CN101239710B - 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-acetic acid-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, acetic acid, water, but its total concentration of metal ions that contains 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, acetic acid, 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 discharging, to remove metal ion, reclaim the treatment unit of the nitration mixture aqueous solution simultaneously with high yield.
To the initial stage that the nitration mixture aqueous solution waste liquid of discharging from Al metal etch device is made with extra care, be to adopt evaporation or distillation method to make volatile matter (major part of nitric acid, acetic acid, 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 general method that the metal ion that exists in solution is separated, 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 the nitric acid oxidation in the nitration mixture aqueous solution waste liquid causes
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 recycling phosphoric acid.
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 referring to certain precipitate, the material of solubility accompanies and the phenomenon of precipitation with it.Coprecipitation phenomena causes because of the generation of mixed crystal sometimes, also causes because the generative process intermediate ion in precipitation is adsorbed 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, comes the system of the purification of phosphoric acid that recycling reclaims.
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 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, by cooling the inorganic salt crystallization is separated out, from inorganic salt, separate the metal of co-precipitation, filter then, reclaim inorganic salt, and prepare inorganic salt solution by the inorganic salt that reclaim, 1) described (1) (a) carry out recycling in the operation.
5) a kind of for implementing 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 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; For the organic solvent evaporation device with heater means that organic poor solvent and water are evaporated from filtrate.
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 inorganic salt of crystallization of inorganic salt and the filtration unit that the inorganic salt crystallization of separating out is separated once again by cooling in the refining partial crystallization groove of above-mentioned inorganic salt then.
7) a kind of recycling method of etching solution 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, acetic acid and water in use reclaims;
Evaporate from above-mentioned nitration mixture aqueous solution waste liquid by the major part that makes nitric acid, acetic acid and water, fractionation becomes the distillate that contains nitric acid, acetic acid 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) the recycling method of described etching solution, it is characterized in that, further comprise and separate out operation, namely, 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 with filtration unit 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, 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, come the system of the purification of phosphoric acid that recycling reclaims.
In addition, be assembled in by the device with acquisition purification of phosphoric acid of the present invention on the streamline of metal etch device, 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 that expression is as the figure of 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 the 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 carry out recycling.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, acetic acid 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, the 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 to become the phosphate aqueous solution that contains multiple metal ion of handling object and be concentrated to the above concentration of about 90 quality %.Become phosphoric acid concentration in the phosphate aqueous solution of handling 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 (namely, 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 with the inorganic salt co-precipitation of partial crystallization, with the complete partial crystallization of inorganic salt, inorganic salt are not remained in the phosphate aqueous solution.
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 handling 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 from the water-soluble liquid bath of nitration mixture, while spray quinoline etched material is carried out etching.
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 that expression is as the synoptic diagram of 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.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, on one side water flowing steam heats nitration mixture aqueous solution waste liquid in the reboiler, thereby nitric acid, acetic acid, 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, acetic acid and water, be stored in the distillate receiver after, the raw material recycling of adjusting as etchant concentration.
Heated up in a steamer the concentrated phosphoric acid of nitric acid, acetic acid and water 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 from the nitration mixture aqueous solution waste liquid that etching system is discharged, be separated into concentrated phosphoric acid and distillate (nitric acid, acetic acid and water).
Distillate is transferred to and is carried out recycling in the etchant concentration setting device.
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 a dissolving such as alcohols, ketone less than the solvent of 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 carry out solid-liquid separation to filtration unit.The 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, carry out recycling.
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 carry out recycling in the inorganic salt dissolving tank.
The crystallization of the inorganic salt in above-mentioned partial crystallization and the co-precipitation groove, interpolation by organic poor solvent, changes in solubility according to the part in the place of adding takes place, so crystal form is coarse and micropore arranged, metal ion generation co-precipitation under the state that is adsorbed by tissue that should be coarse.; in the refining partial crystallization groove of inorganic salt, reach cooling tank integral body by concentrating of liquid and remain on uniform state; therefore the crystallization that produces is firm and fine and close; by using the refining mother liquor that is attached on the crystal surface of centrifugal filter device (more than the G=1500), can obtain the not crystallization of metal ion.
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.
The concentrated phosphoric acid that will separate in evaporation unit is transferred in the fusion partial crystallization device, is 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, carry out recycling.
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.
Embodiment 1
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 minute quantity, therefore ignore.
Table 1
| Phosphoric acid | Nitric acid | Acetic acid | 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 | Acetic acid | 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 | Acetic acid | 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 according to the inorganic salt that add, therefore 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 transferred in the organic solvent evaporation device, IPA is evaporated with water separate, adopting does not have illustrated IPA recovery to carry out recycling with water distilling apparatus recovery IPA.In addition, in order from phosphoric acid, to heat up in a steamer IPA fully, add water in the phosphoric acid after heating up in a steamer to IPA, make it revaporization, carry out desolventizing by azeotropic.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 |
Above-mentioned residue (about 10.9kg) is transferred to crystallization composed as follows of the refining inorganic salt (about 7.5kg) after handling in the refining partial crystallization groove of inorganic salt, recycling is no problem in the inorganic salt dissolving tank.
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, according to system of the present invention, can be with about 98 quality % recyclings of the phosphoric acid in the nitration mixture aqueous solution waste liquid, the input amount that can cut down the new liquid of the nitration mixture aqueous solution significantly.
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 with the inorganics amount, similarly to Example 1.
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 according to the inorganic salt that add Na ion and SO are arranged
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, carry out recycling 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 following salt is separated out from the phosphate aqueous solution that contains multiple metal ion, make partial crystallization and the co-precipitation operation of metal ion co-precipitation, comprising:
(a) be the operation of mixing the aqueous solution of following salt in the phosphate aqueous solution more than the 90 quality % to the phosphoric acid concentration that contains multiple metal ion,
(b) dissolve in organic poor solvent of phosphoric acid and the following salt of insoluble solution by further mixing, when the crystallization that makes following salt is separated out, make the operation of described metal ion co-precipitation,
(c) filtration contains the crystallization of the following 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],
Described salt is SODIUM PHOSPHATE, MONOBASIC, potassium primary phosphate, primary ammonium phosphate, trimagnesium phosphate, sodium sulfate, ammonium sulfate, sodium acetate or ammonium acetate,
Described organic poor solvent is Virahol, isopropylcarbinol, acetone or mibk.
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. the method for acquisition purification of phosphoric acid as claimed in claim 1 or 2, it is characterized in that, the crystallization of the salt that contains metal ion that obtains in the operation that water is dissolved in described [1], then, by cooling the crystallization of salt is separated out, from salt, separate the metal of co-precipitation, filter then, reclaim salt, and prepare the aqueous solution of salt by the salt that reclaims, (a) carry out recycling in the operation in claim 1 described [1].
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: dissolved salt, the salt dissolving tank of the aqueous solution of preparation salt; Aqueous solution for phosphate aqueous solution and organic poor solvent and this salt that will contain multiple metal ion is separated out the crystallization of salt, makes the partial crystallization with stirrer and the co-precipitation groove of metal ion co-precipitation simultaneously; The crystallization of the salt of resulting metal ion is filtered, thereby carry out the filtration unit of solid-liquid separation; For the organic solvent evaporation device with heater means that organic poor solvent and water are evaporated from filtrate.
6. device as claimed in claim 5, it is characterized in that, further have: adopt the crystallization of the salt of the metal ion that described filtration unit filters out with warm water dissolving, separate out the filtration unit that the salt refining partial crystallization groove of the crystallization of salt separates with crystallization to the salt of separating out once again by cooling in described salt refining partial crystallization groove then.
7. the recycling method of an etching solution 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, acetic acid and water in use reclaims;
Evaporization process evaporates from described nitration mixture aqueous solution waste liquid by the major part that makes nitric acid, acetic acid and water, and fractionation becomes the distillate that contains nitric acid, acetic acid and water and contains phosphoric acid and the concentrated phosphoric acid of multiple metal ion;
Refining step requires 5 or 6 described devices that the metal ion in the described concentrated phosphoric acid is carried out co-precipitation by right to use and separates, obtain 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. the recycling method of etching solution as claimed in claim 7, it is characterized in that, further comprise and separate out operation, namely, make the concentrated phosphoric acid that in described evaporization process, obtains in fusion partial crystallization device, separate out the phosphoric acid semihydrate crystal, then with filtration unit 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, 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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| JP4927670B2 (en) * | 2007-09-07 | 2012-05-09 | 住友精密工業株式会社 | Etching waste liquid recycling method and recycling apparatus |
| CN101439849B (en) * | 2008-12-31 | 2010-12-08 | 孟庆深 | Comprehensive utilization process for waste aluminum etching solution |
| WO2011148463A1 (en) * | 2010-05-25 | 2011-12-01 | エム・テクニック株式会社 | Method for producing precipitated substances with controlled amounts of dopant element |
| CN101857216B (en) * | 2010-06-29 | 2012-04-25 | 贵州川恒化工有限责任公司 | Method for extracting and purifying wet-process phosphorous acid to produce industrial-grade phosphorous acid |
| CN102502547A (en) * | 2011-10-10 | 2012-06-20 | 浙江兴达活性炭有限公司 | Process for removing impurity in phosphoric acid from activated carbon production by phosphoric acid method |
| CN102730656A (en) * | 2012-06-26 | 2012-10-17 | 瓮福（集团）有限责任公司 | Method for preparing phosphoric acid with high concentration by microwave heating of raffinate acid |
| US9597609B2 (en) * | 2013-01-14 | 2017-03-21 | Sulzer Chemtech Ag | Multi-stage crystallisation process and apparatus to purify a compound |
| JP5962538B2 (en) * | 2013-02-27 | 2016-08-03 | Ｊｆｅエンジニアリング株式会社 | Water treatment method and apparatus |
| CN103979509B (en) * | 2014-04-28 | 2016-04-06 | 合肥茂腾环保科技有限公司 | A kind of method reclaiming phosphoric acid in waste aluminum etching solution |
| JP6268054B2 (en) * | 2014-07-09 | 2018-01-24 | 株式会社アナック | Method and apparatus for producing fertilizer by treating phosphoric acid mixed acid waste liquid |
| JP2016059855A (en) | 2014-09-17 | 2016-04-25 | 株式会社東芝 | Treatment apparatus and method for recycling treatment liquid |
| CN107089650B (en) * | 2017-05-27 | 2019-10-11 | 深圳市深投环保科技有限公司 | The preparation method of chemical polishing waste phosphoric acid processing method and monoammonium phosphate |
| CN108837551B (en) * | 2018-07-28 | 2024-04-02 | 湖南懋天世纪新材料有限公司 | Superfine ammonium paratungstate evaporation crystallization device and crystallization method |
| KR20200054890A (en) * | 2018-11-12 | 2020-05-20 | 주식회사 동진쎄미켐 | Method for preparing purified phosphoric acid from used etchant |
| CN109942408A (en) * | 2019-03-24 | 2019-06-28 | 雒晓兵 | A kind of waste utilization method of useless etching mixed acid solution |
| CN110980675A (en) * | 2019-12-30 | 2020-04-10 | 南京乐透思环保科技有限公司 | Defluorination method of wet-process phosphoric acid |
| CN112499606B (en) * | 2021-01-20 | 2022-04-08 | 江苏电科环保有限公司 | Purification method of phosphoric acid waste liquid |
| WO2023034158A1 (en) * | 2021-09-03 | 2023-03-09 | Texas Tech University System | Preparation of ionic pharmaceutical cocrystals using solid and liquid components |
| CN114534501B (en) * | 2022-01-04 | 2024-09-06 | 中国原子能科学研究院 | Electrodialysis device and method for separating nitric acid and acetic acid |
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| TW200846280A (en) | 2008-12-01 |
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