CN105217865A - Improve the photo-resist high boiling point stripping waste liquor regeneration method of regeneration yield - Google Patents
Improve the photo-resist high boiling point stripping waste liquor regeneration method of regeneration yield Download PDFInfo
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- CN105217865A CN105217865A CN201510638926.8A CN201510638926A CN105217865A CN 105217865 A CN105217865 A CN 105217865A CN 201510638926 A CN201510638926 A CN 201510638926A CN 105217865 A CN105217865 A CN 105217865A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
- H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
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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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02002—Preparing wafers
- H01L21/02005—Preparing bulk and homogeneous wafers
- H01L21/02032—Preparing bulk and homogeneous wafers by reclaiming or re-processing
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02041—Cleaning
- H01L21/02079—Cleaning for reclaiming
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Abstract
The present invention relates to the photo-resist high boiling point stripping waste liquor regeneration method that improve regeneration yield, the method can solve the problem producing stench due to the basic by-product in high boiling point residue in 2 step for regeneration effectively, can improve regeneration yield further.The invention is characterized in, also comprise: N-process, during the high boiling point residue comprising high-boiling-point impurity of discharging being removed in 1 step for regeneration in neutralization reaction pond carries out and, in high boiling point residue, make to comprise the high-boiling-point impurity solidification of basic by-product; Cured article removing process, cured article removing device in remove from and reaction tank conveying high boiling point residue in cured article; Moisture removing process, heats the described high boiling point residue eliminating cured article and removes moisture in water distilling apparatus; And 4 still-process, heating is carried out to the high boiling point residue eliminating moisture by described moisture removing process and reclaims high boiling point stripping solvent further.
Description
Technical field
The present invention relates to a kind of photo-resist high boiling point stripping waste liquor regeneration method, more specifically, relate to following photo-resist high boiling point stripping waste liquor regeneration method, the method can solve effectively carries out the manipulation of regeneration of 2 property to the high boiling point residue of discharging in 1 step for regeneration and reclaims the problem producing stench when high boiling point peels off solvent due to the basic by-product in high boiling point residue in 2 step for regeneration further in stripping waste liquor regenerative process, can improve the regeneration yield of stripping waste liquor regenerative process compared to existing technology further.
Background technology
In recent years, along with to become in the fine circuit composition of semiconductor wafer and circuit substrate etc. core sensitizer and for diluting and removing the rush of demand of stripping liquid of costliness of this sensitizer, be more and more necessary to recycle the stripping waste liquor after using.
Such as, stripping waste liquor mainly in the electronic unit manufacturing processes such as semiconductor wafer, liquid crystal indicator, glass substrate for the formation of the photo-mask process of circuit pattern in produce, except peeling off except solvent also containing impurity such as etch-resist resin, moisture, heavy metals in stripping waste liquor.
Described stripping waste liquor major part is all carrying out waste treatment by burning or burying after simple preprocessing process, from producing waste liquid until removing waste liquid exists the problem etc. of environmental problem and cost processing costs, finally can weaken the enterprise competitiveness of IT industry, the requirement therefore realizing resource utilization by the regeneration of solvent slop constantly expands, strengthens.
Along with the fast development of the electronic unit and equipment that combine IT technology, thinner needed for manufacturing process and the kind of stripping liquid, function are more and more diversified, however, to be recovered in the current main stripping liquid solvent used in the manufacturing process of the electronic unit as TET-LCD (ultrathin membrane liquid crystal indicator) etc. and the amount of purifying and being reused is a minimum part.
And then along with in TET-LCD field, substrate maximizes and panel price drop gradually, improves the requirement of saving engineering cost, in addition, be subject to the impact of rise of the oil price in recent years, the prices of raw and semifnished materials of thinner and stripping liquid, also in rise, are therefore necessary the competitive power that raises the cost.
Therefore, require a kind of to recycle as starting material through the purification process stripping liquid (that is, stripping waste liquor) that will give up, thus starting material usage quantity can be saved and the technology of the more and more serious environmental problem of improvement and processing costs problem.
Therefore, as prior art, propose regeneration (Recycling) technology of stripping waste liquor, regenerate the technology of stripping solvent by removing the high boiling substances such as low-boiling point material and etch-resist resin such as moisture from stripping waste liquor and make the minimized high-recovery renovation process of the loss amount in step for regeneration etc.
But, in recent years along with the fast development of LCD and Semiconductor Materials Industry, the photoresist of new structure is brought into use due to the exploitation of novel memory semiconductor, need easily to dissolve photoresist in manufacturing process and the stripping organic solvent of high functionality peeled off in the operation peeling off photoresist, therefore, the usage quantity peeling off the high boiling stripping solvent of solubleness excellence increases, but being used in the renovation process adopted in above-mentioned prior art is limited to regenerate high boiling stripping solvent.
Particularly, high boiling point is peeled off organic solvent and is difficult to because high viscosity, thermolysis and colourity change contour boiling nature carry out separating-purifying from the etch-resist resin and metal ingredient of heavy (Heavy), and in order to avoid operation trouble (Trouble) and make its excess residual, therefore existence can residual together with most of high-boiling-point impurity after to go out of use the limitation processed.
In addition, although surging in the requirement of relevant industry to the resource reutilization recovery technology of the high boiling point stripping organic solvent of exploitation costliness, practical situation are at present both at home and abroad all without relevant alternative regeneration techniques.
Therefore, be badly in need of the reengineer technology guaranteeing a kind of height, can not only from the photo-resist resistates (Residue) of the process that goes out of use, carry out regeneration purification to the general stripping organic solvent in photo-resist stripping waste liquor and reclaim, and can regeneration purification be carried out to the high boiling point stripping organic solvent of costliness and reclaim.
In addition, if the reengineer technology can passing through height reclaims in a large number using high-recovery recycle as the high boiling point stripping solvent all from the valuable resource of the costliness of external import, not only in high efficient energy sources management layer, and also can get twice the result with half the effort in the competitive power of strengthening IT relevant enterprise, thus the effect of more substantial environmental protect can be expected.
Therefore, the applicant of the application has applied for the patent of " photo-resist high boiling point stripping waste liquor regenerating unit " and has obtained patent right [existing patent 1: No. 10-1330654th, Korean registered patent (2013.11.12)], this patent can by removing No. 1 water distilling apparatus of lower-boiling impurity from photo-resist high boiling point stripping waste liquor, while removing comprises the high boiling point residue of high-boiling-point impurity, No. 2 water distilling apparatus of solvent composition thing are peeled off in regeneration, and from the stripping solvent composition thing of regeneration, remove No. 3 the water distilling apparatus closing stripping exsolution agent constituent back and forth of micro-moisture, and then the high boiling point gone out of use as distillation leftover together with high-boiling-point impurity before can being regenerated further by No. 4 water distilling apparatus etc. reclaiming stripping solvent from described high boiling point residue further peels off solvent, thus significantly can improve the regeneration yield that expensive high boiling point peels off solvent.
In addition, the applicant of the application has applied for the patent of " photo-resist high boiling point stripping waste liquor regeneration method " and has obtained patent right [existing patent 2: No. 10-1330653rd, Korean registered patent (2013.11.12)], (namely this patent can by removing the 1st removing step of lower-boiling impurity from photo-resist high boiling point stripping waste liquor, 1 still-process), while removing comprises the high boiling point residue of high-boiling-point impurity, (namely regeneration peel off the 2nd removing step of solvent composition thing, 2 still-process), and the 3rd removing step of micro-moisture is removed (namely from the stripping solvent composition thing of regeneration, 3 still-process) closing stripping exsolution agent constituent back and forth, and then can by reclaiming the step of stripping solvent further (namely from described high boiling point residue, 4 still-process) etc. regenerate further before the high boiling point that goes out of use as distillation leftover together with high-boiling-point impurity peel off solvent, thus significantly can improve the regeneration yield that expensive high boiling point peels off solvent.
