CN101511452B - Process and equipment for the recovery of phosphoric acid from phosphoric acid-containing water - Google Patents
Process and equipment for the recovery of phosphoric acid from phosphoric acid-containing water Download PDFInfo
- Publication number
- CN101511452B CN101511452B CN200780031927XA CN200780031927A CN101511452B CN 101511452 B CN101511452 B CN 101511452B CN 200780031927X A CN200780031927X A CN 200780031927XA CN 200780031927 A CN200780031927 A CN 200780031927A CN 101511452 B CN101511452 B CN 101511452B
- Authority
- CN
- China
- Prior art keywords
- phosphoric acid
- water
- concentrated
- acid
- liquid chamber
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
- Treatment Of Water By Ion Exchange (AREA)
- Heat Treatment Of Water, Waste Water Or Sewage (AREA)
Abstract
A process and equipment which make it possible to recover high-purity phosphoric acid useful as a recycled matter in the form of a portable high-concentration liquid from phosphoric acid-containing water at high efficiency by simple constitution and operation. The process comprises subjecting phosphoric acid-containing water to both cation exchange and anion exchange, subjecting the resulting water to reverse osmosis under the condition of pH of 3 or below, preferably under the conditions of pH of 3 or below and a phosphoric acid concentration of 1 to 15wt%, to transmit acids (except phosphoric acid) and water to a permeating fluid chamber side with phosphoric acid concentrated on a concentrated fluid chamber side, desalting the permeating fluid with an ion exchanger to recover pure water, and evaporating the concentrated fluid with an evaporator to remove volatile components and water and recover a concentrated phosphoric acid solution.
Description
Technical field
The present invention relates to a kind ofly from phosphorous sour water (phosphoricacid-containing water), reclaim the method and apparatus of phosphoric acid, particularly relate to a kind of method and apparatus of recovery phosphoric acid of the pure water that is suitable for from the cleaning draining that contains phosphoric acid behind etching crystal liquid substrate or wafer and other electronic equipments, reclaiming valuable material such as phosphoric acid and conduct processing water through reverse osmosis unit.
Background technology
In the etching of crystal liquid substrate or wafer and other electronic equipments, use the etching solution that contains phosphoric acid.The high concentration spent etching solution that in etching work procedure, produces is recovered regeneration, but when cleaning the electronic equipment after the etching with pure water, generates a large amount of low concentration cleaning drainings.In such cleaning draining, except liquid etching composition phosphoric acid, nitric acid, acetic acid, other acid become to grade, also contain metal ion and other impurity in addition, but major part is a pure water owing to the stripping of etching institute.
Such etching is cleaned draining and is being handled through mixing with other drainings before.The treatment technology of the common draining that contains phosphoric acid or fluoric acid can be enumerated coagulating sedimentation (coagulationsedimentation) and handle.Yet when the coagulating sedimentation that carries out phosphoric acid or fluoric acid is handled since use a large amount of medicaments and produce a large amount of mud produce the processing cost rising, to the problems such as burden increase of environment.In addition; Owing to a large amount of medicaments that add in coagulating sedimentation is handled increase water soluble ion; Cause thereupon and carrying out water when reclaiming, because the operating pressure of reverse osmosis membrane processing rises and makes that power cost increases, water quality treatment worsens, produces incrustation scale and the use amount increase of regenerative agent in ion-exchange.
In patent documentation 1 (open 2006-75820 number of Japan Patent), utilize ion exchange resin to remove phosphoric acid, nitric acid plasma, reclaim pure water and phosphate.Yet, in the method, be recovered as phosphate (sodium dihydrogen phosphate etc.), but phosphate is at a discount basically, and the solubility of the sodium salt of phosphoric acid is less, therefore the containing ratio at aqueous phosphoric acid down is lower, difficult, it is relatively more expensive to process the required caustic potash of sylvite.In addition; Disclosed in order to make it become sodium dihydrogen phosphate liquid has been passed into the method in the H type resin cation; But have following shortcoming: the regeneration of resin cation need consume acid such as hydrochloric acid, and the NaOH that uses in the regeneration of resin anion (R.A.) also wastes and is discharged from etc.
Patent documentation 1: open 2006-75820 number of Japan Patent
[inventing problem to be solved]
Problem of the present invention is to propose a kind of method and apparatus that reclaims phosphoric acid; Can utilize simple formation and operation, low-cost, from phosphorous sour water, reclaim and can carry down and can be expeditiously high concentration aqueous as the high-purity phosphoric acid of regenerant.
Summary of the invention
The present invention is the following method and apparatus that from the phosphoric acid ionized water, reclaims phosphoric acid.
(1) a kind of recovery method of phosphoric acid, it is the method that from remove cationic phosphorous sour water, reclaims phosphoric acid, it is characterized in that:
In the pH value for being less than or equal under 3 the condition; To remove cationic phosphorous sour water supplies to and carries out reverse-osmosis treated in the reverse osmosis unit; Make acid and water beyond the phosphoric acid together be penetrated into infiltration liquid chamber side, reclaim Phosphoric Acid Concentration liquid at concentrated liquid chamber side concentrated phosphoric acid.
(2) a kind of recovery method of phosphoric acid, it is the method that from remove cationic phosphorous sour water, reclaims phosphoric acid, it is characterized in that:
The pH value for be less than or equal to 3 and phosphoric acid concentration be under the condition of 1 percentage by weight～15 percentage by weights; To remove cationic phosphorous sour water supplies to and carries out reverse-osmosis treated in the reverse osmosis unit; Make acid and water beyond the phosphoric acid together be penetrated into infiltration liquid chamber side, reclaim Phosphoric Acid Concentration liquid at concentrated liquid chamber side concentrated phosphoric acid.
(3) according to above-mentioned (1) or (2) described method, it is characterized in that: be recycled to the process that concentrates in the liquid chamber after having concentrate extraction, and interpolation is processed phosphorous sour water and carries out reverse-osmosis treated in the concentrate of circulation concentrated liquid chamber.
(4) according to above-mentioned (1) or (2) described method, it is characterized in that: have and be recycled to the process that concentrates in the liquid chamber after the concentrate that concentrates liquid chamber extracted out, and in the concentrate of circulation, add dilution water and carry out reverse-osmosis treated.
(5) according to above-mentioned (1) or (2) described method, it is characterized in that: before phosphorous sour water is supplied to reverse osmosis unit, carry out preliminary treatment and remove and comprise cation and/or anionic impurity.
(6) according to above-mentioned (1) or (2) described method, it is characterized in that: removal comprises the impurity of acid and reclaims pure water from the infiltration water of reverse osmosis unit.
(7) according to above-mentioned (6) described method, it is characterized in that: carry out the removal of impurity through ion interchange unit.
(8) method according to claim 1 and 2 is characterized in that: purifying is carried out in the acid through anion exchange from Phosphoric Acid Concentration liquid, removes beyond the phosphoric acid.
(9) method according to claim 1 and 2 is characterized in that evaporation and concentration Phosphoric Acid Concentration liquid, and water and volatile ingredient are together removed and concentrated.
(10) a kind of phosphoric acid retracting device, it is the device that from remove cationic phosphorous sour water, reclaims phosphoric acid, it is characterized in that having:
Reverse osmosis unit carries out reverse-osmosis treated for being less than or equal under 3 the condition to removing cationic phosphorous sour water in the pH value, acid beyond the phosphoric acid together is penetrated into water permeates the liquid chamber side, at concentrated liquid chamber side concentrated phosphoric acid;
Former water supply unit will be removed the concentrated liquid chamber side that cationic phosphorous sour water supplies to reverse osmosis membrane apparatus in the pH value for being less than or equal under 3 the condition;
Penetrating fluid extraction portion extracts penetrating fluid out from the infiltration liquid chamber side of reverse osmosis unit; And
Concentrated phosphoric acid liquid extraction portion extracts concentrated phosphoric acid liquid out from the concentrated liquid chamber side of reverse osmosis unit.
(11) a kind of phosphoric acid retracting device, it is the device that from remove cationic phosphorous sour water, reclaims phosphoric acid, it is characterized in that having:
Reverse osmosis unit; The pH value for be less than or equal to 3 and phosphoric acid concentration be to carry out reverse-osmosis treated to removing cationic phosphorous sour water under the condition of 1 percentage by weight～15 percentage by weights; Make acid and water beyond the phosphoric acid together be penetrated into infiltration liquid chamber side, at concentrated liquid chamber side concentrated phosphoric acid;
Phosphorous sour water supply unit, the pH value for be less than or equal to 3 and phosphoric acid concentration be will remove the concentrated liquid chamber side that cationic phosphorous sour water supplies to reverse osmosis unit under the condition of 1 percentage by weight～1 5 percentage by weights;
Penetrating fluid extraction portion extracts penetrating fluid out from the infiltration liquid chamber side of reverse osmosis unit;
Concentrated phosphoric acid liquid extraction portion extracts concentrated phosphoric acid liquid out from the concentrated liquid chamber side of reverse osmosis unit; And
Circulating path is recycled to the concentrated phosphoric acid liquid of from concentrated phosphoric acid liquid extraction portion, extracting out and concentrates the liquid chamber side.
(12) according to above-mentioned (10) or (11) described device, it is characterized in that: have the dilution water supply unit, in the concentrate that follows the endless path circulation, add dilution water.
