CN103080070A - Process for producing tetraalkylammonium salt, and process for producing tetraalkylammonium hydroxide using same as raw material - Google Patents
Process for producing tetraalkylammonium salt, and process for producing tetraalkylammonium hydroxide using same as raw material Download PDFInfo
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- B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
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- B01J49/00—Regeneration or reactivation of ion-exchangers; Apparatus therefor
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Abstract
[Problem] In a case where tetraalkylammonium (TAA) ions are recovered from waste liquor from development or the like using a cation-exchange resin in a conventional manner, the obtained TAA salt is contaminated with metal ions. Therefore, attempts to produce TAA hydroxide using the TAA salt as raw material result in products which are significantly contaminated with metal impurities. [Solution] A TAA salt solution with a low metal ion concentration can be obtained by a process which comprises bringing a solution that contains both metal ions and TAA ions, such as a waste liquor from the development of a photoresist, into contact with a cation-exchange resin to make the TAA ions adsorbed on the cation-exchange resin, and then passing an acid through the resulting cation-exchange resin to recover a TAA salt, and in which the recover is stopped before the pH of the obtained TAA salt solution lowers to a prescribed level or lower and/or before the change in the electric conductivity thereof reaches a prescribed margin or more. Further, a high-purity TAAH solution can be obtained either by bringing the TAA salt thus obtained into contact with an anion-exchange resin which has previously been converted to the OH form or by subjecting the TAA salt thus obtained to electrolysis.
Description
Technical field
The present invention relates to a kind of new manufacture method of the tetraalkylammonium salt of Zeo-karb of using and reaches with its manufacture method as the tetraalkylammonium hydroxide of raw material.
Background technology
Generally speaking, tetraalkylammonium hydroxide (below, referred to as TAAH) be as the reference liquid of the alkali in the nonaqueous titration as an example of phase-transfer catalyst example or the useful compound of the organic system alkaline agent in the organic synthesis.In addition, also can be used as in the manufacturing of unicircuit or large-scale integrated circuit, the treatment agent of the video picture of the washing of semiconductor substrate, etching, photoresistance etc. uses.
Especially in the purposes of semi-conductor aspect, because semiconductor substrate can be contaminated, thereby need not contain as far as possible the highly purified TAAH of impurity.
On the other hand, be used in as mentioned above in the waste liquid of video picture of photoresistance, metal ion and TAAH except photoresistance, have also been comprised, therefore in order to reduce environmental pressure, reclaim TAAH and recycle the technology of TAAH more aobvious important (below, also have the waste liquid that to comprise photoresistance and TAAH to be called the situation of " photoresistance video picture waste liquid ") from this waste liquid.So far, process in the method for photoresistance video picture waste liquid, discarded after concentrated take Pervaporation method or reverse osmosis embrane method (incinerating or transfer to the dealer collects) method, utilize active sludge to carry out biological decomposition to process again method that row releases as main flow.Yet, as mentioned above, from showing loving care for the angle of environment, about the trial of reclaiming TAAH from this waste liquid and recycled most schemes have been proposed.
Specifically, with regard to high video picture waste liquid, except behind the removing photoresistance composition, carry out electrodialysis or electrolysis with the method that reclaims TAAH be widely known by the people already (referring to patent documentation 1 to 3) through neutralizing treatment for concentrated waste liquid or original TAAH concentration.But, in the situation of processing the low waste liquid of TAAH concentration, because before till reaching the concentration conditions that can supply electrodialysis or electrolysis, pair needs that the TAAH waste liquid concentrates are arranged, therefore with respect to these methods, proposed to carry out electrodialysis or electrolysis, can reclaim from photoresistance video picture waste liquid the method (referring to patent documentation 4) of TAAH.With concrete grammar, at first, see through photoresistance video picture waste liquid is contacted with Zeo-karb, and make tetraalkyl ammonium ion (TAA ion) be adsorbed to Zeo-karb.Then, hydrochloric acid is passed in this Zeo-karb to reclaim TAA salt, in resulting solution, added chloric acid and become tetra-allkylammonium perchlorate (TAA perchlorate).Afterwards, after refining, resulting TAA perchlorate is contacted through crystallization with anionite-exchange resin the TAA perchlorate, reclaim by this method of TAAH.
In addition, more disclose and make the TAA ionic adsorption to ion exchange resin, and reclaim TAA salt from thin developing-solution, again with its electrolysis to make the technology (patent documentation 5 and 6) of TAAH.But, since uncontrollable make TAA salt from amberlite liposoluble from when condition, can be mixed with metal ion in the resulting TAA salts solution, with regard to the result, can have the problem of sneaking into the metal ion of higher concentration in the TAAH solution after the electrolysis.
The prior art document
Patent documentation 1: Unexamined Patent 04-228587 communique
Patent documentation 2: Unexamined Patent 05-106074 communique
Patent documentation 3: No. 3216998 communique of patent
Patent documentation 4: JP 2004-66102 communique
Patent documentation 5: No. 2688009 communiques of patent
Patent documentation 6: special table 2002-509029 communique
Summary of the invention
Technical problem
If according to preceding method, although can reclaim the TAA ion with high recovery rate, according to the inventor's etc. self-criticism, can learn that there is still room for improvement in following each point.Aforesaid method is when reclaiming the TAA ion, carry out the measurement of TAA ionic concn, because until the TAA ion is down to 2000ppm, namely reach till the very thin concentration, the most TAA ion that is adsorbed on the Zeo-karb reclaims and still can carry out, so must be recovered.But when reclaiming, when descending along with the TAA ionic concn, can volume sneak into the hydrochloric acid that uses in the recovery, add the metal ion that is adsorbed on the resin and also can sneak into wherein, so has the problem existence that resulting TAA salt contains the impurity of volume.
