CN101239710A - Method and apparatus for obtaining purified phosphoric acid from phosphoric acid aqueous solution containing plural metal ions - Google Patents
Method and apparatus for obtaining purified phosphoric acid from phosphoric acid aqueous solution containing plural metal ions Download PDFInfo
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Abstract
Method and apparatus for obtaining purified phosphoric acid from phosphoric acid aqueous solution containing plural metal ions A method for obtaining purified phosphoric acid from a phosphoric acid aqueous solution containing a plurality of metal ions includes: [1] crystallizing and coprecipitating that separate out an inorganic salt crystal from a phosphoric acid aqueous solution containing a plurality of metal ions and coprecipitate metal ions including: (a) mixing a phosphoric acid aqueous solution containing a plurality of metal ions with an inorganic salt aqueous solution; (b) separating out an inorganic salt crystal and coprecipitating simultaneously the metal ions by further mixing an organic poor solvent which is soluble in phosphoric acid and does not dissolve an inorganic salt with the above resultant mixture; and (c) solid-liquid separating by filtering the inorganic salt crystal containing the metal ions; and [2] evaporating that obtains purified phosphoric acid by evaporating an organic poor solvent and water in a filtrate obtained by the filtration, wherein the amount of metal ions dissolved in the phosphoric acid / organic poor solvent mixture in the separating is less than the amount of metal ions in the phosphoric acid solution used in the mixing.
Description
Technical field
The mixed aqueous solution of employed nitric acid-acetate-phosphoric acid in the metal etch operation etc. (below, be called the nitration mixture aqueous solution), with the service limits in the etching (usually, benchmark is counted about 500～1000ppm by weight) above concentration is discharged from as the waste liquid that contains multiple metal ion, the present invention relates to from such nitration mixture aqueous solution that contains multiple metal ion (hereinafter referred to as nitration mixture aqueous solution waste liquid) etc., remove metal ion, obtain the method and apparatus of purification of phosphoric acid.The method and apparatus that particularly relates to the processing that is suitable for phosphate aqueous solution, described phosphate aqueous solution be adopt fusion-crystallization method and solvent-extraction process etc. to carry out handling for 1 time and the residual phosphate aqueous solution that obtains (now, processing directly goes out of use to these phosphate aqueous solution former states), be the phosphate aqueous solution that contains metal ion with high density (benchmark is counted 500ppm～be dissolved in as the metal ion concentration of the upper limit in the phosphate aqueous solution by weight).
Background technology
In the metal etch operation of Al in semiconductor fabrication factory, liquid-crystal display are made etc., as the new liquid of the nitration mixture aqueous solution, for example can use the mixture of phosphoric acid, nitric acid, acetate, water, but total concentration of metal ions that it contained is below the 100ppb.Yet, this nitration mixture aqueous solution, along with the dissolving of metal is carried out in use, concentration of metal ions rises, simultaneously because the evaporation of volatile matter (nitric acid, acetate, water), to adhering to of etched material etc., composition changes, etch capabilities reduces, and therefore part or all and new liquid is exchanged in the past, suppresses total concentration of metal ions (benchmark count 500～be no more than about 1000ppm) by weight low, suppress the variation of composition simultaneously, keep etch capabilities.Yet in the past, the nitration mixture aqueous solution waste liquid that contains multiple metal ion of discharging in the metal etch operation was followed the rising of concentration of metal ions, and etch capabilities reduces, and therefore carried out waste treatment.Therefore, seek from the nitration mixture aqueous solution waste liquid of being discharged, to remove metal ion, reclaim the treatment unit of the nitration mixture aqueous solution simultaneously with high yield.
The nitration mixture aqueous solution waste liquid of discharging from Al metal etch device is carried out the initial stage of purified, is to adopt evaporation or distillation method to make volatile matter (major part of nitric acid, acetate, water) thereby evaporate to separate.Because phosphoric acid and metal ion all are non-volatile substances, can not separate when therefore adopting this evaporation or distillation.The phosphoric acid in this stage (below, be called concentrated phosphoric acid), its concentration is about 90 quality %, contains the water of the 10 quality % that have an appointment.
As the metal ion that exists in solution being carried out isolating general method, the absorption method that has ion-exchange-resin process, diffusive dialysis method, barrier film electroosmose process, electroosmose process, use gac to carry out.Yet, even these methods are used for nitration mixture aqueous solution waste liquid or concentrated phosphoric acid because high concentrations of phosphoric acid corrodibility is strong, as metal ion contain negatively charged ion, positively charged ion these two, and problem described as follows takes place, therefore separating metal ion fully.
Ion-exchange-resin process is difficult to the metal ion that is dissolved in the high concentrated acid is carried out ion-exchange.Know that also regeneration of resin efficient is low.In diffusive dialysis method, resulting phosphoric acid is diluted, and a large amount of dialysis raffinates also takes place.In the barrier film electroosmose process, the NO that nitric acid oxidation caused in the nitration mixture aqueous solution waste liquid
xBecome problem.In electroosmose process, because the ionic radius of phosphate anion and molybdenum acid ion is approximate, translational speed is equal, therefore can not separate.In the absorption method that the use gac carries out, nitration mixture aqueous solution waste liquid is painted because of gac.
On the other hand, as one of process for purification of concentrated phosphoric acid, METAL EXTRACTION agent method (patent documentation 1) is arranged.But the reduction of Al does not comply with one's wishes though Mo reduces.In addition, if be dissolved with metal (positively charged ion (Al in the concentrated phosphoric acid
3+Deng) and negatively charged ion (MoO
4 2-Deng), the ion of form that metal is oxidized), then need this device that 2 kinds of positively charged ions are used and negatively charged ion is used of extraction column and anti-extraction column for the ion that reduces by two sides, not only need huge cost of equipment, and can be contemplated to the rising of running funds, be difficult to give full play to the advantage of utilizing phosphoric acid again.
As the process for purification of other concentrated phosphoric acid liquid, show partial crystallization (crystallization is separated out) method (patent documentation 2～3), but all are batch process methods, need delicate temperature control, there are problems such as treatment time length.
In addition, usually know the technology (non-patent literature 1) of continuous crystallization as the process for purification crowd.Yet, this method is used for the occasion of concentrated phosphoric acid, because the refining purity of phosphoric acid semihydrate crystal depends on the mother liquor metal concentration, so the limit of its yield is about about 80 quality %, considers to wish further to improve yield from the viewpoint of utilization of resources.
On the other hand, co-precipitation related to the present invention is recorded in 74 pages of non-patent literature 2 as following.
" so-called co-precipitation, when being meant certain precipitate, the material of solubility accompanies and sedimentary phenomenon with it.Coprecipitation phenomena causes because of the generation of mixed crystal sometimes, also causes because of being adsorbed at sedimentary generative process intermediate ion sometimes.In fact the former occasion impurity enter in the sedimentary lattice.The latter's occasion is the phenomenon of ion precipitated thing traction in the process of condensation of being adsorbed ".
Yet non-patent literature 2 just is illustrated general coprecipitation phenomena, to the co-precipitation not record fully of the metal ion in the concentrated phosphoric acid as the present invention.
Patent documentation 1: Japanese patent application 2005-142444 number
Patent documentation 2: Japanese patent application 2004-255388 number
Patent documentation 3: No. 3382561 communique of Japanese Patent
Non-patent literature 1: " augmenting partial crystallization " the 73rd～82 page, augment clear and on December 25th, 58, the distribution of (strain) chemical industry society
Non-patent literature 2: the 74th page of " quantitative analysis of chemical " (the 17th printing of revised edition), R.A.Di, Jr.A.L.Under wood original work,, the shop distribution of (strain) training wind in 1992
Summary of the invention
Therefore, the present invention who under described background, proposes, its purpose is to provide to separate from the phosphate aqueous solution that contains multiple metal ion removes metal ion, obtain the method and apparatus of purification of phosphoric acid, and then its purpose is, the nitration mixture aqueous solution waste liquid that contains high concentrations of phosphoric acid by being applied to discharge in the metal etch operation is provided, utilizes the system of the purification of phosphoric acid that is reclaimed again.
Above-mentioned problem can be by following 1)～8) invention solve.
1) a kind of method that obtains purification of phosphoric acid is characterized in that, comprises (1) partial crystallization and co-precipitation operation and (2) evaporization process,
Described (1) partial crystallization and co-precipitation operation are that the crystallization of inorganic salt is separated out from the phosphate aqueous solution that contains multiple metal ion, make the partial crystallization and the co-precipitation operation of metal ion co-precipitation, comprising:
(a) operation of the mixed inorganic aqueous solution in the phosphate aqueous solution that contains multiple metal ion,
(b) dissolve in organic poor solvent of phosphoric acid and non-dissolve inorganic salts by further mixing, when the crystallization that makes inorganic salt is separated out, make the operation of above-mentioned metal ion co-precipitation,
(c) filtration contains the crystallization of the inorganic salt of above-mentioned metal ion, carries out the operation of solid-liquid separation;
Described (2) evaporization process is by making the evaporation of organic poor solvent in the filtrate that above-mentioned filtration obtains and water, obtain the evaporization process of purification of phosphoric acid,
And, in above-mentioned (1) operation (b), be dissolved in the amount of metal ion in above-mentioned phosphoric acid-organic poor solvent mixed solution, lack than the amount of metal ion in the phosphate aqueous solution that (a) uses in the operation in above-mentioned (1).
2) as 1) method of described acquisition purification of phosphoric acid, it is characterized in that, by to adopting 1) purification of phosphoric acid that obtains of described method further repeatedly repeats the operation of above-mentioned (1) and (2), obtains the purification of phosphoric acid of greater concn.
3) as 1) or 2) method of described acquisition purification of phosphoric acid, it is characterized in that the above-mentioned phosphate aqueous solution that contains multiple metal ion contains by weight benchmark and counts 500ppm to the metal ion that is dissolved in the concentration of the upper limit in this phosphate aqueous solution as metal ion.
4) as 1)～3) the method for each described acquisition purification of phosphoric acid, it is characterized in that, the inorganic salt crystallization that contains metal ion that obtains in the operation that water is dissolved in above-mentioned (1), then, the inorganic salt crystallization is separated out, from inorganic salt, separate the metal of co-precipitation by cooling, filter then, reclaim inorganic salt, and prepare inorganic salt solution, 1 by the inorganic salt that reclaim) described (1) (a) utilize in the operation again.
5) a kind ofly be used to implement 1)～3) the device of each described method, it is characterized in that having at least: dissolve inorganic salts, the inorganic salt dissolving tank of preparation inorganic salt solution; Be used for to contain phosphate aqueous solution and the organic poor solvent and the mixing of this inorganic salt solution of multiple metal ion, the crystallization of inorganic salt is separated out, make the partial crystallization with stirrer and the co-precipitation groove of metal ion co-precipitation simultaneously; The crystallization of the inorganic salt of resulting metal ion is filtered, thereby carry out the filtration unit of solid-liquid separation; Be used for organic solvent evaporation device that organic poor solvent and water are evaporated from filtrate with heater means.
6) as 5) described device, it is characterized in that, further have: adopt the crystallization of the inorganic salt of the metal ion that above-mentioned filtration unit filters out with warm water dissolving, separate out the refining partial crystallization groove of crystalline inorganic salt of inorganic salt once again and isolating filtration unit is carried out in the inorganic salt crystallization of separating out in the refining partial crystallization groove of above-mentioned inorganic salt by cooling then.
7) a kind of etching solution utilize method again, it is characterized in that, comprising:
The recovery process that the used nitration mixture aqueous solution waste liquid that contains multiple metal ion that produces in the metal etch operation to the nitration mixture aqueous solution that comprises phosphoric acid, nitric acid, acetate and water in use reclaims;
Evaporate from above-mentioned nitration mixture aqueous solution waste liquid by the major part that makes nitric acid, acetate and water, fractionation becomes the distillate that contains nitric acid, acetate and water and contains phosphoric acid and the evaporization process of the concentrated phosphoric acid of multiple metal ion;
By using above-mentioned 5) or above-mentioned 6) described device carries out co-precipitation with the metal ion in the above-mentioned concentrated phosphoric acid and separate, and obtains the refining step of purification of phosphoric acid;
Adjust strength of fluid by in resulting purification of phosphoric acid, adding above-mentioned distillate, then it is adjusted operation as the concentration that the recirculation nitration mixture aqueous solution is used for the metal etch operation once again.
8) as 7) described etching solution utilize method again, it is characterized in that, further comprise and separate out operation, promptly, make the concentrated phosphoric acid that in above-mentioned evaporization process, obtains in fusion partial crystallization device, separate out the phosphoric acid semihydrate crystal, then the phosphoric acid semihydrate crystal is carried out solid-liquid separation, then resulting phosphoric acid semihydrate crystal is transferred to above-mentioned concentration and adjusts in the operation with filtration unit, and the filtrate that metal ion has been concentrated is transferred to above-mentioned 5) or above-mentioned 6) in described partial crystallization and the co-precipitation groove.
The invention effect
According to the present invention, can provide and from the phosphate aqueous solution that contains multiple metal ion, remove metal ion easily, obtain the method and apparatus of purification of phosphoric acid, and then the nitration mixture aqueous solution waste liquid that contains high concentrations of phosphoric acid by being applied to discharge in the metal etch operation can be provided, utilize the system of the purification of phosphoric acid that is reclaimed again.
In addition, be assembled in by device on the streamline of metal etch device acquisition purification of phosphoric acid of the present invention, below the concentration of metal ions of the water-soluble liquid bath of nitration mixture always can being remained on necessarily, can when etching work procedure is stable, reduce the increment (below 10 former quality %) of the new liquid of the nitration mixture aqueous solution significantly.
Description of drawings
Fig. 1 is the figure of the device summary of expression metal etch operation.
Fig. 2 is the figure of expression as the summary of the evaporation unit of a nitration mixture aqueous solution refining plant part.
Fig. 3 is the figure of the summary of explanation one routine metal etch liquid recirculation system.
Fig. 4 is the figure of the material budget of each the basic square among the expression embodiment 3.
Fig. 5 is the figure of the summary of another routine metal etch liquid recirculation system of explanation.
Fig. 6 is the figure of the material budget of each the basic square among the expression embodiment 5.
Fig. 7 is the figure of the mechanism of expression co-precipitation of the present invention.
Embodiment
Below, the invention described above is at length described.
What present inventors studied with great concentration found that: by utilizing effective especially partial crystallization of phosphate aqueous solution and the coprecipitation phenomena to the metal ion that contains high density (benchmark is counted 500ppm to the concentration that is dissolved in the upper limit in the phosphate aqueous solution as metal ion by weight), separate the method and apparatus of removing metal ion, obtaining purification of phosphoric acid; Also find: be applied to the concentrated phosphoric acid that contains multiple metal ion in the metal etch operation, can reclaim phosphoric acid with high-level efficiency and utilize again.Moreover said purification of phosphoric acid among the present invention is to separate the phosphoric acid of having removed metal ion, and concentration of phosphoric acid is about 90 quality %.
Method of the present invention comprises following principle.The major part of heating up in a steamer nitric acid, acetate and water in the nitration mixture aqueous solution waste liquid that contains multiple metal ion after using etching obtains concentrated phosphoric acid, adds inorganic salt in resulting concentrated phosphoric acid.This moment since inorganic salt generally have and easily be dissolved in water, and the difficult character that is dissolved in organic solvent and the dense thick phosphoric acid, so the part of inorganic salt is dissolved in a spot of water in the concentrated phosphoric acid, but the inorganic salt of other surplus do not dissolve.When wherein adding organic poor solvent, be dissolved in the inorganic salt partial crystallization in the concentrated phosphoric acid, in addition, be accompanied by the partial crystallization of these inorganic salt, the metal ion that is dissolved in the concentrated phosphoric acid precipitates.The said co-precipitation of the present invention that Here it is.Then, by filtering the suspension that partial crystallization and co-precipitation obtain takes place, solid-liquid separation becomes by the crystallization of inorganic salt and is dissolved in solids component and the organic poor solvent-phosphate aqueous solution that the metal ion in the concentrated phosphoric acid constitutes.And then by resulting filtrate is distilled, organic poor solvent of fractionation and phosphate aqueous solution obtain purification of phosphoric acid.Fig. 7 is the figure of expression co-precipitation mechanism of the present invention.
Among the present invention, the nitration mixture aqueous solution waste liquid that contains multiple metal ion after will using in etching concentrates, in resulting concentrated phosphoric acid, add inorganic salt, but when the phosphate aqueous solution in this pretreatment procedure concentrated insufficient, moisture content in the concentrated phosphoric acid increases, after adding inorganic salt solution, even add organic poor solvent, in the moisture in concentrated phosphoric acid contained inorganic salt also difficulty separate out, owing to inorganic salt are not sometimes separated out and be left behind, so the refining degree variation of phosphoric acid.Therefore, wish that the phosphate aqueous solution that contains multiple metal ion that becomes process object is concentrated to the above concentration of about 90 quality %.Become phosphoric acid concentration in the phosphate aqueous solution of process object when lower than about 90 quality %, the ratio of moisture increases, and therefore the inorganic salt that are dissolved in this moisture remain in the filtrate morely, are difficult to obtain effect of the present invention.
In addition, among the present invention, in above-mentioned co-precipitation operation, be dissolved in phosphoric acid-organic poor solvent mixed solution amount of metal ion than the phosphate aqueous solution before the above-mentioned mixed processes (promptly, concentrated phosphoric acid) contained amount of metal ion for a long time in, do not have refining effect in fact, can not obtain the high purification of phosphoric acid of purity.Therefore, importantly: after adding inorganic salt solution, when making the metal ion that is dissolved in the concentrated phosphoric acid,, inorganic salt are not remained in the phosphate aqueous solution with the complete partial crystallization of inorganic salt with the inorganic salt co-precipitation of partial crystallization.
In addition, remove the concentration of object metal ion when low, in the filtrate after partial crystallization and co-precipitation, solid-liquid separation among the contained positively charged ion, the shared ratio of positively charged ion that constitutes inorganic salt increases, owing to exchange nothing but the metal ion that will want to remove and the positively charged ion of inorganic salt, therefore be difficult to obtain effect of the present invention.Therefore, containing the concentration of metal ions of the phosphate aqueous solution of multiple metal ion must be than the solubleness height of the inorganic salt in the phosphoric acid-organic poor solvent mixed solution that adds behind organic poor solvent.Specifically, become in the phosphate aqueous solution of process object concentration of metal ions by weight the benchmark meter be preferably concentration above about 500ppm.
As the embodiments of the present invention example, with reference to accompanying drawing on one side the method and apparatus of handling the nitration mixture aqueous solution waste liquid that contain multiple metal ion of in metal etch operation discharging described on one side.
Fig. 1 is the figure of the device summary of expression metal etch operation, comprise have an etching liquid receiver carry out etched part, the water-soluble liquid bath of nitration mixture, nitration mixture aqueous solution waste liquid tank, nitration mixture aqueous solution refining plant of the present invention, and pipe arrangement that their are connected etc.The flow process of operation is as follows.
At first, the new liquid of the nitration mixture aqueous solution is supplied in the water-soluble liquid bath of nitration mixture, then, draw the nitration mixture aqueous solution, etched material is carried out etching while spray quinoline from the water-soluble liquid bath of nitration mixture.
The etched nitration mixture aqueous solution of being through with turns back in the water-soluble liquid bath of nitration mixture through the liquid of etching liquid receiver after as etching.
When supplying to the new liquid of the nitration mixture aqueous solution in the water-soluble liquid bath of nitration mixture, transfer to the nitration mixture aqueous solution waste liquid tank as nitration mixture aqueous solution waste liquid from the nitration mixture aqueous solution that the water-soluble liquid bath of nitration mixture overflows.
The nitration mixture aqueous solution waste liquid that is collected in the nitration mixture aqueous solution waste liquid tank is supplied in the nitration mixture aqueous solution refining plant, by partial crystallization and coprecipitation method the metal ion that is dissolved in the nitration mixture aqueous solution when the etching is carried out separation and purification, the nitration mixture aqueous solution that has recycled makes it to turn back in the water-soluble liquid bath of nitration mixture.A part is discharged as waste liquid.
Fig. 2 is the synoptic diagram of expression as the evaporation unit of a nitration mixture aqueous solution refining plant part.Evaporation unit can be the general evaporation device, but because the viscosity height of phosphoric acid, so preferred film downward flow type evaporation unit.The operation and the function of device are as follows.
At first, will supply to the liquid receiver by reboiler by the nitration mixture aqueous solution waste liquid that the nitration mixture aqueous solution waste liquid tank of Fig. 1 is supplied with.
Then, make and remain on 2000～7000Pa in the system, the liquid temperature is remained on about 60 ℃～90 ℃, utilize pump that nitration mixture aqueous solution waste liquid is circulated between liquid receiver and reboiler on one side, water flowing steam heats nitration mixture aqueous solution waste liquid in reboiler on one side, thereby nitric acid, acetate, water evaporation are heated up in a steamer.
The condensation in the condenser of circulation water coolant of the nitric acid that heats up in a steamer, acetate and water, be stored in the distillate receiver after, utilize again as the raw material of etchant concentration adjustment.
The concentrated phosphoric acid that has heated up in a steamer nitric acid, acetate and water is to partial crystallization and co-precipitation operation or the transfer of fusion partial crystallization operation.
Fig. 3 is the figure of the summary of the explanation example that the device of acquisition purification of phosphoric acid of the present invention is assembled in the metal etch liquid recirculation system on the streamline of metal etch device.
Etching system and evaporation unit be respectively with at Fig. 1, identical device illustrated in fig. 2.Unless otherwise specified, service temperature and pressure are normal temperature, normal pressure.
As mentioned above, will transfer to the evaporation unit, be separated into concentrated phosphoric acid and distillate (nitric acid, acetate and water) from the nitration mixture aqueous solution waste liquid that etching system is discharged.
Distillate is transferred in the etchant concentration setting device and is utilized.
Concentrated phosphoric acid is transferred in partial crystallization and the co-precipitation groove, mixes with the inorganic salt solution that is pre-mixed in the inorganic salt dissolving tank.As inorganic salt, can enumerate phosphoric acid salt such as SODIUM PHOSPHATE, MONOBASIC, potassium primary phosphate, primary ammonium phosphate, trimagnesium phosphate, or vitriol such as sodium sulfate, ammonium sulfate, acetates such as sodium acetate, ammonium acetate etc., preferably phosphate, vitriol.
Just add organic poor solvent if mixed fully, the crystallization of inorganic salt is separated out, make the metal co-precipitation in the concentrated phosphoric acid simultaneously.The amount of organic poor solvent, by measure than meter, for phosphoric acid 2～10 times are preferably about 3～5 times.As organic poor solvent, must use the solvent of a dissolving such as alcohols, ketone less than the inorganic salt about 0.1 quality %.Can enumerate Virahol (below, be called IPA), isopropylcarbinol, acetone, mibk etc. as concrete example.
If partial crystallization and co-precipitation are finished, just slurries are shifted to filtration unit and carry out solid-liquid separation.Preferred pressure filter of filtration unit or suction type strainer.
Moreover the kind of inorganic salt and organic poor solvent and addition thereof are suitably determined to get final product according to the concentration of metal ions in the concentrated phosphoric acid.
Shift to the organic solvent evaporation device from the filtrate (mixture of phosphoric acid, organic poor solvent, water) that filtration unit passes through, heat up in a steamer organic poor solvent and water.Organic poor solvent in the dehydration of organic solvent device, dewater refining after, in partial crystallization and co-precipitation groove, utilize again.
Heated up in a steamer the purification of phosphoric acid of organic poor solvent, in the etchant concentration setting device, mix with the distillate of above-mentioned evaporation unit, additional not enough composition makes and reaches and the new liquid phase of nitration mixture aqueous solution degree together, as the recycle in etching system of the recirculation nitration mixture aqueous solution.
Method and apparatus of the present invention is well suited for: adopt fusion crystallization and solvent-extraction process etc. the phosphate aqueous solution of the metal ion that contains low concentration (benchmark is counted less than 500ppm by weight) to be carried out the processing of the phosphate aqueous solution of the metal ion that contains high density (benchmark is counted 500ppm to the upper limit that is dissolved in phosphate aqueous solution as metal ion by weight) that goes out of use after the primary treatment.
Filtration unit residue (inorganic salt that contain the co-precipitation metal) is supplied with water (not diagram) and is dissolved, and shifts in the refining partial crystallization groove of inorganic salt.The amount of water is about 1.5 times of level of residue.
After inorganic salt are made with extra care in the partial crystallization groove, are heated up in a steamer a certain amount of water, with the groove internal cooling, make the inorganic salt partial crystallization, keep after about 0.5～1 hour, shift to centrifugal filter device, be separated into refining inorganic salt and waste water.
Refining inorganic salt utilize in the inorganic salt dissolving tank again.
The crystallization of the inorganic salt in above-mentioned partial crystallization and the co-precipitation groove, interpolation by organic poor solvent, partial changes in solubility according to the place of being added takes place, so crystal form is coarse and micropore arranged, metal ion generation co-precipitation under by the state that should coarse tissue adsorbs.; in the refining partial crystallization groove of inorganic salt, reach cooling tank integral body and remain on uniform state by concentrating of liquid; therefore the crystallization that produces is firm and fine and close; by using centrifugal filter device (more than the G=1500) refining, can obtain the not crystallization of metal ion attached to the mother liquor on the crystal surface.
Fig. 5 is the figure that explanation is assembled in the device of acquisition purification of phosphoric acid of the present invention another routine summary of metal etch liquid recirculation system on the streamline of metal etch device.
System more different represented with Fig. 3 is to be provided with fusion partial crystallization device before partial crystallization and co-precipitation groove, and the situation of other and Fig. 3 is roughly the same.
To in evaporation unit, transfer in the fusion partial crystallization device by isolating concentrated phosphoric acid, be cooled to about 10 ℃, the phosphoric acid semihydrate crystal is separated out after, in filtration unit (not diagram), carry out solid-liquid separation.
Transfer in the etchant concentration setting device after the isolated phosphoric acid semihydrate crystal heat fused, behind the additional not enough composition, in the metal etch operation, utilize again.
The filtrate that has concentrated metal ion is transferred in partial crystallization and the co-precipitation groove, below similarly handles with the situation of Fig. 3.
But, the concentration of having heated up in a steamer metal ion contained in the purification of phosphoric acid of organic poor solvent at evaporation unit with an organic solvent is the occasion of the level that can not fully satisfy, and can turn back in the fusion partial crystallization device (path of representing with the dotted line among Fig. 5) and handle.
Moreover, Fig. 5 shows the example that fusion partial crystallization device was set before partial crystallization and co-precipitation groove, but because the amount of metal from the phosphoric acid semihydrate crystal that fusion partial crystallization device is discharged depends on the mother liquor metal concentration, therefore the high occasion of concentration of metal ions of concentrated phosphoric acid also can be changed the order of fusion partial crystallization device and partial crystallization and co-precipitation groove.
Embodiment
Below enumerate embodiment and be described more specifically the present invention, but the present invention is not limited by these embodiment.
Use recirculation system shown in Figure 3 to carry out the processing of the nitration mixture aqueous solution waste liquid of Al etching work procedure.Moreover the unit of component is " kg ", and " N.D. " expression detects below the lower limit.
The nitration mixture aqueous solution waste liquid (about 100kg) of discharging from etching work procedure composed as follows.Because the metal ion beyond Al and the Mo is a minute quantity, therefore ignore.
Table 1
| Phosphoric acid | Nitric acid | Acetate | Water | Al | Mo |
| 65 | 10 | 3.5 | 21.5 | 0.030 | 0.045 |
In addition, composed as follows from the distillate (about 27.8kg) of evaporation unit.
Table 2
| Phosphoric acid | Nitric acid | Acetate | Water | Al | Mo |
| N.D. | 10 | 3.5 | 14.3 | N.D. | N.D. |
In addition, the concentrated phosphoric acid that passes through from evaporation unit (about 72.2kg) is composed as follows.
Table 3
| Phosphoric acid | Nitric acid | Acetate | Water | Al | Mo |
| 65 | N.D. | N.D. | 7.2 | 0.030 | 0.045 |
Then, SODIUM PHOSPHATE, MONOBASIC 7.4kg is dissolved in the water of 10kg, is added in partial crystallization and the co-precipitation groove, mix fully with concentrated phosphoric acid.After fully stirring, add the anhydrous IPA of 260kg while stir.Composed as follows at the treatment solution (about 349.6kg) in this stage.
Moreover Na is the composition that derives from inorganic salt, is contained in the inorganics, to the metal ion explanation, has put down in writing composition for convenience.For filtrate described later, residue, purification of phosphoric acid too.
Table 4
| Phosphoric acid | Water | Inorganics | IPA | Al | Mo | (Na) |
| 65 | 17.2 | 7.4 | 260 | 0.030 | 0.045 | 1.43 |
In addition, the filtrate of passing through from filtration unit (about 338.7kg) is composed as follows.
Table 5
| Phosphoric acid | Water | Inorganics | IPA | Al | Mo | (Na) |
| 64 | 16.7 | 0.04 | 258 | 0.003 | 0.016 | 0.008 |
In addition, the residue of filtration unit (about 10.9kg) is composed as follows.
Table 6
| Phosphoric acid | Water | Inorganics | IPA | Al | Mo | (Na) |
| 1 | 0.5 | 7.36 | 2 | 0.027 | 0.029 | 1.422 |
Al in above-mentioned filtrate and the residue, Mo amount is compared, and Al, Mo shift (co-precipitation) to residue as can be known, and be separated by Al, Mo in this operation concentrated phosphoric acid., owing to added the Na ion, therefore must be removed according to the inorganic salt that add as far as possible.In addition, in order to improve the purity of phosphoric acid, must remove the inorganics that is dissolved in the concentrated phosphoric acid as far as possible.
Then, filtrate is transferred in the organic solvent evaporation device, IPA is evaporated with water separate, adopting does not have illustrated IPA recovery to utilize with water distilling apparatus recovery IPA again.In addition,, add entry in the phosphoric acid after IPA heats up in a steamer, make it revaporization, desolvate by azeotropic in order from phosphoric acid, to heat up in a steamer IPA fully.Obtain purification of phosphoric acid from the bottom of organic solvent evaporation device.
Resulting purification of phosphoric acid (about 71.1kg) composed as follows.
Table 7
| Phosphoric acid | Water | Inorganics | IPA | Al | Mo | (Na) |
| 64 | 7.1 | 0.04 | N.D. | 0.003 | 0.016 | 0.008 |
Above-mentioned purification of phosphoric acid has carried out partial crystallization and co-precipitation once and has obtained, but should form unappeasable occasion, carries out same operation once again, carries out removing of metal ion and gets final product, and below enumerates this example.
Because the concentration of metal ions of mother liquor is lower than the 1st time, the addition that therefore makes inorganic salt (SODIUM PHOSPHATE, MONOBASIC) is that 1/5 amount is carried out.
Resulting purification of phosphoric acid (about 70.5kg) composed as follows can obtain the higher purification of phosphoric acid of purity.
Table 8
| Phosphoric acid | Water | Inorganics | IPA | Al | Mo | (Na) |
| 63.5 | 7.0 | 0.02 | N.D. | 0.00004 | 0.00061 | 0.004 |
The crystalline of above-mentioned residue (about 10.9kg) being transferred to the refining inorganic salt (about 7.5kg) after handling in the refining partial crystallization groove of inorganic salt is composed as follows, and it is no problem to utilize in the inorganic salt dissolving tank again.
Table 9
| Phosphoric acid | Water | Inorganics | IPA | Al | Mo | (Na) |
| N.D. | 0.5 | 7.0 | N.D. | N.D. | N.D. | 1.34 |
As mentioned above,, about 98 quality % of the phosphoric acid in the nitration mixture aqueous solution waste liquid can be utilized again, can cut down the input amount of the new liquid of the nitration mixture aqueous solution significantly according to system of the present invention.
Embodiment 2
Carried out the processing of the nitration mixture aqueous solution waste liquid of the Al etching work procedure identical with embodiment 1.
The composition of the composition of the nitration mixture aqueous solution waste liquid (about 100kg) of discharging from etching work procedure, the concentrated phosphoric acid (about 72.2kg) that passes through from the composition of the distillate (about 27.8kg) of evaporation unit, from evaporation unit is identical with embodiment 1.
Then, except inorganic salt being made into sodium sulfate 4.43kg, be dissolved in the 18kg water use beyond, carry out operation similarly to Example 1.Composed as follows at the treatment solution (about 354.6kg) in this stage.
Moreover, about the relation of Na amount, similarly to Example 1 with the inorganics amount.
Table 10
| Phosphoric acid | Water | Inorganics | IPA | Al | Mo | (Na) |
| 65 | 25.2 | 4.43 | 260 | 0.030 | 0.045 | 1.43 |
In addition, the filtrate of passing through from filtration unit (about 346.5kg) is composed as follows.
Table 11
| Phosphoric acid | Water | Inorganics | IPA | Al | Mo | (Na) |
| 65 | 24.5 | 0.02 | 258 | 0.002 | 0.010 | 0.006 |
In addition, the residue of filtration unit (about 8.1kg) is composed as follows.
Table 12
| Phosphoric acid | Water | Inorganics | IPA | Al | Mo | (Na) |
| 1 | 0.7 | 4.41 | 2 | 0.028 | 0.035 | 1.424 |
Al in above-mentioned filtrate and the residue, Mo amount is compared, and Al, Mo shift (co-precipitation) to residue as can be known, and be separated by Al, Mo in this operation concentrated phosphoric acid., owing to adding Na ion and SO are arranged according to the inorganic salt that add
4 2-Therefore ion must be removed as far as possible.In addition, in order to improve the purity of phosphoric acid, must remove the inorganics that is dissolved in the concentrated phosphoric acid as far as possible.
Then, filtrate is supplied in the organic solvent evaporation device, carry out the result of operation similarly to Example 1, resulting purification of phosphoric acid (about 71.1kg) composed as follows.About SO
4 2-Ion, it is residual that the Na of minimal residue (0.006kg) forms the part of sodium sulfate salt with not being removed.
Table 13
| Phosphoric acid | Water | Inorganics | IPA | Al | Mo | (Na) |
| 64 | 7.1 | 0.02 | N.D. | 0.002 | 0.010 | 0.006 |
Embodiment 3
Use recirculation system shown in Figure 3, the processing of the nitration mixture aqueous solution waste liquid of Al etching work procedure is carried out in operation similarly to Example 1.Fig. 4 is the figure of the material budget of each basic square of expression.
In the present embodiment, for with the concentration of metal ions (total amount of Al, Mo, Na) of the water-soluble liquid bath of nitration mixture by weight the benchmark meter remain on below the 500ppm, and the treatment capacity that makes nitration mixture aqueous solution waste liquid is 100kg/ hour, the recirculation nitration mixture aqueous solution is 90kg/ hour, with the concentration of metal ions of the recirculation nitration mixture aqueous solution by weight the benchmark meter be suppressed at below the 30ppm, replenish the occasion of 10kg/ hour the new liquid of the nitration mixture aqueous solution (replenish with), the upper limit of etching metal amount is as shown in the formula being 0.0473kg/ hour like that.
100kg/ hour * 0.0005-100kg/ hour * 0.9 * 0.00003=0.0473kg/ hour
Embodiment 4
Use recirculation system shown in Figure 5 to carry out the processing of the nitration mixture aqueous solution waste liquid of Al etching work procedure.The composition of the composition of the nitration mixture aqueous solution waste liquid (about 100kg) of discharging from etching work procedure, the concentrated phosphoric acid (about 72.2kg) that passes through from the composition of the distillate (about 27.8kg) of evaporation unit, from evaporation unit is identical with embodiment 1.
Then, concentrated phosphoric acid is transferred in the fusion partial crystallization device, be cooled to about 10 ℃, partial crystallization goes out the phosphoric acid semihydrate crystal.Then, behind the employing filtration unit solid-liquid separation phosphoric acid semihydrate crystal, transfer to after the heat fused in the etchant concentration setting device, in the metal etch operation, utilize again thereby replenish not enough composition.Resulting phosphoric acid semihydrate crystal composed as follows.
Table 14
| Phosphoric acid | Water | Al | Mo |
| 52 | 4.8 | 0.001 | 0.0015 |
In addition, filtrate is composed as follows.
Table 15
| Phosphoric acid | Water | Al | Mo |
| 13 | 2.4 | 0.029 | 0.0435 |
Above-mentioned filtrate is transferred in partial crystallization and the co-precipitation groove result who carries out processing similarly to Example 1, resulting purification of phosphoric acid (13.8kg) composed as follows.
Table 16
| Phosphoric acid | Water | Inorganics | IPA | Al | Mo | (Na) |
| 12.4 | 1.4 | 0.01 | N.D. | 0.0008 | 0.0035 | 0.002 |
Above-mentioned purification of phosphoric acid is returned to fusion partial crystallization operation, carry out the result with above-mentioned same processing once again, obtained the purification of phosphoric acid of following composition.
Table 17
| Phosphoric acid | Water | Inorganics | IPA | Al | Mo | (Na) |
| 9.9 | 0.9 | 0.0003 | N.D. | 0.00003 | 0.0001 | 0.00007 |
Repeat the fusion partial crystallization if resemble as can be known above-mentioned, then can obtain the high purification of phosphoric acid of purity.
Embodiment 5
Use recirculation system shown in Figure 5, the processing of the nitration mixture aqueous solution waste liquid of Al etching work procedure has been carried out in operation similarly to Example 1.Fig. 6 is the figure of the material budget of each basic square of expression.
In the present embodiment, for with the concentration of metal ions (total amount of Al, Mo, Na) of the water-soluble liquid bath of nitration mixture by weight the benchmark meter remain on below the 500ppm, and the treatment capacity that makes the nitration mixture aqueous solution is 100kg/ hour, the recirculation nitration mixture aqueous solution is 90kg/ hour, with the concentration of metal ions of the recirculation nitration mixture aqueous solution by weight the benchmark meter be suppressed at below the 30ppm, replenish the occasion of 2kg/ hour the new liquid of the nitration mixture aqueous solution (replenish with), the upper limit of etching metal amount is as shown in the formula being 0.04706kg/ hour like that.
100kg/ hour * 0.0005-100kg/ hour * 0.98 * 0.00003=0.04706kg/ hour
Among the present invention the expression numerical range " more than " and " following " comprise given figure.
Claims (8)
1. a method that obtains purification of phosphoric acid is characterized in that, comprises [1] partial crystallization and co-precipitation operation and [2] evaporization process,
Described [1] partial crystallization and co-precipitation operation are that the crystallization of inorganic salt is separated out from the phosphate aqueous solution that contains multiple metal ion, make the partial crystallization and the co-precipitation operation of metal ion co-precipitation, comprising:
(a) operation of the mixed inorganic aqueous solution in the phosphate aqueous solution that contains multiple metal ion,
(b) dissolve in organic poor solvent of phosphoric acid and non-dissolve inorganic salts by further mixing, when the crystallization that makes inorganic salt is separated out, make the operation of described metal ion co-precipitation,
(c) filtration contains the crystallization of the inorganic salt of described metal ion, carries out the operation of solid-liquid separation;
Described [2] evaporization process is by making the evaporation of organic poor solvent in the filtrate that described filtration obtains and water, obtain the evaporization process of purification of phosphoric acid,
And, in described [1] operation (b), be dissolved in the amount of metal ion in described phosphoric acid-organic poor solvent mixed solution, lack than the amount of metal ion in the phosphate aqueous solution that (a) uses in the operation in described [1].
2. the method for acquisition purification of phosphoric acid as claimed in claim 1 is characterized in that, by the purification of phosphoric acid that adopts the described method of claim 1 to obtain further repeatedly being repeated the operation of described [1] and [2], obtains the purification of phosphoric acid of greater concn.
3. the method for acquisition purification of phosphoric acid as claimed in claim 1 or 2, it is characterized in that, the described phosphate aqueous solution that contains multiple metal ion contains benchmark by weight and counts 500ppm to the metal ion that is dissolved in the concentration of the upper limit in this phosphate aqueous solution as metal ion.
4. as the method for each described acquisition purification of phosphoric acid of claim 1～3, it is characterized in that, the crystallization of the inorganic salt that contain metal ion that obtain in the operation that water is dissolved in described [1], then, the crystallization of inorganic salt is separated out, from inorganic salt, separate the metal of co-precipitation by cooling, filter then, reclaim inorganic salt, and prepare inorganic salt solution, (a) utilize again in the operation in claim 1 described [1] by the inorganic salt that reclaim.
5. a purification of phosphoric acid manufacturing installation that is used for each described method of claim 1～3 is characterized in that having at least: dissolve inorganic salts, the inorganic salt dissolving tank of preparation inorganic salt solution; Be used for to contain phosphate aqueous solution and the organic poor solvent and the mixing of this inorganic salt solution of multiple metal ion, the crystallization of inorganic salt is separated out, make the partial crystallization with stirrer and the co-precipitation groove of metal ion co-precipitation simultaneously; The crystallization of the inorganic salt of resulting metal ion is filtered, thereby carry out the filtration unit of solid-liquid separation; Be used for organic solvent evaporation device that organic poor solvent and water are evaporated from filtrate with heater means.
6. device as claimed in claim 5, it is characterized in that, further have: adopt the crystallization of the inorganic salt of the metal ion that described filtration unit filters out with warm water dissolving, separate out the refining partial crystallization groove of crystalline inorganic salt of inorganic salt once again and isolating filtration unit is carried out in the crystallization of the inorganic salt of separating out in the refining partial crystallization groove of described inorganic salt by cooling then.
An etching solution utilize method again, it is characterized in that, comprising:
Recovery process, the used nitration mixture aqueous solution waste liquid that contains multiple metal ion that produces in the metal etch operation to the nitration mixture aqueous solution that comprises phosphoric acid, nitric acid, acetate and water in use reclaims;
Evaporization process evaporates from described nitration mixture aqueous solution waste liquid by the major part that makes nitric acid, acetate and water, and fractionation becomes the distillate that contains nitric acid, acetate and water and contains phosphoric acid and the concentrated phosphoric acid of multiple metal ion;
Refining step separates by using claim 5 or 6 described devices that the metal ion in the described concentrated phosphoric acid is carried out co-precipitation, obtains purification of phosphoric acid;
Concentration is adjusted operation, adjusts strength of fluid by add described distillate in resulting purification of phosphoric acid, then it is used for the metal etch operation once again as the recirculation nitration mixture aqueous solution.
8. etching solution as claimed in claim 7 utilizes method again, it is characterized in that, further comprise and separate out operation, promptly, make the concentrated phosphoric acid that in described evaporization process, obtains in fusion partial crystallization device, separate out the phosphoric acid semihydrate crystal, then the phosphoric acid semihydrate crystal is carried out solid-liquid separation, then resulting phosphoric acid semihydrate crystal is transferred to described concentration and adjusts in the operation with filtration unit, and the filtrate that metal ion has been concentrated is transferred in claim 5 or 6 described partial crystallizations and the co-precipitation groove.
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| JP2007028820A JP5242061B2 (en) | 2007-02-08 | 2007-02-08 | Method and apparatus for obtaining purified phosphoric acid from aqueous phosphoric acid solution containing a plurality of metal ions |
| JP028820/2007 | 2007-02-08 |
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| JP (1) | JP5242061B2 (en) |
| KR (1) | KR101410594B1 (en) |
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| FR2327961A1 (en) * | 1975-10-15 | 1977-05-13 | Cerphos Ctre Etud Rech Phosph | PROCESS FOR THE PURIFICATION OF PHOSPHORIC ACID |
| SU1046346A1 (en) * | 1981-12-25 | 1983-10-07 | Всесоюзный Научно-Исследовательский И Проектный Институт По Очистке Технологических Газов,Сточных Вод И Использованию Вторичных Энергоресурсов Предприятий Черной Металлургии | Method for regenerating waste fluorinaceous solutions |
| JPS62123006A (en) * | 1985-11-22 | 1987-06-04 | Mitsui Toatsu Chem Inc | Method for removing cadmium from extracted residue solution or reextracted residue solution |
| JPS63270303A (en) * | 1987-04-24 | 1988-11-08 | Matsushita Electric Works Ltd | Regeneration of phosphoric acid |
| FR2629812B1 (en) * | 1988-04-12 | 1991-01-25 | Cerphos | PROCESS FOR REMOVAL OF HEAVY METALS, ESPECIALLY CADMIUM, CONTAINED IN PHOSPHORIC ACID |
| CN1039800C (en) * | 1996-01-18 | 1998-09-16 | 昆明理工大学 | Solvent sedimentation method for purifying wet method phosphoric acid |
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| JP3493603B2 (en) * | 2000-11-20 | 2004-02-03 | 独立行政法人産業技術総合研究所 | Method for treating copper chloride-containing etching waste liquid, treatment agent, and method for recovering copper |
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| JP4316946B2 (en) * | 2003-07-01 | 2009-08-19 | 日本化学工業株式会社 | High purity phosphoric acid and method for producing the same |
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- 2007-02-08 JP JP2007028820A patent/JP5242061B2/en active Active
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- 2008-01-30 TW TW097103530A patent/TWI452010B/en active
- 2008-02-02 CN CN2008100048058A patent/CN101239710B/en not_active Expired - Fee Related
- 2008-02-05 KR KR1020080011942A patent/KR101410594B1/en not_active IP Right Cessation
- 2008-02-05 SG SG200801052-2A patent/SG144902A1/en unknown
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Also Published As
| Publication number | Publication date |
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| KR101410594B1 (en) | 2014-06-20 |
| CN101239710B (en) | 2013-07-10 |
| JP5242061B2 (en) | 2013-07-24 |
| SG144902A1 (en) | 2008-08-28 |
| TWI452010B (en) | 2014-09-11 |
| TW200846280A (en) | 2008-12-01 |
| KR20080074791A (en) | 2008-08-13 |
| JP2008189537A (en) | 2008-08-21 |
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