Fig. 2 is the structure iron of the device of existing patent 1 and the photo-resist high boiling point stripping waste liquor regenerative process performing existing patent 2.
By such technology, not only in high efficient energy sources management layer, and also can get twice the result with half the effort in the competitive power of strengthening IT relevant enterprise, thus the effect of more substantial environmental protect can be expected.
But, still do not reach at present and can reclaim using high-recovery the level realizing significantly cost saving as high boiling point stripping solvents such as the HEP (1-piperazine ethanol) all from the valuable resource of the costliness of external import in a large number, that is, do not reach can cheap ground production high-quality regenerated solvent level more than 50% the rate of recovery.
Therefore, the applicant of the application has applied for a kind of apparatus and method, and obtain patent right [existing patent 3: No. 10-1354523rd, Korean registered patent (2014.1.14)/existing patent 4: No. 10-1423967th, Korean registered patent (2014.7.22)], the regeneration yield that the HEP peeling off solvent as high boiling point is regenerated as with the high-recovery of more than 50% in the process of high purity electronic-grade can reclaimed HEP in a large number by this patent from photo-resist high boiling point stripping waste liquor, thus pass through the regenerated solvent of significantly fee cut cheap ground production high-quality.
In addition, following shortcoming is there is in the photo-resist high boiling point stripping waste liquor regenerating unit and method of existing patent 1,2, namely, after 1 step for regeneration that can obtain high purity regenerated mixing stripping liquid, from the 2nd removing step removing by 1 step for regeneration, reclaim high boiling point in the high boiling point residue that comprises high-boiling-point impurity further and peel off in 4 still-process of 2 step for regeneration of solvent, the ult rec that the high boiling points such as HEP (1-piperazine ethanol) peel off solvent is low.
In order to solve such problem, the applicant of the application has applied for the apparatus and method of the regeneration yield that can improve photo-resist high boiling point stripping waste liquor and has obtained patent right [existing patent 5: No. 10-1446542nd, Korean registered patent (2014.9.25)/existing patent 6: No. 10-1446541st, Korean registered patent (2014.9.25)].
According to existing patent 5 and existing patent 6, in 4 still-process of existing 2 step for regeneration, peel off solvent (HEP etc.) making the high boiling point contained by high boiling point residue carry out extracting to the distillation of distillation tower top and undertaken by condenser in the step of condensation and Separation and Recovery, the HEP composition ratio level of the condensate recovery liquid of monitoring containing HEP etc., when HEP content is close to " 2 viscosity rising HEP ratio of componentss ", NMP (N-Methyl pyrrolidone) or MDG (diethylene glycol monomethyl ether) is supplied to the reboiler quantification of No. 4 water distilling apparatus further from additional supply pool, the content of HEP is made to be reduced to " 1 viscosity rising HEP ratio of components " following level of condensate recovery liquid, thus the composition ratio distillation tower distillation to No. 4 water distilling apparatus can being carried out within the condenser the HEP contained by condensate recovery liquid of the high boiling point stripping solvent of condensation and Separation and Recovery after being extracted maintains " 2 viscosity rising HEP ratio of componentss " following level of at least condensate recovery liquid.
Therefore, can the proterties of condensate recovery liquid be suppressed to change by semi-gelled (Semi-gel) while being reduced by condenser to carry out the viscosity of the condensate recovery liquid of the high boiling point stripping solvent of condensation and Separation and Recovery, consequently can improve the reclaim recovery efficiency that the high boiling points such as HEP peel off 2 property of solvents.
On the other hand, in the technology of above-mentioned existing patent 1 ~ 6, be necessary to improve following problem further.
Existing patent proposes a kind of optimum control method, this optimum control method carries out lowest water level adjustment to the waste liquid in reboiler, make the precipitation farthest postponing etch-resist resin in 4 still-process of 2 step for regeneration (Additionalstripperrecycling), and farthest improve the regeneration yield of HEP, but, repeatedly to run the process operations of compound repeatedly in 2 step for regeneration always, therefore step for regeneration will maintain long time running at high temperature, likely produce several inevitable working-procedure problem, be necessary to improve.
Particularly, the problem such as transparency reduction (APHA value variation, thermo-color), the increase of HEP thermolysis degree improving productivity reduction, the operation trouble caused by the process operations contacted with complex method, regenerated solvent is necessary.
In addition, existing patent when reclaiming HEP (1-piperazine ethanol) from photo-resist high boiling point stripping waste liquor, by the non-protonic solvent occurred in 1 removal step (NMP (N-Methyl pyrrolidone), MMF (N-METHYLFORMAMIDE)) the by product that produces of thermolysis and the by product that produced by the thermolysis of the HEP occurred in 1 step for regeneration can be exposed to high temperature (120 ~ 160 DEG C) in 1 step for regeneration, then can cool in the process being transported to No. 4 water distilling apparatus D-4, then in ensuing 2 step for regeneration, high temperature (120 ~ 160 DEG C) can be again exposed to constantly again, therefore, the mist of oil of the stench of high volatility is generated by the interaction with concentrated etch-resist resin and sensitizer etc., thus cause the inconvenience of operation maintenance management and local resident, also exist and make the process of the waste produced in step for regeneration become the problems such as difficulty (offal treatment enterprise of being commissioned is reluctant to receive) because of malodor problem.
Summary of the invention
The problem that invention will solve
Therefore, the present invention completes to solve the above problems, its object is to, a kind of photo-resist high boiling point stripping waste liquor regeneration method that effectively can prevent from producing in 2 step for regeneration due to the basic by-product in the high boiling point residue from 1 step for regeneration discharge stench is provided.
In addition, another object of the present invention is, provides a kind of photo-resist high boiling point stripping waste liquor regeneration method that can improve the regeneration yield of stripping waste liquor regenerative process compared to existing technology further.
For solving the scheme of problem
In order to achieve the above object, the invention provides a kind of photo-resist high boiling point stripping waste liquor regeneration method that improve regeneration yield, the method peels off 1 step for regeneration of solvent as regenerating from photo-resist high boiling point stripping waste liquor and reclaiming high boiling point, comprise: 1 still-process, from photo-resist high boiling point stripping waste liquor, remove lower-boiling impurity; 2 still-process, comprise the high boiling point residue of high-boiling-point impurity from the photo-resist high boiling point stripping waste liquor removing eliminating described lower-boiling impurity, and reclaim high boiling point stripping solvent; And 3 still-process, peel off solvent from the high boiling point of described recovery and remove micro-moisture, the feature of described photo-resist high boiling point stripping waste liquor regeneration method is also to comprise: N-process, in neutralization reaction pond to be removed in described 1 step for regeneration the high boiling point residue of discharging, comprising high-boiling-point impurity carry out in and, make in high boiling point residue comprise basic by-product high-boiling-point impurity solidification; Cured article removing process, cured article removing device in remove from and reaction tank conveying high boiling point residue in cured article; Moisture removing process, heats the high boiling point residue eliminating described cured article and removes moisture in water distilling apparatus; And 4 still-process, heating is carried out to the high boiling point residue eliminating moisture by described moisture removing process and reclaims high boiling point stripping solvent further.
In a preferred embodiment, it is characterized in that, in described N-process, start the stirrer being attached to neutralization reaction pond high boiling point residue is stirred.
In addition, the invention is characterized in, the pH value of the high boiling point residue in neutralization reaction pond is maintained the scope of 6.5 ~ 8.5 in described N-process.