Technical scheme
The inventor etc. are in order to solve above-mentioned problem, self-criticism through attentively endeavouring, found that, by photoresistance video picture waste liquid is contacted with Zeo-karb, and make the TAA ionic adsorption, then, when hydrochloric acid being passed in this Zeo-karb with when reclaiming TAA salt, before the pH of resulting TAA salts solution reaches below the prescribed value and/or the velocity of variation of specific conductivity reach regulation and stop recovery before above, can access by this lower solution of concentration of metal ions, and finish the present invention.
That is to say, the present invention passes in the adsorption tower of the Zeo-karb that is filled with the hydrogen ion type solution that contains metal ion and tetraalkylammonium hydroxide (TAAH), after making tetraalkyl ammonium ion be adsorbed on the Zeo-karb, acid solution is passed in the adsorption tower, reclaim from the manufacture method of recovery liquid with the manufacturing tetraalkylammonium salt that adsorption tower flows out, pH and/or the specific conductivity of measuring the recovery liquid that flows out reclaim the yield of liquid as its feature take decision again.
And the present invention makes resulting like this TAA salt contact with the anionite-exchange resin that changes in advance the OH type, also or carry out electrolysis, and mat and can access highly purified TAAH solution.
In addition, the image-developing liquor that utilizes the tetraalkylammonium hydroxide (TAAH) of the method manufacturing of the invention described above to be suitable as very much liquid-crystal display manufacturing usefulness uses.
Beneficial effect
The method according to this invention, owing to be to measure and/or the simple method of conductivity measurement decides the yield of TAA salts solution with pH, so can obtain efficiently highly purified TAA salt.Therefore, in technique before and after, become to there is no need to arrange and utilize the metal of resin etc. to remove technique, and allow the formation of device oversimplify, then reduce cost.
And, see through this TAA salt is contacted with anionite-exchange resin, also or carry out electrolysis, mat and can access highly purified TAAH solution.
Description of drawings
Fig. 1 is the synoptic diagram of implementing aspect of producing apparatus of the manufacture method of tetraalkylammonium salt of the present invention.
Fig. 2 relates to the graphic representation of embodiments of the invention.
Fig. 3 relates to the graphic representation of embodiments of the invention.
Fig. 4 relates to the graphic representation of embodiments of the invention.
Fig. 5 relates to the graphic representation of embodiments of the invention.
Embodiment
The present invention is a kind of method that produces tetraalkylammonium salt (TAA salt) from the solution that contains metal ion and tetraalkylammonium hydroxide (TAAH), comprise this TAAH solution is contacted with resin cation (R.C.), make the TAA ionic adsorption to this Zeo-karb, acid solution is passed in this adsorption tower, measure again pH and/or the specific conductivity of the recovery liquid that is flowed out by adsorption tower, stop opportunity with the recovery that determines recovery liquid, and obtain the method for TAA salt.
(solution that contains metal ion and tetraalkylammonium hydroxide)
In the present invention, about containing the solution of metal ion and tetraalkylammonium hydroxide, so long as comprise the solution of these compositions, there is no particular restriction (below, be called " material solution ").When considering to comprise these compositions and volume and occur in semiconductor fabrication process, process for manufacturing liquid crystal display etc., comparatively suitable with the photoresistance video picture waste liquid of discharging from this process quilt.These waste liquids mainly contain photoresistance, TAAH and metal ion for the photoresistance after will exposing carries out the waste liquid of being discharged when the video picture with the alkali image-developing liquor.
Photoresistance video picture waste liquid is pH usually between 10～14 alkalescence, is that the acidic groups such as its carboxyl, phenol hydroxy dissolve through acid dissociation in the video picture waste liquid of alkalescence in photoresistance.With the main component of photoresistance, can enumerate indene carboxylic acid that the photolysis that sees through adjacent diazo naphthoquinone sensitizer generates or be example from the phenols of resol.In addition, in the present invention, comprise above-mentioned photoresistance composition person, part or all person who removes in advance the removing photoresistance composition all can be used as object.
In this, the representative waste liquid of discharging for the video picture technique from semi-conductor manufacturing and liquid-crystal display manufacturing is elaborated.In video picture technique, the automatic developing device of common multiplex single wafer processing, but in this device, use comprise TAAH image-developing liquor technique with use the cleaning (substrate washing) of pure water in same groove, to carry out afterwards, at this moment, in cleaning, can use the pure water of 5～1000 times of amounts of image-developing liquor.Therefore, employed image-developing liquor can be diluted into 5～10 times waste liquid usually in video picture technique.The composition of the waste liquid that the result discharges in this video picture technique can become TAAH and account for that 0.001～1 quality % degree, impedance account for 10～100ppm degree and interfacial agent accounts for 0～number 10ppm degree persons.In addition, the situation of the waste liquid of sneaking into other technique is arranged also, TAAH concentration also can become than lower in the above-mentioned scope.Specifically, have the situation that becomes 0.05 quality % following (0.001～0.05 quality % degree).In the photoresistance video picture waste liquid of particularly being discharged by process for manufacturing liquid crystal display, it is more that TAAH concentration becomes the situation of 0.001～0.05 quality % degree, in order to make TAA salt from this photoresistance image-developing liquor, especially can be fit to adopt method of the present invention.
In addition, in photoresistance video picture waste liquid, can comprise plural metal ion species.Such as sodium, potassium etc. are arranged with univalent ion; Calcium, zinc etc. are arranged with divalent ion; Aluminium, nickel, copper, chromium, iron etc. are then arranged as the more representative metal of content in the photoresistance video picture waste liquid with other polyvalent ion.
