CN103732573B - The manufacture method of tetra-allkylammonium salting liquid - Google Patents
The manufacture method of tetra-allkylammonium salting liquid Download PDFInfo
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- CN103732573B CN103732573B CN201280038087.0A CN201280038087A CN103732573B CN 103732573 B CN103732573 B CN 103732573B CN 201280038087 A CN201280038087 A CN 201280038087A CN 103732573 B CN103732573 B CN 103732573B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/04—Processes using organic exchangers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J49/00—Regeneration or reactivation of ion-exchangers; Apparatus therefor
- B01J49/05—Regeneration or reactivation of ion-exchangers; Apparatus therefor of fixed beds
- B01J49/06—Regeneration or reactivation of ion-exchangers; Apparatus therefor of fixed beds containing cationic exchangers
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/82—Purification; Separation; Stabilisation; Use of additives
- C07C209/84—Purification
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
- C02F2001/425—Treatment of water, waste water, or sewage by ion-exchange using cation exchangers
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/40—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture or use of photosensitive materials
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/30—Imagewise removal using liquid means
- G03F7/32—Liquid compositions therefor, e.g. developers
- G03F7/322—Aqueous alkaline compositions
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/42—Stripping or agents therefor
- G03F7/422—Stripping or agents therefor using liquids only
- G03F7/425—Stripping or agents therefor using liquids only containing mineral alkaline compounds; containing organic basic compounds, e.g. quaternary ammonium compounds; containing heterocyclic basic compounds containing nitrogen
Abstract
From the solution that contains metal ion and tetraalkyl ammonium ion of resist development waste liquid etc., remove efficiently metal ion. Make the solution that contains metal ion and tetraalkyl ammonium ion, contact with cationic ion-exchange resin, make these ionic adsorption in this resin, afterwards by alkali metal salt soln and molten from. This alkali metal ion concentration in monitoring eluat, reclaims path, the tetra-allkylammonium salting liquid that the concentration of recyclable alkali metal ion and other metal ions is all low by switching before sharply rising in this alkali metal ion concentration. The tetraalkylammonium salt reclaiming can form tetraalkylammonium hydroxide through electrolysis. During from electrolysis, be difficult to form viewpoints such as hindering material and cost, above-mentioned alkali metal salt soln the best is aqueous sodium carbonate.
Description
Technical field
The present invention relates to use the novel process for preparing of the solution that cationic ion-exchange resin manufacture contains tetraalkylammonium salt, andThe manufacture method of the tetraalkylammonium hydroxide using it as raw material.
Background technology
Tetraalkylammonium hydroxide (hereinafter to be referred as TAAH) is generally with headed by alternate transfer catalyst, as nonaqueous titrationOrganic system basifier in the marking fluid of middle base or organic synthesis is compounds effective. Again as integrated circuit or greatly ruleIn the manufacture of vlsi die, the inorganic agent of the cleaning of semiconductor substrate, etching, photoresistance development etc. uses. Particularly, partly leadingIn the purposes of body, because semiconductor substrate can be contaminated, so require not contain the high-purity TAAH of impurity as far as possible.
On the other hand, the above-mentioned photoresistance waste liquid using that develops, except comprising photoresist, also comprise impurity metal ion andTAAH, the technology that because will reduce carrying capacity of environment, reclaims, recycles TAAH from this waste liquid becomes important and (contains below photoresistanceThe waste liquid of agent and TAAH is also called " photoresistance development waste liquid "). In the past, processing in the method for photoresistance development waste liquid, by evaporationMethod or contrary soak into the method for the concentrated and waste treatment (burn or taken away by dealer) of embrane method, by the biological decomposition place of activated sludgeThe method of managing and release is main flow. But, as mentioned above, from the worry to environment, recovery from this waste liquid, is again proposed moreUtilize the trial of TAAH.
Specifically, known for concentrated waste liquid or originally the high development waste liquid of TAAH concentration go by neutralisation treatmentExcept after photoresistance composition, carry out electrodialysis or electrolysis, reclaim the method (for example, with reference to patent documentation 1 to 3) of TAAH. But, locatingWhen the low waste liquid of reason TAAH concentration, in order to reach the required concentration conditions of electrodialysis or electrolysis, must concentrated TAAH waste liquid, thereforeTo these methods, propose not carry out electrodialysis or electrolysis and from photoresistance development waste liquid, reclaim method (the referenced patent literary composition of TAAHOffer 4). Concrete method is, first makes photoresistance development waste liquid contact with cationic ion-exchange resin, make tetraalkyl ammonium ion (TAA fromSon) be adsorbed in cationic ion-exchange resin. Afterwards, in this cationic ion-exchange resin, pass into hydrochloric acid, reclaim TAA salt, gained moltenIn liquid, add perchloric acid, form tetra-allkylammonium perchlorate (TAA perchlorate). Afterwards by after TAA perchlorate partial crystallization purifying,The perchlorate of gained is contacted with anion exchange resin, reclaim the method for TAAH. But this kind of situation step becomes numerousAssorted, use the perchlorate that has outburst dangerous, industrial manufacture is had any problem.
Again, TAA ionic adsorption, in ion exchange resin, is reclaimed to TAA salt from thin development waste liquid, make its electrolysis withManufacture the technology revealed (patent documentation 5 and 6) of TAAH. But, can not control from amberlite liposoluble from TAA salt timeCondition, therefore becomes the TAA salting liquid pick-up metal ionic impurity of gained, result have in the TAAH solution after electrolysis, sneak into higherThe problem of the impurity metal ion of concentration. Again, patent documentation 5 disclose from amberlite liposoluble from time use the technology of weak acid,But have molten from the tendency that thins out of TAA salting liquid, while particularly using the situation of carbonic acid, this tendency is remarkable. Make againBy the situation of carbonic acid, in liquid, understand gassing, probably cause the obstacle of continuous operation.