In addition, the invention is characterized in, in described N-process, the basic by-product making high boiling point residue comprise in neutralization reaction pond solidifies and separates out, the precipitate solidified in N-process plays the effect of condensation nucleus, makes the high-boiling-point impurity comprising the etch-resist resin of simmer down to paste in high boiling point residue carry out chain solidification.
In addition, the invention is characterized in, the high boiling point residue that have passed through cured article removing device is transported to No. 1 water distilling apparatus carrying out described 1 still-process, thus in No. 1 water distilling apparatus, carry out described moisture removing process.
In addition, the invention is characterized in, peeling off after 1 step for regeneration of solvent terminates for regenerating from photo-resist high boiling point stripping waste liquor and reclaiming high boiling point, by from and the reaction tank high boiling point residue that have passed through cured article removing device be transported to described No. 1 water distilling apparatus and carry out described moisture removing process.
In addition, the invention is characterized in, to the high boiling point residue removing moisture being eliminated cured article by cured article removing device in described moisture removing process, make moisture content become less than 0.1 % by weight.
In addition, the invention is characterized in, described No. 1 water distilling apparatus comprises: distillation tower, holds the high boiling point residue supplied by flowrate control valve; Reboiler, is connected at the bottom of the tower of distillation tower, for heating the high boiling point residue be transported in described distillation tower, moisture is evaporated; Condenser, is connected to the upper end of distillation tower, for making the condensate moisture of distillation; Temporary reservoir pond, is connected with described condenser, carries out temporary reservoir to the moisture of condensation within the condenser; And drawdown pump, be connected to the upper end in temporary reservoir pond, the decompression carrying out the pressure reduced in distillation tower when the high boiling point residue made it possible in described distillation tower is heated operates, start the decompression running that described drawdown pump implements the pressure reduced in distillation tower, and be below 110torr when carrying out underpressure distillation operation by the pressure setting in distillation tower, the temperature in reboiler is set as less than 110 DEG C.
In addition, the invention is characterized in, carry out regenerating from described photo-resist high boiling point stripping waste liquor and reclaim high boiling point peel off solvent 1 step for regeneration during, the high boiling point residue comprising high-boiling-point impurity of discharging being removed in 2 still-process is transported to neutralization reaction pond, then carries out N-process.
In addition, the invention is characterized in, described cured article removing device is solid-liquid separation strainer, described solid-liquid separation strainer to from and the high boiling point residue of reaction tank conveying carry out filtration to remove cured article.
Invention effect
Thus, according to above-mentioned photo-resist high boiling point stripping waste liquor regeneration method of the present invention, following effect can be obtained.
1) by carrying out 2 times following step for regeneration, thus can effectively prevent due to the basic by-product in high boiling point residue and in 2 step for regeneration, produce stench, in described 2 step for regeneration, the high boiling point residue comprising high-boiling-point impurity is made to carry out neutralization reaction, this high boiling point residue peels off when solvent regenerates high boiling point to remove from stripping waste liquor in No. 2 water distilling apparatus of 1 step for regeneration, after the cured article generated when removing neutralization reaction, to the high boiling point residue removing moisture eliminating cured article in No. 1 water distilling apparatus, then from the high boiling point residue eliminating moisture, reclaim the high boiling points such as HEP further peel off solvent.
2) in high boiling point residue and time cured article and the photo-resist cream be concentrated in high boiling point residue of basic by-product of separating out carry out interacting and play the condensation nucleus effect of polymer coagulant, a large amount of etch-resist resin thus contained by photo-resist cream is cured by chain effect and separates out, in cured article removing device, the cured article of the cured article of basic by-product and etch-resist resin etc. can be removed after neutralization procedure simultaneously, therefore, with the high boiling point residue eliminating cured article for object regenerates further, purification high boiling point is peeled off in 2 step for regeneration of solvent, can be more much easier than prior art reclaim high boiling point peel off solvent, the effect of the process conditions that consequently can improve and raising regeneration yield.
3) particularly, significantly can reducing overall operation and use number of times in 2 step for regeneration, the process operations than facilitating many in the past can being carried out, can reduce and use number of times, shortening activity time.This can reduce the thermolysis degree that high boiling points such as will carrying out the HEP reclaimed peels off solvent, and this also contributes to improving the regeneration yield that high boiling point peels off solvent, the effect of the regeneration yield of the whole step for regeneration that can be largely increased.
Accompanying drawing explanation
Fig. 1 is the structure iron of the device carrying out photo-resist high boiling point stripping waste liquor regenerative process of the present invention.
Fig. 2 is the structure iron of the photo-resist high boiling point stripping waste liquor regenerating unit that prior art is shown.
Embodiment
Below, with reference to accompanying drawing, embodiments of the invention are described in detail, make those skilled in the art easily can implement the present invention.
In the term that the present invention uses, " lower-boiling impurity " refers to the low impurity of indivedual stripping solvents that boiling point comprises than photo-resist high boiling point stripping waste liquor, normally as the moisture of washing waste water or as the such a small amount of organic solvent of the IPA of solvent slop.
In addition, in the term that the present invention uses, " high-boiling-point impurity " refers to the high impurity of indivedual stripping solvents that boiling point comprises than photo-resist high boiling point stripping waste liquor, preferably boiling point is the impurity of more than 235 DEG C, be the etch-resist resin be stripped after using in the resist composition of the grid operation of transistor typically, comprise other impurity such as a small amount of nonionic interfacial agent.
In addition, in the term that the present invention uses, " high boiling point stripping solvent " refers to boiling point that photo-resist high boiling point stripping waste liquor comprises exceeds more than 10 DEG C indivedual stripping solvents than about 220 DEG C of the boiling point upper limit as general stripping solvent, preferably boiling point is more than 235 DEG C, solvent peeled off by the photo-resist that uses in stripping process, is the HEP solvent of the stripping solubleness as organic amine solvent with excellence typically.
The photo-resist high boiling point stripping waste liquor regenerating unit that the present invention utilizes addition of following device key element, this device key element is used for the high boiling point residue produced in No. 2 water distilling apparatus of 1 step for regeneration, namely, be mixed with basic by-product, etch-resist resin, the high boiling point residue that the high boiling points such as the HEP (1-piperazine ethanol) that high-boiling-point impurities such as sensitizer and will carrying out reclaim peel off solvent carries out neutralizing and removing the operation of cured article, by there is the above-mentioned device key element neutralizing and remove the operation of cured article to high boiling point residue on the basis of the regeneration yield raising device of existing patent 5 (No. 10-1446542nd, Korean registered patent), thus the photo-resist high boiling point stripping waste liquor regenerating unit of the present invention of regeneration yield maximization can be formed.
As mentioned above, the by product that the by product produced by the thermolysis of non-protonic solvent (NMP, MMF etc.) and the thermolysis of peeling off solvent (HEP etc.) by the high boiling point occurred in 1 step for regeneration produce is basic cpd, therefore, when in high boiling point residue in 2 step for regeneration still remaining have a by product of above-mentioned alkalescence time, basic by-product again can be exposed to the high temperature (120 ~ 160 DEG C) of 2 step for regeneration and produce stench phenomenon.
Thus, there is high boiling point residue treatment unit for neutralizing and remove cured article to high boiling point residue in the present invention, when the high boiling point residue of 1 step for regeneration comprising high-boiling-point impurity being processed in described high boiling point residue treatment unit, the basic by-product producing stench in 2 step for regeneration is made to solidify and remove, more specifically, described high boiling point residue carries out being removed in No. 2 water distilling apparatus of the 2nd removing step discharging in 1 step for regeneration.
In addition, in the present invention, in order to make it through No. 1 water distilling apparatus of 1 step for regeneration to the high boiling point residue removing moisture that have passed through high boiling point residue treatment unit, then make it through 4 still-process of 2 step for regeneration for reclaiming the high boiling point stripping liquids such as HEP in high boiling point residue (that is, high boiling point peels off solvent) further.
