CN101423204B - Method and device capable of purifying phosphoric acid using fractional crystallization - Google Patents
Method and device capable of purifying phosphoric acid using fractional crystallization Download PDFInfo
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- CN101423204B CN101423204B CN2008102128127A CN200810212812A CN101423204B CN 101423204 B CN101423204 B CN 101423204B CN 2008102128127 A CN2008102128127 A CN 2008102128127A CN 200810212812 A CN200810212812 A CN 200810212812A CN 101423204 B CN101423204 B CN 101423204B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/18—Phosphoric acid
- C01B25/234—Purification; Stabilisation; Concentration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D9/00—Crystallisation
- B01D9/0004—Crystallisation cooling by heat exchange
- B01D9/0013—Crystallisation cooling by heat exchange by indirect heat exchange
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D9/00—Crystallisation
- B01D9/0036—Crystallisation on to a bed of product crystals; Seeding
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D9/00—Crystallisation
- B01D9/0059—General arrangements of crystallisation plant, e.g. flow sheets
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/18—Phosphoric acid
- C01B25/234—Purification; Stabilisation; Concentration
- C01B25/237—Selective elimination of impurities
- C01B25/238—Cationic impurities, e.g. arsenic compounds
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Abstract
The present invention relates to a method for purifying phosphoric acid through fractional crystallization and a device thereof. Specifically in the method for purifying polluted phosphoric acid, a first input mixture which takes phosphoric acid as main component and mainly comprises a first group of impurity is mixed with a second input mixture that takes phosphoric acid as main component and mainly comprises a second group of impurities. The impurities with highest concentration in two mixtures are different. The mixed input mixture is crystallized in a multistage crystallization technique. The obtained crystallization layer is heated and melted into fraction for extracting clean phosphoric acid. The device used for realizing the method is characterized by providing a water supplier which is used for adjusting the weight percentage of phosphoric acid in the used mixture to a specific value.
Description
Technical field
According to claim 1,19 with the introduction of 22d, the present invention relates to receive the phosphate compsn that positively charged ion, negatively charged ion, acid and/or organic element pollute through the method purifying of fractional crystallization.
Background technology
In employed engraving method in electronic industry, use acid usually, like phosphoric acid, nitric acid and acetic acid.For example, mix the above-mentioned acid of use and be deposited on aluminium molybdenum alloy on glass with dissolving.This aluminium molybdenum alloy is widely used in the production of TFT (thin film transistor).
Usually, the spent acid that stays behind the etch process contains the phosphoric acid of 60-95% weight, the nitric acid of 1-10% weight, and the acetic acid of 2-30% weight and water (residuum), content depends on reaction conditions.Spent acid also contains aluminium and the molybdenum ion of 100-2000ppm.This spent acid material is diluted subsequently and join in the fertilizer.
Proposed different methods in the past and be used for purifying, like membrane separation process, ion exchange method or liquid extraction by the phosphoric acid of metal ion pollution.
Membrane separation process is favourable in phosphoric acid recovery and purifying field thereof.Yet the cost of membrane separation plant is very high, and its operation is very complicated.And, possibly go wrong owing to nitric acid corrodes employed film.
Ion exchange method makes spent ion exchange resin or scolecite to remove disacidify.Yet this ion-exchanger has its shortcoming, because whole exchange capacity is normally low, so can only handle the acid of lower concentration.
Liquid extraction has the following advantages: this method can operate continuously and also equipment not expensive yet.Yet its shortcoming is to use this method to can not get high-quality phosphoric acid, and said high quality can satisfy the electronic industry demand.
Can know that by JP-A-2006-069845 a kind of being used for from reclaimed the method and apparatus of phosphoric acid by the acidic aqueous solution of metals ion and other acid pollutions arranged.In said method, at first distill away other acid and water.Then, phosphoric acid crystallizes out from the aqueous solution of phosphoric acid residue, then comes out through the distillation fractionation.Mother liquor from crystallisation step is rich in metals ion, abandons as waste product.After this, in the phosphoric acid that distillation purifying is crossed, add hydrochloric acid or acetic acid again.This acid mixture is used for new method as product.
Described purification process is very complicated, because phosphate discharge liquid will come purifying through twice distillation and primary crystallization.
KR-A-20050103570 discloses the method for from the etching solution that pollutes, separating and obtain ultrapure phosphoric acid, nitric acid and acetic acid through the method for layer crystallization and vacuum distilling.The first step is separated nitric acid and acetic acid through vacuum distilling.Remaining level branch joins in the layering mold, and its initial temperature remains between-20 ℃-30 ℃.Solution is with the crystal seed nucleation and be cooled between 60 ℃-20 ℃ then.The different crystallizations that separate formation of density owing to xln and mother liquor.In order to obtain purified phosphoric acid, subsequently the xln that obtains is heated to 0-40 ℃, filtration fraction fused crystallizing layer.Realize that described method need not add additive or solvent.
