collected penetrating fluid volume of per-meate side is 49.5 liters, its pH is through being measured as 7.46, recording Tetramethylammonium chloride conductivity EC with conductoscope is 5530 μ s/cm, being set in wavelength with UV-light-visible light absorptiometer is that to detect its absorbancy be 0.027 to 280nm, the minimizing of photoresist residual quantity is quite a lot of as can be known by the absorbancy before the test, and by the conductivity before the test, can calculate the Tetramethylammonium chloride rate of recovery and be (5530x49.5)/(7170x50.3)=75.90%).
Embodiment 2
Sample solution preparation and nanofiltration membrane (NF film) tripping device starting conditions are with shown in the embodiment 1.PH value and photoresist absorption value (280nm abs) are as shown in table 1 below in the tetramethyl ammonium hydroxide of sample solution (TMAH) concentration, the acid and behind the post chlorization tetramethyl-ammonium conductivity (EC), volume, adjustment.
Detect the conductivity value when the concentrated solution side and be promoted to 20000 μ s/cm when above; This moment, flow was that 0.1L/min, pressure are 14.9kg/cm
2, beginning is added deionized water in thickener with the speed of 0.08/min, and residual solution stops test less than 1L in thickener.
Measure Tetramethylammonium chloride conductivity, volume, pH value and the photoresist absorption value of the penetrating fluid of per-meate side similarly to Example 1, and calculate the Tetramethylammonium chloride rate of recovery, it the results are shown in following table 1.
Comparative example 1
Sample solution preparation and nanofiltration membrane (NF film) tripping device starting conditions be with shown in the embodiment 1, but do not add pure water (deionized water) in sepn process in thickener.PH value and photoresist absorption value (280nm abs) are as shown in table 1 below after the tetramethyl ammonium hydroxide concentration (TMAH) of sample solution, Tetramethylammonium chloride conductivity (EC), volume, the adjustment.
Along with filtration unit starts, sample solution begins to be concentrated in thickener and causes flow to descend with this sample solution, is certain for keeping flow, and pressure need be adjusted to thereupon and be not more than 40kg/cm
2(this is the operation of equipment limit of pressure), residual solution stops test less than 1L in thickener.
Measure Tetramethylammonium chloride conductivity, volume, pH value and the photoresist absorption value of the penetrating fluid of per-meate side similarly to Example 1, and calculate the Tetramethylammonium chloride rate of recovery, it the results are shown in following table 1.
Comparative example 2
Sample solution preparation and nanofiltration membrane (NF film) tripping device starting conditions are with shown in the embodiment 1, but do not add pure water (deionized water) in sepn process in thickener.PH value and photoresist absorption value (280nm after the tetramethyl ammonium hydroxide of sample solution (TMAH) concentration, Tetramethylammonium chloride conductivity (EC), volume, the adjustment
Abs) as shown in table 1 below.
Cause flow to descend along with filtration unit starting sample solution begins to be concentrated in thickener this sample solution, be not more than 40kg/cm for keep the flow certain pressure to be adjusted to thereupon
2, residual solution stops test less than 1L in thickener.
Measure tetramethyl phosphonium chloride ammonium concentration, volume, pH value and the photoresist concentration of the penetrating fluid of per-meate side similarly to Example 1, and calculate the Tetramethylammonium chloride rate of recovery, it the results are shown in following table 1.
Table 1
By the result of last table 1 as can be known, in sepn process, in thickener, do not add the comparative example 1 of pure water and the hydrochlorate of 2 recyclable more a high proportion of tetramethyl-ammoniums according to the Tetramethylammonium chloride ratio that method of the present invention reclaimed, so when the later use electrolysis is changed back tetramethyl ammonium hydroxide with Tetramethylammonium chloride, can obtain the rate of recovery high than comparative example.
Collected penetrating fluid can utilize the method described in Japanese kokai publication sho 57-181385 for example and the U.S. Patent number the 5968338th to carry out electrolysis subsequently in the foregoing description 1 and 2, Tetramethylammonium chloride contained in it can be changed back tetramethyl ammonium hydroxide (alkali salt), and give recycling.
Claims (9)
1. one kind contains the waste liquid recovery of tetraalkylammonium hydroxide and the method for purifying tetraalkylammonium hydroxide certainly, and this waste liquid comprises impurity such as tetraalkylammonium hydroxide and photoresist at least, and this method comprises the following steps: at least
(1) makes tetraalkylammonium hydroxide in this waste liquid convert the hydrochlorate of tetra-allkylammonium to by acid, form the development waste liquid of the hydrochlorate that contains tetra-allkylammonium;
(2) make this waste liquid that contains tetra-allkylammonium by having the tripping device of nano-filtration membrane, the penetrating fluid that obtains to contain the concentrated solution of photoresist and other impurity and contain the hydrochlorate of tetra-allkylammonium in the per-meate side of this nano-filtration membrane in the concentration side of this nano-filtration membrane;
(3) continue to carry out this filtering separation step of step (2), in concentrating the distolateral conductivity value of detect extremely greater than 20000 μ s/cm when above, the penetrating fluid volume of proceeding to filter until permeate side in the filtering membrane concentration side interpolation pure water of this tripping device reaches more than the 90 volume % of the volume that disposes waste liquid at first; And
(4) collect penetrating fluid and carry out electrolysis, make the hydrochlorate of tetra-allkylammonium contained in this penetrating fluid convert hydroxide four alkane ammonium alkali salts to and reclaimed.
2. as claimed in claim 1 from the waste liquid recovery that contains tetraalkylammonium hydroxide and the method for purifying tetraalkylammonium hydroxide, wherein, in the step (1), be that the mat Zeo-karb is adsorbed in tetraalkyl ammonium ion on the Zeo-karb, dash with acid again and propose tetraalkylammonium salt.
3. as claimed in claim 1ly reclaim and the method for purifying tetraalkylammonium hydroxide from the waste liquid that contains tetraalkylammonium hydroxide, wherein, should dash and propose used acid is be selected from cohort that hydrochloric acid, nitric acid, sulfuric acid, carbonic acid forms at least a.
4. as claimed in claim 1 from the waste liquid recovery that contains tetraalkylammonium hydroxide and the method for purifying tetraalkylammonium hydroxide, wherein, this resin cation (R.C.) is a strongly acidic cation-exchange.
5. as claimed in claim 1 from the waste liquid recovery that contains tetraalkylammonium hydroxide and the method for purifying tetraalkylammonium hydroxide, wherein, this resin cation (R.C.) is the weak-type Zeo-karb.
6. as claimed in claim 1 from the waste liquid recovery that contains tetraalkylammonium hydroxide and the method for purifying tetraalkylammonium hydroxide, wherein, in the step (1), be to make tetraalkylammonium hydroxide be converted to tetraalkylammonium salt by directly adding acid.
7. as claimed in claim 6ly reclaim and the method for purifying tetraalkylammonium hydroxide from the waste liquid that contains tetraalkylammonium hydroxide, wherein, this acid is be selected from cohort that hydrochloric acid, nitric acid, sulfuric acid, carbonic acid forms at least a.
8. as claimed in claim 1ly reclaim and the method for purifying tetraalkylammonium hydroxide from the waste liquid that contains tetraalkylammonium hydroxide, wherein, used nano-filtration membrane is 100～1000 nano-filtration membrane pipe for distinguishing molecular weight in the step (2).
9. as claimed in claim 1 from the waste liquid recovery that contains tetraalkylammonium hydroxide and the method for purifying tetraalkylammonium hydroxide, wherein, the pressure by the nano-filtration membrane pipe in the step (2) is 5～25kg/cm
2
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108396327A (en) * | 2018-05-23 | 2018-08-14 | 梁小朝 | A kind of device and method of continuity method production tetramethylammonium hydroxide |
| CN113200869A (en) * | 2021-04-28 | 2021-08-03 | 南京长江江宇环保科技有限公司 | Method for recovering tetramethylammonium chloride from semiconductor development wastewater |
| CN113415934A (en) * | 2021-06-07 | 2021-09-21 | 镇江润晶高纯化工科技股份有限公司 | Method and device for recycling tetramethylammonium hydroxide in developing waste liquid |
-
2010
- 2010-01-25 CN CN2010101003846A patent/CN102134135A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108396327A (en) * | 2018-05-23 | 2018-08-14 | 梁小朝 | A kind of device and method of continuity method production tetramethylammonium hydroxide |
| CN108396327B (en) * | 2018-05-23 | 2024-04-09 | 柏川新材料科技(宁波)有限公司 | Equipment and method for producing tetramethyl ammonium hydroxide by continuous method |
| CN113200869A (en) * | 2021-04-28 | 2021-08-03 | 南京长江江宇环保科技有限公司 | Method for recovering tetramethylammonium chloride from semiconductor development wastewater |
| CN113200869B (en) * | 2021-04-28 | 2023-06-23 | 南京长江江宇环保科技股份有限公司 | Method for recycling tetramethyl ammonium chloride from semiconductor development wastewater |
| CN113415934A (en) * | 2021-06-07 | 2021-09-21 | 镇江润晶高纯化工科技股份有限公司 | Method and device for recycling tetramethylammonium hydroxide in developing waste liquid |
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Application publication date: 20110727 |