Neutralization procedure and cured article removing step is performed in described high boiling point residue treatment unit, wherein, in neutralization procedure, the pH value of high boiling point residue is regulated and maintains the scope of 6.5 ~ 8.5 and make the solidifications (Solidification) such as the basic by-product in high boiling point residue, in cured article removing step, from the high boiling point residue that have passed through described neutralization procedure, remove cured article.
The high boiling point residue that have passed through described neutralization procedure and cured article removing step is transported to No. 1 water distilling apparatus of 1 step for regeneration, the high boiling point residue being transported to No. 1 water distilling apparatus from high boiling point residue treatment unit can remove the impurity such as the basic by-product of a great deal of by neutralization procedure and cured article removing step, but still is the high boiling point residue waste liquid comprising remaining high-boiling-point impurity and comprise the high boiling point stripping liquids such as HEP.
In addition, in No. 1 water distilling apparatus of 1 step for regeneration, from the high boiling point residue that have passed through high boiling point residue treatment unit, namely have passed through in the high boiling point residue waste liquid of neutralization procedure and cured article removing step and remove moisture, then, the high boiling point residue waste liquid eliminating moisture in No. 1 water distilling apparatus is transported to 2 step for regeneration, carries out 4 still-process of 2 step for regeneration for reclaiming the high boiling point stripping liquids such as HEP from high boiling point residue further.
Described 2 step for regeneration (Additionalstripperrecycling) comprising: the step high boiling point residue waste liquid eliminating moisture by No. 1 water distilling apparatus being supplied to No. 4 water distilling apparatus; And from high boiling point residue waste liquid, remove high-boiling-point impurity (high-boiling-point impurity waste liquid) further and the step that the high boiling point stripping solvent reaching high purity electronic-grade level because of removing high-boiling-point impurity is extracted and reclaimed.
Accompanying drawing 1 is the structure iron of the device of the photo-resist high boiling point stripping waste liquor regenerative process performing embodiments of the invention, eliminate the diagram that the photo-resist high boiling point stripping waste liquor regenerating unit (invention of existing patent 5,6) carrying out patent registration to the applicant by the application carries out the part-structure in illustrated Fig. 2, and the structure of the high boiling point residue treatment unit of additional illustration for improving regeneration.
First, comprising No. 1 water distilling apparatus (performing the 1st removing step) of the lower-boiling impurities such as the moisture in removing photo-resist high boiling point stripping waste liquor, removing comprise the high-boiling-point impurity such as etch-resist resin and sensitizer high boiling point residue and carry out high boiling point stripping waste liquor substantial regeneration (namely, the recovery of high boiling point stripping liquid) No. 2 water distilling apparatus (perform the 2nd removing step), and from reclaimed by No. 2 water distilling apparatus (namely, eliminate high boiling point residue) remove in the basic apparatus structure of 1 step for regeneration of No. 3 water distilling apparatus (performing the 3rd removing step) of micro-moisture in high boiling point stripping liquid, difference is not had compared with the structure of existing patent 5, and then, in the basic apparatus structure etc. of 2 step for regeneration comprising No. 4 water distilling apparatus reclaiming the such high boiling point stripping liquid of HEP for carrying out 2 manipulation of regeneration to high boiling point residue further, with existing patent 1 to 4 or existing patent 5, the structure of 6 is compared does not have difference yet.
Only, in existing patent, comprise etch-resist resin and sensitizer, and the high boiling point residue waste liquid of the such high-boiling-point impurity of the basic by-product to be produced by the thermolysis of non-protonic solvent and HEP etc. is delivered directly to 2 step for regeneration for reclaiming the high boiling point stripping liquids (high boiling point stripping solvent) such as HEP from described high boiling point residue waste liquid further from No. 2 water distilling apparatus of 1 step for regeneration, but in the present invention, not be transported to 2 step for regeneration, but be transported to the high boiling point residue treatment process carrying out neutralizing and removing cured article.
For this reason, be provided with pipeline, this pipeline is used in No. 2 water distilling apparatus (comprising the distillation tower that Reference numeral is D-2), being removed the high boiling point residue waste liquid comprising high-boiling-point impurity of discharging being transported to high boiling point residue treatment process by carry out 1 removing to the lower-boiling impurities such as moisture (lower-boiling impurity waste liquid) in No. 1 water distilling apparatus of 1 step for regeneration after, at this, pipeline can be the pipeline extended from the temporary reservoir pond (Reference numeral 13 Fig. 2) of No. 2 water distilling apparatus.
High boiling point residue waste liquid is transported to high boiling point residue treatment unit by described pipeline, in described high boiling point residue waste liquid, what be mixed with high-boiling-point impurity and a great deal of remains in the high boiling point stripping liquids such as the HEP of (Reference numeral 6 in Fig. 2) at the bottom of the tower of No. 2 water distilling apparatus and reboiler (Reference numeral 7 in Fig. 2).
As shown in Figure 1, described high boiling point residue treatment unit comprises neutralization reaction pond NT and cured article removing device, wherein, described neutralization reaction pond NT is connected by described pipeline with No. 2 water distilling apparatus (comprising the water distilling apparatus that Reference numeral is D-2), and be attached to stirrer in inside, described cured article removing device is arranged on and is connected to the pipeline of the inlet side of No. 1 water distilling apparatus from the outlet of described neutralization reaction pond NT, be configured in the rear end (downstream side) of neutralization reaction pond NT, in the N-process of high boiling point residue waste liquid, remove the cured article that have cured.
In a preferred embodiment, cured article removing device can be solid-liquid separation filter F T, this solid-liquid separation filter F T to from and the high boiling point residue waste liquid of reaction tank conveying filter and remove cured article.
In addition, install pipeline between No. 2 water distilling apparatus and neutralization reaction pond NT of 1 step for regeneration has the transferpump 34 for the high boiling point residue waste liquid comprising high-boiling-point impurity to be transported to neutralization reaction pond NT from No. 2 water distilling apparatus, in and the install pipeline that connects between the outlet of reaction tank NT and filter F T entrance have the 4th flowrate control valve 31 and transferpump 35.
Described 4th flowrate control valve 31 be for opening/closing by high boiling point residue from and reaction tank NT be transported to the valve of the pipeline of filter F T, can according to circumstances regulate from and reaction tank NT be transported to the operational throughput of the high boiling point residue of filter F T.
Described transferpump 35 is the pumps for the high boiling point residue of neutralization reaction pond NT being transported to filter F T, utilize the 4th such flowrate control valve 31 and transferpump 35 to control, the high boiling point residue comprising cured article in the NT of neutralization reaction pond is supplied to the filter F T as cured article removing device.
Meanwhile, other transferpump 36 can also be set at the pipeline being connected to the inlet end of No. 1 water distilling apparatus from filter F T outlet, make the high boiling point residue that have passed through filter F T can be transported to No. 1 water distilling apparatus (comprising the distillation tower that Reference numeral is D-1).
Now, pipeline for the high boiling point residue that have passed through filter F T being transported to No. 1 water distilling apparatus can be connected with the pipeline that photo-resist high boiling point stripping waste liquor is supplied to No. 1 water distilling apparatus from raw material supplying pond T-1, as an example, the pipeline for the high boiling point residue that have passed through filter F T being transported to No. 1 water distilling apparatus can be connected to the pipeline between raw material supplying pond T-1 for supplying photo-resist high boiling point stripping waste liquor and transferpump F-1 and 1 No. time water distilling apparatus.