When patent documentation 7 discloses amberlite liposoluble from absorption TAA ion from TAA ion, use metal hydrogen-oxygen again,Compound is manufactured the technology of TAAH. But the method has the organic matter of resist contained in development waste liquid (resist) etc. to sneak intoProblem in TAAH.
[prior art document]
[patent documentation]
Patent documentation 1: Japanese kokai publication hei 04-228587 communique
Patent documentation 2: Japanese kokai publication hei 05-106074 communique
Patent documentation 3: No. 3216998 communique of Japanese Patent
Patent documentation 4: TOHKEMY 2004-66102 communique
Patent documentation 5: No. 2688009 communiques of Japanese Patent
Patent documentation 6: Japanese Unexamined Patent Application Publication 2002-509029 communique
Patent documentation 7: Japanese Unexamined Patent Application Publication 2004-512315 communique
Summary of the invention
The problem that invention will solve
As mentioned above, use cationic ion-exchange resin from development waste liquid, to reclaim TAA ion with high yield, but this sideIn method, there is the removal of resist composition insufficient, can only obtain the problem of the thin TAA salting liquid of pick-up metal ionic impurity.
For solving the method for problem
The inventor etc. study in order to solve above-mentioned problem. Found that, by by photoresistance development waste liquid with sun fromSub-exchange resin contacts and makes TAA ionic adsorption in this cationic ion-exchange resin, passes into afterwards in this cationic ion-exchange resinSalting liquid, reclaims in TAA salt, and the concentration of metal ions in the TAA of gained salting liquid stops back before becoming certain concentrationReceive, can obtain the TAA salt that impurity metal ion concentration is low, it is carried out to electrolytic treatments, can effectively decompose and remove resist composition,Thereby can manufacture the not TAAH containing resist composition, to having completed the present invention.
That is the present invention is that the solution from containing metal ion and tetraalkylammonium hydroxide obtains and contains metal ion contentThe manufacture method of tetra-allkylammonium salting liquid of the solution of the tetraalkylammonium salt that ratio reduces, is characterized in that, comprise following (1),(2) step:
(1) being filled with in the adsorption tower of hydrogen ion type cationic ion-exchange resin, pass into and contain metal ion and hydroxideThe solution of tetra-allkylammonium, makes tetraalkyl ammonium ion in solution be adsorbed in the adsorption step of cationic ion-exchange resin;
(2) being filled with the adsorption tower that has adsorbed the cationic ion-exchange resin of tetraalkyl ammonium ion in above-mentioned adsorption step,Pass into the solution of alkali metal salt, the tetraalkyl ammonium ion that makes to be adsorbed in this resin form above-mentioned salt and molten from, by this adsorption tower instituteThe efflux flowing out is recycled to the recycling step of retention basin; And in recycling step, measure in the efflux that flows out of adsorption tower onState alkali metal ion concentration, before this alkali metal ion concentration sharply rises, stop the efflux of this retention basin recovery fourThe manufacture method of alkylammonium salt solution.
Other inventions are, comprise the step identical with above-mentioned (1) adsorption step and (2) recycling step, and at recycling stepIn, measure the above-mentioned alkali metal ion concentration in the efflux of adsorption tower, reaching this alkali metal ion concentration and be set as 0.5～The time point of the certain concentration between 10mg/L, the manufacturer who stops the tetra-allkylammonium salting liquid of the recovery of the efflux of this retention basinMethod.
Moreover according to the present invention, so the TAA salt of gained, through electrolysis, can obtain the TAAH solution that purity is high.
Invention effect
The method according to this invention, can reduce the amount of metal ion in the TAA salting liquid of recovery, therefore can be efficiently fromIn photoresistance waste liquid, obtain the TAA salt that impurity metal ion is few. Therefore, can reduce before or after step by chelating resin etc.The load of metal removal step, and reduce costs.
And, by carrying out the electrolysis of this TAA salt, can obtain the not highly purified TAAH of containing metal composition and resist compositionSolution.
Brief description of the drawings
Fig. 1 is the schematic diagram that shows an embodiment of the manufacturing equipment of the manufacture method of tetraalkylammonium salt of the present invention.
Fig. 2 reclaims tetraalkylammonium salt (TAA salt) for showing from photoresistance development waste liquid, manufactures hydroxide four alkane from this TAA saltThe flow chart of preferred embodiments when base ammonium (TAAH).
Detailed description of the invention
The present invention for to manufacture metal ion content from the solution that contains metal ion and tetraalkylammonium hydroxide (TAAH)The method of tetraalkylammonium salt (TAA salt) solution that ratio reduces, makes this TAAH solution contact with cationic ion-exchange resin, makes TAAIonic adsorption, after this cationic ion-exchange resin, passes into this adsorption tower by salting liquid, measures the recovery liquid flowing out from adsorption towerConcentration of metal ions, decision stops reclaiming the time point of liquid, obtains TAA salt. Described " reduction of metal ion content ratio " tableShow the relative quantity of TAA ion is reduced.
(solution that contains impurity metal ion and tetraalkylammonium hydroxide)
In the present invention, the solution that contains metal ion and tetraalkylammonium hydroxide is not particularly limited, but is preferably halfThe photoresistance development waste liquid producing in conductor manufacturing process, liquid crystal display manufacturing process etc. These waste liquids are the light after exposureThe waste liquid of being discharged when resist is developed with alkaline-based developer, mainly comprises photoresist, TAAH and metal ion. These waste liquids are commonFor the aqueous solution.