(13) according to above-mentioned (10) or (11) described device, it is characterized in that: have pretreatment unit at former water supply unit, removal comprises cation and/or anionic impurity.
(14) according to above-mentioned (10) or (11) described device, it is characterized in that: have impurity removal means, from the infiltration water of reverse osmosis unit, remove the impurity that comprises acid.
(15) according to above-mentioned (14) described device, it is characterized in that: impurity removal means is an ion interchange unit.
(16) according to above-mentioned (10) or (11) described device, it is characterized in that: have purification devices, from Phosphoric Acid Concentration liquid, remove the acid beyond the phosphoric acid through anion exchange.
(17) according to above-mentioned (10) or (11) described device, it is characterized in that: have evaporation concentration device, evaporation and concentration Phosphoric Acid Concentration liquid is together removed volatile ingredient and water and is concentrated.
In the present invention; Become the phosphorous sour water of process object, so just can become object ad lib, preferably contain the phosphate ion of 50 mg/L～1 0000 mg/L, particularly contain the phosphate ion of 50 mg/L～2000 mg/L so long as contain the water of phosphoric acid; The pH value for be less than or equal to 3, particularly the pH value is for being less than or equal to 2.8; And also can pH value under any situation be more than or equal to 1, particularly the pH value be more than or equal to 1.8 acid water as process object, except that phosphate ion, can also contain sour compositions such as nitrate ion, acetic acid ion; Cations such as other anion and metal ion, other impurity.The present invention is particularly suitable for from the phosphorous sour water that contains other sour compositions such as nitrate ion, acetic acid ion, removes other sour compositions such as nitrate ion, acetic acid ion and reclaims the higher phosphoric acid of purity.
Particularly as process object and preferred phosphorous sour water can be after utilizing the phosphoric acid etching solution to carry out etching to crystal liquid substrate or wafer and other electronic equipments, the low concentration that carries out producing when pure water cleans cleans draining.The example of the cleaning draining after such etching can be the phosphate ion that contains 50mg/L～2000mg/L, the nitrate ion of 10mg/L～500mg/L, the acetic acid ion of 5mg/L～300mg/L, and the pH value is 1.8～2.8 acid water.
In the present invention, in order from phosphorous sour water, to reclaim phosphoric acid, preferably the pH value for be less than or equal to 3 and phosphoric acid concentration be under the condition of 1 percentage by weight～15 percentage by weights, phosphorous sour water is supplied in the reverse osmosis membrane apparatus and carries out reverse-osmosis treated.And in the present invention, before supplying to phosphorous sour water in the reverse osmosis membrane apparatus, preferably carry out preliminary treatment, removing cationic phosphorous sour water, and then remove and contain anionic impurity as process object.At this moment, can remove solid content, remove cations such as metal ion through cationic ion-exchange resin, and remove chloric acid or anion such as molybdic acid, organic acid complex compound etc. through anion exchange resin through precipitate and separate, filtration etc.The common device that can adopt according to above-mentioned purpose as the pretreatment unit that uses in such pretreatment process.
Metal ions such as the indium that contains in the cleaning draining after the etching, iron, aluminium become the reason that counter-infiltration in the film separation circuit (RO) film stops up; Reach the reason that high concentration can become membrane damage so if cross chloric acid or molybdic acid etc.; Therefore through removing these cations and anion, can prevent that film from stopping up or damage etc. and preferred.Cationic ion-exchange resin can use highly acid or weak-acid cation-exchange resin; Remove these cations if use H type storng-acid cation exchange resin to exchange; Sour composition in the treatment fluid is increased and be adjusted to pH value and be less than or equal to 3, therefore preferably.Cationic ion-exchange resin also can be chelating resin (chelate resin).Anion exchange resin can use strong basicity or weak-base anion-exchange resin.Anion exchange resin uses acid types such as phosphatic type, makes process such as phosphoric acid, nitric acid, acetic acid and removes other impurity anion.
In the present invention; Reverse osmosis unit in the film separation circuit is also referred to as the RO device; Constitute in such a way: be divided into infiltration liquid chamber and concentrated liquid chamber by counter-infiltration (RO) film; For being less than or equal under 3 the condition, and is under the condition of 1 percentage by weight～15 percentage by weights at phosphoric acid concentration further preferably in the pH value, phosphorous sour water is supplied to concentrate the liquid chamber side and carry out reverse osmosis membrane processing; Make acid and water beyond the phosphoric acid together be penetrated into infiltration liquid chamber side, and at concentrated liquid chamber side concentrated phosphoric acid.Concentrated liquid chamber side at reverse osmosis membrane apparatus has formed the phosphorous sour water supply unit of supplying with phosphorous sour water and the concentrated phosphoric acid liquid extraction portion of extracting concentrated phosphoric acid liquid out.Infiltration liquid chamber side at reverse osmosis membrane apparatus has formed the penetrating fluid extraction portion of extracting penetrating fluid out.Between concentrated phosphoric acid liquid extraction portion and phosphorous sour water supply unit, formed circulating path, made the concentrated phosphoric acid liquid of extracting out from concentrated phosphoric acid liquid extraction portion be recycled to concentrated liquid chamber side.Reverse osmosis membrane is to utilize osmotic pressure to make water infiltration, perhaps is pressurized to the pressure higher than osmotic pressure on the contrary and supplies with and be processed liquid, makes the water infiltration through counter-infiltration, does not make salinity, organic matter, other solute penetrations on the other hand and with the pellicle of its prevention.
If having above-mentioned characteristic, the material of reverse osmosis membrane do not have special restriction; For example can enumerate polyamide-based permeable membrane, polyimides is permeable membrane, cellulose-based permeable membrane etc.; Also can be asymmetric reverse osmosis membrane, preferably on little porous carrier, form the complex reverse osmosis membrane that has selection active surface separatory in fact.Get final product if reverse osmosis unit has such reverse osmosis membrane, preferably have make reverse osmosis membrane and supporting mechanism, the integrated membrane module that forms (membrane module) such as the mechanism that catchments.Membrane module does not have special restriction, for example can enumerate tubular film assembly, planar film assembly, spiral membrane assembly, hollow-fibre membrane (hollow fiber membrane) assembly etc.Reverse osmosis unit with these assemblies can use known reverse osmosis unit, the preferred high osmosis reverse osmosis unit of operation under low pressure.
Among the present invention; In the film separation circuit; In the pH value for being less than or equal under 3 the condition and being under the condition of 1 percentage by weight～15 percentage by weights further preferably at phosphoric acid concentration; Further be preferably under the condition of 2 percentage by weights～10 percentage by weights, phosphorous sour water supplied to carry out reverse-osmosis treated in the reverse osmosis membrane apparatus.When the pH value obtains phosphorous sour water down for being less than or equal to 3 state, can not regulate the pH value and directly supply in the reverse osmosis membrane apparatus, also can regulate the pH value through pH value conditioning agents such as interpolation hydrochloric acid, nitric acid as required.Also identical through utilizing cations such as cationic ion-exchange resin removal metal ion to be adjusted to the pH value in preliminary treatment for being less than or equal at 3 o'clock.Cleaning draining after etching crystal liquid substrate or wafer etc.; Usually in pH value for being less than or equal to acquisition under 3 the state; Therefore can not regulate pH value and directly supply in the reverse osmosis membrane apparatus, even the addition of pH value conditioning agent also tails off under the situation of adjusting pH value.
At phosphoric acid concentration is when obtaining phosphorous sour water under 1 percentage by weight～15 percentage by weights; Can directly carry out reverse-osmosis treated and utilize the separation of counter-infiltration; Yet when phosphoric acid concentration less than 1 percentage by weight; One side makes concentrate carry out reverse-osmosis treated through circulating path circulation one side, and can it be concentrated to phosphoric acid concentration thus is more than or equal to 1 percentage by weight.Perhaps can carry out concentration in advance, also can add the high concentration phosphorus acid solution of recovery through the enrichment facilities such as RO device of other setting.
Make concentrate carry out reverse-osmosis treated through one side through circulating path circulation one side; Be concentrated to phosphoric acid concentration for the time more than or equal to 1 percentage by weight; Also can carry out one side the phosphorous sour water circulation one side of low concentration is concentrated, be the batch processing that changes to new circulation fluid more than or equal to the time point of 1 percentage by weight being concentrated to phosphoric acid concentration; Perhaps; Preferably one side makes and is concentrated to the concentrate circulation that phosphoric acid concentration is 1 percentage by weight～15 percentage by weights; One side is added the phosphorous sour water that is processed of low concentration in the concentrate of circulation, extract a part of concentrate out as Phosphoric Acid Concentration liquid at every turn, handles and carry out apparent blanket formula.After extracting the concentrate that concentrates liquid chamber out, be recycled in the process that concentrates in the liquid chamber, carry out reverse-osmosis treated, can improve the clearance of the acid beyond the phosphoric acid through in the concentrate of circulation, adding dilution water.Dilution water can use the recycle-water of from infiltration water, having removed impurity.