In addition, can the pipeline for supplying photo-resist high boiling point stripping waste liquor and the meet for the pipeline that supplies the high boiling point residue that have passed through filter F T arranges for by photo-resist high boiling point stripping waste liquor with have passed through the high boiling point residue of filter F T (namely, have passed through the high boiling point residue of high boiling point residue treatment unit) be optionally supplied to the 5th flowrate control valve 32 of No. 1 water distilling apparatus, described 5th flowrate control valve 32 is valves of the supply for controlling the high boiling point residue to No. 1 water distilling apparatus, can be common 3 logical valves.
In addition, 1 step for regeneration No. 1 water distilling apparatus to 2 step for regeneration No. 4 water distilling apparatus (comprising the distillation tower that Reference numeral is D-4) between the high boiling point residue be provided with for the distillation tower D-1 by No. 1 water distilling apparatus after high boiling point residue treatment unit being eliminated moisture be transported to the pipeline of No. 4 water distilling apparatus of 2 step for regeneration.
Now, the pipeline being connected to No. 4 water distilling apparatus can diverge from the pipeline being connected to No. 2 water distilling apparatus by No. 1 water distilling apparatus and be connected to No. 4 water distilling apparatus, can the pipeline being connected to No. 2 water distilling apparatus and the turnoff of the pipeline being connected to No. 4 water distilling apparatus be provided with the 6th flowrate control valve 33 of the optionally pipeline of opening/closing No. 2 water distilling apparatus sides and the pipeline of No. 4 water distilling apparatus sides, described 6th flowrate control valve 33 is the valves for controlling from No. 1 water distilling apparatus to No. 2 water distilling apparatus and No. 4 water distilling apparatus supply high boiling point residues, can be common 3 logical valves.
On the other hand, supplying photo-resist high boiling point stripping waste liquor from raw material supplying pond T-1 during carrying out regenerating, be mixed with the high boiling point residue of high-boiling-point impurity and high boiling point stripping liquid from No. 2 water distilling apparatus of 1 step for regeneration to described neutralization reaction pond NT conveying and fill described neutralization reaction pond NT.
At this, high-boiling-point impurity is basic by-product, etch-resist resin, the sensitizer etc. such as the by product produced by the thermolysis of non-protonic solvent (NMP, MMF) and the by product produced by the thermolysis of the HEP occurred in 1 step for regeneration, the high boiling point residue waste liquid being mixed with such high-boiling-point impurity and the such high boiling point stripping liquid of a large amount of HEP (that is, high boiling point peels off solvent) is transported to neutralization reaction pond NT.
In described neutralization reaction pond NT, under the state starting stirrer, carry out the pH value of the high boiling point residue waste liquid of No. 2 the water distilling apparatus conveyings from 1 step for regeneration regulate and maintain in the scope of 6.5 ~ 8.5 and operation.
In such neutralization procedure, basic by-product in the NT of neutralization reaction pond in high boiling point residue waste liquid is cured (Solidification) and separates out, the cured article of now separating out is by with concentrated and the photo-resist cream be included in high boiling point residue waste liquid carries out interacting and play the effect of the condensation nucleus with the such effect of polymer coagulant, consequently, a large amount of etch-resist resin contained by described cream is solidified by chain effect, separates out.
Thus, the high boiling point residue waste liquid of NT inside, neutralization reaction pond is included in the cured article occurred because of basic by-product and etch-resist resin solidification in N-process, such high boiling point residue waste liquid is transferred pump 35 and is transported to the filter F T removing device as cured article, filters and remove cured article in filter F T to high boiling point residue waste liquid.
The high boiling point residue waste liquid eliminating cured article is like this transported to No. 1 water distilling apparatus of 1 step for regeneration and removes moisture, after this high boiling point residue waste liquid eliminating moisture be supplied to No. 4 water distilling apparatus and carry out 2 manipulation of regeneration, thus reclaiming the such high boiling point stripping liquid of HEP further.
In order to carry out 2 times such manipulation of regeneration, utilize the 5th flowrate control valve 32 to close raw material supplying pond T-1 side ducts, make raw material waste liquid, namely the photo-resist high boiling point stripping waste liquor of raw material supplying pond T-1 can not be transported to No. 1 water distilling apparatus, and opened filter FT side ducts, the high boiling point residue waste liquid that have passed through filter F T is made to be transported to No. 1 water distilling apparatus, now in No. 1 water distilling apparatus, carry out dewatered operation, a small amount of moisture content of in the high boiling point residue waste liquid making in neutralization reaction pond and generate in operation less than 3 % by weight is down to the level of less than 0.1 % by weight.
The condition of described moisture removal step is as follows, namely, in order to prevent the thermal damage as the thermolysis of HEP, the decompression that the drawdown pump 21 that startup is connected with the distillation tower D-1 of No. 1 water distilling apparatus implements to reduce distillation tower D-1 internal pressure operates, preferably underpressure distillation working pressure is set as below 110torr, the temperature in reboiler 3 is set as less than 110 DEG C.
In aforesaid high boiling point residue and and cured article removing process and be transported in the high boiling point residue of No. 1 water distilling apparatus, the concentration of etch-resist resin can be reduced to concentrated lower concentration level in the past, therefore, although the theoretical stage of the distillation tower D-1 of No. 1 water distilling apparatus does not have the distillation tower D-3 of No. 3 water distilling apparatus so high, under these conditions still can with carry out comparably moisture content being down to 0.1 % by weight with lower horizontal moisture removal step in No. 3 water distilling apparatus.
Disclosed in existing patent 1 (Korean registered patent 10-1330653) and existing patent 2 (Korean registered patent 10-1330654), described No. 1 water distilling apparatus plays the effect removing the lower-boiling impurity such as moisture, IPA from stripping waste liquor in photo-resist high boiling point stripping waste liquor regenerative process, but, in the present invention, during carrying out 2 step for regeneration, be also used as the high boiling point residue removing moisture to have passed through neutralization reaction pond NT and cured article removing device (strainer) FT.
Now, in order to carry out the regeneration of photo-resist high boiling point stripping waste liquor, as shown in Figure 2, described No. 1 water distilling apparatus comprises: the distillation tower D-1 holding photo-resist high boiling point stripping waste liquor; Be connected at the bottom of the tower of distillation tower D-1, the reboiler 3 lower-boiling impurity being evaporated for heating the stripping waste liquor be transported in distillation tower D-1; Be connected to the upper end of distillation tower D-1, for the condenser 1 of the lower-boiling impurity that condensation is extracted; Be connected with condenser 1, the lower-boiling impurity of condensation within the condenser carried out to the temporary reservoir pond 2 of temporary reservoir; Be connected to the outlet side in temporary reservoir pond 2, for discharging the 2nd transferpump 1-1 and the collecting tank T-2 of the lower-boiling impurity be recovered in temporary reservoir pond 2; And be connected to the outlet of reboiler 3, for the stripping waste liquor eliminating lower-boiling impurity being transported to the 3rd transferpump 1-2 of No. 2 water distilling apparatus.
In addition, can thermolysis be promoted when being heated to prevent the high boiling point stripping waste liquor in distillation tower D-1, being connected with drawdown pump 21 in the upper end in temporary reservoir pond 2, make it possible to the decompression running implementing the pressure reduced in distillation tower D-1.
As previously mentioned, No. 1 water distilling apparatus with said structure can be used as removing the moisture removing water distilling apparatus that have passed through neutralization reaction pond NT and the moisture as the high boiling point residue of the filter F T of cured article removing device during carrying out 2 step for regeneration, the high boiling point residue (have passed through the high boiling point residue of neutralization reaction pond and strainer) supplied by the 5th flowrate control valve 32 is held in distillation tower D-1, reboiler 3 is utilized to heat the high boiling point residue be transported in distillation tower D-1 and moisture is evaporated, in order to the condenser 1 making the condensate moisture of distillation utilize the upper end being connected to distillation tower D-1.