TAAH in the photoresistance image-developing liquor is for when being used in various electronic package manufacturings etc., the alkali in the image-developing liquor of employed photoresistance.With the concrete example of TAAH, can enumerate tetramethyl ammonium hydroxide (being designated hereinafter simply as TMAH), tetraethyl ammonium hydroxide, tetrabutylammonium, hydroxide methyl triethyl ammonium, hydroxide trimethylammonium ethyl ammonium, hydroxide dimethyl diethyl ammonium, hydroxide trimethylammonium (2-hydroxyethyl) ammonium, hydroxide triethyl (2-hydroxyethyl) ammonium, hydroxide dimethyl two (2-hydroxyethyl) ammonium, hydroxide diethyl two (2-hydroxyethyl) ammonium, hydroxide methyl three (2-hydroxyethyl) ammonium, hydroxide ethyl three (2-hydroxyethyl) ammonium, hydroxide four (2-hydroxyethyl) ammonium etc. is example.Wherein, be used the most widely with TMAH.
(making tetraalkyl ammonium ion be adsorbed on technique on the Zeo-karb)
In the present invention, material solution described above is passed in the adsorption tower of Zeo-karb of the hydrogen ion type that is filled with (following also be called " H type "), so that TAA is adsorbed on this Zeo-karb.
That is, because the TAA ion is positively charged ion, contacts with the Zeo-karb of H type so see through, and then be adsorbed on this resin with the hydrogen ion generation ion-exchange of this Zeo-karb.Therefore, can efficient reclaim the TAA ion from waste liquid well.Even if the waste liquid in the situation that especially TAAH concentration is lower still can low-costly reclaim the TAA ion.
In this, because common metal ion also is positively charged ion, adsorbable to Zeo-karb so see through this logical liquid.The present invention is by adopting method described later, but and can allow the metal ion and the TAA ion efficient that are adsorbed on this Zeo-karb be separated from each other well.In addition, even if be metal ion, still can be owing to the chemical equilibrium reactions such as coordination allow in this situation as negatively charged ion of ionic species that metal comprises in material solution, will be difficult to be adsorbed to Zeo-karb and discharge from adsorption tower.
On the other hand, material solution is in the situation of photoresistance waste liquid, is generally the form of negatively charged ion owing to come from the organic composition of the photoresistance of dissolving, thus be difficult to be adsorbed to Zeo-karb, and major part can be removed.In addition, even if having in the situation of composition of nonionic, in this technique, be discharged from (outflow) owing to not being adsorbed to Zeo-karb, so major part can be removed.The minority photoresistance that in addition, will residue in again afterwards Zeo-karb is washed with flushings such as ultrapure water or highly purified TAAH solution also can.
(Zeo-karb)
In the present invention, with above-mentioned Zeo-karb, be not particularly limited, can use known resin.Specifically, can use ion-exchange group is anyly in sulfonic storng-acid cation exchange resin, the weakly acidic cation-exchange resin of ion-exchange group as carboxyl all can.Wherein, more from loading capacity the greater, and the viewpoint that can reduce employed amount of resin considers, uses weakly acidic cation-exchange resin comparatively suitable.And, in the situation of weakly acidic cation-exchange resin, carry out the molten from also comparatively easy of aftermentioned TAA ion.
In addition, resin be configured to gel-type or (macroporous type, Macroporous) resin all can for the MR type.Resin be shaped as powdery, granular, membranaceous, fibrous etc. anyly all can.With regard to viewpoints such as processing efficiency, operability, economy, use the Zeo-karbs such as the polystyrene of granular grade or acrylic acid series comparatively suitable.
The gegenion of Zeo-karb usually with hydrogen ion (H type) or sodium ion (Na type) in peddling on the market, but for the adsorption efficiency that prevents that sodium ion from sneaking into last resulting TAAH solution and promoting the TAA ion, it is comparatively suitable that gegenion is set as hydrionic H type.In the situation of using commercially available Na type Zeo-karb, in advance hydrochloric acid or sulfuric acid are passed in the Zeo-karb when the use, fully wash etc. with ultrapure water, so that gegenion is used as hydrogen ion.
Take the concrete example of storng-acid cation exchange resin, can enumerate DAION SK1B, the DAION PK228 of AMBERLITE IR120B, AMBERLITE IR124, the Mitsubishi Chemical society system of Rohm and Haas society system, firmly change DUOLITE C255LFH, the LEWATITMonoPlus S100 of LANXESS society, the PUROLITE C160 of PUROLITE society etc. of CHEMTEX society system as example.In addition, take the concrete example of weakly acidic cation-exchange resin, can enumerate the DAION WK40L of AMBERLITE IRC76, the Mitsubishi Chemical society system of Rohm and Haas society system, firmly change DUOLITE C433LF, DUOLITE C476, the LEWATIT CNP80WS of LANXESS society, the PUROLITE C104 of PUROLITE society etc. of CHEMTEX society system as example.
(with the method for solution toward the logical liquid of adsorption tower of filling male ion-exchange resin)
In the present invention, make material solution pass into the adsorption tower of the Zeo-karb of filling above-mentioned H type and contact with Zeo-karb, mat and make TAA that ionic adsorption is to Zeo-karb.
In addition, for making this material solution pass into the method for the adsorption tower of filling male ion-exchange resin, according to the kind of Zeo-karb or shape and can suit to adopt known method.Specifically, for example use top to have the tubular adsorption tower that ostium, bottom have taphole, filling male ion-exchange resin in this adsorption tower, the mode of utilizing gravity that material solution is passed through continuously is comparatively suitable.Adopt in the situation of this method, the large I of this adsorption tower is made suitable the decision corresponding to the performance of Zeo-karb and is got final product.For efficient is adsorbed the TAA ion well, as being the photoresistance waste liquid of 0.001～1 quality % for the TAA amount, then the height (L) of adsorption tower and the ratio of diameter (D) are set as between 0.5～30, it is comparatively suitable that the space velocity (space velocity, SV) of this waste liquid is set as above 150 (the l/ times) of 1 (l/ time).
In addition, the amount with the stock liquid that passes into is set as the amount that can not penetrate the degree of the Zeo-karb that has been filled in adsorption tower, and is comparatively suitable from the viewpoint of can efficient making well TAA salt.