Summary of the invention
Therefore, the objective of the invention is to obtain the available method and apparatus, can reduce the acid waste liquid of a great deal of.Its specific purposes are to propose a method, institute's energy requirement seldom, and its operation can realize commercial size.Another purpose is to adopt the diverse ways step as few as possible.
Detailed Description Of The Invention
According to the present invention, above purpose is accomplished in the method according to the aforementioned characteristic of claim 1, in the method:
-phosphoric acid is as first input mixture of staple, and it mainly contains first group of impurity, mixes with second input mixture of phosphoric acid as staple;
-said second input mixture mainly contains second group of impurity,
-wherein two kinds of impurity of operating maximum concentration in the mixture are different each other, and
The crystallization in the multistep crystallization method of-said input mixture that converges, crystallizing layer that heating obtains and classification are to extract purified phosphoric acid.
Can find out, when different commercial runs use or come from the raw phosphoric acid of various processes when mixed, and when only coming purifying afterwards, come purifying phosphoric acid more cost effectively to realize through crystallization through crystallization.Purifying through crystallization method has following having a few: the minimizing of different impurities does not have very big association each other.The inventor finds that for example, the phosphoric acid (being called as " pickling acid ") that is used for extensive pickling has the impurity beyond the phosphoric acid that is used for LCD production, and for this reason, the relevant purifying of phosphoric acid that pollutes during purifying LCD produces is very favorable.
Preferred first and second groups of impurity contain different basically acid, negatively charged ion, positively charged ion or other chemical substances each other.In this case, because diluting effect, impurity has had part to reduce in the combination mixture.This means that for the mixture dominant component (being different major impurities) of different use, dilution effect can be saved one or two recrystallize step, promptly so-called crystallized region.Especially preferably change according to one, be used for the semi-conductor industry etch process, particularly the phosphoric acid of LCD production mixes with the phosphoric acid that is used for etch.In this way, very big saving can be arranged, be relatively low because need to handle the phosphoric acid amount that maybe will manufacture fertilizer.It will also be appreciated that the ortho acid that so-called " wet technology " obtains mixes with other above-mentioned acid, said ortho acid does not have the enough purity of in LCD produces, using.
First group advantageously contains molybdenum and/or aluminum ion, and second group contains ion and/or sodium ion and/or phosphorated acid as major impurity.These impurity can most ofly be removed through the crystalline method.Do not limit the purifying of two kinds of different input mixtures according to the method for the invention, also can purifying more than two kinds of input mixtures that have different impurities respectively.
Theme of the present invention also is according to the method for the aforementioned characteristic of claim 7, it is characterized in that:
-carry out crystallization at a plurality of crystallized regions,
-if desired, through adding water the weight content of phosphoric acid in the exhausted mixture is adjusted to 91.5% weight,
-cooling off the exhausted mixture then, the phosphoric acid hemihydrate deposits to crystal surface as crystallizing layer, and said crystallizing layer postheating and classification are to obtain the phosphoric acid of purifying.
The advantage of this method is: do not contain positively charged ion, negatively charged ion, acid and/or organic cpds in the phosphoric acid, so this phosphoric acid can utilize again.The benefit of adding water is that heavy metal ion is washed out faster.Through adding water, this method is controlled to obtain phosphoric acid-hemihydrated mode.If the initial amount of phosphoric acid just need be done between about 63%-92% weight like this.The advantage of in this scope, operating is: contained higher degree (for example because before distillation) and compare with being used for the crystalline original mixture, can obtain obviously lower phosphorus acid content in the crystallization raffinate.If the weight content of phosphoric acid is between 80-91%, it is very favorable all in original mixture, adding a large amount of water at every turn.The advantage of doing like this is: on the one hand, do not need thermal barrier to have extremely low temperature for obtaining the ideal productive rate, on the other hand, tangible water accumulation is arranged in the raffinate, this helps separating unwanted ion.In addition, crystallizer does not need very strong thermal isolation.It is favourable having only phosphorus acid content to reach between the 89-90.5% weight through interpolation water at every turn.Operation is energy-conservation especially in this scope.Under these conditions, the crystallization of phosphoric acid hemihydrate rather than phosphoric acid self is impeccable, because the phosphoric acid of purifying all is dilute with water when at any time further using.