If will remove cationic phosphorous sour water under 3 the condition and supply to and carry out reverse-osmosis treated in the reverse osmosis unit for being less than or equal in the pH value; Acid beyond the phosphoric acid such as nitric acid, acetic acid and water together permeate from reverse osmosis membrane and transfer to infiltration liquid chamber side so, and extract out from infiltration liquid chamber side.Phosphoric acid stops the infiltration of reverse osmosis membrane, remains in to concentrate the liquid chamber side and concentrated, and therefore can reclaim with the form of Phosphoric Acid Concentration liquid from concentrating the liquid chamber side.The concentrate that concentrates the liquid chamber side also can be summed up formula and pass through, and also can make its circulation in addition and improves enrichment factor.In the pH value for to be less than or equal under the condition of 3 (and phosphoric acid concentration less than 1 percentage by weights); Phosphorous sour water is supplied to when carrying out reverse-osmosis treated in the reverse osmosis unit, and can to make the pressure that supplies to the phosphorous sour water in the reverse osmosis unit be 0.3MPa～3MPa, be preferably 0.5MPa～1.5MPa.
Though the acid in concentrate beyond residual a spot of phosphoric acid; If but be to carry out reverse-osmosis treated under the condition of 1 percentage by weight～15 percentage by weights at phosphoric acid concentration; The prevention rate of the acid beyond the phosphoric acid is understood step-down so; And permeability uprises, and therefore can reclaim the Phosphoric Acid Concentration liquid of purity.The pH value for be less than or equal to 3 and phosphoric acid concentration be under the condition of 1 percentage by weight～15 percentage by weights; Phosphorous sour water is supplied to when carrying out reverse-osmosis treated in the reverse osmosis unit, and can to make the pressure that supplies to the phosphorous sour water in the reverse osmosis unit be 0.3MPa～5MPa, be preferably 0.5MPa～3MPa.
If will compare at the ionic substance in the reverse osmosis membrane infiltration and the infiltration of nonionic material; Even we can say so under the situation of the molecular weight of same degree; Ionic substance is compared with the nonionic material, and the reverse osmosis membrane prevention rate of ionic substance receives inundatory prevention more easily.Yet; People such as present inventor have carried out research repeatedly; The result finds different with such general knowledge is, if be to be less than or equal under 3 the condition to carry out reverse osmosis membrane processing in the pH value that phosphoric acid is difficult to dissociate, phosphoric acid is compared with nitric acid or acetic acid so; The prevention rate of phosphoric acid uprises overwhelmingly, can acid beyond the phosphoric acid such as nitric acid or acetic acid and phosphoric acid separately be reclaimed.Supposition phosphoric acid under lower pH value by the reason that reverse osmosis membrane stops strongly is: phosphoric acid becomes the form of heavy phosphoric acid and causes the molecule quantitative change big, and the prevention rate raises.
In the pH value for being less than or equal under 3 the condition; The prevention rate of the acid beyond the phosphoric acid such as nitric acid, acetic acid is lower; And the prevention rate when common phosphoric acid etching solution being carried out the film processing is for being less than or equal to 1%; Yet phosphoric acid concentration is high more, and the prevention rate of the acid beyond the phosphoric acid becomes low more, becomes negative value in the prevention rate of phosphoric acid concentration acid beyond the phosphoric acid for more than or equal to 1 percentage by weight the time.Wherein, so-called prevention rate is the ratio that reverse osmosis membrane stops solute penetration, shown in following formula (1).
Prevention rate (%)=(1-C
3/ (C
1C
2)
1/2) * 100... (1)
(in the formula (1), C
1Be solute concentration, the C that supplies with the liquid inlet
2Be solute concentration, the C of concentrated solution outlet
3It is the solute concentration of penetrating fluid.)
In formula (1), ((C
1C
2)
1/2) expression geometrical mean (geometric average), (C
3/ (C
1C
2)
1/2) concentration of expression penetrating fluid solute is with respect to the ratio of (how much) mean concentration of concentrate solute.Therefore the prevention rate is low more, and the expression solute is penetrated into permeate side more.Think easily that in common notion the prevention rate does not become negative value; But in formula (1), can exist the prevention rate to become the phenomenon of negative value owing to the formation of formula; This situation representes that the solute concentration of penetrating fluid is higher than the solute concentration of concentrate, and solute permeates with high permeability.
When the prevention rate of phosphoric acid concentration acid beyond the phosphoric acid for more than or equal to 1 percentage by weight the time becomes negative value; This means when phosphoric acid concentration for more than or equal to 1 percentage by weight, particularly more than or equal to 2 percentage by weights the time; Remain in the acid concentration step-down beyond the phosphoric acid in the concentrate, obtain the higher Phosphoric Acid Concentration liquid of purity.If the phosphoric acid concentration of concentrate is too high, can not carry out film and handle owing to the relation of osmotic pressure becomes so, so the phosphoric acid concentration of concentrate on be limited to 15 percentage by weights, be preferably 10 percentage by weights.One side makes the concentrate circulation of such phosphoric acid concentration; One side interpolation in the concentrate of circulation is processed phosphorous sour water; Each extract a part of concentrate out and sum up the formula processing, can keep above-mentioned phosphoric acid concentration so and handle expeditiously as Phosphoric Acid Concentration liquid.
One side makes concentrate circulation one side carry out film when handling, and the cycle-index of concentrate is many more, and the acid beyond the phosphoric acid contacts with reverse osmosis membrane and the chance of from film, permeating becomes many more so, can further reduce the phosphoric acid concentration of acid in concentrate in addition.If this moment, phosphoric acid concentration surpassed 15 percentage by weights; Osmotic pressure (operation is pressed) becomes too high so; Become and to carry out film and handle, therefore dilute and make its circulation, carry out reverse-osmosis treated through in concentrate, adding dilution water; The concentration of the acid beyond the phosphoric acid can be further reduced, highly purified Phosphoric Acid Concentration liquid can be reclaimed.Dilution water can recycle the recycle-water of from infiltration water, having removed impurity.
Contain the acid such as phosphoric acid, nitric acid, acetic acid of infiltration the infiltration water of the reverse osmosis membrane apparatus of extracting out from infiltration liquid chamber side,, can reclaim pure water therefore through utilizing impurity removal means from the infiltration water of reverse osmosis membrane apparatus, to remove these sour and other impurity.At this moment, impurity removal means can adopt the ion interchange unit that has used ion exchange resin.Make infiltration water pass through anion exchange resin layer, can remove these acid, other anion; Make infiltration water pass through cation exchange resin layer and anion exchange resin layer or their mixed bed (mixed bed) in addition, can remove acid, other anion and residual cation beyond the phosphoric acid such as acetic acid or nitric acid, thereby reclaim pure water.Anion exchange resin used herein is preferably OH type strong basicity or weak-base anion-exchange resin, and in addition, cationic ion-exchange resin is preferably H type storng-acid cation exchange resin.
In common ion interchange unit; In regeneration of ion-exchange resin; Use acid as regenerative agent during the cation regenerant exchanger resin, use alkali during the anion regenerant exchanger resin, but in these renovation process, have essential regenerative agent as regenerative agent; And produce unfavorable factors such as regeneration liquid waste, the electric regenerative ion interchange unit of therefore preferred employing.Electricity regenerative ion interchange unit is to divide resinbed with cation exchange resin membrane and anion-exchange resin membrane; Disposed the device of negative electrode and anode at both ends; Identical with electric dialyzator, one side energising on negative electrode and anode is regenerated and is simultaneously fed liquid and carry out ion-exchange.At this moment, can need not the special operation and the regenerative agent that are used for regenerating, extract acid and other impurity out continuously and reclaim pure water.The ion exchange resin that in electric regenerative ion interchange unit, uses only is when removing acid and other anion; Can only fill anion exchange resin; Be under the situation of purpose to remove other residual cations, can filling male ion-exchange resin and the mixed bed of anion exchange resin.The sour concentrate of discharging owing to regeneration becomes the concentrate of phosphoric acid, nitric acid, acetic acid etc., so can handle through the biological denitrificaion method.
On the other hand, removed the major part the acid beyond the phosphoric acid such as nitric acid or acetic acid, can further utilize the purifying of post processing, be used for they removals are improved purity, the concentration that reclaims phosphoric acid liquid from the Phosphoric Acid Concentration liquid that concentrates the extraction of liquid chamber side.The purifying that utilizes post processing can be to carry out purifying through the acid that anion exchange is removed from Phosphoric Acid Concentration liquid beyond the phosphoric acid.At this moment, the anion exchange device is set, makes concentrate pass through anion exchange resin layer, can from concentrate, remove strong acid ions such as nitric acid, reclaim the high-concentration phosphoric acid that is substantially free of strong acid ions such as nitric acid as purification devices.In reverse osmosis unit, make concentrate circulation and when concentrating, purification devices can be arranged on the concentrate recycle circuit of reverse osmosis unit, perhaps preferably is arranged on the circuit of extraction concentrate from recycle circuit.Anion exchange resin is preferably OH type or PO
4The strong-base anion-exchange resin of type.
In Phosphoric Acid Concentration liquid during residual acetic acid; Acetic acid can not be removed by anion exchange resin fully; Improve purity, the concentration that reclaims phosphoric acid liquid in order to remove volatile ingredients such as acetic acid; Can be in evaporation concentration device evaporation and concentration Phosphoric Acid Concentration liquid, volatile ingredient and water are together removed and are concentrated, reclaim the high-concentration phosphoric acid that is substantially free of volatile ingredients such as acetic acid.Evaporation concentration device can use known devices such as rotary evaporator.