In addition, whether because passing into the cationic material solution of the above amount of the exchange capacity that contains Zeo-karb the TAA ion is not adsorbed and flows out (penetrating), can be by utilizing ion chromatography analysis to analyze and confirmed by the TAA ionic concn in the liquid that flows out again in the adsorption tower.More in simple terms, the shared height of Zeo-karb of measuring in the adsorption tower gets final product.When the gegenion of Zeo-karb became the TAA ion from hydrogen ion, although different according to the kind of Zeo-karb, volume can expand into two times of degree.Therefore, can confirm the absorption of TAA ion by the volume of measuring Zeo-karb.
In addition, the pH of material solution is in the situation of the alkalescence more than 10, when the TAA ion is not adsorbed and by in the adsorption tower time, because the pH of the liquid that has passed through becomes alkalescence, utilizes the pH time meter also can confirm.In addition, as a rule, by containing in the situation of TAA ion in the liquid that flows out again in the adsorption tower, because the specific conductivity of liquid can rise, also can be confirmed according to specific conductivity.
(reclaiming the technique of tetraalkylammonium salt from the Zeo-karb that adsorbs tetraalkyl ammonium ion)
In the present invention, utilize aforesaid method to make the TAA ionic adsorption to Zeo-karb, acid solution is passed in the adsorption tower of filling this Zeo-karb, reclaim the recovery liquid that flows out from adsorption tower to produce tetraalkylammonium salt.
That is, the end of acid solution from adsorption tower is directed in the adsorption tower, liquid is flowed out from the other end lead to liquid, being contained in by this interior excessive hydrogen ion that gets of this acid solution can sequentially replace with the TAA ion, and then flows out from adsorption tower as the hydrochlorate of the acid of using the TAA ion.
With this acid solution, when considering cost etc., for aqueous solution person comparatively suitable.
When spendable acid in addition during illustration, is example though can enumerate hydrochloric acid, sulfuric acid, nitric acid, carbonic acid, acetic acid etc. with concrete example, from the point of the TAA salt of easy stripping high density, the hydrochloric acid, sulfuric acid, the nitric acid that belong to strong acid are comparatively suitable.Among these strong acid, be difficult to the viewpoint damaged from remove easily the low section's material that makes the liquid contact of excessive acid and acidifying power by concentrating under reduced pressure, the most suitable with hydrochloric acid.
Though the concentration of acid solution can be selected in the scope of 0.1N to 10N aptly, but flow out and the viewpoint that is easy to prevent that the metal impurity from sneaking into from the TAA salt that makes high density, the scope of 0.5N～4N is suitable especially.
In addition, though the logical liquid speed of acid solution can suit to set corresponding to the concentration of the kind of the size of adsorption tower, Zeo-karb or usage quantity, acid solution etc., the space velocity of acid is comparatively suitable below 50 more than 1.In the situation less than this scope, the treatment time will become tediously long.
(recovery of effluent liquid)
By passing into above-mentioned acid solution, become TAA salt because the TAA ion can will be used as gegenion with the corresponding acid group of employed acid (such as Cl-etc.) and flow out (molten from) from an end of adsorption tower, stay groove so this effluent liquid can be recovered in storage, and this effluent liquid is provided as electrolysis use described later.
The invention is characterized in, measure pH and/or the specific conductivity of this effluent liquid, will reach the time point of predetermined observed value as the time point that stops to stay groove to reclaim towards toward above-mentioned storage.
That is, as previously mentioned, Zeo-karb in the adsorption tower also can adsorbing metal ions except the TAA ion, but see through when the pH of effluent liquid reach in the preset value point and/or conductivity variations the regulation amplitude stop to reclaim mat and the amount of the metal ion of sneaking into can being suppressed at than low degree before above.
In addition, time point after the time point that pH and/or the specific conductivity of this effluent liquid reaches this preset value, though make liquid stop also can from the state itself that adsorption tower flows out, but stream change means such as switching valve are set, when arriving the time point of this preset value, can be toward staying other different storage of groove to stay groove recovery mode for suitable with above-mentioned storage.
In addition, the measurement means of pH and/or specific conductivity there is no any special restriction, also can use known approaches.
(preset value of pH and measuring method thereof)
The preset value of pH is according to the kind of employed acid and different.For example use in the situation of hydrochloric acid as acid that belongs to strong acid, because the salt that flows out, be that chlorination TAA (hereinafter referred to as " TAAC ") is neutrality, so under the state that the TAA ion fully exists in adsorption tower, effluent liquid almost is neutral (situation of storng-acid cation exchange resin) or weakly alkaline～neutrality (situation of weakly acidic cation-exchange resin), but along with the TAA ion is fewer and feweri, can begin at leisure to be acid.
In the situation of equilibrium state, even effluent liquid is slightly acidic, though contain TAA ion (TAAC) in the effluent liquid but can reduce gradually, on the other hand, along with the acid grow that circulates in the liquid in the adsorption tower, the molten of the metal ion of strong adsorption on Zeo-karb also can increase gradually from amount.
Therefore, when continuing to pass into acid solution, contain hardly when the time comes the TAA ion in the effluent liquid, and can contain the metal ion of volume.In this, in the situation of the rate of recovery of paying attention to TAA, the pH value that this is predetermined is set for lower, and in the situation that the mixed volume of attention metal ion reduces, then sets for higher.
The strong acid such as use hydrochloric acid are used as in the situation of acid, measurement is from the pH of the recovery liquid of adsorption tower outflow, reach at pH that point stops to reclaim the contained lower liquid of concentration of metal ions in the TAA salts solution that can be recycled by this in the preset value in the scope below 8 more than 3.Lower in order further concentration of metal ions to be set as, it is comparatively suitable that preset value is set in more than the pH5.In addition, by the pH that preset value is set for below 7, and can reclaim TAA salt with high-recovery.In addition, so-called strong acid refers to that in 25 ℃ of lower acid ionization constant pKa be 3 following persons.