Photoresistance development waste liquid presents the alkalescence of pH10～14 conventionally, photoresist in alkaline development waste liquid, its carboxyl, phenolThe acidic group of hydroxyl etc. is understood acid dissociation and is dissolved. Adjacent diazo naphthoquinone (the o-of for example emulsion of main photoresistDiazonaphthoquinone) decompose the indene carboxylic acid (indenecarboxylicacid) that generates or from varnish through lightThe phenols of resin (novolacresin).
The representative waste liquid of herein, the development step in semiconductor manufacture and liquid crystal display manufacture being discharged carries out in detailDescribe in detail bright. Development step is the automatic developing devices that use one chip conventionally more, in this device, use the step containing the developer solution of TAAHSuddenly and afterwards carry out in same groove with the step of pure water moistening (substrate cleaning), now in moistening step, use developer solutionThe pure water of the amount of 5～10 times. Therefore the developer solution, using in development step is generally the waste liquid of 5～10 times of dilutions. Result thisWaste liquid that development step is discharged composition, TAAH is approximately 0.001～1 quality %, resist is about 10～100ppm, surfactantBe zero to approximately tens ppm. Also have the situation of sneaking into waste liquid in other steps, it is low that TAAH concentration also can become more above-mentioned scope. ToolBody also has the situation that becomes 0.05 quality % following (approximately 0.001～0.05 quality %). Particularly liquid crystal display manufacturing step instituteThe photoresistance development waste liquid of discharging, TAAH concentration multiform becomes the situation of 0.001～0.5 quality %, and method of the present invention can particularly suitableManufacture TAA salt person in from then on planting photoresistance development waste liquid.
In photoresistance development waste liquid, comprise multiple metal ions. Such as monovalent ion has sodium, potassium etc., and divalent ion has calcium, zincDeng, other multivalent ions have aluminium, nickel, copper, chromium, iron etc., are the representative metal being rich in photoresistance development waste liquid. These metals are logicalBe everlasting in photoresistance development waste liquid containing having an appointment 0.1～100ppb.
Photoresistance developer solution when TAAH in photoresistance development waste liquid is the manufacture for various electronic building bricks etc. is usedAlkali. For example tetramethyl ammonium hydroxide of the concrete example of TAAH (hereinafter to be referred as TMAH), tetraethyl ammonium hydroxide, hydroxide 4 thirdBase ammonium, tetrabutylammonium, hydroxide methyl triethyl ammonium, hydroxide trimethyl ethyl ammonium, hydroxide dimethyl diethylAmmonium, hydroxide trimethyl (2-ethoxy) ammonium, hydroxide triethyl group (2-ethoxy) ammonium, hydroxide dimethyl two (2-ethoxy)Ammonium, hydroxide diethyl two (2-ethoxy) ammonium, hydroxide methyl three (2-ethoxy) ammonium, hydroxide ethyl three (2-ethoxy)Ammonium, hydroxide four (2-ethoxy) ammonium etc. Among these, TMAH is the most extensively used.
(making tetraalkyl ammonium ion be adsorbed in the step of cationic ion-exchange resin)
In the present invention, being filled with the adsorption tower of cationic ion-exchange resin of hydrogen ion type (hereinafter to be referred as " H type "), pass intoContain the solution of metal ion and tetraalkylammonium hydroxide as above-mentioned, make TAA ionic adsorption in this cationic ion-exchange resin.
That is TAA ion is cation, by contacting with the cationic ion-exchange resin of H type, with this cationic ion-exchange resinThe hydrogen ion generation ion-exchange having, and be adsorbed in this resin. Therefore can from waste liquid, reclaim more efficiently TAA fromSon. Particularly in the low waste liquid of TAAH concentration, also can low cost reclaim TAA ion.
Herein, conventionally impurity metal ion is also cation, is passed into liquid and is adsorbed in cationic ion-exchange resin by this.The present invention is by adopting aftermentioned method, makes to be adsorbed in the impurity metal ion of such cationic ion-exchange resin and TAA ion moreSeparate efficiently. Again, even if there is impurity metal ion, anti-via the chemical balance that forms compound etc. in this development waste liquidShould, when this situation as anion of the contained ionic species of metal, be difficult to be adsorbed in cationic ion-exchange resin, and from adsorption towerBe discharged from.
On the other hand, the organic components from photoresist of above-mentioned dissolving is generally anionic form, is therefore difficult to inhaleInvest cationic ion-exchange resin and major part is removed, only some is adsorbed in ion exchange resin, the TAA therefore continuingIn the recycling step of salt, sneak in TAA salting liquid (this removal of stating organic principle will illustrate in aftermentioned).
(cationic ion-exchange resin)
In the present invention, the cationic ion-exchange resin that adsorbs above-mentioned TAA ion is not particularly limited, and can use known person. ToolSay, can use ion-exchange group is the weak acid that sulfonic storng-acid cation exchange resin, ion-exchange group are carboxylic acid bodyProperty cationic ion-exchange resin any one. Among these, many from the large person of ion exchange capacity, can to reduce the amount of resin of use sightsPoint, it is good using weak-acid cation-exchange resin. Moreover, be the situation of weak-acid cation-exchange resin, at TAA described laterIon molten from also easy.
Again, the structure of resin can be glue type or MR type (microporous type). The shape of resin can be powdery, granular, filmShape, fibrous etc. any one. From viewpoints such as treatment effeciency, operability, economy, use polystyrene or the propylene system of granular gradeDeng cationic ion-exchange resin be good.
The counter ion (counterion) of cationic ion-exchange resin is conventionally with hydrogen ion (H type) or sodium ion (Na type) dealerSell, but in order to prevent that the final TAAH solution obtaining from sneaking into sodium ion and promoting the adsorption efficiency of TAA ion, counter ion isThe H type of hydrogen ion type. Use the situation of the commercially available cationic ion-exchange resin of Na type, use current events logical prior to cationic ion-exchange resinEnter the acid such as hydrochloric acid or sulfuric acid, with ultra-pure water fully clean etc., make counter ion become hydrogen ion use. According to aftermentioned method, make againTAA ion is molten from rear, because form the alkali metal type of Na etc., can be through above-mentioned same operation, and regeneration H type and using.
For example ROHM AND HAAS of the concrete example of storng-acid cation exchange resin (RohmandHaas) company systemAmberliteIR120B, AmberliteIR124; DIAIONSK1B, the DIAIONPK228 of Mitsubishi Chemical Ind's system; LiveChange the DuoliteC255LFH of Chemtex company system; The LEWATITMonoplusS100 of LANXESS company system,The PuroliteC160 of Purolite company system etc. For example ROHM AND HAAS of the concrete example of weak-acid cation-exchange resin(RohmandHaas) DIAIONWK40L of the AmberliteIRC76 of company's system, Mitsubishi Chemical Ind's system, firmly changeDuoliteC433LF, the DuoliteC476 of Chemtex company system, the LEWATITCNP80WS of LANXESS company system,The PuroliteC104 of Purolite company system etc.
(passing into the method for solution to the adsorption tower that is filled with cationic ion-exchange resin)
In the present invention, to filled the adsorption tower of cationic ion-exchange resin of above-mentioned H type, passed into contain metal ion andThe solution of TAAH, by contacting with cationic ion-exchange resin, makes TAA ionic adsorption in cationic ion-exchange resin.
For the method that this solution is passed into the adsorption tower that is filled with cationic ion-exchange resin, can be according to cation exchange treeThe kind of fat or shape, suitably adopt known method. Concrete example as, cationic ion-exchange resin is filled in to post, make this solutionThe post mode that continuity is passed through is good. Adopt this situation of stating post mode, the performance of visual cationic ion-exchange resin etc. are suitable certainlyFixed, but in order to adsorb more efficiently TAA ion, if be that the content of TAAH is the solution of 0.001～1 quality %, the height of postThe ratio (L/D) of degree (L) and column diameter (D) is more than 0.5, the space velocity of this waste liquid (SV) be 1 (1/ hour) above, 200 (1/Hour) following person is good.
From can effectively manufacturing the viewpoint of TAA salt, the amount of solution of logical liquid is to be no more than the sun that is filled in adsorption towerThe amount of ion exchange resin is good.
Again, pass into the cationic solution of the amount more than exchange capacity that contains cationic ion-exchange resin, whether not absorptionAnd flow out (leakage) TAA ion, can analyze by flowing out in adsorption tower via ion chromatography (ionchromatography)Liquid in TAA ion concentration and confirming. More easily, can measure the shared height of cationic ion-exchange resin in adsorption tower. SunWhen the counter ion of ion exchange resin becomes TAA ion from hydrogen ion, though determine body according to the kind of cationic ion-exchange resinLong-pending swelling is to approximately 2 times. By measuring the volume of cationic ion-exchange resin, can confirm the absorption of TAA ion.
Again, be more than 10 alkaline situations at the pH of this solution, TAA ion does not adsorb and by adsorption tower time, because ofFor the pH of the liquid that passes through becomes alkalescence, also can see through pH pH meter and confirm. Conventionally in the liquid by adsorption tower, contain againThere is the situation of TAA ion, because the electrical conductivity of liquid rises, therefore also can see through electrical conductivity and confirm.
(reclaiming the step of tetraalkylammonium salt from the cationic ion-exchange resin of absorption tetraalkyl ammonium ion)
In the present invention, make TAA ionic adsorption after cationic ion-exchange resin through said method, be filled with this cation friendshipThe adsorption tower that changes resin passes into the solution of alkali metal salt, reclaims the recovery liquid flowing out from adsorption tower, manufactures tetraalkylammonium salt.
That is, the solution of alkali metal salt is imported to adsorption tower from one end of adsorption tower, other end trickle, carries out liquidPass into, superfluous alkali metal ion contained this salting liquid and TAA ion are exchanged to the acid of the salt of using as TAA ionSalt, flows out from adsorption tower.
Alkali metal, from solubility or the viewpoint easily obtaining etc., is preferably sodium or potassium, especially taking sodium as good.
In the present invention, above-mentioned alkali metal salt can be inorganic acid salt or acylate. Can be again the salt of weak acid or the salt of strong acid.This states weak acid is that the dissociation constant K of 25 DEG C is 10-3Following acid.
Provide aftermentioned electrolysis step by the TAA salt with method manufacture of the present invention, be difficult to when being transformed to TAAH produce mixedThe viewpoint that enters the negative effect of organic principle etc., alkali metal salt is preferably inorganic acid salt. This inorganic acid for example carbonic acid, nitrous acid,Hydrofluoric acid, hypochlorous acid etc. The carboxylic acids of organic acid such as acetic acid, oxalic acid, formic acid, benzoic acid etc. or phenols, cresols class.
In inorganic acid salt, the viewpoint of electrolysis step easness during from toxicity or stability, formation TAAH etc., is preferably carbonHydrochlorate. The carbonic acid alkali metal salt of two base acid is carbonate (M2CO3: M represents alkali metal) and bicarbonate (MHCO3), but fromCan more improve the viewpoint that reclaims TAA ion concentration in liquid, be preferably carbonate. Specially suitable alkali metal salt in the present invention, exampleAs sodium carbonate, sodium acid carbonate, potash and saleratus, in these taking sodium carbonate as best.