The phosphoric acid that reclaims by the way can be used as regenerant, and can carry down the aqueous of high concentration, and can be recovered as highly purified concentrated phosphoric acid.At this moment, carry out reverse-osmosis treated for being less than or equal under 3 the condition, obtain down for being less than or equal to 3 acid state in pH value usually as the phosphorous sour water of former water in the pH value, therefore can adjusting easily through pH conditioning agent such as injection hydrochloric acid.
In addition; In order to the method and apparatus that reclaims; Can utilize simple formation and operation, for being less than or equal to 3, according to circumstances further under phosphoric acid concentration is the condition of 1 percentage by weight～15 percentage by weights, carrying out reverse-osmosis treated, reclaim Phosphoric Acid Concentration liquid thus in the pH value.Can reduce the use amount of regenerative agent, the growing amount of discarded object through this mode, reduce processing cost, reclaim highly purified concentrated phosphoric acid and pure water.
[invention effect]
As stated; According to the present invention; Through in the pH value for being less than or equal under 3 the condition; To remove cationic phosphorous sour water and supply to and carry out reverse-osmosis treated in the reverse osmosis unit, and acid beyond the phosphoric acid together will be penetrated into water permeate the liquid chamber side, reclaim Phosphoric Acid Concentration liquid at concentrated liquid chamber side concentrated phosphoric acid; Can utilize simple formation and operation, low-cost, from phosphorous sour water, reclaim and can carry down and can be expeditiously high concentration aqueous as the high-purity phosphoric acid of regenerant.
In addition; According to the present invention; Through the pH value for be less than or equal to 3 and phosphoric acid concentration be will remove cationic phosphorous sour water under the condition of 1 percentage by weight～15 percentage by weights to supply to and carry out reverse-osmosis treated in the reverse osmosis unit; Make acid and water beyond the phosphoric acid together be penetrated into infiltration liquid chamber side,, reclaim Phosphoric Acid Concentration liquid at concentrated liquid chamber side concentrated phosphoric acid; Can utilize simple formation and operation, further low-cost, from phosphorous sour water, reclaim and can carry down and can be expeditiously high concentration aqueous as the high-purity phosphoric acid of regenerant.
Description of drawings
Fig. 1 is phosphoric acid recovery method and a flow chart of device in the example.
Fig. 2 is phosphoric acid recovery method and the flow chart of device in other examples.
Fig. 3 is the result's of expression embodiment 3 a coordinate diagram.
[explanation of symbol]
1: former tank 1a: former water
2: cation exchange tower 2a: cation exchange resin layer
3: concentrate liquid bath 3a: concentrate
4: reverse osmosis unit 4a: reverse osmosis membrane
4b: infiltration liquid chamber 4c: concentrate liquid chamber
5: anion exchange tower 5a, 5c: anion exchange resin layer
5b: the 2nd anion exchange tower 6: electric regenerative ion interchange unit
6a: the 6b of desalting chamber: enriched chamber
6c: anion-exchange membrane 6d, 6f: cation-exchange membrane
6e: cathode chamber 6g: anode chamber
6h, 6i: mix bed formula ion exchange layer 7: reclaim tank
7a: recycle-water 8: evaporation concentration device
9: reclaim phosphoric acid groove 9a: reclaim phosphoric acid liquid
10: biological denitrification apparatus P: force (forcing) pump
P2: pump
L1, L2, L3, L4, L5, L6, L7, L8, L9, L10, L11, L12, L13, L14, L15, L16, L17, L18, L21, L22, L23, L24, L25, L26, L27, L28, L31, L32, L33, L34, L35, L36, L37, L38, L39, L40, L41, L42, L43: circuit
The specific embodiment
Through Fig. 1 an example of the present invention is explained.Fig. 1 is the flow chart of a phosphoric acid retracting device in the example.The 1st, former tank is used for accumulating former water 1a.The 2nd, cation exchange tower has cation exchange resin layer 2a.The 3rd, concentrate liquid bath, be used for accumulating concentrate 3a.The 4th, reverse osmosis unit is divided into infiltration liquid chamber 4b and concentrated liquid chamber 4c by reverse osmosis membrane 4a.The 5th, anion exchange tower has anion exchange resin layer 5a.The 7th, reclaim tank, be used for accumulating recycle-water 7a.5b is the 2nd anion exchange tower, has anion exchange resin layer 5c.The 8th, evaporation concentration device makes volatile ingredient together evaporate with water through distillation and separates concentrated phosphoric acid liquid.The 9th, reclaim phosphoric acid groove, be used for accumulating recovery phosphoric acid liquid 9a.
In Fig. 1, P is a force (forcing) pump, together constitutes former water supply unit with former tank 1, cation exchange tower 2 and concentrated liquid bath 3, and wherein cation exchange tower 2 constitutes pretreatment units.Anion exchange tower 5 constitutes penetrating fluid extraction portions with recovery tank 7, and wherein anion exchange tower 5 constitutes impurity removal means.In addition, the 2nd anion exchange tower 5b, evaporation concentration device 8 and recovery phosphoric acid groove 9 constitute concentrated phosphoric acid liquid extraction portions, and wherein the 2nd anion exchange tower 5b and evaporation concentration device 8 constitute purification devices.
To in above-mentioned phosphoric acid retracting device, carry out pretreatment process and utilize the former water 1a (phosphoric acid ionized water) of removal impurity such as precipitate and separate, filtration to import to the former tank 1 from circuit L1.Former water 1a in the former tank 1 is imported in the cation exchange tower 2 from circuit L2 and passes through, carry out cation exchange, with cation exchange sorptions such as the aluminium that contains in the former water, indium, other metal ions and remove at cation exchange resin layer 2a.Preferably in cation exchange resin layer 2a, use H type storng-acid cation exchange resin.When cation exchange resin layer 2a reaches capacity, feed the regenerative agent that contains acid such as hydrochloric acid from circuit L3 and make its regeneration, from circuit L4, reclaim and dissolve the cation that leaves.
To be decationized Y sieve water from circuit L5 import to concentrates the liquid bath 3 and accumulate with the processing water of cation exchange tower 2.Usually in pH value for being less than or equal under 3 the acid state acquisition as the phosphorous sour water of former water; Even and under pH value condition with higher; Make it become the pH value through generate acid as pretreated cation exchange for being less than or equal to 3 state; Therefore be to be less than or equal to when carrying out reverse-osmosis treated under 3 the condition in pH value, can directly supply in the reverse osmosis unit 4.The higher former water of pH value being carried out the pH value when regulating, obtain phosphorous sour water down near 3 state in pH value, so can come easily to regulate through pH conditioning agents such as injection hydrochloric acid in circuit L5 or concentrated liquid bath 3.
The decationized Y sieve water (concentrate 3a) of concentrated liquid bath 3 is pressurizeed by force (forcing) pump P and from circuit L6, imports among the concentrated liquid chamber 4c of reverse osmosis unit 4; Carry out reverse-osmosis treated through reverse osmosis membrane 4a; Make acid and water beyond the phosphoric acid such as nitric acid, acetic acid together be penetrated into infiltration liquid chamber 4b side, at concentrated liquid chamber 4c side concentrated phosphoric acid.If phosphorous sour water is neutralized, under the state of neutrality, carry out reverse-osmosis treated, the salt of the acid beyond the phosphoric acid such as nitric acid, acetic acid and the salt of phosphoric acid all can not penetrate from reverse osmosis membrane 4a so, concentrate in concentrated liquid chamber 4c side.With respect to this; If phosphorous sour water is not neutralized; Carry out reverse-osmosis treated in the pH value for being less than or equal to import in the reverse osmosis unit 4 under 3 the condition; Because phosphoric acid is stoped infiltration by reverse osmosis membrane 4a and concentrates in concentrated liquid chamber 4c side, the acid beyond the phosphoric acid such as nitric acid, acetic acid together is penetrated into infiltration liquid chamber 4b side with water and separates so.Import to phosphorous sour water in the reverse osmosis unit 4 by decationized Y sieve, therefore do not stop up reverse osmosis membrane 4a, can the efficient of reverse-osmosis treated be maintained higher level.
The penetrating fluid that is penetrated among the infiltration liquid chamber 4b of reverse osmosis unit 4 imports to the anion exchange tower 5 from circuit L7, and 5a carries out anion exchange through anion exchange resin layer.The anion of removing beyond the phosphate ions such as the nitric acid that contains in the penetrating fluid, acetic acid through the exchange sorption thus carries out purifying, will handle water and from circuit L8, be retracted in the recovery tank 7, accumulates as recycle-water 7a.In anion exchange tower 5, use the anion exchange resin layer 5a filled OH type strong-base anion-exchange resin, also can adopt with the multilayer of H type cationic ion-exchange resin or mix a bed formula, remove the impurity beyond the anion.When the anion of anion exchange resin layer 5a beyond phosphate ion reaches capacity; The regenerative agent that contains alkali of alkaline aqueous solution and so on that can from circuit L9, feed 2 percentage by weights～10 percentage by weights of NaOH, potassium hydroxide etc. makes its regeneration, discharges from circuit L10 dissolving the salt that leaves.When using cationic ion-exchange resin, can feed the regenerative agent that contains acid and make its regeneration.