On the other hand, employed acid is in the situation of the weak acid such as acetic acid, carbonic acid, because the solution of resulting TAA salt is weakly alkaline, so can be between 4～9 in order to the better pH scope that reduces the metal ion mixed volume.In addition, so-called weak acid refers to that acid ionization constant pKa under 25 ℃ is than 3 high persons also.
With the measuring method of pH, prior art method can suit to adopt.Particularly, the effluent liquid that for example will flow out from adsorption tower is according to a certain amount of sampling, uses pH test pater or electrode type pH meter etc. measuring the method for pH, or with effluent liquid be directed to storage stay the pipe arrangement that waits on the way in, method that type pH meter along the line measured etc. is set.As use type pH meter along the line, then need not liquid extracted out in the way and can stop the moment outside pH reaches prescribed value reclaiming, and the loss that can suppress to reclaim liquid, so comparatively suitable.
In addition, although according to the pH measurement means and different, but when using general vitreous electricity polar form pH meter in the pH of measurement fluid along the line, take its on characteristic and the unhomogeneity of the occupied state of the resin in the adsorption tower as essential factor, and most likely produce the error of ± 0.2 degree.In the present invention, carry out statistical treatment in the pH value that this situation can be shown with this pH meter, reach the time point of preset value at this statistical value, stop again reclaiming towards the effluent liquid that stays groove toward storage and get final product.
The method of this statistical treatment is suitable to adopt known treatment process to get final product, for example obtain in advance the value of per scheduled time (for example 0.1 second), average or the mean value that multiplies each other reaches preset value when the addition of the scheduled time (for example between 2 seconds), and it is set as predetermined pH value.The aforementioned statistical treatment means of tool are also arranged among commercially available pH meter, and the pH meter of the function of the pH after the tool demonstration statistical treatment, in the present invention, also can directly use this pH meter.
The timed interval of in addition, carrying out statistical treatment mainly can with good grounds effluent liquid flow (flow velocity) and the needs of change.During with high flow rate circulation solution, because the pH of effluent liquid variation generation is comparatively rapid, so have shortening to measure the needs at interval for the solution that obtains expecting state (concentration of metal ions).
(velocity of variation of specific conductivity and measuring method thereof)
The velocity of variation of specific conductivity and pH be in the same manner according to the kind of employed acid and different to some extent, and also can be according to circulating in acid concentration in the adsorption tower and different.That is contained TAA salt concn can be denseer in the denseer then effluent liquid from adsorption tower of acid concentration, then can become lighter state when acid concentration is lighter.Then, (keep certain if flow out speed) in the situation that has sufficient TAA ion in the adsorption tower, effluent liquid will keep its CONCENTRATION STATE to flow out (following also be called " concentration is kept state ").
When the TAA ion that enough allows acid solution continue circulation from Zeo-karb molten from the time, the contained TAA salt concn of effluent liquid diminishes gradually, free acid and metal salt concentrations then can rise simultaneously.At this moment, usually because the specific conductivity of the specific conductivity of TAA salts solution and free acid and metal-salt is different, can detect the opportunity that free acid and metal-salt begin to sneak into so see through the measurement specific conductivity.
Particularly, use tetramethyl-ammonium (TMA) as the hydrochloric acid of TAA ion, 2N as acid, be set as at flow velocity (SV) in 1 the situation, when the liquid that flows out from tubing string then is the 80mS/cm degree when be not hydrochloric tetramethyl ammonium chloride (TMAC), along with sneaking into of hydrochloric acid, then conference rises to till the 500mS/cm degree (2N hydrochloric acid).
In addition, keep specific conductivity under the state in concentration, because except the kind and concentration of above-mentioned acid, also can change to some extent according to the shape of the kind of Zeo-karb, tubing string, flow velocity etc., so necessity according to the operating condition prior confirmation that installs is arranged.
When unhomogeneity of the occupied state of the shape of considering measuring accuracy because of the electrical conductivity meter of normal operation (gamut ± below 1%), tubing string, ion exchange resin etc. causes the observed value of specific conductivity that deviation is arranged, keep the amplitude of fluctuation of the specific conductivity under the state still less than ± 5% in above-mentioned concentration.So, be identified as the situation of rising in the conductivity that surpasses this amplitude of fluctuation, can be judged as in the liquid of outflow and begin to sneak into hydrochloric acid.
In the present invention, conductivity value that can this electrical conductivity meter is shown in this situation carries out statistical treatment, reaches specific concentration at this statistical value and keeps specific conductivity large time point more than 5% also under the state, stops reclaiming towards the effluent liquid that stays groove toward storage getting final product again.
The method of this statistical treatment only need suit to adopt known treatment process to get final product, for example can enumerate the value that obtains in advance per scheduled time (for example 0.1 second), to be set as predetermined specific conductivity be example for the average or mean value that multiplies each other with the addition of the scheduled time (for example between 2 seconds).The aforementioned statistical treatment means of tool are also arranged among commercially available electrical conductivity meter, and the electrical conductivity meter of the function of the specific conductivity after the tool demonstration statistical treatment, in the present invention, can directly use this electrical conductivity meter.
The timed interval of in addition, carrying out statistical treatment mainly can with good grounds effluent liquid flow (flow velocity) and the needs of change.During with high flow rate circulation solution, because the generation of the conductivity variations of effluent liquid is comparatively rapid, so have shortening to measure the needs at interval for the solution that obtains expecting state (concentration of metal ions).
(producing the method for tetraalkylammonium hydroxide from tetraalkylammonium salt)
In the present invention, with aforesaid method contained TAA salt from the solution that waste liquid reclaims is carried out electrolysis, or it is contacted with the anionite-exchange resin with hydroxide ion as gegenion, mat and can produce TAAH.