According to method on the other hand, this embodiment comprises second heat-exchanger surface, and it is installed in has a bit of distance with exchanger surfaces or be in direct contact with it, and remains on low temperature always.This second heat-exchanger surface is used for keeping the phosphoric acid continuously effective crystallization of mold, and it is provided at the crystal seed of the evenly quick nucleation of first heat-exchanger surface in the crystalline starting stage.For example, preferred tray around pipe can be used as second heat-exchanger surface, it is installed between first heat-exchanger surface.
Crystallization is advantageously carried out at a plurality of crystallized regions, and wherein the purity of input mixture increases from low crystallized region to higher crystalline section.Crystallization is preferably carried out at least 3 crystallized regions, preferably at least 4 crystallized regions.Though the phosphoric acid that pollutes basically at first distills, the preferred phosphoric acid that pollutes directly adds crystallization method to be handled.If the weight content of distillation formerly-adopt-obtain acid is>92%-93%.This means advantageously dilute with water of distillage, to obtain required H in follow-up crystallisation process kind
3PO
41/2H
2O.According to the phasor of phosphoric acid/water system, the remaining level of non-dilution divides direct crystallization only can phosphorus acid content in the raffinate be reduced to about 93% weight.
A certain section crystal salt is advantageously used for the next upper sector importation in (or next up stage).As a result, use any purity of acquisition that described crystallization method can be feasible.A certain section nubbin is advantageously collected also as next low section importation charging.Can maximize recovery phosphoric acid like this.A certain section exfiltrating part can be collected and join in the importation with section.
The present invention also aims to be used for the equipment of purifying phosphoric acid, it is characterized in that providing water supply installation, be used for input mixture phosphoric acid weight percent is adjusted to certain value according to the aforementioned characteristic of claim 19.The advantage of this device has further obtained discussing in aforementioned method involving is described.In this, a kind of device of measuring the water yield of phosphoric acid and adding preferably is provided.This type device is all known for persons skilled in the art.According to embodiment preferred, second heat-exchanger surface has a bit of distance with first heat-exchanger surface or directly contacts with first exchanger surfaces in mold, and wherein second thermal barrier passes through from second heat-exchanger surface when operation.Comprise that verified to stop the compound of nucleation for those through overcooling trend be very useful to second heat-exchanger surface.
The present invention also aims to purification devices according to the aforementioned characteristic of claim 21; Wherein second heat-exchanger surface has a bit of distance with first heat-exchanger surface or directly contacts with first exchanger surfaces in mold, and wherein second heat exchange carrier passes through from second heat-exchanger surface when operation.This means provides two heating, so that the thermal barrier of differing temps flows through first and second heat-exchanger surfaces.This purification devices is generally used for the product as phosphoric acid, if there is not this second heat-exchanger surface, it tended to cold and suppressed and delay nucleation, and crystallization that conversely can be initial is carried out under uncontrollable mode.Obtained in the above discussing according to the more advantage of the embodiment of apparatus of the present invention.
The present invention will discuss through the mode with reference to the embodiment of accompanying drawing.Therein, identical reference number is used for the identical parts of each embodiment.Accompanying drawing is following:
Fig. 1. get crystallization apparatus figure according to the present invention, have the stationary crystallization device and be used to receive the jar that different phosphoric acid levels are divided with four;
Fig. 2. according to the partial cross section figure of the crystallization apparatus of Fig. 1, it shows first embodiment of water feeder;
Fig. 3. second embodiment of water feeder;
Fig. 4. the phasor of phosphoric acid;
Fig. 5. according to the embodiment of purification process mass balance of the present invention.
Fig. 1 illustrates has stationary crystallization device 11 and four crystallization apparatus that are used to store the jar 13,15,17,19 that different phosphoric acid levels divide.The level branch of input is transported to jar 13 through pipeline 21, and pipeline 21 can be closed through valve 23.The level branch of input is delivered into mold 11 through first supply line 25 with pump 33 then.Outlet 29 is positioned at the bottom of the mold on 27, and the pipeline 31 with shut-off valve is connected with said outlet.Pipeline 31 is connected with collector 41, and said collector is communicated with jar 13,15,17 and 19 through pipeline 43,45,47 and 49. Pipeline 43,45,47 and 49 is equipped with valve 44,46,48 and 50, and these valves are used for cutting out respectively each pipeline.The exhausted material can be carried in pipeline 25,52,53 and 52 through pump 33,35,37 and 39.
According to the input mixture composition, purification devices can have more or less jar that middle phosphoric acid level is divided that is used to store.In this embodiment, jars 15 be used for collecting and store than jars 13 store more purified phosphoric acid level branch, this container links to each other with mold 11 through pipeline 52, carries out further purification phase in the mold for mixture is added to.