In described condenser 1, the moisture of condensation is stored in temporary reservoir pond 2, starts drawdown pump 21, and the decompression can carrying out the pressure reduced in distillation tower when the high boiling point residue in described distillation tower D-1 is heated operates.
Now, start drawdown pump 21, implement the decompression running of the pressure reduced in distillation tower D-1, when carrying out underpressure distillation operation, being below 110torr by the pressure setting in distillation tower D-1, the temperature in reboiler 3 is set as less than 110 DEG C.
During carrying out described moisture removal step, the high boiling point residue eliminating moisture in the distillation tower D-1 of No. 1 water distilling apparatus is transported to the distillation tower D-4 of No. 4 water distilling apparatus through reboiler 3 and the 6th flow control valve 33 by the startup of the 3rd transferpump 1-2, wherein, the high boiling point residue that moisture is removed to the level of less than 0.1 % by weight is transported to the distillation tower D-4 of No. 4 water distilling apparatus, then carries out 2 step for regeneration of the prior art for reclaiming the high boiling point stripping liquids such as HEP further.
Consequently, the neutralization reaction pond NT that is attached to stirrer and the high boiling point residue treatment unit for cured article removing device (strainer) FT that removes cured article is comprised in the present invention by utilizing, thus and can filter remove basic by-product from high boiling point residue by solidification, precipitation, can prevent thus as in the past because of in 2 step for regeneration the basic by-product of high boiling point residue be again exposed to high temperature (120 ~ 160 DEG C) and produce the phenomenon of stench.
In addition, different from the prior art of the high boiling point residue of the etch-resist resin comprising the etch-resist resin paste concentrated with high density being carried out to 2 step for regeneration, in the present invention, 2 manipulation of regeneration (4 still-process) can be carried out to the high boiling point residue that the concentration of etch-resist resin is down to the scope of 2 ~ 5% of concentration level in initial feed waste liquid (photo-resist high boiling point stripping waste liquor).
Therefore, in 2 step for regeneration utilizing No. 4 water distilling apparatus, can be more much easier than prior art regenerate further from high boiling point residue, purification high boiling point stripping liquid, can expect to improve the effect of the rate of recovery than to take a step forward, the effect of removing basic by-product and the stench that is removed can not only be passed through, but also the effect of can improve process conditions and raising regeneration yield.
Particularly, in the control methods of carrying out in 4 still-process of 2 step for regeneration (Additionalstripperrecycling) in existing patent 1 (Korean registered patent 10-1330653) and existing patent 2 (Korean registered patent 10-1330654), namely, in the optimum control method making it possible to the regeneration yield improving HEP while the precipitation at utmost postponing etch-resist resin by carrying out lowest water level adjustment to the waste liquid in reboiler, need the process operations always repeatedly using repeatedly compound in 2 step for regeneration, but, in 2 step for regeneration of the present invention, significantly (general less than 1/3 level) whole operation utilization number of times can be reduced, therefore, the process operations than facilitating many in the past can be carried out, can reduce and use number of times and shorten activity time.
In addition, the thermolysis of HEP can be reduced further, and then can obtain, than with the effect of the reclaim recovery efficiency improving high boiling point stripping liquid that takes a step forward, significantly can improving the final HEP total yield (total yield is 70% level to the maximum) by whole step for regeneration.
Below, be described with reference to the process of Fig. 1 to the regeneration realizing photo-resist high boiling point stripping waste liquor.
First, photo-resist high boiling point stripping waste liquor is sent to raw material supplying pond T-1, then starts the distillation tower D-1 that the photo-resist high boiling point stripping waste liquor of raw material supplying pond T-1 is transported to No. 1 water distilling apparatus by the 1st transferpump F-1.
Now, 5th flowrate control valve 32 is when it is manual operating valve, manually operation opens the pipeline of T-1 side, raw material supplying pond, the photo-resist high boiling point stripping waste liquor of raw material supplying pond T-1 is made it possible to be supplied to No. 1 water distilling apparatus, if or it is electrovalve, then controlled the pipeline of its open T-1 side, raw material supplying pond by the electrical signal (valve control signal) of not shown controller.
In the present invention, be not only the 5th flowrate control valve 32, even if when the 4th flowrate control valve 31 described later and the 6th flowrate control valve 33, also can carry out work when it is manual operating valve by the manual operation of staff, or control its work when electrovalve by the electrical signal of controller.
In addition, in the present invention, the transferpump of whole operation can start (On)/cut out (Off) by the manual operation of staff, or controls its work by the electrical signal (pump control signal) of controller.
1 still-process of 1 step for regeneration is carried out in described No. 1 water distilling apparatus, namely, carry out the 1st removing step for removing the lower-boiling impurity such as moisture, IPA from stripping waste liquor, stripping waste liquor is heated to more than the boiling point of moisture in the distillation tower D-1 of No. 1 water distilling apparatus, the lower-boiling impurity such as moisture, IPA can be evaporated.
Namely, the purification condition of regulation is maintained while the lower-boiling impurity such as moisture, IPA is distilled to distillation tower top extracts in distillation tower D-1, the lower-boiling impurity etc. extracted condensation and be recovered to temporary reservoir pond 2 in condenser 1, then starts the 2nd transferpump 1-1 and is transported to collecting tank T-2 and discards.
Then, the photo-resist high boiling point stripping waste liquor eliminating lower-boiling impurity by 1 still-process (the 1st removing step) of 1 step for regeneration is transported to the distillation tower D-2 of No. 2 water distilling apparatus via reboiler (Reference numeral 3 in Fig. 2) by the startup of the 3rd transferpump 1-2.
Now, 6th flowrate control valve 33 becomes the pipeline the state of cutting out the pipeline of No. 4 water distilling apparatus sides that open No. 2 water distilling apparatus sides, makes the photo-resist high boiling point stripping waste liquor eliminating lower-boiling impurity can be transported to No. 2 water distilling apparatus by the 3rd transferpump 1-2.
Carry out comprising 2 still-process of 1 step for regeneration of the high boiling point residue (comprising a large amount of high boiling point stripping liquids) of high-boiling-point impurity for removing from the stripping waste liquor eliminating lower-boiling impurity in described No. 2 water distilling apparatus, i.e. the 2nd removing step, in the distillation tower D-2 of No. 2 water distilling apparatus, removing comprises the high boiling point residue of high-boiling-point impurity and carries out the substantial regeneration (that is, the recovery of high boiling point stripping liquid) of high boiling point stripping waste liquor.
Namely, in the distillation tower D-2 of No. 2 water distilling apparatus, be heated to the stripping waste liquor eliminating lower-boiling impurity to peel off the temperature of more than the boiling point of the highest composition of boiling point in solvent composition, make all stripping solvent composition things (high purity regenerated mixing stripping liquid) of formation stripping liquid be distilled to distillation tower D-2 top once and extract thus.
In addition, the all stripping solvent composition things extracted are sent to condenser (Reference numeral 4 in Fig. 2) and carry out condensation and separated, and being now dissolved in the high-boiling-point impurities such as the etch-resist resin in stripping waste liquor can concentrate and remain in (Reference numeral 6 in Fig. 2) at the bottom of tower and reboiler (Reference numeral 7 in Fig. 2).
In addition, the stripping solvent composition thing extracted from stripping waste liquor by distillation tower D-2 in 2 still-process (the 2nd removing step) can in condensation in condenser (Reference numeral 4 in Fig. 2), then be recycled to temporary reservoir pond 5, remove high boiling point residue like this and the high boiling point stripping liquid that is recycled to temporary reservoir pond 5 is transported to the distillation tower D-3 of No. 3 water distilling apparatus by transferpump (Reference numeral 2-1,2-2 in Fig. 2).
Then, 3 still-process of 1 step for regeneration from the high boiling point stripping liquid removing micro-moisture by 2 still-process regeneration are carried out in the distillation tower D-3 of No. 3 water distilling apparatus, i.e. the 3rd removing step, solvent is peeled off in the regeneration can being reclaimed high purity electronic-grade level by 3 still-process.
Like this, carry out by 1 still-process the 1st removing step removing lower-boiling impurity from stripping waste liquor raw material in 1 step for regeneration, then carry out removing from the stripping waste liquor eliminating lower-boiling impurity by 2 still-process to comprise the high boiling point residue of high-boiling-point impurity and extract the stripping solvent composition thing in waste liquid, purify and reclaim and be regenerated as the 2nd removing step of high boiling point stripping liquid, undertaken removing micro-moisture from the high boiling point stripping liquid regenerated as described above by 3 still-process and the 3rd removing step of solvent is peeled off in the regeneration of reclaiming high purity electronic-grade level, by described 1 time that carries out as continuous print operation, 2 times, the still-process of 3 times can regenerate, reclaim highly purified stripping liquid.
Be illustrated 1 time that carries out as series-operation, 2 times, 3 times still-process above, 1 time such step for regeneration does not have difference compared with existing patent 1 to 6 in operation, is therefore no longer described in detail.
On the other hand, the photo-resist high boiling point stripping waste liquor eliminating lower-boiling impurity by 1 still-process is sent to the distillation tower D-2 of No. 2 water distilling apparatus, then extract from stripping waste liquor in No. 2 water distilling apparatus and peel off solvent composition thing, and the high boiling points such as the HEP that part is not recovered in leaching process peel off solvent and high-boiling-point impurity is together stored in temporary reservoir pond (Reference numeral 13 of Fig. 2).
At this, as previously mentioned, high-boiling-point impurity comprises by non-protonic solvent (NMP, MMF) by product that thermolysis produces, and basic cpd and the etch-resist resin etc. such as the by product to be produced by the thermolysis of the HEP occurred in 1 step for regeneration, the high boiling point residue being stored in temporary reservoir pond 13 comprises the high boiling point stripping liquids such as high-boiling-point impurity so in a large number and the HEP that is not recovered, carrying out comprising 1 step for regeneration (as 1 time of series-operation, 2 times, 3 still-process) whole stripping waste liquor step for regeneration during, such high boiling point residue is transported to aforesaid high boiling point residue treatment unit by the startup of transferpump 34 and processes.
In the treatment process of the high boiling point residue of discharging from described No. 2 water distilling apparatus, first, the high boiling point residue comprising the high boiling point stripping liquids such as the high-boiling-point impurity such as basic by-product and etch-resist resin and HEP is transferred pump 34 and is transported to the neutralization reaction pond NT being attached to stirrer and fills.
Then, in the NT of neutralization reaction pond, under the state of stirrer work, the pH value of high boiling point residue regulated and maintain the scope of 6.5 ~ 8.5, carrying out the neutralization procedure of the solidification such as basic by-product, etch-resist resin making to exist in high boiling point residue.
Then, after the N-process carrying out the specified time, open 4th flowrate control valve 31 also starts transferpump 35,36, the high boiling point residue comprised in the neutralization reaction pond NT of cured article is transported to the distillation tower D-1 of No. 1 water distilling apparatus.
Now, high boiling point residue by by be arranged on from and reaction tank NT extend on the pipeline of the position residing for the 5th flowrate control valve 32 cured article removing device, namely, by filter F T, the high boiling point residue eliminating cured article by this filter F T is transported to the distillation tower D-1 of No. 1 water distilling apparatus.
In addition, now operation or control the 5th flowrate control valve 32 open the pipeline extended from the filter F T of high boiling point residue treatment unit, make it possible to the high boiling point residue by being eliminated cured article as described above by filter F T, the high boiling point residue namely processed by high boiling point residue treatment unit is transported to the distillation tower D-1 of No. 1 water distilling apparatus.
In described high boiling point residue treatment process, in the distillation tower D-1 of No. 1 water distilling apparatus, carry out dewatered still-process from high boiling point residue, the high boiling point residue eliminating moisture in No. 1 water distilling apparatus is transported to by starting transferpump 4-1 No. 4 water distilling apparatus carrying out 2 step for regeneration by the 6th flowrate control valve 33.
Now, operation or control the 6th flowrate control valve 33 and open the pipeline is connected with No. 4 water distilling apparatus, and the pipeline that closedown is connected with No. 2 water distilling apparatus.
The neutralization procedure undertaken by described neutralization reaction pond NT, the cured article removing step of being undertaken by cured article removing device FT and the moisture removing step of carrying out in No. 1 water distilling apparatus are described in detail above, have therefore omitted further instruction.
Be described as follows 2 step for regeneration reclaiming the high boiling point stripping liquids such as HEP from high boiling point residue further, this high boiling point residue have passed through the treating processes comprised in the high boiling point residue treatment unit of described neutralization reaction pond NT and cured article removing device FT and the distillation tower D-1 of No. 1 water distilling apparatus.
Substantially, 2 step for regeneration and existing patent 5 are compared with existing patent 6 does not have difference, in Fig. 2 that photo-resist high boiling point stripping waste liquor regenerating unit of the present invention is shown, perform the structure of No. 4 water distilling apparatus of 2 step for regeneration, the structure namely comprising No. 4 water distilling apparatus of distillation tower D-4 and existing patent 5 are compared with existing patent 6 does not have difference.
In FIG, identical Reference numeral has been marked for the integrant identical with existing patent 6 with existing patent 5 in each integrant of No. 4 water distilling apparatus.
Only, the difference of the present invention and existing patent 1 to 6 is, the operation object of 2 step for regeneration has been through the high boiling point residue of high boiling point residue treatment unit and No. 1 water distilling apparatus, namely, be in high boiling point residue treatment process, eliminate the impurity such as basic by-product and etch-resist resin to a certain extent after, in the moisture removal step of No. 1 water distilling apparatus, remove moisture and make moisture content be the high boiling point residue of the level of less than 0.1 % by weight.
The high boiling point residue eliminating moisture like this in the distillation tower D-1 of No. 1 water distilling apparatus is transported to No. 4 water distilling apparatus, then from high boiling point residue, reclaims the high boiling point stripping liquids such as HEP by the distillation tower D-4 of No. 4 times water distilling apparatus further.
Above embodiments of the invention are described in detail, but interest field of the present invention is not limited thereto, the various distortion that those skilled in the art utilize the key concept of the present invention defined in detail in the claims to carry out and mode of ameliorating also belong to interest field of the present invention.
Description of reference numerals
T-1: raw material supplying pond;
T-2, T-3: collecting tank;
T-4, T-5, T-6, T-7, T-8: solvent storage pond is peeled off in regeneration;
F-1,1-1,1-2,2-1,2-2,3-1,3-2,4-1,4-2,4-3,4-4,4-5: transferpump;
D-1, D-2, D-3, D-4, D-5: distillation tower;
1,4,8,9,14: condenser;
2,5,10,13,15: temporary reservoir pond;
3,7,11,16: reboiler;
6,17: at the bottom of tower;
12: micro-strainer;
18: viscometer;
18A: controller;
19,20: flowrate control valve;
21,22,23,24,25: drawdown pump;
31: the 4 flowrate control valves;
32: the 5 flowrate control valves;
33: the 6 flowrate control valves;
34,35,36: transferpump;
NT: neutralization reaction pond;
FT: cured article removing device (strainer).
Claims (10)
1. one kind improves the photo-resist high boiling point stripping waste liquor regeneration method of regeneration yield, 1 step for regeneration of solvent is peeled off as regenerating from photo-resist high boiling point stripping waste liquor and reclaiming high boiling point, comprise: 1 still-process, from photo-resist high boiling point stripping waste liquor, remove lower-boiling impurity; 2 still-process, are separated the high boiling point residue comprising high-boiling-point impurity from the photo-resist high boiling point stripping waste liquor eliminating described lower-boiling impurity, and reclaim the high boiling point stripping solvent being separated described high boiling point residue; And 3 still-process, peel off solvent from the described high boiling point reclaimed and remove micro-moisture, described in improve the photo-resist high boiling point stripping waste liquor regeneration method of regeneration yield feature be, also comprise:
N-process, in the high boiling point residue comprising described high-boiling-point impurity being carried out in neutralization reaction pond and, make the high-boiling-point impurity solidification comprising basic by-product in the described high boiling point residue that generates in 1 step for regeneration, wherein, this high boiling point residue is separated from the photo-resist high boiling point stripping waste liquor eliminating described lower-boiling impurity in described 1 step for regeneration and discharges;
Cured article removing process, cured article removing device in remove from and reaction tank conveying high boiling point residue in cured article;
Moisture removing process, heats the high boiling point residue eliminating described cured article and removes moisture in water distilling apparatus; And
4 still-process, heat the high boiling point residue eliminating moisture by described moisture removing process and reclaim high boiling point stripping solvent further.
2. the photo-resist high boiling point stripping waste liquor regeneration method that improve regeneration yield according to claim 1, is characterized in that,
In described N-process, start the stirrer being attached to neutralization reaction pond stir high boiling point residue.
3. the photo-resist high boiling point stripping waste liquor regeneration method that improve regeneration yield according to claim 1, is characterized in that,
The pH value of the high boiling point residue in neutralization reaction pond is maintained the scope of 6.5 ~ 8.5 in described N-process.
4., according to claim 1 or the photo-resist high boiling point stripping waste liquor regeneration method that improve regeneration yield according to claim 3, it is characterized in that,
In described N-process, the basic by-product making high boiling point residue comprise in neutralization reaction pond solidifies and separates out, the precipitate solidified in N-process plays the effect of condensation nucleus, makes the high-boiling-point impurity comprising the etch-resist resin of simmer down to paste in high boiling point residue carry out chain solidification.
5. the photo-resist high boiling point stripping waste liquor regeneration method that improve regeneration yield according to claim 1, is characterized in that,
The high boiling point residue that have passed through cured article removing device is transported to No. 1 water distilling apparatus carrying out described 1 still-process, thus in No. 1 water distilling apparatus, carries out described moisture removing process.
6. the photo-resist high boiling point stripping waste liquor regeneration method that improve regeneration yield according to claim 5, is characterized in that,
Peeling off after 1 step for regeneration of solvent terminates for regenerating from photo-resist high boiling point stripping waste liquor and reclaiming high boiling point, by from and the reaction tank high boiling point residue that have passed through cured article removing device be transported to described No. 1 water distilling apparatus and carry out described moisture removing process.
7., according to claim 1 or the photo-resist high boiling point stripping waste liquor regeneration method that improve regeneration yield according to claim 5, it is characterized in that,
To the high boiling point residue removing moisture being eliminated cured article by cured article removing device in described moisture removing process, moisture content is made to become less than 0.1 % by weight.
8. the photo-resist high boiling point stripping waste liquor regeneration method that improve regeneration yield according to claim 5, is characterized in that,
Described No. 1 water distilling apparatus comprises:
Distillation tower, holds the high boiling point residue from described cured article removing unit feeding;
Reboiler, is connected at the bottom of the tower of distillation tower, for heating the high boiling point residue be transported in described distillation tower, moisture is evaporated;
Condenser, is connected to the upper end of distillation tower, for making the condensate moisture of distillation;
Temporary reservoir pond, is connected with described condenser, carries out temporary reservoir to the moisture of condensation within the condenser; And
Drawdown pump, is connected to the upper end in temporary reservoir pond, and the decompression carrying out the pressure reduced in distillation tower when the high boiling point residue made it possible in described distillation tower is heated operates,
Start described drawdown pump, implement the decompression running of the pressure reduced in distillation tower, and be below 110torr when carrying out underpressure distillation operation by the pressure setting in distillation tower, the temperature in reboiler is set as less than 110 DEG C.
9. the photo-resist high boiling point stripping waste liquor regeneration method that improve regeneration yield according to claim 1, is characterized in that,
Carry out regenerating from described photo-resist high boiling point stripping waste liquor and reclaim high boiling point peel off solvent 1 step for regeneration during, by separated in 2 still-process and discharge the high boiling point residue comprising described high-boiling-point impurity be transported to neutralization reaction pond, then carry out N-process.
10. the photo-resist high boiling point stripping waste liquor regeneration method that improve regeneration yield according to claim 1, is characterized in that,
Described cured article removing device is solid-liquid separation strainer, described solid-liquid separation strainer to from and the high boiling point residue of reaction tank conveying filter and remove cured article.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020150024043A KR101547195B1 (en) | 2015-02-17 | 2015-02-17 | Recycling process of waste high boiling point photoresist stripper with improved recycle yield rate |
| KR10-2015-0024043 | 2015-02-17 |
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| CN105217865A true CN105217865A (en) | 2016-01-06 |
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| CN201510638926.8A Pending CN105217865A (en) | 2015-02-17 | 2015-09-30 | Improve the photo-resist high boiling point stripping waste liquor regeneration method of regeneration yield |
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| KR (1) | KR101547195B1 (en) |
| CN (1) | CN105217865A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108840495A (en) * | 2018-05-13 | 2018-11-20 | 四川久远化工技术有限公司 | A kind of stripping waste liquor method of purification |
| CN109432874A (en) * | 2018-12-29 | 2019-03-08 | 上海亿鼎电子系统集成有限公司 | A kind of the purification recyclable device and its methods and applications of organic solvent |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109550273A (en) * | 2018-12-28 | 2019-04-02 | 上海亿鼎电子系统集成有限公司 | A kind of purifying plant and method of organic solvent |
| KR102527187B1 (en) * | 2023-02-28 | 2023-04-27 | 한만길 | Waste organic solvent recycling system |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5249305B2 (en) * | 2010-10-29 | 2013-07-31 | 水ｉｎｇ株式会社 | Electronic component factory waste liquid treatment method and apparatus therefor |
| KR101330653B1 (en) | 2013-02-25 | 2013-11-19 | 주식회사 코렉스 | Recycling process of waste high boiling point photoresist stripper |
| KR101330654B1 (en) * | 2013-03-06 | 2013-11-19 | 주식회사 코렉스 | Recycling system of waste high boiling point photoresist stripper |
| KR101354523B1 (en) | 2013-11-27 | 2014-01-21 | 주식회사 코렉스 | Recycling apparatus for recycling 1-piperazineethanol from waste high boiling point photoresist stripper |
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2015
- 2015-02-17 KR KR1020150024043A patent/KR101547195B1/en active IP Right Grant
- 2015-09-30 CN CN201510638926.8A patent/CN105217865A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108840495A (en) * | 2018-05-13 | 2018-11-20 | 四川久远化工技术有限公司 | A kind of stripping waste liquor method of purification |
| CN108840495B (en) * | 2018-05-13 | 2020-12-22 | 四川久远化工技术有限公司 | Method for purifying stripping waste liquid |
| CN109432874A (en) * | 2018-12-29 | 2019-03-08 | 上海亿鼎电子系统集成有限公司 | A kind of the purification recyclable device and its methods and applications of organic solvent |
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| KR101547195B1 (en) | 2015-08-25 |
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