The concentrate that concentrates at the concentrated liquid chamber 4c of reverse osmosis unit 4 imports to from circuit L11 among the 2nd anion exchange tower 5b and passes through; And carry out anion exchange at anion exchange resin layer 5c; Anion exchange sorption beyond the phosphate ion such as residual nitric acid, acetic acid in the concentrate is removed, to carry out purifying.At this moment, anion exchange resin layer 5c uses OH type or PO
4The strong-base anion-exchange resin of type.Anion exchange resin is higher than phosphate ion for the anionic selectivity beyond the phosphate ions such as nitric acid in low pH value scope, therefore separate with phosphate ion easily.When the anion of anion exchange resin layer 5c beyond phosphate ion reaches capacity, contain the regenerative agent of alkali and make its regeneration, discharge from circuit L13 dissolving the salt that leaves from circuit L12 feeding.
Even when in the 2nd anion exchange tower 5b, having removed anionic phosphoric acid solution beyond the phosphate ion and having contained volatile ingredient such as acetic acid; From circuit L14, import in the evaporation concentration device 8 and distill; Volatile ingredient is together evaporated with water and it is separated, from circuit L15, discharge.The Phosphoric Acid Concentration liquid of in evaporation concentration device 8, removing volatile ingredient and concentrating imports to the recovery phosphoric acid groove 9 from circuit L16, accumulates as reclaiming phosphoric acid liquid 9a.Evaporation concentration device 8 can use known evaporation concentration devices such as rotary evaporator.Concentrate among the concentrated liquid chamber 4c of reverse osmosis unit 4 can be recycled to concentrate the liquid bath 3 and improve enrichment factor from circuit L17 or L18, and accumulates and be concentrate 3a.
The phosphoric acid liquid 9a that utilizes said method to reclaim can be used as regenerant, and owing to be can carry out the carrying in the practicality aqueous the recovery down of high concentration, and can be used as highly purified concentrated phosphoric acid and reclaim.At this moment; Though carry out reverse-osmosis treated for being less than or equal under 3 the condition in the pH value, be to be less than or equal under 3 the acid state acquisition in pH value usually as the phosphorous sour water of former water, even and under pH value condition with higher; Also can become the pH value for being less than or equal to 3 state through make it as pretreated cation exchange; Therefore be to be less than or equal to when handling under 3 the condition in pH value, can directly supply with, and need not to regulate especially the pH value.The cation that medicaments such as acid, alkali only limit in the cation exchange tower 2 is used regenerative agent with the anion among regenerative agent and anion exchange tower 5 and the 2nd anion exchange tower 5b, need not to be used to reclaim the medicament of phosphoric acid.In addition, in order to the method and apparatus that reclaims, can simply constitute and operation through utilizing, be to be less than or equal under 3 the condition to carry out reverse-osmosis treated in pH value, reclaims as Phosphoric Acid Concentration liquid.Can reduce the use amount of regenerative agent, the growing amount of discarded object thus, reduce processing cost, reclaim highly purified concentrated phosphoric acid and pure water.
As stated; In the pH value for being less than or equal under 3 the condition; Phosphorous sour water is supplied in the reverse osmosis unit 4, utilize reverse osmosis membrane 4a to carry out reverse-osmosis treated, make acid and water beyond the phosphoric acid together be penetrated into infiltration liquid chamber 4b side; At concentrated liquid chamber 4c side concentrated phosphoric acid; Reclaim pure water and Phosphoric Acid Concentration liquid, can utilize simple formation and operation thus, low-cost, from phosphorous sour water, reclaiming expeditiously can be at the aqueous high-purity phosphoric acid of carrying down and can being used as regenerant of high concentration.
Then other examples of the present invention are explained through Fig. 2.Fig. 2 is phosphoric acid recovery method and the flow chart of device in other examples.The 1st, former tank is in order to accumulate former water 1a.The 2nd, cation exchange tower has cation exchange resin layer 2a.The 3rd, concentrate liquid bath, be used for accumulating concentrate 3a.The 4th, reverse osmosis unit is divided into infiltration liquid chamber 4b and concentrated liquid chamber 4c by reverse osmosis membrane 4a.The 5th, anion exchange tower has anion exchange resin layer 5a.The 6th, electric regenerative ion interchange unit; Be divided into 6a of desalting chamber and the 6b of enriched chamber by anion-exchange membrane 6c; The outside at the 6a of desalting chamber marks off cathode chamber 6e by cation-exchange membrane 6d, and the outside of 6b marks off the 6g of anode chamber by cation-exchange membrane 6f in the enriched chamber, at 6a of desalting chamber and the 6b of enriched chamber mixed bed formula ion exchange layer 6h, 6i is being set; At cathode chamber 6e negative electrode (-) is being set, 6g is being provided with anode (+) in the anode chamber.The 7th, reclaim tank, be used for accumulating recycle-water 7a.The 8th, evaporation concentration device makes volatile ingredient together evaporate with water through distillation and separates, and concentrated phosphoric acid liquid.The 9th, reclaim phosphoric acid groove, be used for accumulating recovery phosphoric acid liquid 9a.The 10th, biological denitrification apparatus.
In Fig. 2, P is a force (forcing) pump, together constitutes former water supply unit with former tank 1, cation exchange tower 2, anion exchange tower 5 and concentrated liquid bath 4, and wherein cation exchange tower 2 constitutes pretreatment units with anion exchange tower 5.Electricity regenerative ion interchange unit 6 constitutes penetrating fluid extraction portions with recovery tank 7, and wherein electric regenerative ion interchange unit 6 constitutes impurity removal means.In addition, evaporation concentration device 8 constitutes concentrated phosphoric acid liquid extraction portions with recovery phosphoric acid groove 9, and wherein evaporation concentration device 8 constitutes purification devices.
Will be in above-mentioned phosphoric acid retracting device, carried out pretreatment process and former water 1a (phosphoric acid ionized water) through removal impurity such as precipitate and separate, filtrations imports to the former tank 1 from circuit L21.Former water 1a in the former tank 1 imports to the cation exchange tower 2 and passes through from circuit L22, carries out cation exchange at cation exchange resin layer 2a, with cation exchange sorptions such as the aluminium that contains in the former water or indium, other metal ions and remove.Preferably in cation exchange resin layer 2a, use H type storng-acid cation exchange resin.When cation exchange resin layer 2a reaches capacity, from circuit L23, feed the regenerative agent contain acid such as hydrochloric acid and make its regeneration, reclaim the molten cation that leaves from circuit L24.
With the processing water in the cation exchange tower 2 is that decationized Y sieve water imports in the anion exchange tower 5 from circuit L25 and passes through; Carry out anion exchange at anion exchange resin layer 5a, the anion exchange sorption such as chloric acid or molybdic acid, organic acid complex compound excessively that contains in the former water is removed.Preferably in anion exchange resin layer 5a, use the strong-base anion-exchange resin of phosphatic type.When anion exchange resin layer 5a reaches capacity, from circuit L26, feed the regenerative agent that contains alkali such as NaOH and make its regeneration, reclaim from circuit L27 and dissolve the anion that leaves., from circuit L26 feed acid such as phosphoric acid, make anion exchange resin become phosphatic type thereafter.
Processing water in the anion exchange tower 5 is imported to the concentrated liquid bath 3 from circuit L28.Usually pH value for be less than or equal to 3 acid state down acquisition, can directly supply in the reverse osmosis unit 4 in being to be less than or equal to when carrying out reverse-osmosis treated under 3 the condition in the pH value as the phosphorous sour water of former water.The higher former water of pH being carried out the pH value when regulating, obtain phosphorous sour water down near 3 state in pH value, so can easily regulate through pH conditioning agent such as injection hydrochloric acid in circuit L28 or concentrated liquid bath 3.
Phosphorous sour water in the concentrated liquid bath 3 is pressurizeed by force (forcing) pump P and from circuit L31, imports among the concentrated liquid chamber 4c of reverse osmosis unit 4; Carry out film through reverse osmosis membrane 4a and separate (reverse-osmosis treated); Make acid and water beyond the phosphoric acid such as nitric acid, acetic acid together be penetrated into infiltration liquid chamber 4b side, at concentrated liquid chamber 4c side concentrated phosphoric acid.If reverse-osmosis treated is carried out in phosphorous sour water neutralization under the state of neutrality, the salt and the phosphate of the acid beyond the phosphoric acid such as nitric acid, acetic acid all can not penetrate from reverse osmosis membrane 4a so, concentrate in concentrated liquid chamber 4c side.With respect to this; If phosphorous sour water is not neutralized; Carry out reverse-osmosis treated in the pH value in the reverse osmosis unit 4 for being less than or equal to import under 3 the condition; So because phosphoric acid is stoped infiltration by reverse osmosis membrane 4a, and phosphoric acid is concentrated in concentrated liquid chamber 4c side, the acid beyond the phosphoric acid such as nitric acid, acetic acid and water together are penetrated into and permeate liquid chamber 4b side and separate.Import to phosphorous sour water in the reverse osmosis unit 4 by decationized Y sieve, therefore do not stop up reverse osmosis membrane 4a, can the efficient of reverse-osmosis treated be maintained higher level.