Raffinate from purification process is handled through pipeline 51.The phosphoric acid of purifying is supplied with through pipeline 53 and is used for utilizing again.
The particular feature of the purification devices of Fig. 1 is that water can add in jars 15 through pipeline 54, is used for phosphorus acid content is adjusted to certain value, preferably in the scope of about 90% weight.Pipeline 54 is closed through the device of valve 56.
First heat-exchanger surface is by reference number 55 expressions, and it links to each other with primary heater/water cooler (heat generator/cooling generator) through pipeline 57,59.The particular feature of mold is to provide second heat-exchanger surface, 60, the second thermal mediums in operating process, to pass through second heat-exchanger surface 60 through pipeline 64,66.As for area, second heat-exchanger surface 61 is significantly less than first heat-exchanger surface, only is used for making the purpose of phosphoric acid crystal continuously effective as the crystal seed of mold.For this reason, second heat-exchanger surface 60 is installed in and first heat-exchanger surface, 55 a bit of distances, or even directly is in contact with it.Heat-eliminating medium flows through second heat-exchanger surface in the crystallizer operation process, preferably it remains under the low temperature always.Through doing like this, can be implemented in the process of filler in mold, crystal is in growth on second heat-exchanger surface 60 at once after very short time, and it has skipped first heat-exchanger surface 55, makes that crystal evenly grows up into possibility there.
Fig. 2 illustrates two kinds of different solutions that in the exhausted mixture, add water with Fig. 3.According to Fig. 2, use to have closing circulation 61 and can under controllable mode, in mixture, adding water of variable valve 63.Connecting pipeline 65 between pipeline 52 and the jar 15 makes the input mixture circulation.In working cycle, can add entry simultaneously.According to the position of valve 67,69, the input mixture entering mold that can circulate also can be pumped into mold.
According to the embodiment of Fig. 3, the dilution that its place that is different from Fig. 2 is input mixture is directly carried out in the process that gets into mold.For this purpose, (static state) mixing tank 71 is provided, it has a plurality of baffle plates 73.It is in order to realize turbulent flow that baffle plate 73 is provided, thereby realizes mixing fully of input mixture and interpolation water.
With reference to phosphoric acid phasor (see figure 4), operations according to the instant invention can obtain phosphoric acid hemihydrate (H
3PO
41/2H
2O) carry out in zone.Preferably, crystallization is carried out in following phase graph region: the H in the input mixture
3PO
4Part by weight is between 63%-91.5%, preferably between 80%-91% weight.Such advantage is phosphoric acid hemihydrate (H
3PO
41/2H
2O) crystallization has just been carried out at about 24 ℃.
EXPERIMENTAL EXAMPLE
Crystallization (first section) for the first time
The ortho acid of the product device of producing from TFT has following parameter:
The Mo ion, ppm 1,359
The Al ion, ppm 1,361
Density, d
2041.7554
H
3PO
4Content, wt% about 93.2
The stationary crystallization device is as purification devices.In container, preferably have the heat-exchanger surface of a plurality of arranged verticals, thermal barrier is from wherein flowing through in the operating process.
In ortho acid (spent acid), be mixed into certain pure water so that H
3PO
4Content be reduced to about 90% weight.The input mixture that this mode produces is loaded in the crystallization control device and crystallization.The temperature of thermal barrier is adjusted to 25 ℃ at first in the mold.With after being used for crystallization and getting mixture and add mold to, the thermal barrier temperature was reduced to 15 ℃ in six hours.
In input mixture is cooled to 15 ℃ process, pure H
3PO
41/2H
2The O crystallizing layer forms at heat-exchanger surface.After the crystallization that this mode is carried out was accomplished, noncrystalline raffinate was discharged.The thermal barrier temperature was increased to 35 ℃ in 7 hours subsequently.During this period of time, crystallizing layer begins fusing (sweat).In this temperature rise period, collect the level of fusing and divide.
After fusing, the thermal barrier temperature is increased to 50 ℃ with the remaining crystalline of fusion.Determination data is summarised in the following table.
First section crystalline data of table 1 are summed up
Crystallization (second section) for the second time
The crystallization stage branch that produces in first crystallized region is that (centre) level is divided, and it can be further purified and as the input stage branch of second crystallized region.In input stage used herein is divided, add entry, its add-on makes in the phosphoric acid content in about 90% weight.Second crystallized region carries out under temperature/temporal mode in being similar to first crystallized region.The crystalline result is summarised in the following table 2 for the second time.