(the manufacturing of TAAH: the electrolysis process of TAA salt)
, resulting TAA salt obtains the electrolysis process of TAAH for being carried out electrolysis, there is no any special restriction, can use known method, it is comparatively suitable wherein to be made with the electrolysis of the use anode put down in writing in No. the 2059469th, the patent, negative electrode, cationic exchange membrane.
(the manufacturing of TAAH: the contact process of TAA salt and anionite-exchange resin)
In addition, produce the method for TAAH for from the solution that waste liquid reclaims contained TAA is contacted with anionite-exchange resin, can adopt the method for putting down in writing among JP 52-003009 or the Patent 2009-197778.This method is that TAA salt is contacted with the anionite-exchange resin with hydroxide ion (OH type anionite-exchange resin) as gegenion, mat and produce the method for TAAH from TAAC.This method need not carry out electrodialysis or electrolysis can produce highly purified TAAH from TAAC simply.
As mentioned above, can obtain highly purified TAA salt according to the present invention.In addition, compare with prior art method, because the metal ions such as resin are removed technique and nonessential, process required total cost so can cut down.In addition, reclaiming from photoresistance video picture waste liquid in the situation of TAA salt, metal impurity amount can be reduced to below 1/10th from amount originally.And, using the TAA salt that reclaims to make in the situation of TAAH with aforesaid method, resulting TAAH is fit to be used in the image-developing liquor that liquid-crystal display is used.
Embodiment
Below, for further specifically understanding the present invention, hereby enumerate embodiment and comparative example is elaborated, but the present invention is defined in this a little embodiment.
(manipulation of regeneration of Zeo-karb (H type Zeo-karb))
When the use employed Zeo-karb is filled in the glass tower, leads to liquid according to the order of ultrapure water, 1N-HCl (hydrochloric acid) and ultrapure water, and with hydrogen ion as gegenion.Each liquid is space velocity SV to be made as for 5 (l/ times) lead to liquid, and the fluid volume that makes of each liquid is set as the 10L/L-resin.
(concentration determination)
Tetramethyl ammonium hydroxide (TMAH), tetramethyl ammonium chloride (TMAC) concentration, chloride ion can utilize ion chromatography analysis analyzed.
Particularly, can use the ICS2000 processed of DIONEX society, wherein, during cation analysis, tubing string can use ION-pac CS12A, during anion analysis, tubing string then can use ION-pac AS15, in addition, during cation analysis, eluat can use methanesulfonic, and during anion analysis, eluat then can use potassium hydroxide analysis.
Contained concentration of metal ions can utilize high-frequency induction coupling electricity slurry mass analysis (ICP-MS) method (measuring apparatus: HP-4500 (Agilent society system)) or high-frequency induction coupling electricity slurry emmission spectrometric analysis (ICP-OES) method (measuring apparatus: iCAP6500DUO (THERMO ELECTRON Co., Ltd. system)) to be measured in the solution.
The pH of solution can utilize pH electrode method (measuring apparatus: HM-30R, DKK Toa Corp.'s system) to be measured.Specific conductivity then can be used the electric SC time meter (model: SC72-21JAA) measured processed in horizontal river.
Embodiment 1
Weakly acidic cation-exchange resin DIAION WK40L (Mitsubishi Chemical society system) 1000ml is filled in the glass tube column of diameter 22mm * 750mm, carries out again above-mentioned manipulation of regeneration.
(absorbing process of TAA ion)
0.5 quality %TMAH waste liquid (photoresistance video picture waste liquid with 8000ml, the photoresistance amount is scaled 42ppm through COD, concentration of metal ions Na:9.0ppb, Al:4.4ppb, K:1.1ppb, Ca:12.9ppb, Cr:5.5ppb, Fe:16.4ppb, Ni:1.2ppb, Cu:0.14ppb) in this tubing string, lead to liquid with space velocity SV=20 (l/ time).
(washing process)
Subsequently, the 0.5 quality %TMAH of 100ml is led to liquid with space velocity SV=1 (l/ time), with washing impedance composition.
＜with the recovery technique of the contact process/TAAC of hydrochloric acid＞
Then, the 1N-HCl of 800ml is led to liquid as eluat with space velocity SV=1 (l/ time), make the TMA ion of absorption form stripping behind the TMAC.Sequentially obtain respectively dissolution fluid, and can be distinguished into 12 kinds of liquid shown below.Till 0 to 500ml, every 100ml distinguishes and tells 5 kinds and (distinguish liquid A～E); Till 500 to 600ml, then every 20ml distinguishes and tells 5 kinds (distinguish liquid F-1～5); Till 600 to 800ml, then every 100ml distinguishes and tells 2 kinds and (distinguish liquid G～H), be divided into altogether 12 kinds of liquid.These are distinguished liquid measure TMAC concentration with ion chromatography respectively, measure concentration of metal ions with the ICP mass analysis, measure pH with the pH time meter.Its result is shown among table 1, the 2nd figure and the 3rd figure.
[table 1]
Can be understood by table 1 and to learn that the concentration of metal ion can uprise from pH becomes F-3 below 7.No matter any metal is all below the 10ppb concentration of metal ions of the total liquid till from the differentiation liquid B to F-2, and TMAC concentration is 7.8 quality % (0.71mol/l), and does not contain HCl.The TMAC rate of recovery of this moment is 90.0%.
Use the hydrochloric acid of 2N be used as molten from when employed acid, except will carrying out under the following condition with operating in of the contact process of hydrochloric acid, other all utilizes the operation identical with embodiment 1, to obtain TMAC.Show the result in the table 2.
(with the recovery technique of the contact process/TAAC of hydrochloric acid)
Then, the 2N-HCl of 600ml is led to liquid as eluat with space velocity SV=1 (l/ time), make the TMA ion of absorption form stripping behind the TMAC.Sequentially obtain respectively dissolution fluid, and can be distinguished into 12 kinds of liquid shown below.Till 0 to 400ml, every 80ml distinguishes and tells 5 kinds and (distinguish liquid A～E); Till 400 to 500ml, then every 20ml distinguishes and tells 5 kinds (distinguish liquid F-1～5); Till 500 to 600ml, then every 50ml distinguishes and tells 2 kinds (distinguishing liquid G, H), is divided into altogether 12 kinds of liquid.These are distinguished liquid measure TMAC concentration with ion chromatography respectively, measure concentration of metal ions with the ICP mass analysis, measure pH with the pH time meter.Its result is shown in table 2.
[table 2]
Can learn as pH from table 2 to become 7 when following, concentration of metal ions will rise.
Embodiment 3
Use the hydrochloric acid of 4N be used as molten from when employed acid, except will carrying out under the following condition with operating in of the contact process of hydrochloric acid, other all utilizes the operation identical with embodiment 1, to obtain TMAC.Show the result in the table 3.
(with the recovery technique of the contact process/TAAC of hydrochloric acid)
Then, the 4N-HCl of 600ml is led to liquid as eluat with space velocity SV=1 (l/ time), make the TMA ion of absorption form stripping behind the TMAC.Sequentially obtain respectively dissolution fluid, and can be distinguished into 12 kinds of liquid shown below.Till 0 to 250ml, every 50ml distinguishes and tells 5 kinds and (distinguish liquid A～E); Till 250 to 500ml, then every 50ml distinguishes and tells 5 kinds (distinguish liquid F-1～5); Till 500 to 600ml, then every 50ml distinguishes and tells 2 kinds (distinguishing liquid G, H), is divided into altogether 12 kinds of liquid.These are distinguished liquid measure TMAC concentration with ion chromatography respectively, measure concentration of metal ions with the ICP mass analysis, measure pH with the pH time meter.Its result is shown in the table 3 respectively.
Can learn as pH from table 3 to become 7 when following, concentration of metal ions will rise.
[table 3]
Embodiment 4
The resulting TMAC of the method for utilizing embodiment 1 is carried out evaporation concentration, to modulate the TMAC solution of 27.5 quality %.Resulting concentrated TMAC solution carries out the manufacturing of TAAH according to following electrolysis process.
In addition, in electrolysis process, use the three Room type electrolyzers that begun sequentially to dispose respectively one piece of anion-exchange membrane and one piece of cationic exchange membrane (arbitrary exchange membrane is all NAFION90209 (society of Du Pont system)) from anode.The effective film area of above-mentioned ion-exchange membrane is made as 2dm2, the luxuriant and rich with fragrance film of receiving then be with the tool carboxylic acid group one facing to the cathode side setting.Use platinum plating person on the titanium plate is used as anode, and negative electrode then uses SUS316.Make respectively the sulfuric acid of 0.5 regulation at the anolyte compartment of above-mentioned electrolyzer internal recycle; Make above-mentioned chlorination TMA solution in the intermembranous circulation of the cationic exchange of anion-exchange membrane and cathode side; And make pure water at the cathode compartment internal recycle, and current density is maintained 18A/dm2, when temperature then maintains 40 ℃, implement continuously electrolysis.In continuous operation, the tetramethyl ammonium hydroxide concentration of cathode compartment is set as 18 quality %.In the same manner, the concentration that is circulated in the liquid of each chamber is configured to certain value, when concentration thickens, adds pure water, when concentration is thin out, then add its ingredient.
After electrolysis begins, after running condition enters stable 12 hours (stable time), and be shown in the table 4 at the analytical results that continuous operation has carried out 3 months the resulting TAAH solution of time point.
Embodiment 5
To utilize the method identical with embodiment 4 to carry out electrolysis and produce TMAH with the resulting TMAC of the method for embodiment 2.Show the result in the table 4.
[table 4]
Embodiment 6
(manipulation of regeneration of Zeo-karb (H type Zeo-karb))
Zeo-karb 1000ml is filled in the polyvinyl chloride tubulation post of diameter 50mm * 2000mm, the space velocity SV that leads to when the liquid with ultrapure water, 1N-HCl was made as for 4 (l/ times), except the fluid volume that makes with each liquid is set as the 5L/L-resin, other all carries out manipulation of regeneration in the same manner with embodiment 1.
(absorbing process of TAA ion)
0.5 quality %TMAH waste liquid of 80l and embodiment 1 same composition is led to liquid with space velocity SV=20 (l/ time).
(washing process)
Subsequently, the 0.5 quality %TMAH of 2l is led to liquid with space velocity SV=5 (l/ time), with washing impedance composition.
(with the recovery technique of the contact process/TAAC of hydrochloric acid)
Then, the 1N-HCl of 8000ml is led to liquid as eluat with space velocity SV=5 (l/ time), make the TMA ion of absorption form stripping behind the TMAC.Sequentially obtain respectively dissolution fluid, and can be distinguished into 23 kinds of liquid shown below.At first, distinguish 0～1000ml (differentiation liquid A); Till 1000 to 5000ml, every 500ml distinguishes and tells 8 kinds and (distinguish liquid B～I); Till 5000 to 6000ml, then every 100ml distinguishes and tells 10 kinds (distinguish till the liquid J-1～J-10), 6000 to 8000ml, then every 500ml distinguishes and tells 4 kinds and (distinguish liquid K～N), be divided into altogether 23 kinds of liquid.These are distinguished liquid measure TMAC concentration with ion chromatography respectively, measure concentration of metal ions with the ICP mass analysis, measure pH with the pH time meter.Its result is shown among table 5, the 4th figure and the 5th figure.In addition, pH, specific conductivity, TMAC concentration, the concentration of metal ions of distinguishing the total liquid of liquid B～J-5 is shown in Table 6.
[table 5]
[table 6]
(7.7wt%)
Can be understood by table 5 and to learn that the concentration of metal ion can uprise from pH becomes J-6 below 7.In addition, can learn from the result of table 6 and to distinguish liquid B no matter any metal is all below the 3.5ppb to the concentration of metal ions of the total liquid of J-5 that TMAC concentration is 7.7 quality % (0.71mol/l), and does not contain HCl.The TMAC rate of recovery of this moment is 87.8%.
Claims (5)
1. the manufacture method of a tetra-allkylammonium salts solution, this manufacture method are to utilize the solution that contains metal ion and tetraalkylammonium hydroxide to obtain containing the solution of tetraalkylammonium salt, it is characterized in that, comprise:
(1) solution that contains metal ion and tetraalkylammonium hydroxide is passed in the adsorption tower of the Zeo-karb that is filled with the hydrogen ion type, make tetraalkyl ammonium ion in this solution be adsorbed on absorbing process on the Zeo-karb; And
(2) in described absorbing process, acid solution is passed into be filled with in the adsorption tower of the Zeo-karb that is adsorbing tetraalkyl ammonium ion, make the tetraalkyl ammonium ion that is adsorbed in this resin molten from the described hydrochlorate of one-tenth, and will be recycled to from the effluent liquid that this adsorption tower flows out the recovery technique that groove is stayed in storage;
And, in described recovery technique, measurement is from pH and/or the specific conductivity of the effluent liquid of adsorption tower, when putting in point and/or specific conductivity in the pH of this effluent liquid reaches predetermined pH have only changed the variable quantity of predetermined specific conductivity, stops towards recovery that staying the effluent liquid of groove toward described storage.
2. the manufacture method of tetra-allkylammonium salts solution according to claim 1 is characterized in that, in described recovery technique, described acid solution is strong acid, makes towards the predetermined pH of the effluent liquid that stays the recovery of effluent liquid of groove to stop toward storage between 3～8 scope.
3. the manufacture method of tetra-allkylammonium salts solution according to claim 1, it is characterized in that, in described recovery technique, maintain the state under certain state with concentration and the specific conductivity of the time point that flows out with respect to tetraalkylammonium salt, making towards the variable quantity of the predetermined specific conductivity of the effluent liquid that stays the recovery of the effluent liquid of groove to stop toward storage is 5%.
4. the manufacture method of a tetraalkylammonium hydroxide is characterized in that, comprises:
After producing tetraalkylammonium salt with any described method of claims 1 to 3, resulting tetraalkylammonium salt is used as raw material to make the technique of tetraalkylammonium hydroxide.
5. manufacturing installation, this manufacturing installation are in order to making the tetra-allkylammonium salts solution from tetraalkylammonium hydroxide solution, it is characterized in that, comprise:
Be filled with the adsorption tower of Zeo-karb;
Recovery is stayed groove from the storage of the effluent liquid that this adsorption tower flows out; And
Measure assembly and/or in order to the conductivity measurement assembly of the specific conductivity of measuring this effluent liquid in order to the pH of the pH that measures this effluent liquid.
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| 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 |
| CN104176867A (en) * | 2013-05-22 | 2014-12-03 | 北京思践通科技发展有限公司 | Recovery method for amine |
| CN114920658A (en) * | 2022-06-28 | 2022-08-19 | 大连理工大学盘锦产业技术研究院 | Method for purifying choline hydroxide by using ion exchange resin |
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| JP5808221B2 (en) * | 2011-10-28 | 2015-11-10 | 株式会社トクヤマ | Method for producing tetraalkylammonium salt solution |
| JP2016174979A (en) * | 2013-07-30 | 2016-10-06 | 株式会社トクヤマ | Production method of tetraalkylammonium salt aqueous solution |
| ES2690325T3 (en) | 2013-12-17 | 2018-11-20 | Judo Wasseraufbereitung Gmbh | Mixing control with determination of the hardness of untreated water through the conductivity of soft and mixed water |
| KR200486055Y1 (en) | 2016-10-11 | 2018-03-28 | 이요람 | Stool for Farm Work |
| CN114147052B (en) * | 2020-09-05 | 2023-01-24 | 中国石油化工股份有限公司 | High-boiling-point substance metal ion adsorption renewable system and process |
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| JP2003340449A (en) * | 2002-05-27 | 2003-12-02 | Babcock Hitachi Kk | Method for treating waste water containing tetraalkylammonium hydroxide |
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| JP4385407B2 (en) * | 2007-04-05 | 2009-12-16 | オルガノ株式会社 | Method for treating tetraalkylammonium ion-containing liquid |
| KR20120070564A (en) * | 2009-09-24 | 2012-06-29 | 가부시끼가이샤 도꾸야마 | Process for production of tetraalkylammonium hydroxide |
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| JP2003340449A (en) * | 2002-05-27 | 2003-12-02 | Babcock Hitachi Kk | Method for treating waste water containing tetraalkylammonium hydroxide |
| JP2004066102A (en) * | 2002-08-06 | 2004-03-04 | Babcock Hitachi Kk | Waste liquid treatment method and equipment therefor |
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| CN104176867A (en) * | 2013-05-22 | 2014-12-03 | 北京思践通科技发展有限公司 | Recovery method for amine |
| 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 |
| CN114920658A (en) * | 2022-06-28 | 2022-08-19 | 大连理工大学盘锦产业技术研究院 | Method for purifying choline hydroxide by using ion exchange resin |
| CN114920658B (en) * | 2022-06-28 | 2024-05-03 | 大连理工大学盘锦产业技术研究院 | Method for purifying choline hydroxide by ion exchange resin |
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| KR20130138191A (en) | 2013-12-18 |
| TW201228729A (en) | 2012-07-16 |
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| JPWO2012090699A1 (en) | 2014-06-05 |
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