The phosphorous sour water of the former water of conduct that obtains from circuit L28 is that 1 percentage by weight～15 percentage by weights are when obtaining with phosphoric acid concentration; Can directly carry out the film separating treatment and utilize counter-infiltration to separate; When phosphoric acid concentration less than 1 percentage by weight; The concentrate that to from concentrate liquid chamber 4c, extract out through circuit L32, one side are that circuit L33 is recycled to and concentrates the liquid bath 3 one side and carry out the film separating treatment from circulating path, can be concentrated to phosphoric acid concentration thus for more than or equal to 1 percentage by weight.At this moment, can carry out one side the phosphorous sour water circulation one side of low concentration is concentrated, be the batch processing that 1 percentage by weight or the time point more than 1 percentage by weight change to circulation fluid being concentrated to phosphoric acid concentration; Perhaps; Preferably one side makes and is concentrated to the concentrate circulation that phosphoric acid concentration is 1 percentage by weight～15 percentage by weights; One side is added the phosphorous sour water that is processed of low concentration in the concentrate of circulation; The a part of concentrate of each extraction is handled and carry out apparent blanket formula as Phosphoric Acid Concentration liquid from circuit L34.
The penetrating fluid that is penetrated among the infiltration liquid chamber 4b of reverse osmosis unit 4 imports to the 6a of desalting chamber of electric regenerative ion interchange unit 6 from circuit L35; One side applies voltage and carries out electricity regeneration between anode (+) and negative electrode (-), one side is carried out desalination through ion-exchange.Remove anion such as the phosphoric acid that contains in the penetrating fluid, nitric acid, acetic acid and residual cation thus through the exchange sorption and carry out purifying, will handle water to be retracted to the recovery tank 7, accumulate as recycle-water 7a from circuit L36.In the 6a of desalting chamber; Sorption is penetrated among the 6b of enriched chamber through anion-exchange membrane 6c at the anion such as acid that mix bed formula ion exchange layer 6h; Sorption is mixing on the bed formula ion exchange layer 6i; Therefore simultaneously the part of penetrating fluid is flow into the 6b of enriched chamber from circuit L37, simultaneously utilize regeneration that the anion of sorption is dissolved and leave, deliver to from circuit L 38 and carry out the biological denitrificaion processing the biological denitrification apparatus 10.Sorption at the cation permeability that mixes bed formula ion exchange layer 6h in cathode chamber 6e, so electrode solution 6g flows to cathode chamber 6e through circuit L39 from the anode chamber, discharge from circuit L40.
The part of the concentrate that concentrates at the concentrated liquid chamber 4c of reverse osmosis unit 4, extracts out from circuit L 34 imports to the evaporation concentration device 8 distills, and volatile ingredient such as acetic acid is together evaporated with water and it is separated, and discharges from circuit L41.The Phosphoric Acid Concentration liquid of in evaporation concentration device 8, removing volatile ingredient and concentrating imports to the recovery phosphoric acid groove 9 from circuit L42, accumulates as reclaiming phosphoric acid liquid 9a.Evaporation concentration device 8 can use known evaporation concentration devices such as rotary evaporator.
Through the pH of phosphorous sour water value for be less than or equal to 3 and phosphoric acid concentration be that the film that carries out reverse osmosis unit 4 under the condition of 1 percentage by weight～15 percentage by weights separates (reverse-osmosis treated); Acid beyond the phosphoric acid is permeated with high permeability; Improve the purity of phosphoric acid; Yet,, can increase chances of these acid infiltrations and improve permeability through the chance that concentrate circulation increasing film is separated in order further to reduce the concentration of the acid beyond the phosphoric acid in the concentrate.At this moment, also cause the infiltration of water, so circulation fluid is concentrated.Therefore, carry out reverse-osmosis treated, can improve the clearance of the acid beyond the phosphoric acid through in the concentrate of circulation, adding dilution water.Dilution water can use the recycle-water of from infiltration water, having removed impurity.
Therefore; In Fig. 2; From reclaim tank 7, recycle-water 7a is supplied in the concentrated liquid bath 3 as dilution water through circuit L43 with pump P2; Dilute the concentrate 3a of circulation and carry out reverse-osmosis treated, can further reduce the concentration of the acid beyond the phosphoric acid thus, can reclaim highly purified Phosphoric Acid Concentration liquid.Supplying to the amount that concentrates the recycle-water 7a in the liquid bath 3 is that the concentrate that circulates is kept the amount that phosphoric acid concentration is the condition of 1 percentage by weight～15 percentage by weights.Can prevent that thus the concentrate height that circulates from concentrating the infiltration efficient reduction of the acid beyond the phosphoric acid that is caused, and can improve the phosphoric acid purity of concentrate.
The recovery phosphoric acid liquid 9a that reclaims through said method can be used as regenerant, and owing to be that in high concentration aqueous time reclaimed and can be carried out the carrying in the practicality, and can be used as highly purified concentrated phosphoric acid and reclaim.At this moment, carry out reverse-osmosis treated for being less than or equal under 3 the condition in the pH value, usually pH value for be less than or equal to 3 acid state down acquisition so can directly supply with as the phosphorous sour water of former water, need not to regulate especially the pH value.The cation that medicaments such as acid, alkali only limit in the cation exchange tower 2 is used regenerative agent with the anion in regenerative agent and the anion exchange tower 3, need not to be used to the medicament that reclaims the medicament of phosphoric acid and be used for the purifying infiltration water.In addition,, can simply constitute and operation through utilizing in order to the method and apparatus that reclaims, pH value for be less than or equal to 3 and phosphoric acid concentration be to carry out reverse-osmosis treated under the condition of 1 percentage by weight～15 percentage by weights, and recovery Phosphoric Acid Concentration liquid.Can reduce the use amount of medicament, the growing amount of discarded object thus, reduce processing cost, reclaim highly purified concentrated phosphoric acid and pure water.
In the phosphoric acid recovery method and device of Fig. 2; The pH value for be less than or equal to 3 and phosphoric acid concentration be under the condition of 1 percentage by weight～15 percentage by weights phosphorous sour water to be supplied in the reverse osmosis unit 4; Carry out reverse-osmosis treated through reverse osmosis membrane 4a; Make acid and water beyond the phosphoric acid together be penetrated into infiltration liquid chamber 4b side,, reclaim pure water and Phosphoric Acid Concentration liquid at concentrated liquid chamber 4c side concentrated phosphoric acid; Can utilize simple formation and operation thus, low-cost, from phosphorous sour water, reclaim and can carry down and can be expeditiously high concentration aqueous as the high-purity phosphoric acid of regenerant.
In addition, example of the present invention is not to be defined in Fig. 1, Fig. 2, for example in Fig. 2, in order further to improve the purity that reclaims phosphoric acid liquid, can the 2nd anion exchange tower be set at the leading portion of the evaporation concentration device 8 of circuit L34 yet.In addition; In this example; Purifying is from the simple and easy electric regenerative ion interchange unit that is divided into 6a of desalting chamber and the 6b of enriched chamber by anion-exchange membrane 6c of electric regenerative ion interchange unit 6 uses of the penetrating fluid of reverse osmosis unit 4; Also can use between cathode chamber and anode chamber and to arrange anion-exchange membrane and cation-exchange membrane and form desalting chamber and enriched chamber alternately, and in this desalting chamber, fill the common electrodeionization device of ion exchanger.
Embodiment
Below, embodiments of the invention are explained.In each example, % except expression prevention rate and special indication, the expression percentage by weight.
[embodiment 1, comparative example 1]:
< reverse-osmosis treated >:
The electrical conductivity that will contain phosphoric acid 550mg/L, nitric acid 50mg/L, acetic acid 50mg/L is that 122mS/m, pH value are 2.4 former water; Under 0.7MPa, be passed among the reverse osmosis membrane ES-20 that Nitto Denko Corp. makes and carry out reverse-osmosis treated, obtain to have concentrated 6 times concentrate (salt solution) (embodiment 1).On the other hand, in former water, inject sodium hydrate aqueous solution the pH value is adjusted to 6, (comparative example 1) likewise makes an experiment.The result of the prevention rate of phosphoric acid, nitric acid, acetic acid is shown in the table 1, can knows that phosphoric acid is removed in embodiment 1, nitric acid, acetic acid infiltration and separate with respect to this, all are removed in comparative example 1, do not separate.
Table 1 clearance
| ? | |
Comparative example 1 |
| The pH value | 2.4 | 6 |
| Phosphoric acid (%) | 97.8 | 99.6 |
| Nitric acid (%) | 10 | 99.5 |
| Acetic acid (%) | 4 | 99.0 |
[embodiment 2]:
< recovery of phosphoric acid and pure water >:
The electrical conductivity that will contain phosphoric acid 550mg/L, nitric acid 50mg/L, acetic acid 50mg/L, indium 0.3mg/L, sodium 1mg/L is that 122mS/m, pH value are that cleaning draining after 2.4 the crystal liquid substrate etching is handled with the device of Fig. 1, reclaims phosphoric acid and pure water.Filled the H type storng-acid cation exchange resin (manufacturing of Mitsubishi Chemical limited company, Diaion SK1B) of 10L in the cation exchange tower 2, regenerated with hydrochloric acid.Filled the OH type strong-base anion-exchange resin (manufacturing of Mitsubishi Chemical limited company, Diaion SA11A) of 10L in the anion exchange tower 5 respectively, regenerated with NaOH.Filled the PO of 10L among the 2nd anion exchange tower 5b
4Type strong-base anion-exchange resin (manufacturing of Mitsubishi Chemical limited company, Diaion SA11A) behind NaOH regeneration OH type, makes it become PO with Phosphoric Acid Concentration liquid
4Type.Reverse osmosis unit 4 is the devices with spiral membrane assembly of the reverse osmosis membrane ES-20 that Nitto Denko Corp. makes, under 0.7MPa, carries out reverse-osmosis treated in wherein feeding liquid, and concentrates 6 times.Use rotary evaporator as evaporation concentration device 8, being concentrated to phosphoric acid concentration is 75%.The concentration of each composition in each operation is shown in the table 2.