Second section crystalline data of table 2 are summed up
Crystallization for the third time (the 3rd crystallized region)
In the 3rd crystallized region, the xln level after the multiple crystallization second time divides mixture to be further purified.Add enough water once more so that the original bulk of phosphoric acid amount reaches about 90% weight.Use similar temperature-temporal mode.The result lists in the table 3.
The 3rd section crystalline data of table 3 are summed up
The 4th crystallization (the 4th crystallized region)
In the 4th crystallized region, the xln level after the multiple crystallization for the third time divides mixture to be further purified.Further class of operation is similar to the 3rd crystallized region.The result of the 4th crystallized region sees table 4.
The 4th section crystalline data of table 4 are summed up
Can find out from table 4, the consumption factor that in the 4th continuous crystallisation section, can obtain metals ion (for example being Mo and Al at this) is at 25-50.Basically can introduce further crystallized region certainly, it further consumes metal ion content.Wherein:
-the crystallization stage branch of section can be introduced next higher section as the input stage branch separately,
-the residue level branch of section can be collected and be mixed in the input stage branch of next lower section separately,
-the input stage branch of the subsequent segment circulation (being called circulation) of same section can collected and be mixed to the fusing level branch of section separately.
-all to, input stage add water in dividing at every turn, and the water yield of adding makes phosphoric acid concentration in 85%-91% weight, preferably in 89%-90.3% weight.
The 5th section crystalline data of table 5 are summed up
The 6th section crystalline data of table 6 are summed up
The acid of two kinds of different sourcess mixes
From exhausted LCD acid and the mixed of other a kind of acid with 7:3.If no special instructions, all data of impurity all are ppm in the table.
The data of two kinds of mixing acid of table 7 are summed up
The operation of mixing acid
Blended acid has been studied the obtainable separation case of single ion in crystallization experiment by this way.Experiment comprises two purification section and a recovery zone (purge zone).
Beginning (or initial) mixture crystallization in two said stages 1, the material that in the stage 1, produces q.s is used for the ensuing stage 2.Data are summarised in following table 8 and the table 9.
| Level is divided | Quality [g] | Mo | Al | Fe | Na | Si | SO 4 | H 3PO 3 | H 3PO 4[% weight] |
| Amount | 10,800 | 941 | 953 | 96 | 80 | 10 | 60 | 125 | 90.0 |
| Raffinate | 1,507 | 2,498 | 2,412 | 194 | 236 | 24 | 190 | 339 | 86.0 |
| The fusing level is divided | 3,535 | 1,242 | 1,161 | 99 | 113 | 14 | 80 | 156 | 89.3 |
| Xln | 5,758 | 349 | 443 | 69 | 19 | 4 | 14 | 50 | 91.5 |
| Level is divided | Quality [g] | Mo | Al | Fe | Na | Si | SO 4 | H 3PO 3 | H 3PO 4[% weight] |
| |
10，840 | 1,039 | 1,021 | 96 | 91 | 11 | 66 | 135 | 89.9 |
| Raffinate | 1,636 | 2,795 | 2,573 | 195 | 255 | 25 | 214 | 361 | 85.9 |
| The fusing level is divided | 3,163 | 1,381 | 1,240 | 99 | 138 | 17 | 87 | 171 | 89.1 |
| Xln | 6,041 | 385 | 486 | 69 | 22 | 4 | 16 | 55 | 91.4 |
The input stage branch in second stage 1 comprises the fusing level branch of fs 1.
The crystallization stage branch that dissolves from two stages 1 mixes, and the level that obtains is thus divided the material of the section of being used for 2.
Table 10The data of section 2 are summed up
| Level is divided | Quality [g] | Mo | Al | Fe | Na | Si | SO 4 | H3PO 3 | H 3PO 4[% weight] |
| Amount | 10,975 | 367 | 465 | 69 | 20 | 4 | 15 | 53 | 89.5 |
| Raffinate | 3,045 | 795 | 936 | 117 | 50 | 9 | 36 | 108 | 86.4 |
| The fusing level is divided | 3,107 | 336 | 408 | 60 | 18 | 4 | 14 | 49 | 89.6 |
| Xln | 4,823 | 117 | 205 | 44 | 2.8 | 1.5 | 2.0 | 20 | 91.4 |
Recovery zone
The raffinate in two stages 1 is mixed in together, the crystallization in recovery zone of a part of component.
Table 11 recovery zone data are summed up
| Level is divided | Quality [g] | Mo | Al | Fe | Na | Si | SO 4 | H 3PO 3 | H 3PO 4[% weight] |
| Amount | 2,392 | 2,653 | 2,496 | 195 | 246 | 25 | 202 | 350 | 2,392 |
| Raffinate | 355 | 6,125 | 5,298 | 412 | 733 | 61 | 601 | 925 | 335 |
| The fusing level is divided | 690 | 4,201 | 3,832 | 217 | 365 | 35 | 305 | 488 | 690 |
| Xln | 1,367 | 1,020 | 1,134 | 30 | 66 | 10 | 53 | 140 | 1,367 |
In this test, only used a recovery zone.Yet can consider, collect the raffinate of this recovery zone and processing again in one or more further recovery zones.In the mixing acid experiment, having obtained to be similar to previous experiments only uses the Mo of exhausted LCD acid respective stage effectively to separate with A l ionic.
Fig. 5 is with reference to exhausted LCD acid and other acid, shown that like the possible binding mixture of pickling acid the ratio of how using according to the method for the invention waste phosphoric acid is reduced to minimum degree.Single type of ionic content reduces through aforementioned dilution effect in the said input mixture that converges.In this way, for the raffinate of purity with identical pure acid and same ion content, can not mix the higher pure sour productive rate of acquisition separately than two kinds of acid through mixing.Among the embodiment here, can promptly reclaim one ton of pure acid and 400kg raffinate in 1.4 tons of mixing acid from one ton of LCD acid and the acid of 400kg corrosion-tank finishing process.Carry out independent purifying, can obtain pure acid of about 840kg and 560kg raffinate.
Through using " the etch acid " that obtains the phosphate discharge liquid amount, 100% phosphoric acid can recycle in the LCD production technique once more.
In the purification process that pollutes phosphoric acid; Phosphoric acid is as first input mixture of staple; Mix with second input mixture of phosphoric acid as staple, wherein first input mixture mainly contains first group of impurity, and second input mixture mainly contains second group of impurity.The impurity of maximum concentration is different in two groups of each mixtures.The crystallization in the multistage crystallization processes of the said input mixture that converges, the crystallizing layer that heating obtains is to extract pure phosphoric acid and to be molten in the level branch.The equipment that is used to realize this method is characterised in that the water device for supplying is provided, to regulate in the input mixture phosphoric acid weight percent to certain value.
Index
11 stationary crystallization devices
13,15,17,19 phosphoric acid levels are divided jar
21 raw phosphoric acid supply lines
23 supply line shut-off valves
25 first transfer limess
At the bottom of 27 molds
29 outlets
31 pipelines
32 shut-off valves
33,35,37,39 transferpumps
41 collectors
Connecting pipeline between 43,45,47,49 collectors and the jar
46,46,48,50 shut-off valves
51 discharge the raffinate pipeline
53 purifying phosphoric acid pipelines
54 water supply pipelines
55 first heat-exchanger surfaces
The shut-off valve of 56 pipelines 54
57,59 thermal barrier pipelines
60 second heat-exchanger surfaces
61 control loops
63 valves
Connection line between 65 pipelines 52 and the jar 15
67,89 valves
71 mixing tanks
73 baffle plates
Claims (24)
1. pass through the method for the phosphate aqueous solution of crystalline method purifying pollution; Relate to following input mixture, wherein said mixture contains plurality of impurities, and this impurity is selected from positively charged ion, negatively charged ion, acid and organic cpds; In the method; Contain the input mixture crystallization and the partial melting of contaminated phosphoric acid, the phosphoric acid with separation and purification is characterized in that:
-phosphoric acid is as first input mixture of staple, and it mainly contains first group of impurity, mixes with second input mixture of phosphoric acid as staple;
-said second input mixture mainly contains second group of impurity,
-wherein the impurity of maximum concentration is different each other in two kinds of input mixtures, and
-input mixture crystallization in the multistep crystallization method of converging, crystallizing layer that heating obtains and fusion classification are to extract the phosphoric acid of purifying.
2. according to the method for claim 1, it is characterized in that first and second groups of impurity all have different basically acid, negatively charged ion, positively charged ion or other chemical composition.
3. according to the method for claim 1 or claim 2, it is characterized in that first group contains molybdenum and/or aluminum ion as major impurity.
4. according to the method for claim 1 or claim 2, it is characterized in that second group contains iron and/or sodium ion and/or phosphorated acid as major impurity.
5. according to the method for claim 1 or 2, it is characterized in that first and second input mixtures are respectively the phosphoric acid that uses in the etch process, the phosphoric acid that is used for etch or raw phosphoric acid.
6. according to the method for claim 1 or 2, it is characterized in that using the input mixture more than two kinds, every kind has different major impurities.
7. a purifying is called as the method for the contaminated phosphoric acid of input mixture; Wherein said acid contains impurity; This impurity is selected from positively charged ion, negatively charged ion, acid and organic cpds, and wherein input mixture crystallization and partial melting in said method is characterized in that with the phosphoric acid of separation and purification:
-crystallization is carried out at a plurality of crystallized regions
-if desired, the content of phosphoric acid is adjusted to＜91% weight through adding water in the input mixture,
-cooling off said input mixture then, phosphoric acid deposits to crystal surface as crystallizing layer, and said crystallizing layer melts also classification subsequently to obtain the phosphoric acid of purifying.
8. according to the method for claim 7, be characterised in that through adding this method of water management to obtain the phosphoric acid hemihydrate.
9. according to the method for claim 7 or claim 8, be characterised in that the water yield that at every turn joins in the input mixture makes the content of phosphoric acid between 63%-91% weight.
10. according to the method for claim 7 or claim 8, be characterised in that the water yield that at every turn joins in the input mixture makes the content of phosphoric acid between 80%-91% weight.
11., be characterised in that the water yield that joins in the input mixture makes the content of phosphoric acid between 89%-90.5% weight at every turn according to the method for claim 7 or claim 8.
12. according to the method for claim 7 or 8, being characterised in that second heat-exchanger surface is installed in has a bit of distance with heat-exchanger surface or is in direct contact with it, and remains on low temperature always.
13. according to the method for claim 7 or 8, be characterised in that crystallization carries out at a plurality of crystallized regions, wherein the purity of input mixture increases to the higher crystalline section from low crystallized region.
14., be characterised in that crystallization carries out at least 3 crystallized regions according to the method for claim 13.
15., be characterised in that crystallization carries out at least 4 crystallized regions according to the method for claim 13.
16. according to the method for claim 7 or 8, be characterised in that the pollution phosphoric acid from industrial manufacture process directly joins in the hierarchical layer crystallization method, do not need preceding distillation.
17., be characterised in that the xln of certain crystallized region uses as next upper sector input mixture according to the method for claim 7 or 8.
18., be characterised in that the remaining level branch of collecting certain crystallized region and be mixed into next low crystallized region according to the method for claim 7 or 8.
19., be characterised in that the fusing level of collecting certain crystallized region respectively divides and join in the input mixture of same crystallized region according to the method for claim 7 or 8.
20. one kind is used for purifying by positively charged ion, negatively charged ion, acid, and/or the equipment of the phosphoric acid of orgnic compound pollution, has stationary crystallization device (11), this stationary crystallization utensil has first heat-exchanger surface; First thermal barrier flows through this surface and passes through pipeline (31,41,43,45; 49) with jar (13,15,17; 19) connect, be used for the intermediate storage of exhausted mixture, be characterised in that
Water feeder (54,56) is provided, is adjusted to certain value in order to part by weight with phosphoric acid in the input mixture.
21., be characterised in that generator is used for the measurement to phosphorus acid content and amount of water according to the equipment of claim 20.
22. equipment according to claim 20 or 21; Be characterised in that in the mold (11) second heat-exchanger surface is provided; Second thermal barrier flows through this surface in the operation, and second heat-exchanger surface (60) is installed in to be had a bit of distance with first heat-exchanger surface (55) or directly contact.
23. have the equipment of stationary crystallization device (11), it has first heat-exchanger surface (55), first thermal barrier is crossed and through pipeline (31,41 from this surface current; 43,45,49) with jar (13,15; 17,19) connect the intermediate storage that is used for the exhausted mixture, it is characterized in that:
Second heat-exchanger surface (60) is provided in the mold (11), and second thermal barrier flows through this surface in the operation, and said second heat-exchanger surface (60) is installed in to be had a bit of distance with first heat-exchanger surface (55) or directly contact.
24. according to the equipment of claim 23, being characterised in that provides first and second heater/coolers, itself and first and second heat-exchanger surfaces (55,60) connect.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH01401/07 | 2007-09-06 | ||
| CH01401/07A CH701939B1 (en) | 2007-09-06 | 2007-09-06 | Method and apparatus for the purification of aqueous phosphoric acid. |
Publications (2)
| Publication Number | Publication Date |
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| CN101423204A CN101423204A (en) | 2009-05-06 |
| CN101423204B true CN101423204B (en) | 2012-11-14 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN2008102128127A Active CN101423204B (en) | 2007-09-06 | 2008-09-05 | Method and device capable of purifying phosphoric acid using fractional crystallization |
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| Country | Link |
|---|---|
| JP (1) | JP5566585B2 (en) |
| KR (1) | KR101524742B1 (en) |
| CN (1) | CN101423204B (en) |
| CH (1) | CH701939B1 (en) |
| TW (1) | TWI491559B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2471739A1 (en) * | 2011-01-04 | 2012-07-04 | Solvay Sa | Process for the purification of phosphoric acid |
| HUE056370T2 (en) | 2013-01-14 | 2022-02-28 | Sulzer Management Ag | Multi-stage crystallisation process and apparatus to purify a compound |
| CN105668535B (en) * | 2015-12-31 | 2017-10-20 | 贵州开磷集团股份有限公司 | A kind of wet-process phosphoric acid concentration method and device |
| CN112661722B (en) * | 2021-01-30 | 2024-04-02 | 蔚林新材料科技股份有限公司 | Novel green cleaning process for refining 2-mercaptobenzothiazole |
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|---|---|---|---|---|
| US3890097A (en) * | 1974-05-06 | 1975-06-17 | Agrico Chem Co | Method of purifying wet process phosphoric acid |
| US4655790A (en) * | 1985-05-08 | 1987-04-07 | Freeport Research And Development Company | Phosphoric acid crystallization process |
| CN1403367A (en) * | 2002-09-28 | 2003-03-19 | 云南三环化工有限公司 | Purifying process of phosphoric acid produced via wet process |
| CN1843900A (en) * | 2006-05-08 | 2006-10-11 | 朱健 | Method for preparing electronic grade phosphoric acid by fusion crystallization method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4487750A (en) * | 1983-08-01 | 1984-12-11 | Freeport Minerals Company | Stabilization of wet process phosphoric acid |
| US4655789A (en) * | 1985-05-08 | 1987-04-07 | Freeport Research And Engineering Company | Phosphoric acid crystallization process |
| JP3131433B2 (en) * | 1989-12-21 | 2001-01-31 | 日本化学工業株式会社 | Method for producing high-purity phosphoric acid |
| JPH0716563A (en) * | 1993-06-30 | 1995-01-20 | Tosoh Corp | Separation of phosphate ion from phosphate ion-containing aqueous solution |
| JP3382561B2 (en) * | 1999-06-28 | 2003-03-04 | 日本化学工業株式会社 | High purity phosphoric acid |
| KR20040095151A (en) * | 2003-05-06 | 2004-11-12 | 류광현 | A method of refining phosphoric acid |
| KR100582524B1 (en) * | 2004-06-25 | 2006-05-23 | 주식회사 에이제이테크 | A method of recycling used etchant containing phosphoric acid |
| JP4766858B2 (en) * | 2004-09-02 | 2011-09-07 | 日本リファイン株式会社 | Method and apparatus for recovering phosphoric acid from metal-containing mixed acid aqueous solution containing phosphoric acid and at least one acid other than phosphoric acid |
| JP2008247733A (en) * | 2007-03-14 | 2008-10-16 | Niro Process Technology Bv | Purification of phosphoric acid rich stream |
-
2007
- 2007-09-06 CH CH01401/07A patent/CH701939B1/en unknown
-
2008
- 2008-08-19 TW TW097131576A patent/TWI491559B/en active
- 2008-08-25 JP JP2008215377A patent/JP5566585B2/en active Active
- 2008-09-05 KR KR1020080087617A patent/KR101524742B1/en active IP Right Grant
- 2008-09-05 CN CN2008102128127A patent/CN101423204B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3890097A (en) * | 1974-05-06 | 1975-06-17 | Agrico Chem Co | Method of purifying wet process phosphoric acid |
| US4655790A (en) * | 1985-05-08 | 1987-04-07 | Freeport Research And Development Company | Phosphoric acid crystallization process |
| CN1403367A (en) * | 2002-09-28 | 2003-03-19 | 云南三环化工有限公司 | Purifying process of phosphoric acid produced via wet process |
| CN1843900A (en) * | 2006-05-08 | 2006-10-11 | 朱健 | Method for preparing electronic grade phosphoric acid by fusion crystallization method |
Non-Patent Citations (1)
| Title |
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| JP特开2006-69845A 2006.03.16 |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI491559B (en) | 2015-07-11 |
| TW200916409A (en) | 2009-04-16 |
| KR20090026087A (en) | 2009-03-11 |
| KR101524742B1 (en) | 2015-05-29 |
| CN101423204A (en) | 2009-05-06 |
| JP5566585B2 (en) | 2014-08-06 |
| JP2009096709A (en) | 2009-05-07 |
| CH701939B1 (en) | 2011-04-15 |
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