The solvent that forms the above-mentioned alkali-metal salt of weak acid solution using in the present invention is this alkali metal salt of solubilizedLiquid, is not particularly limited, but does not produce when the electrolysis of manufacturing use from the dissolving easness of alkali metal salt, cost and TAAH negativeThe viewpoints such as impact, are preferably water. This water can use ion exchange water, pure water, ultra-pure water etc.
In the present invention, the concentration of above-mentioned alkali metal salt soln can be suitably selected in the scope of 0.1N to 10N, but high from flowing outThe TAA salt of concentration and easily prevent the viewpoint of sneaking into of metal ion, especially taking the scope of 0.5N～4N as good.
Again, the logical liquid speed of alkali metal salt soln look the kind of volume, cationic ion-exchange resin of adsorption tower or use amount,The concentration of salting liquid etc., can suitably set, but that the space velocity (SV) that is preferably alkali metal salt soln is 1 (1/ hour) is above,Below 50 (1/ hours). Than this scope hour, can extend the time of processing.
Alkali metal salt soln and TAA ion and the method that the cationic ion-exchange resin with counter ion contacts, be preferably byThis cationic ion-exchange resin is filled in post, the post mode that alkali metal salt soln continuity is passed through. Adopt the situation of post mode,From the effective viewpoint of implementation and operation, to use same post, on the cationic ion-exchange resin being filled in this post, adsorb TAA fromAfter son, then making alkali metal salt soln is good by person.
(recovery of efflux)
Via passing into above-mentioned alkali metal salt soln, the TAA ion of adsorption tower one end, depending on the anion of the salt of use (for exampleIf carbonate is CO3 2-Deng) be counter ion, form TAA salt and flow out (molten from), this efflux is recovered in retention basin.
One of feature of the present invention is to measure the alkali metal ion concentration in this efflux, in this alkali metal ion concentrationTime point before sharply raising, stops the recovery of above-mentioned retention basin.
That is the cationic ion-exchange resin in adsorption tower is gone back adsorbing metal ions as aforementioned except TAA ion, but logicalCross alkali metal salt soln is passed into this adsorption tower, the exchange of TAA ion and alkali metal ion, preferential outflow (molten from). On the other hand,Other metal ions are in being maintained at the previous status of ion exchange resin. While further continuing to pass into alkali metal salt soln, originallyCoexist in metal ion in TAA solution and the alkali metal ion that forms the alkali metal salt soln that passes into adsorption tower start molten from.Because it is just rarer originally to coexist in the original concentration of metal ion in TAA solution, so be difficult to direct-detection, it starts streamGo out. Herein, according to the inventor's etc. research, the molten alkali that imports adsorption tower from movement demonstration and high concentration of these metal ionsThe molten of metal ion has identical tendency from movement, front and back start molten from, therefore measure the molten from movement of this alkali metal ion, makeThe high concentration flow fluid of this alkali metal ion not with before hardly the recovery liquid that contains TAA ion of metal ion mix,Can obtain and contain high concentration TAA ion, and the recovery liquid that significantly reduces of each concentration of metal ions.
More particularly, at the adsorption tower that is filled with the cationic ion-exchange resin that has adsorbed TAA ion, pass into even if startAlkali metal salt soln, the alkali metal ion concentration in initial efflux is that extremely low concentration (conventionally less than 0.1ppm) is stablized,But in the time that TAA ion and alkali metal ion exchange, this alkali metal ion concentration starts sharply to rise, considerably beyond1ppm, reaches tens to hundreds of ppm. Now, only this rising is about to start before partially recycled in retention basin, stream afterwardsFluid separates in addition, can obtain high-recovery and highly purified TAA salt.
At this, the judgment standard whether alkali metal ion concentration starts sharply to rise is, when this alkali metal ion concentrationDetermination unit is during for highly sensitive situation extremely, is set as 10 to 10000 times of stationary value reaching, and is preferably 10 to 5000 timesPoint any concentration (particular value) before, better before being about to reach any concentration, stop the recovery to retention basin.
On the other hand, while adopting the lower determination unit of the sensitivity of ion electrode etc., initial stage stationary value can be less than surveyFix the situation of limit value. This kind of situation can be set as dense arbitrarily between 0.5～10mg/L reaching alkali metal ion concentrationThe front replacement of retrieving stopping to retention basin of degree (particular value). For example the restriction of the mensuration of general alkali metal ion electrode mostly isThe situation of 1mg/L, is therefore being recovered in retention basin lower than the lower limit of measuring, and shows that the later efflux of 1mg/L value just stopsBe recovered in retention basin.
The method that stopped efflux and be recovered in retention basin before reaching the alkali metal ion concentration of above-mentioned particular value, does not haveBe particularly limited, can enumerate example as shown in Figure 1, establish in the below of the device (metal ion electrode) of measuring alkali metal ion concentrationPut flow channel switching valve, in alkali metal ion concentration rises to particular value in this metal ion electrode induced flow fluid, cutChange the method for the stream of valve etc.
Reach the time point after the time point of particular value at the concentration of metal ions of this efflux, stop liquid is from inhaling voluntarilyAttached tower flows out, but in order to make cationic ion-exchange resin regeneration, can again to be utilized, the better stream conversion with above-mentioned transfer valve etc.Unit, is recovered in efflux in retention basin different from above-mentioned retention basin etc.
The assay method of concentration of metal ions can suitably adopt known method. Concrete example as, gather a certain amount of from adsorption towerThe efflux flowing out, uses the method for the mensuration metal ions such as metal ion electrode or at the pipe that efflux is imported to retention basinThe metal ion electrode of embedded (inline) type is set and method for measuring etc. in road. If use embedded (inline) typeMetal ion electrode, without taking out liquid on the way, and the moment that can arrive particular value at concentration of metal ions stops reclaiming,Can suppress to reclaim the loss of liquid and be good.
Again taking measure the time interval as main, must change according to the flow of efflux (flow velocity). Flow with high flow rateThe situation of solution, the concentration of metal ions of efflux sharply changes, and therefore in order to obtain desired character, (metal ion is assortedThe concentration of matter) liquid, must shorten measure interval.
(manufacturing the method for tetraalkylammonium hydroxide from tetraalkylammonium salt)
In the present invention, the solution reclaiming in said method from waste liquid, contained TAA salt carries out electrodialysis, electrolysis etc., canManufacture TAAH.
And, before carrying out electrodialysis or electrolysis, also can carry out the purifying of gained TAA salt or concentrate. This TAA salting liquidPurification process for example make this TAA salting liquid and cationic ion-exchange resin (but making in advance counter ion be replaced into TAA ion) and/orChelating resin contact, removes the method for metal cation component in TAA salt, or makes adsorbent or the moon of TAA salt and activated carbon etc.Ion exchange resin contact, the organic method of removal photoresist etc. etc.
The method for concentration of TAA salt, specifically can enumerate by electrodialysis, evaporator, carry out concentrated method etc. against soaking into film.
(manufacture of TAAH: the electrolysis step of TAA salt)
The electrolysis step that forms TAAH for making gained TAA salt electrolysis, is not particularly limited the TAA salt of visual recoveryKind (being equivalent to form the sour composition of the alkali metal salt that uses), use known method. The TAA salt for example reclaiming is carbonThe situation of hydrochlorate, as specially permit No. 3109525 communiques (two Room electrolysis: raw material supplying is in anode chamber) record use anode, negative electrode,The electrolysis of cation-exchange membrane, makes TAA salt form TAAH person for good.
Embodiment
For the present invention is more specifically described, enumerate following examples and comparative example explanation, but the present invention is not limited to this.
(the regeneration processing (H type cationic ion-exchange resin) of cationic ion-exchange resin)
The cationic ion-exchange resin using is filled in glass tower in use, sequentially passes into ultra-pure water, 1NHCl (hydrochloric acid)And ultra-pure water, counter ion is hydrogen ion. Each liquid passes into space velocity SV=5 (I/ hour), and the fluid volume that makes of each liquid is 10L/L-Resin.
(concentration determination)
Analyze tetramethyl ammonium hydroxide (TMAH), tetramethyl ammonium (TMA salt) concentration with ion chromatography.
Be specially, use the ICS2000 of DIONEX company system, in cation analysis, post uses ION-pacCS12A,In anion analysis, post uses ION-pacAS15, and in cation analysis, eluat uses Loprazolam analysis, and anion dividesAnalyse middle eluat and use potassium hydroxide, analyze.
Concentration of metal ions contained in solution is in ion electrode (Portable water quality) method (model: IM-32P (East AsiaDKK company system)), high-frequency induction coupled plasma mass spectrum (ICP-MS) method (determinator: HP-4500 (Agilent companySystem)) and high-frequency induction coupled plasma spectrum (ICP-OES) method (determinator: iCAP6500DUO (THERMOELECTRON company system)) measure. As not have restriction, each concentration be quality criteria.
Embodiment 1
(TMA ion waste liquid adsorption step)
Weak-acid cation-exchange resin DIAIONWK40L (Mitsubishi Chemical Ind's system) 1000ml is filled in to diameterThe post of 50mm, resin height 510mm.
In above-mentioned post, pass into TMAH waste liquid (the photoresistance development of 0.045 quality % with SV (space velocity)=100 (1/ hour)Waste liquid, photoresist content is scaled 10ppm with COD, concentration of metal ions: Na:2.5ppb, K:5.4ppb, Ca:4.1ppb, Al:3.2ppb, Ni:2.0ppb, Cu:2.0ppb, Cr:2.5ppb, Fe:5.3ppb) 1000L, carries out the absorption of TMA ion.
(TMA ion molten from step)
Afterwards, pass into as the 2N sodium carbonate of the 5000ml of eluat using SV=4 (1/ hour), make the TMA ion shape of absorptionBecome TMA carbonate and molten from. Efflux divides and gets successively with each 500ml, takes out respectively 10 liquid (liquid A～J respectively). MeasureThese are TMA carbonate concentration, the concentration of metal ions of liquid respectively. Result is as shown in table 1.
As can be known from Table 1, Na ion concentration is I more than lower limit, and concentration of metal ions increases. Liquid C to H returns respectivelyThe yield in time receiving adds up to 3000ml, and the concentration of TMA carbonate is 9.7 quality % (0.46mol/l).
[table 1]
Embodiment 2
(TMA ionic adsorption step)
Weak-acid cation-exchange resin LEWATITCNP80WS (LANXESS company system) 1000ml is filled in to diameterThe post of 50mm, resin height 510mm.
In above-mentioned post, pass into TMAH waste liquid (the photoresistance development of 0.045 quality % with SV (space velocity)=100 (1/ hour)Waste liquid, photoresist content is scaled 10ppm with COD, concentration of metal ions: Na:2.5ppb, K:5.4ppb, Ca:4.1ppb, Al:3.2ppb, Ni:2.0ppb, Cu:2.0ppb, Cr:2.5ppb, Fe:5.3ppb) 1000L, carries out the absorption of TMA ion.
(TMA ion molten from step)
Afterwards, pass into as the 2N potash of the 5000ml of the molten eluat from step of TMA ion using SV=5 (1/ hour),Make absorption TMA ion form TMA carbonate and molten from. Efflux divides and gets successively with each 500ml, takes out respectively 10 liquid(liquid A～J respectively). Measure these TMA carbonate concentration, concentration of metal ions of liquid respectively. Result is as shown in table 2.
As can be known from Table 2, potassium concentration is I more than lower limit, and concentration of metal ions increases. Liquid C to H returns respectivelyThe yield in time receiving adds up to 3000ml, and the concentration of TMA carbonate is 9.1 quality % (0.44mol/l).
[table 2]
Embodiment 3
(TMA ionic adsorption step)
Weak-acid cation-exchange resin DuoliteC476 (Zhu Hua Chemtex company system) 1000ml is filled in to diameterThe post of 50mm, resin height 510mm.
In above-mentioned post, pass into TMAH waste liquid (the photoresistance development of 0.045 quality % with SV (space velocity)=100 (1/ hour)Waste liquid, photoresist content is scaled 10ppm with COD, concentration of metal ions: Na:2.5ppb, K:5.4ppb, Ca:4.1ppb, Al:3.2ppb, Ni:2.0ppb, Cu:2.0ppb, Cr:2.5ppb, Fe:5.3ppb) 1000L, carries out the absorption of TMA ion.
(TMA ion molten from step)
Afterwards, pass into as the 1N sodium carbonate of the 8000ml of the molten eluat from step of TMA ion using SV=3 (1/ hour),Make absorption TMA ion form TMA carbonate and molten from. Efflux divides and gets successively with each 500ml, takes out respectively 16 liquid(liquid A～P respectively). Measure these TMA carbonate concentration, concentration of metal ions of liquid respectively. Result is as shown in table 3.
As can be known from Table 3, Na ion concentration is N more than lower limit, and concentration of metal ions increases. Liquid C to M returns respectivelyThe yield in time receiving adds up to 5500ml, and the concentration of TMA carbonate is 6.2 quality % (0.30mol/l).
[table 3]
Embodiment 4
(purification step)
Prepare respectively the chelating resin (RohmeandHaas that in advance contacts, regenerated with hydrochloric acid, ultra-pure water and processThe DuoliteC747 of company's system) the 1000ml diameter 50mm post (resin height 510mm) of filling, and fill cation and hand overChange the diameter 50mm post (resin height 510mm) of resin (Amberlist15J of RohmeandHaas company system) 1000ml.
C～the H of liquid respectively of embodiment 1 is passed into above-mentioned chelating resin post, obtain treatment fluid A. Afterwards, treatment fluid A is logicalEnter cation exchange resin column, obtain treatment fluid B. Treatment fluid A, B are carried out to fluid analysis, and result is as shown in table 4.
[table 4]
The treatment fluid B obtaining from embodiment 4 is concentrated into TMA carbonate concentration through evaporation concentration device and reaches 26.1 matterAmount %. The TMA carbonate of gained is carried out to electrolysis step, carry out the manufacture of TMAH.
Electrolysis step is used two of configuration anode, cation-exchange membrane (Nafion90209 (DuPont company system)), negative electrodeChamber type electrolytic cell. The effective film area of above-mentioned amberplex is 2dm2, Nafion film have carboxylic acid group one towards cathode sideArrange. Anode uses the titanium plate that has platinum plating, and negative electrode uses SUS316. The anode chamber of above-mentioned electrolytic cell follows with TMA carbonateRing, cathode chamber circulates with pure water, current density 18A/dm2, temperature maintains 40 DEG C, and implements continuously electrolysis simultaneously. Fortune continuouslyIn turning, the TMAH concentration of cathode chamber becomes 18 quality %. In the same manner, the concentration of the liquid of each chamber circulation maintains necessarily, and concentration thickensShi Tianjia pure water, adds its composition when thinning.
After electrolysis starts, make operating condition stable, carry out the continuous operation of (while stablizing) after 12 hours and 3 months, gainedThe analysis result of TMAH as shown in table 5.
[table 5]
Comparative example 1
Except the efflux in embodiment 1 does not carry out the mensuration of metal ion electrode, and carry out the mensuration of conductance and pHIn addition, all the other carry out with embodiment 1. TMA ion is molten in step, and each 500ml divides successively and gets efflux, takes out respectively 10Liquid (liquid A～J respectively). Measure these TMA carbonate concentration, concentration of metal ions, conductance and pH of liquid respectively. Result asShown in table 6.
The rate of change of as can be known from Table 6, sneaking into conductance in the H of liquid respectively, the I of sodium ion or pH value does not have difference. ThisWhen a little situation that is eluat at alkali metal salt, show with conductance or pH value and be difficult to control impurity metal ion in recovery liquidSneak into.
[table 6]
Claims (6)
1. a manufacture method for tetra-allkylammonium salting liquid, it is that solution from containing metal ion and tetraalkylammonium hydroxide obtainsMust contain the manufacture method of the tetra-allkylammonium salting liquid of the solution of the tetraalkylammonium salt of metal ion content ratio reduction, its featureBe,
The step that comprises following (1), (2):
(1) being filled with in the adsorption tower of hydrogen ion type cationic ion-exchange resin, pass into and contain metal ion and hydroxide four alkaneThe solution of base ammonium, makes tetraalkyl ammonium ion in this solution be adsorbed in the adsorption step of cationic ion-exchange resin;
(2) being filled with the adsorption tower that has adsorbed the cationic ion-exchange resin of tetraalkyl ammonium ion in above-mentioned adsorption step, pass intoThe solution of alkali carbonate, the tetraalkyl ammonium ion that makes to be adsorbed in this resin form above-mentioned carbonate and molten from, by this absorptionThe efflux that tower flows out is recycled to the recycling step of retention basin,
And in recycling step, measure above-mentioned alkali metal ion concentration in the efflux that flows out of adsorption tower, this alkali metal fromBefore sub-concentration sharply rises, stop the recovery of efflux to this retention basin.
2. a manufacture method for tetra-allkylammonium salting liquid, it is that solution from containing metal ion and tetraalkylammonium hydroxide obtainsMust contain the manufacture method of the tetra-allkylammonium salting liquid of the solution of the tetraalkylammonium salt of metal ion content ratio reduction, its featureBe,
The step that comprises following (1), (2):
(1) being filled with in the adsorption tower of hydrogen ion type cationic ion-exchange resin, pass into and contain metal ion and hydroxide four alkaneThe solution of base ammonium, makes tetraalkyl ammonium ion in this solution be adsorbed in the adsorption step of cationic ion-exchange resin;
(2) being filled with the adsorption tower that has adsorbed the cationic ion-exchange resin of tetraalkyl ammonium ion in above-mentioned adsorption step, pass intoThe solution of alkali carbonate, the tetraalkyl ammonium ion that makes to be adsorbed in this resin form above-mentioned carbonate and molten from, by this absorptionThe efflux that tower flows out is recycled to the recycling step of retention basin;
And in recycling step, measure above-mentioned alkali metal ion concentration in the efflux that flows out of adsorption tower, this alkali metal fromSub-concentration reaches the time point of the normal concentration of setting between 0.5～10mg/L, stops the recovery of efflux to this retention basin.
3. the manufacture method of tetra-allkylammonium salting liquid as claimed in claim 1 or 2, wherein, this alkali carbonate is for being selected fromOne kind or two or more in the group being formed by sodium carbonate and potash.
4. a manufacture method for tetraalkylammonium hydroxide, is characterized in that, by described in any one in claims 1 to 3Method is manufactured after tetra-allkylammonium salting liquid, taking the tetraalkylammonium salt of gained as raw material, manufactures tetraalkylammonium hydroxide.
5. the manufacture method of tetraalkylammonium hydroxide as claimed in claim 4, wherein, by any one in claims 1 to 3Described method is manufactured after tetra-allkylammonium salting liquid, before manufacturing tetraalkylammonium hydroxide, by chelating resin and/or sun fromSub-exchange resin is removed the contained impurity metal ion of tetraalkylammonium salt.
6. the manufacture method of the tetraalkylammonium hydroxide as described in claim 4 or 5, wherein, by appointing in claims 1 to 3Method described in one is manufactured after tetra-allkylammonium salting liquid, also comprises the step of concentrated this solution.
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| PCT/JP2012/077779 WO2013062100A1 (en) | 2011-10-28 | 2012-10-26 | Method for producing tetraalkylammonium salt solution |
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| WO2020067365A1 (en) * | 2018-09-28 | 2020-04-02 | 株式会社トクヤマ | Method for producing organic solvent solution of quaternary ammonium hydroxide |
| CN112999694A (en) * | 2021-03-24 | 2021-06-22 | 沧州信联化工有限公司 | Raw material refining device for processing tetramethylammonium hydroxide and use method thereof |
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| JP2003340449A (en) * | 2002-05-27 | 2003-12-02 | Babcock Hitachi Kk | Method for treating waste water containing tetraalkylammonium hydroxide |
| CN1469845A (en) * | 2000-10-20 | 2004-01-21 | ��������ķ������ | Process for recovering onium hydroxides from solutions containing onium compounds |
| WO2011074495A1 (en) * | 2009-12-15 | 2011-06-23 | 株式会社トクヤマ | Method for reusing waste liquid from which tetraalkylammonium ions have been removed |
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| JP3109525B2 (en) | 1990-12-27 | 2000-11-20 | クロリンエンジニアズ株式会社 | Method for regenerating tetraalkylammonium hydroxide |
| JP3110513B2 (en) | 1991-10-16 | 2000-11-20 | クロリンエンジニアズ株式会社 | Method for regenerating tetraalkylammonium hydroxide |
| JP2688009B2 (en) | 1992-11-26 | 1997-12-08 | 多摩化学工業株式会社 | Method for recovering organic quaternary ammonium hydroxide from waste liquid |
| US5439564A (en) * | 1992-11-10 | 1995-08-08 | Tama Chemicals Co. Ltd. | Method of processing organic quaternary ammonium hydroxide-containing waste liquid |
| JP3216998B2 (en) | 1996-08-12 | 2001-10-09 | 昭和電工株式会社 | Purification and recovery of tetraalkylammonium hydroxide from waste developer |
| US5968338A (en) | 1998-01-20 | 1999-10-19 | Sachem, Inc. | Process for recovering onium hydroxides from solutions containing onium compounds |
| JP2004066102A (en) | 2002-08-06 | 2004-03-04 | Babcock Hitachi Kk | Waste liquid treatment method and equipment therefor |
| JP4385407B2 (en) | 2007-04-05 | 2009-12-16 | オルガノ株式会社 | Method for treating tetraalkylammonium ion-containing liquid |
| JP5483958B2 (en) * | 2009-06-03 | 2014-05-07 | 株式会社トクヤマ | Method for producing tetraalkylammonium hydroxide |
| JP5887279B2 (en) * | 2010-12-28 | 2016-03-16 | 株式会社トクヤマ | Method for producing tetraalkylammonium salt and method for producing tetraalkylammonium hydroxide using the same as raw material |
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| CN1469845A (en) * | 2000-10-20 | 2004-01-21 | ��������ķ������ | Process for recovering onium hydroxides from solutions containing onium compounds |
| JP2003340449A (en) * | 2002-05-27 | 2003-12-02 | Babcock Hitachi Kk | Method for treating waste water containing tetraalkylammonium hydroxide |
| WO2011074495A1 (en) * | 2009-12-15 | 2011-06-23 | 株式会社トクヤマ | Method for reusing waste liquid from which tetraalkylammonium ions have been removed |
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| TWI549753B (en) | 2016-09-21 |
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