Table 2
| ? | The pH value | Phosphoric acid | Nitric acid | Acetic acid | Cation |
| Unit | ? | (mg/L) | (mg/L) | (mg/L) | (mg/L) |
| |
2.4 | 550 | 50 | 50 | 1＞ |
| Decationized Y sieve water (3a) | 2.3 | 550 | 50 | 50 | 1＞ |
| Penetrating fluid (L7) | 2.4 | 20 | 45 | 47 | 1＞ |
| Recycle- |
6.7 | 1＞ | 1＞ | 1＞ | 1＞ |
| Concentrate (L11) | 2.2 | 3300 | 45 | 47 | 1＞ |
| The 2nd anion exchange liquid (L14) | 2.2 | 3300 | 0.3 | 47 | 1＞ |
| Reclaim |
1.7 | 75(％) | 1000＞ | 1000＞ | 100＞ |
[reference example 1, reference example 2]:
< reverse-osmosis treated >:
The electrical conductivity that will contain phosphoric acid 550mg/L, nitric acid 50mg/L, acetic acid 50mg/L is that 122mS/m, pH value are 2.4 former water; Under 0.7MPa, be passed among the reverse osmosis membrane ES-20 that Nitto Denko Corp. makes and carry out reverse-osmosis treated, obtain to have concentrated 5 times concentrate (salt solution) (reference example 1).On the other hand, in former water, inject sodium hydrate aqueous solution the pH value is adjusted to 6, (reference example 2) likewise makes an experiment.The result of the prevention rate of phosphoric acid, nitric acid, acetic acid is shown in the table 3, can knows that phosphoric acid is prevented from reference example 1, nitric acid, acetic acid infiltration with respect to this, all are prevented from reference example 2, not infiltration.
Table 3 prevention rate
| ? | Reference example 1 | Reference example 2 |
| The pH value | 2.3 | 6 |
| Phosphoric acid (%) | 97.8 | 99.6 |
| Nitric acid (%) | Less than 1 | 99.5 |
| Acetic acid (%) | Less than 1 | 99.0 |
[embodiment 3]:
In reference example 1, the phosphoric acid concentration during with the cycle-index that improves concentrate in the concentrate changes and the relation table of the prevention rate of nitric acid is shown among Fig. 3.
By Fig. 3 can know phosphoric acid concentration in the concentrate be 1 percentage by weight or 1 percentage by weight when above the prevention rate of nitric acid become negative value and linearity descends, particularly phosphoric acid concentration be 2 percentage by weights or below 2 percentage by weights, further be the infiltration that 4 percentage by weights or 4 percentage by weights promote nitric acid when following at phosphoric acid concentration.About acetic acid, also obtain same result.
[embodiment 4, embodiment 5]:
In the device of Fig. 2; Use with reference example 1 in identical reverse osmosis membrane; Will be with after identical phosphorous sour water in the reference example 1 be handled with the cation exchange tower that fill H type storng-acid cation exchange resin (Mitsubishi Chemical limited company makes, Diaion SK1B) and the anion exchange tower of having filled phosphatic type weak-base anion-exchange resin (Mitsubishi Chemical limited company makes, DiaionWA30); Supply to the dilution of carrying out concentrate in the reverse osmosis unit; One side makes its circulation, and one side is carried out film and separated and concentrated 100 times (embodiment 4); The recycle-water that in addition penetrating fluid is formed after the desalination in electric regenerative ion interchange unit is as dilution water; Supply to and concentrate in the liquid bath (supplying with 20 percents by volume of the former water yield); The dilution concentrate; One side makes its circulation one side carry out the film separation and concentrate 100 times (embodiment 5), and the solute concentration in the concentrate of both of these case is shown in the table 4.Suppose the concentrate of gained in the reference example 1 is passed through distillation and whole concentrated 100 times, will routine 1 charge in the table in the lump as a reference according to the solute concentration that calculating is obtained.
Table 4 solute concentration
| ? | |
|
Reference example 1 |
| Phosphoric acid (%) | 5.4 | 5.4 | 5.3 |
| Nitric acid (mg/L) | 160 | 30 | 310 |
| Acetic acid (mg/L) | 170 | 40 | 380 |
Can know by table 4; Become more than or equal to the condition of 1 percentage by weight through the phosphoric acid concentration in concentrate and to carry out reverse-osmosis treated; Acid concentration beyond the phosphoric acid in the concentrate reduces; Further the dilution concentrate simultaneously makes its circulation one side carry out reverse-osmosis treated, can further reduce the acid concentration beyond the phosphoric acid in the concentrate thus, reclaims highly purified Phosphoric Acid Concentration liquid.
Utilizability on the industry
The present invention can be used for from phosphorous sour water reclaiming the method and apparatus of phosphoric acid and pure water, particularly is suitable for from the cleaning draining behind etching crystal liquid substrate or wafer and other electronic equipments, reclaiming in valuable material such as phosphoric acid and the method and apparatus as the recovery phosphoric acid of the pure water of processing water.
Claims (17)
1. the recovery method of a phosphoric acid, it is the method that from remove cationic phosphorous sour water, reclaims phosphoric acid, it is characterized in that:
In the pH value for being less than or equal under 3 the condition; To remove cationic phosphorous sour water supplies to and carries out reverse-osmosis treated in the reverse osmosis unit; Make acid and water beyond the phosphoric acid together be penetrated into infiltration liquid chamber side, reclaim Phosphoric Acid Concentration liquid at concentrated liquid chamber side concentrated phosphoric acid.
2. the recovery method of a phosphoric acid, it is the method that from remove cationic phosphorous sour water, reclaims phosphoric acid, it is characterized in that:
The pH value for be less than or equal to 3 and phosphoric acid concentration be under the condition of 1 percentage by weight～15 percentage by weights; To remove cationic phosphorous sour water supplies to and carries out reverse-osmosis treated in the reverse osmosis unit; Make acid and water beyond the phosphoric acid together be penetrated into infiltration liquid chamber side, reclaim Phosphoric Acid Concentration liquid at concentrated liquid chamber side concentrated phosphoric acid.
3. method according to claim 1 and 2 is characterized in that: be recycled to the process that concentrates in the liquid chamber after having the concentrate extraction with concentrated liquid chamber, and interpolation is processed phosphorous sour water and carries out reverse-osmosis treated in the concentrate of circulation.
4. method according to claim 1 and 2 is characterized in that: have and be recycled to the process that concentrates in the liquid chamber after the concentrate that concentrates liquid chamber extracted out, and in the concentrate of circulation, add dilution water and carry out reverse-osmosis treated.
5. method according to claim 1 and 2 is characterized in that: before phosphorous sour water is supplied to reverse osmosis unit, carry out preliminary treatment and remove and comprise cation and/or anionic impurity.
6. method according to claim 1 and 2 is characterized in that: removal comprises the impurity of acid and reclaims pure water from the infiltration water of reverse osmosis unit.
7. method according to claim 6 is characterized in that: carry out the removal of impurity through ion interchange unit.
8. method according to claim 1 and 2 is characterized in that: purifying is carried out in the acid through anion exchange from Phosphoric Acid Concentration liquid, removes beyond the phosphoric acid.
9. method according to claim 1 and 2 is characterized in that: evaporation and concentration Phosphoric Acid Concentration liquid, and water and volatile ingredient are together removed and concentrated.
10. phosphoric acid retracting device, it is the device that from remove cationic phosphorous sour water, reclaims phosphoric acid, it is characterized in that having:
Reverse osmosis unit for being less than or equal under 3 the condition, carries out reverse-osmosis treated to removing cationic phosphorous sour water in the pH value, acid beyond the phosphoric acid together is penetrated into water permeates the liquid chamber side, at concentrated liquid chamber side concentrated phosphoric acid;
Former water supply unit, in the pH value for being less than or equal under 3 the condition, with removing the concentrated liquid chamber side that cationic phosphorous sour water supplies to reverse osmosis membrane apparatus;
Penetrating fluid extraction portion extracts penetrating fluid out from the infiltration liquid chamber side of reverse osmosis unit; And concentrated phosphoric acid liquid extraction portion, extract concentrated phosphoric acid liquid out from the concentrated liquid chamber side of reverse osmosis unit.
11. a phosphoric acid retracting device, it is the device that from remove cationic phosphorous sour water, reclaims phosphoric acid, it is characterized in that having:
Reverse osmosis unit; The pH value for be less than or equal to 3 and phosphoric acid concentration be under the condition of 1 percentage by weight～15 percentage by weights; Carry out reverse-osmosis treated to removing cationic phosphorous sour water, make acid and water beyond the phosphoric acid together be penetrated into infiltration liquid chamber side, at concentrated liquid chamber side concentrated phosphoric acid;
Phosphorous sour water supply unit, the pH value for be less than or equal to 3 and phosphoric acid concentration be under the condition of 1 percentage by weight～15 percentage by weights, with removing the concentrated liquid chamber side that cationic phosphorous sour water supplies to reverse osmosis unit;
Penetrating fluid extraction portion extracts penetrating fluid out from the infiltration liquid chamber side of reverse osmosis unit;
Concentrated phosphoric acid liquid extraction portion extracts concentrated phosphoric acid liquid out from the concentrated liquid chamber side of reverse osmosis unit; And
Circulating path is recycled to the concentrated phosphoric acid liquid of from concentrated phosphoric acid liquid extraction portion, extracting out and concentrates the liquid chamber side.
