CN102690206A - Recovery system and method of tetramethylammonium hydroxide - Google Patents
Recovery system and method of tetramethylammonium hydroxide Download PDFInfo
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- CN102690206A CN102690206A CN2011100736897A CN201110073689A CN102690206A CN 102690206 A CN102690206 A CN 102690206A CN 2011100736897 A CN2011100736897 A CN 2011100736897A CN 201110073689 A CN201110073689 A CN 201110073689A CN 102690206 A CN102690206 A CN 102690206A
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- ammonium hydroxide
- tetramethyl ammonium
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Abstract
The invention relates to a recovery system and a method of tetramethylammonium hydroxide; the equipment system and the process flow of the invention mainly provide a simplified arrangement and process flow for separating tetramethylammonium hydroxide (TMAH) from a light resistance agent; the purity of the tetramethylammonium hydroxide is improved by reduce equipment cost and flow; and the environment pollution caused by discharged waste water is further reduced.
Description
Technical field
The present invention refers to the recovery system and the method for tetramethyl ammonium hydroxide (TMAH) developing solution especially about a kind of chemical substance recovery system and method.
Background technology
Tetramethyl ammonium hydroxide (tetra-methyl-ammonia hydroxide, TMAH, hereinafter to be referred as TMAH or claim tetramethyl ammonium hydroxide) usually as the usefulness of alkaline-based developer.And for environmental protection and save considering of resource, manufacturer can design recovery system usually, and tetramethyl ammonium hydroxide is reclaimed, and solves environmental issue on the one hand, reduces resource on the one hand and consumes and save the cost expenditure.
The Taiwan patent is openly announced No. 201102362, and a kind of " recovery system of tetramethyl ammonium hydroxide and method thereof " is provided, according to the contained content of its specification sheets, and the recovery method of this tetramethyl ammonium hydroxide (TMAH), it includes in regular turn:
One filtration step, one first reverse osmosis step, an adsorption chromatography step and a zwitterion exchange step; Tetramethyl ammonium hydroxide in this waste water is reclaimed again and utilize; To reduce influence and the harm that tetramethyl ammonium hydroxide causes environment; And the manufacturer can be reclaimed once more and utilize tetramethyl ammonium hydroxide in manufacture of semiconductor, saving dealer's cost of manufacture, and further increase manufacturer's competitive power.
But the problem of this prior art is, owing to the reverse osmosis step can be removed tetramethyl ammonium hydroxide (TMAH) together with photoresist usually in the lump, so is difficult to meet the requirements of the recovery benefit on the practice.And the specification sheets according to this prior art is described, and it must be provided with photoresist accumulator tank and adsorption layer system, therefore is provided with flow process comparatively loaded down with trivial details.
Summary of the invention
Because the problem of this prior art, the present inventor thinks should have a kind of system of improvement and method, designs a kind of tetramethyl ammonium hydroxide recovery system for this reason, comprising: a receiving tank; One strainer, this strainer is connected with this receiving tank; One resin cation(R.C.) tower is connected with this strainer; One sulfuric acid feed chute; One first regeneration liquid bath is communicated with this resin cation(R.C.) tower; One second regeneration liquid bath is communicated with this resin cation(R.C.) tower, and is communicated with this sulfuric acid feed chute; One wastewater trough is communicated with this resin cation(R.C.) tower; One electrodialysis groove is communicated with this first regeneration liquid bath.The present invention also relates to a kind of tetramethyl ammonium hydroxide recovery method, and step comprises at least:
The tetramethyl ammonium hydroxide that (1) will contain photoresist is directed at a receiving tank;
(2) filter (to comprise coarse filtration reaches how meter level filters (Nanofiltration, NF)) with this photoresist removal, via strainer to obtain tetramethyl ammonium hydroxide filtrating;
(3) this tetramethyl ammonium hydroxide filtrating is directed at a resin cation(R.C.) tower, cation-adsorption tetramethyl-ammonia salt (tetramethyl ammonium salt, TMA) ion and disengage hydrogen ion;
Owing to the product water PH through the resin cation(R.C.) tower changes according to Sorensen value; Seeing through the judgement (it is saturated that promptly whether this resin cation(R.C.) tower reaches absorption) of adopting water detects with pH value; When TMAH concentration rises in producing water; PH can rise thereupon, is judged to be this moment to see through to adopt water (the resin cation(R.C.) tower is in state of saturation);
(4) the saturated resin tower of absorption need use the sulfuric acid in the sulfuric acid feed chute to regenerate as regenerated liquid; The TMA of cation-adsorption in the resin cation(R.C.) tower and the hydrogen ion of black sulfuric acid are done IX, contain the TMA and the sulfate ion of high density in the born again desorbed solution;
The desorbed solution that (5) will contain high density TMA and sulfate ion separates TMA and sulfate ion and improves concentration through the electrodialysis groove again, and TMA changes TMAH into and sulfate radical changes sulfuric acid into.
In addition, the present invention asks the water yield and the TMAH content that more can reduce regenerative agent cost and regenerative wastewater, in regenerative process, regeneration step is divided into three kinds of situations: from the desorbed solution that above-mentioned steps (4) is come out,
A, set concentration greater than one, then be directed in the electrodialysis groove and separate and refining program when the concentration of this tetramethyl ammonium hydroxide;
B, set concentration less than one when the concentration of this tetramethyl ammonium hydroxide, and vitriolic concentration then is directed at the second regeneration liquid bath when setting concentration greater than one, this sulfuric acid through mixes with high-concentration sulfuric acid adjust concentration after, be used as regenerated liquid next time;
C, set concentration less than one when the concentration of this tetramethyl ammonium hydroxide, and vitriolic concentration is also set concentration less than one, drains into wastewater trough.
Produce the water quality requirements if need obtain higher resin tower, after two reclaim(ed) sulfuric acid regeneration of above-mentioned reproducer, must supply regeneration next time to use through regenerated liquid being caused the second regeneration liquid bath with highly purified regeneration of sulfuric acid.
Device systems of the present invention and this flow process mainly provide a kind of equipment and flow process of comparatively simplifying; Can tetramethyl ammonium hydroxide (TMAH) be separated with this photoresist; And promote the purity of tetramethyl ammonium hydroxide with the equipment cost of comparatively simplifying and flow process, and further reduce the pollution of the waste water that emits for environment.
Description of drawings
Fig. 1 is a system architecture diagram of the present invention.
Fig. 2 is a schema of the present invention.
[main element nomenclature]
1 receiving tank, 2 strainers, 21 storage tanks, 22 waste pipes
3 resin cation(R.C.) towers, 4 sulfuric acid feed chutes, 5 vitriol oil storage tanks
61 first regeneration liquid baths, 62 second regeneration liquid baths, 63 wastewater troughs
7 electrodialysis grooves
Embodiment
Below auxiliary by accompanying drawing, content of the present invention, characteristic and embodiment are described, so that the present invention can further be understood.
See also shown in Figure 1ly, the present invention comprises about a kind of tetramethyl ammonium hydroxide recovery system:
One receiving tank 1: can provide and collect the trade effluent that contains photoresist and tetramethyl ammonium hydroxide.Again in this trade effluent except that photoresist, also possibly comprise the metal or the impurity such as aluminium, calcium, iron, copper, potassium, magnesium, sodium of lower concentration.
One strainer 2: be connected with this receiving tank 1; As filtering from the waste water of this receiving tank 1 and separating this trade effluent.This strainer 2 can connect a storage tank 21 filtrates to collect, and this strainer 2 can connect a waste pipe 22.
One resin cation(R.C.) tower 3: be connected with this strainer 2 (through this storage tank); These resin cation(R.C.) tower 3 inner filling male ion-exchange resins, this Zeo-karb can be the porous polymethyl vinylformic acid (porous polymethacrylic crosslinked with divinylbenzene) of crosslinked divinylbenzene.
One sulfuric acid feed chute 4: can provide and load the sulfuric acid of concentration more than 15%, and receive the sulfuric acid that refluxes.This sulfuric acid mainly is that tetramethyl ammonium hydroxide that Zeo-karb is adsorbed dashes and puts forward.
One vitriol oil storage tank 5: be communicated with this sulfuric acid feed chute 4; Can provide and load the sulfuric acid of concentration more than 20%.One first regeneration liquid bath 61: be communicated with this resin cation(R.C.) tower 3; One second regeneration liquid bath 62: be communicated with this resin cation(R.C.) tower 3; And be communicated with this sulfuric acid feed chute 4;
One wastewater trough 63: be communicated with this resin cation(R.C.) tower 3; One electrodialysis groove 7: be communicated with this first regeneration liquid bath 61.
Seeing also shown in Figure 2ly, with regard to method of the present invention, is a kind of tetramethyl ammonium hydroxide recovery method, comprises step at least:
1. the tetramethyl ammonium hydroxide that will contain photoresist is directed at a receiving tank 1;
2. (this filtration procedure comprises coarse filtration and how meter level filters (Nanofiltration via filtering; NF)) this photoresist is removed; To obtain tetramethyl ammonium hydroxide filtrating: promptly via a strainer 2, this photoresist is removed, to obtain tetramethyl ammonium hydroxide filtrating; Photoresist can accumulate on strainer 2 surfaces in the strainer 2 filtration photoresist processes; During by each machine strainer 2 being carried out big yield forward washes; Can this photoresist be gone out by strainer 2 surfaces, and derive, to reduce the frequency that strainer 2 cleans and to increase the service life through this waste pipe 22.
3. this tetramethyl ammonium hydroxide filtrating is directed at a resin cation(R.C.) tower 3, resin cation(R.C.) tower 3 absorption tetramethyl-ammonia salts (tetramethyl ammonium salt, TMA) ion and disengage hydrogen ion;
Owing to the product water PH through resin cation(R.C.) tower 3 changes according to Sorensen value; Seeing through the judgement (it is saturated whether resin cation(R.C.) tower 3 reaches) of adopting water detects with pH value; When TMAH concentration rises in producing water; PH can rise thereupon, is judged to be this moment to see through to adopt water (being that resin cation(R.C.) tower 3 reaches capacity).
4. adsorbing saturated resin cation(R.C.) tower 3 needs to use sulfuric acid to regenerate as regenerated liquid (being stored in sulfuric acid feed chute 4); The TMA of resin cation(R.C.) tower 3 internal adsorption and the hydrogen ion of regenerated liquid are done IX, contain the TMA and the sulfate ion of high density in the born again desorbed solution.
5. the desorbed solution that will contain high density TMA and sulfate ion separates TMA and sulfate ion and improves concentration through electrodialysis groove 7 again, and TMA changes TMAH into and sulfate radical changes sulfuric acid into.In addition, the present invention asks the water yield and the TMAH content that more can reduce regenerative agent cost and regenerative wastewater, in regenerative process, regeneration step is divided into three kinds of situation: from the desorbed solution that above-mentioned steps 4 is come out,
A, when the concentration of this tetramethyl ammonium hydroxide is set concentration greater than one, then be directed in the electrodialysis groove 7 and separate and refining program;
B, set concentration less than one when the concentration of this tetramethyl ammonium hydroxide; And vitriolic concentration is when setting concentration greater than one; Then be directed at the second regeneration liquid bath 62; Be directed at then in the sulfuric acid feed chute 4, through mix adjustment concentration with vitriol oil storage tank 5 high-concentration sulfuric acids after, be used as regenerated liquid next time with the sulfuric acid in the sulfuric acid feed chute 4;
The concentration of C, this tetramethyl ammonium hydroxide is set concentration less than one, and sulfuric acid concentration is also set concentration less than one, drains into wastewater trough.
Produce the water quality requirements if need obtain higher resin tower, after two reclaim(ed) sulfuric acid regeneration of above-mentioned reproducer, must supply regeneration next time to use through regenerated liquid being caused the second regeneration liquid bath with highly purified regeneration of sulfuric acid.
Device systems of the present invention and this flow process mainly provide a kind of equipment and flow process of comparatively simplifying; Can tetramethyl ammonium hydroxide (TMAH) be separated with this photoresist; And promote the purity of tetramethyl ammonium hydroxide with the equipment cost of comparatively simplifying and flow process, and further reduce the pollution of the waste water that emits for environment.
The above person is merely a preferred embodiment of the present invention, when can not with qualification scope of the present invention.The equalization of promptly doing according to claim of the present invention generally changes and modifies, and all should still belong in the scope that patent of the present invention contains.
Claims (9)
1. a tetramethyl ammonium hydroxide recovery system is characterized in that comprising: a receiving tank; A strainer is connected with this receiving tank;
A resin cation(R.C.) tower is connected with this strainer;
A sulfuric acid feed chute;
One first regeneration liquid bath is communicated with this resin cation(R.C.) tower;
One second regeneration liquid bath is communicated with this resin cation(R.C.) tower; And be communicated with this sulfuric acid feed chute;
A wastewater trough is communicated with this resin cation(R.C.) tower;
An electrodialysis groove is communicated with this first regeneration liquid bath.
2. tetramethyl ammonium hydroxide recovery system as claimed in claim 1 is characterized in that: more establish a vitriol oil storage tank, communicate with this sulfuric acid feed chute.
3. tetramethyl ammonium hydroxide recovery method is characterized in that comprising at least step:
The tetramethyl ammonium hydroxide that (1) will contain photoresist is directed at a receiving tank;
(2) filter this photoresist removal through strainer, to obtain tetramethyl ammonium hydroxide filtrating;
(3) this tetramethyl ammonium hydroxide filtrating is directed at a resin cation(R.C.) tower, resin cation(R.C.) tower absorption tetramethyl-ammonia salt ion also disengages hydrogen ion; (4) will adsorb saturated resin cation(R.C.) tower uses the sulfuric acid in the sulfuric acid feed chute to regenerate as regenerated liquid; The TMA of resin cation(R.C.) tower internal adsorption and the hydrogen ion of regenerated liquid are done IX, contain the TMA and the sulfate ion of high density in the born again desorbed solution;
The desorbed solution that (5) will contain high density TMA and sulfate ion separates TMA and sulfate ion and improves concentration through the electrodialysis groove again, and TMA changes TMAH into and sulfate radical changes sulfuric acid into.
4. tetramethyl ammonium hydroxide recovery method as claimed in claim 3 is characterized in that: the communication path by this receiving tank to this strainer, forward wash, to reduce the obstruction and the cleaning frequency of strainer.
5. tetramethyl ammonium hydroxide recovery method as claimed in claim 3 is characterized in that: more establish a vitriol oil storage tank, the inner installing vitriol oil when sulfuric acid concentration in this sulfuric acid feed chute is not enough, is able to charging and replenishes.
6. tetramethyl ammonium hydroxide recovery method as claimed in claim 3 is characterized in that: said filtration comprises coarse filtration and how meter level filters.
7. tetramethyl ammonium hydroxide recovery method as claimed in claim 3; It is characterized in that: the saturated judgement of this resin cation(R.C.) tower absorption detects with pH value; When TM AH concentration rose in producing water, PH can rise thereupon, was judged to be the resin cation(R.C.) tower this moment and adsorbed saturated.
8. tetramethyl ammonium hydroxide recovery method as claimed in claim 3 is characterized in that: more establish a regeneration step, this step is divided into three kinds of situations: from the desorbed solution that above-mentioned steps (4) is come out,
(1) sets concentration when the concentration of this tetramethyl ammonium hydroxide greater than one, then be directed in this electrodialysis groove and separate and refining program;
(2) set concentration less than one when the concentration of this tetramethyl ammonium hydroxide, and vitriolic concentration is set concentration greater than one, then is directed at the second regeneration liquid bath, in this desorbed solution sulfuric acid through mixes with high-concentration sulfuric acid adjust concentration after, be used as regenerated liquid next time;
(3) set concentration less than one when the concentration of this tetramethyl ammonium hydroxide, and sulfuric acid concentration is also set concentration less than one, drains into wastewater trough.
9. tetramethyl ammonium hydroxide recovery method as claimed in claim 3 is characterized in that: said regenerated liquid is a sulfuric acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100736897A CN102690206A (en) | 2011-03-25 | 2011-03-25 | Recovery system and method of tetramethylammonium hydroxide |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100736897A CN102690206A (en) | 2011-03-25 | 2011-03-25 | Recovery system and method of tetramethylammonium hydroxide |
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| CN102690206A true CN102690206A (en) | 2012-09-26 |
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| CN2011100736897A Pending CN102690206A (en) | 2011-03-25 | 2011-03-25 | Recovery system and method of tetramethylammonium hydroxide |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103304430A (en) * | 2013-07-05 | 2013-09-18 | 武汉科梦环境工程有限公司 | Process for recovering organic amine from catalyst production wastewater |
| CN106431830A (en) * | 2016-08-11 | 2017-02-22 | 刘定忠 | Decomposition method of tetramethyl ammonium hydroxide solution and decomposition device thereof |
Citations (6)
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|---|---|---|---|---|
| US6083670A (en) * | 1998-01-05 | 2000-07-04 | Organo Corporation | Process and equipment for rejuvenation treatment of photoresist development waste |
| CN1334796A (en) * | 1998-12-07 | 2002-02-06 | Basf公司 | Method for producing or purifying onium hydroxides by means of electrodialysis |
| CN1567090A (en) * | 2003-06-27 | 2005-01-19 | 友达光电股份有限公司 | Reclaiming system for tetramethylammonium hydroxide developing liquid and method therefor |
| TW200921298A (en) * | 2007-11-09 | 2009-05-16 | San Fu Chemical Co Ltd | Method for recycling tetramethylammonium hydroxide (TMAH) from waste developer |
| TW201040133A (en) * | 2009-05-01 | 2010-11-16 | Mega Union Technology Inc | Equipment for recycling tetramethyl ammonium hydroxide and method thereof |
| TW201102362A (en) * | 2009-07-14 | 2011-01-16 | Mega Union Technology Inc | Recycling equipment for tetramethyl ammonium hydroxide and method thereof |
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2011
- 2011-03-25 CN CN2011100736897A patent/CN102690206A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6083670A (en) * | 1998-01-05 | 2000-07-04 | Organo Corporation | Process and equipment for rejuvenation treatment of photoresist development waste |
| CN1334796A (en) * | 1998-12-07 | 2002-02-06 | Basf公司 | Method for producing or purifying onium hydroxides by means of electrodialysis |
| CN1567090A (en) * | 2003-06-27 | 2005-01-19 | 友达光电股份有限公司 | Reclaiming system for tetramethylammonium hydroxide developing liquid and method therefor |
| TW200921298A (en) * | 2007-11-09 | 2009-05-16 | San Fu Chemical Co Ltd | Method for recycling tetramethylammonium hydroxide (TMAH) from waste developer |
| TW201040133A (en) * | 2009-05-01 | 2010-11-16 | Mega Union Technology Inc | Equipment for recycling tetramethyl ammonium hydroxide and method thereof |
| TW201102362A (en) * | 2009-07-14 | 2011-01-16 | Mega Union Technology Inc | Recycling equipment for tetramethyl ammonium hydroxide and method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 高彦春等: "四丁基氢氧化铵制备方法及应用", 《石油化工技术与经济》, vol. 27, no. 1, 28 February 2011 (2011-02-28), pages 33 - 37 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103304430A (en) * | 2013-07-05 | 2013-09-18 | 武汉科梦环境工程有限公司 | Process for recovering organic amine from catalyst production wastewater |
| CN106431830A (en) * | 2016-08-11 | 2017-02-22 | 刘定忠 | Decomposition method of tetramethyl ammonium hydroxide solution and decomposition device thereof |
| CN106431830B (en) * | 2016-08-11 | 2020-03-31 | 刘定忠 | Method and apparatus for decomposing tetramethylammonium hydroxide solution |
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Application publication date: 20120926 |