12., it is characterized in that: have the dilution water supply unit, in the concentrate that follows the endless path circulation, add dilution water according to claim 10 or 11 described devices.
13. according to claim 10 or 11 described devices, it is characterized in that: have pretreatment unit at former water supply unit, removal comprises cation and/or anionic impurity.
14., it is characterized in that: have impurity removal means, from the infiltration water of reverse osmosis unit, remove the impurity that comprises acid according to claim 10 or the described device of l1.
15. device according to claim 14 is characterized in that: impurity removal means is an ion interchange unit.
16., it is characterized in that: have purification devices, from Phosphoric Acid Concentration liquid, remove the acid beyond the phosphoric acid through anion exchange according to claim 10 or 11 described devices.
17. according to claim 10 or 11 described devices, it is characterized in that: have evaporation concentration device, evaporation and concentration Phosphoric Acid Concentration liquid is together removed volatile ingredient and water and is concentrated.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006264640A JP5135749B2 (en) | 2006-09-28 | 2006-09-28 | Method and apparatus for recovering phosphoric acid from phosphoric acid-containing water |
| JP264640/2006 | 2006-09-28 | ||
| JP2007093943A JP5277559B2 (en) | 2007-03-30 | 2007-03-30 | Method and apparatus for recovering phosphoric acid from phosphoric acid-containing water |
| JP093943/2007 | 2007-03-30 | ||
| PCT/JP2007/068881 WO2008038740A1 (en) | 2006-09-28 | 2007-09-27 | Process and equipment for the recovery of phosphoric acid from phosphoric acid-containing water |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101511452A CN101511452A (en) | 2009-08-19 |
| CN101511452B true CN101511452B (en) | 2012-05-30 |
Family
ID=39351664
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200780031927XA Active CN101511452B (en) | 2006-09-28 | 2007-09-27 | Process and equipment for the recovery of phosphoric acid from phosphoric acid-containing water |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP5135749B2 (en) |
| CN (1) | CN101511452B (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI424964B (en) * | 2008-03-26 | 2014-02-01 | Kurita Water Ind Ltd | Method of recycling phosphoric acid from phosphoric acid containing water and device thereof |
| JP5245596B2 (en) * | 2008-07-15 | 2013-07-24 | 栗田工業株式会社 | Reverse osmosis membrane performance recovery method and membrane separation treatment method |
| JP2010036160A (en) * | 2008-08-07 | 2010-02-18 | Kurita Water Ind Ltd | Method and device for recovering water from discharged water |
| JP5212268B2 (en) * | 2009-06-19 | 2013-06-19 | 住友金属鉱山株式会社 | Method for producing porous valve metal anode body |
| JP2011236467A (en) * | 2010-05-11 | 2011-11-24 | Ecocycle Corp | Etching acid waste liquid disposal system, etching acid waste liquid disposal method and etching acid waste liquid disposal apparatus applied thereto |
| CN102181867A (en) * | 2011-04-11 | 2011-09-14 | 江阴市润玛电子材料有限公司 | Novel acidic molybdenum aluminum etching liquid and preparation process thereof |
| CN103030123B (en) * | 2012-12-27 | 2015-01-14 | 苏州浩中环保设备有限公司 | Recovery and treatment equipment and process of waste diluted phosphoric acid containing metal salt |
| CN105142763B (en) * | 2013-04-25 | 2019-11-12 | 索尔维公司 | For purify hydrofluoric acid and nitric acid mixture it is reverse osmosis |
| CN107792981A (en) * | 2016-08-30 | 2018-03-13 | 广东益诺欧环保股份有限公司 | A kind of waste acid concentration and reclaiming system containing heavy metal and particulate matter |
| CN108996771A (en) * | 2018-09-29 | 2018-12-14 | 西安建筑科技大学 | The multicolumn distributor of chemical constituent in a kind of concentration extraction micropollutant water |
| CN111591966B (en) * | 2020-04-20 | 2021-08-06 | 同济大学 | Device and method for recovering phosphoric acid in aluminum etching waste liquid |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002086147A (en) * | 2000-09-19 | 2002-03-26 | Nippon Paint Co Ltd | Method for recovering processing agent component in washing water of metallic surface treatment |
| JP2002332583A (en) * | 2001-05-07 | 2002-11-22 | Nippon Paint Co Ltd | Method and apparatus for treating cleaning water for phosphate film chemical conversion |
| JP2004533541A (en) * | 2001-06-08 | 2004-11-04 | ヘンケル・コマンディットゲゼルシャフト・アウフ・アクチエン | Method of preventing membrane blockage in wastewater treatment in phosphate treatment |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5910430B2 (en) * | 1976-04-19 | 1984-03-08 | 日本ペイント株式会社 | Phosphate film chemical conversion treatment method |
| JP2002085942A (en) * | 2000-09-19 | 2002-03-26 | Nippon Paint Co Ltd | Recovery process of liquid chemical component in water used for washing metal surface treatment |
| JP4096576B2 (en) * | 2002-02-22 | 2008-06-04 | 栗田エンジニアリング株式会社 | Chemical cleaning method |
| JP4098669B2 (en) * | 2003-05-27 | 2008-06-11 | 日本パーカライジング株式会社 | Recovery and reuse of phosphate chemical conversion solution |
| JP4813106B2 (en) * | 2004-08-10 | 2011-11-09 | 株式会社神鋼環境ソリューション | Waste water treatment method and waste water treatment equipment |
| JP4834993B2 (en) * | 2004-12-27 | 2011-12-14 | 栗田工業株式会社 | Waste water treatment apparatus and treatment method |
-
2006
- 2006-09-28 JP JP2006264640A patent/JP5135749B2/en active Active
-
2007
- 2007-09-27 CN CN200780031927XA patent/CN101511452B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002086147A (en) * | 2000-09-19 | 2002-03-26 | Nippon Paint Co Ltd | Method for recovering processing agent component in washing water of metallic surface treatment |
| JP2002332583A (en) * | 2001-05-07 | 2002-11-22 | Nippon Paint Co Ltd | Method and apparatus for treating cleaning water for phosphate film chemical conversion |
| JP2004533541A (en) * | 2001-06-08 | 2004-11-04 | ヘンケル・コマンディットゲゼルシャフト・アウフ・アクチエン | Method of preventing membrane blockage in wastewater treatment in phosphate treatment |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101511452A (en) | 2009-08-19 |
| JP2008080277A (en) | 2008-04-10 |
| JP5135749B2 (en) | 2013-02-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101511452B (en) | Process and equipment for the recovery of phosphoric acid from phosphoric acid-containing water | |
| US6056878A (en) | Method and apparatus for reducing scaling in electrodeionization systems and for improving efficiency thereof | |
| TWI428293B (en) | Method and apparatus for recovering phosphoric acid from phosphoric acid-containing water | |
| CN104445755A (en) | Method for resourceful treatment of ammonia chloride wastewaters | |
| JP3800450B2 (en) | Method and apparatus for treating organic wastewater containing high concentrations of salts | |
| CN102774994A (en) | Combined new process for recovery of salt-containing wastewater through membrane separation | |
| CN106966536A (en) | Strong brine zero-emission film concentration technology and equipment | |
| CA2151753C (en) | A method for treating waste water containing neutral salts comprising monovalent ions | |
| JP5277559B2 (en) | Method and apparatus for recovering phosphoric acid from phosphoric acid-containing water | |
| CN104291502A (en) | Device for treating ammonium nitrate wastewater by adoption of integrated membrane technology | |
| CN109982976A (en) | Hyperpure water manufacturing systems and ultrapure water manufacturing method | |
| JP5115271B2 (en) | Method and apparatus for recovering phosphoric acid from phosphoric acid-containing water | |
| CN203461910U (en) | Device for treating ammonium nitrate wastewater by integrated membrane technology | |
| CN111875153A (en) | Method for treating cyclized wastewater generated in epichlorohydrin production process | |
| JP2008081791A (en) | Method and apparatus for recovering phosphoric acid from phosphoric ion-containing water | |
| CN115124118B (en) | Thiadiazole production wastewater treatment method | |
| CN104291501A (en) | Method of treating ammonium nitrate wastewater by adoption of integrated membrane technology | |
| CN103420520B (en) | Processing method of vanadium-containing aluminum-containing wastewater | |
| KR101621835B1 (en) | Process and equipment for recovering phosphoric acid from phosphoric acid-containing water | |
| KR20100044397A (en) | Recycling method and apparatus of waste etching solution | |
| JP2010036160A (en) | Method and device for recovering water from discharged water | |
| CN206089336U (en) | Zero discharging equipment of sewage recycling | |
| CN114455771B (en) | Waste acid treatment system and method | |
| JP3293475B2 (en) | Method for concentrating nitric acid aqueous solution and its concentrating device | |
| KR101480751B1 (en) | Purifying system of electropolishing waste water and method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |