CN100389075C - Drainage disposal method and device - Google Patents
Drainage disposal method and device Download PDFInfo
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- CN100389075C CN100389075C CNB2005100902410A CN200510090241A CN100389075C CN 100389075 C CN100389075 C CN 100389075C CN B2005100902410 A CNB2005100902410 A CN B2005100902410A CN 200510090241 A CN200510090241 A CN 200510090241A CN 100389075 C CN100389075 C CN 100389075C
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Abstract
To provide a method for treating waste water, by which a phosphate ion can easily be recovered selectively from the waste water containing the phosphate ion and other ions such as a nitrate ion, a sulfate ion and an iodide ion.In the waste water treating method for recovering the phosphate ion from the waste water containing the phosphate ion and at least one ion selected from the nitrate ion, the sulfate ion and the iodide ion, the waste water is brought into contact with an anion exchange resin on condition of acidity so as to exchange the ion contained in the waste water from among the nitrate ion, the sulfate ion and the iodide ion, and after that, the ion-changed waste water is brought with the anion exchange resin again so as to allow the anion exchange resin to exchange the phosphate ion in order to recover the phosphate ion. (C)2006,JPO&NCIPI.
Description
Technical field
The present invention relates to drainage processing method, relate to contain the treatment process and the treatment unit of the acid effluent of phosphate ion in detail.
Background technology
As the substrate of LCD panel etc., use on insulating material, to be formed with aluminum monolayer or by the substrate of the figure of aluminium and this two-layer conductive layer that forms of molybdenum.
When forming the figure of this conductive layer, people use utilization to carry out etching method by the etching solution that the mixture of nitric acid, phosphoric acid, acetic acid forms all the time.
When making the substrate of such LCD panel etc.,, therefore migrate easily to other purposes owing to the liquid waste concentration height of the etching solution that is produced, circulate easily.On the other hand, washed the draining of the crystal liquid substrate after the etching, compared with the waste liquid of etching solution, its phosphate ion concentration is lower, does not therefore circulate, and carries out biological processes equally with other waste liquids.In this biological processes, because the phosphate ion amount substantially constant that time per unit consumed, so, change the water area load according to the phosphate ion concentration that contains in the draining.That is,, change the treatment capacity of time per unit and handle according to draining.
But,, carry out circular treatment so also expect the such low draining of ionic concn of draining of this having been washed the crystal liquid substrate after the etching because environment in recent years consciousness improves.Phosphorus composition particularly, because utility value is higher, therefore attempting phosphate ion is carried out selective recovery, disclosing in the patent documentation 1 by electric field and in the draining that contains phosphate ion, add iron ion or aluminum ion, its form with tertiary iron phosphate or aluminum phosphate is precipitated.
But, in the method that patent documentation 1 is put down in writing, must adjust the iron ion or the aluminum ions amount that are generated according to the variation of the ionic concn that contains in the draining, handle and become numerous and diverse.
And then, owing to utilize electric field to produce into iron ion or aluminum ion, so need very high cost of energy, particularly be difficult to make phosphate ion concentration to reach the solubleness of tertiary iron phosphate or aluminum phosphate or below it, therefore phosphoric acid concentration is low more, then processing efficiency is low more, is difficult to adopt phosphate ion concentration to be for example 1% or the draining of its following lower concentration etc. in practice.
In addition, the throw out of Huo Deing might contain phosphoric acid salt molysite or aluminium salt in addition like this, and not talkative phosphate ion is reclaimed by selectivity.
In addition, in order to reclaim phosphate ion, it is also conceivable that and utilize anionite-exchange resin etc. to carry out ion-exchange, but it is known, usually, negatively charged ion such as nitrate ion, sulfate ion, iodide ion are the same with phosphate ion, carry out ion-exchange with anionite-exchange resin easily, reclaim phosphate ion thereby can not make draining carry out ion-exchange with anionite-exchange resin.
Like this, in handling, the draining of prior art exists the problem that is difficult to optionally reclaim phosphoric acid.
In addition, during the draining that this problem does not exist only in selective recovery phosphate ion from the such draining that contains the low phosphorus acid ion of the draining of for example having washed crystal liquid substrate is handled, and during the draining that is present in selective recovery phosphate ion from the draining of the ion that contains nitrate ion, sulfate ion, iodide ion etc. and phosphate ion handles.
[patent documentation 1] spy opens flat 10-225690 communique
Summary of the invention
Problem of the present invention provides a kind of drainage processing method in view of the above problems, and this method selective recovery phosphate ion easily from the draining of the ion that contains nitrate ion, sulfate ion, iodide ion etc. and phosphate ion also provides a kind of drain treatment apparatus.
Phosphate ion is the same with negatively charged ion such as nitrate ion, sulfate ion, iodide ions, carries out ion-exchange with anionite-exchange resin easily, does not also carry out in the prior art utilizing anionite-exchange resin to separate these ions and phosphate ion.
But, the present inventor furthers investigate for this problem, discovery is under the tart situation in draining, compare with negatively charged ion such as nitrate ion, sulfate ion, iodide ions, phosphate ion can be counted as the ion that is difficult to carry out with anionite-exchange resin ion-exchange, has finished the present invention thus.
Promptly, the present invention is in order to solve above-mentioned problem, a kind of drainage processing method is provided, this method is to be selected from nitrate ion from containing, sulfate ion, reclaim the drainage processing method of phosphate ion at least a kind of ion of iodide ion and the draining of phosphate ion, it is characterized in that, be under the tart state, draining is contacted with anionite-exchange resin, make the nitrate ion that contains in the above-mentioned draining, sulfate ion, ion in the iodide ion carries out ion-exchange, and then contact with anionite-exchange resin, make phosphate ion and anionite-exchange resin carry out ion-exchange, reclaim phosphate ion.The present invention also provides a kind of drain treatment apparatus, this device is from containing at least a kind of ion being selected from nitrate ion, sulfate ion, the iodide ion and phosphate ion and being the drain treatment apparatus that reclaims phosphate ion in the draining of acid state, it is characterized in that, for make above-mentioned draining by and can implement 2 times or anionresin more than it, series arrangement has 2 or its above anion exchanger that is equipped with anionite-exchange resin.
According to the present invention, be under the tart state in draining, compare with nitrate ion, sulfate ion, iodide ion, phosphate ion is difficult to carry out ion-exchange with anionite-exchange resin, thereby can contact with anionite-exchange resin by making draining, at first, make nitrate ion, sulfate ion, iodide ion and anionite-exchange resin carry out ion-exchange, then, draining is contacted with anionite-exchange resin, make phosphate ion and this anionite-exchange resin optionally carry out ion-exchange, reclaim.
And then, even under the situation that phosphate ion concentration changes in draining, also, handle so can carry out stable draining because that the draining treatment capacity of time per unit is become is constant.
In addition, also need not the high-energy cost as the intermediate processing that utilizes electric field, can be applicable to phosphate ion concentration in the draining and be 1% or its following lower concentration, for example until the draining of several ppm.
Description of drawings
Fig. 1 is for showing the block diagram of the drain treatment apparatus that uses in first embodiment.
Fig. 2 changes chart for the ionic concn of the drainage water situation of first, second anion exchange tower of demonstration first embodiment.
Fig. 3 changes chart for the ionic concn of the drainage water situation of second anion exchange tower of demonstration first embodiment.
Fig. 4 is the block diagram of the sodium phosphate salt retrieving arrangement of demonstration first embodiment.
Fig. 5 is for showing the block diagram of the drain treatment apparatus that uses in second embodiment.
The explanation of symbol
1: the first anion exchange tower
2: the second anion exchange towers
3: water injection pipe
4: pipe connecting
5: water shoot
6: magnetic valve
11,12: anion exchanger
21,12: anion exchanger
19,29: the alkaline regeneration solution storagetank
Embodiment
Below, preferred implementation of the present invention is described.
At first, the drain treatment apparatus that will use in the drainage processing method of present embodiment is as first embodiment, and describes based on Fig. 1.
Above-mentioned drain treatment apparatus has following formation: first anion exchange tower 1, and it makes draining contact with anionite-exchange resin, makes the ion of nitrate ion, sulfate ion, iodide ion etc. carry out ion-exchange; First storagetank 13, its temporary storage have passed through the draining of this first anion exchange tower 1; Second anion exchange tower 2, it contacts the draining of having passed through above-mentioned first anion exchange tower 1 once more with anionite-exchange resin, make phosphate ion carry out ion-exchange; Second storagetank 23, its temporary storage have passed through the draining of second anion exchange tower 2.
In addition, above-mentioned drain treatment apparatus has, and is used for importing to above-mentioned first anion exchange tower 1 water injection pipe 3 of draining; Be used for to import the pipe connecting 4 of second anion exchange tower 2 with the contacted draining of the anionite-exchange resin of first anion exchange tower 1; The draining that to carry out anionresin in second anion exchange tower 2 is expelled to the vent pipe 5 outside the system.
Further, above-mentioned drain treatment apparatus has, and the draining that the draining that will pass through first anion exchange tower 1 turns back to first return line 14 of first anion exchange tower 1 once more and will pass through second anion exchange tower 2 is back to second return line 24 of second anion exchange tower 2 once more.
Be equipped with two anion exchangers 11,12 in above-mentioned first anion exchange tower 1, they are the interchangers that are filled with weak base anion-exchange resin in the container that is equipped with water filling port and water port.In addition, these two anion exchangers 11,12 formation is, the water filling port of two anion exchangers links to each other with water injection pipe, and utilizes magnetic valve 6 to switch the draining current to each anion exchanger, so that using an anion exchanger to carry out the draining processing, carrying out along with the draining processing, under the situation that the anionresin performance of anionite-exchange resin is tending towards reducing, the flow direction of draining can be switched to another anion exchanger, proceed draining and handle.In addition, each water port links to each other with first water shoot 15 that draining is imported above-mentioned first storagetank 13.In addition, the unmarked symbol in position beyond the magnetic valve 6 of Fig. 1, but use the position of identical mark to represent to use magnetic valve with the magnetic valve 6 of Fig. 1.
In addition, above-mentioned second anion exchange tower 2 also has and the same formation of above-mentioned first anion exchange tower 1, two anion exchangers 21,22, and its water filling port is connected with pipe connecting 4, and water port is connected with second water shoot 25.
In addition, be equipped with total organic carbon (TOC) tester in water injection pipe 3, first water shoot 15 and second water shoot 25, further be equipped with specific conductivity (EC) tester in first water shoot 15 and second water shoot 25, mensuration flows through the TOC and the EC of the draining of pipe, is used for judging the ion that the draining of flowing through each pipe contains.
As the weak base anion-exchange resin that is filled in such anion exchanger, can use loading capacity is the resin of 1.1～1.7eq/L-resin.
In addition, its form is not particularly limited, can uses usually to form the resin of diameter smaller or equal to the bead of several mm.
Then, for use such drain treatment apparatus come the processing and utilizing etching solution carry out etch processes the drainage processing method of the acid effluent that produces with the pure water washing of crystal liquid substrate, set forth with reference to Fig. 2, the time that this Fig. 2 shows the ionic concn of the draining of flowing through first water shoot and second water shoot changes.
In the acid effluent that crystal liquid substrate produces with the pure water washing, usually contain the phosphate ion of 100～1000ppm, the nitrate ion of 5～50ppm, and then, also contain 10～100ppm than the acetic acid ion that the phosphate ion in the acid effluent more is difficult to carry out with anionite-exchange resin ion-exchange, pH is become be about 2.
To each the ionic ionic concn that contains in this acid effluent, adopt ionometer etc. to measure in advance, so that hold the ion-exchange situation of anion exchanger according to the water-flowing amount of acid effluent.Then, by general liquid transporting apparatus, for example pump (do not have diagram) etc. is directed into acid effluent in the above-mentioned drain treatment apparatus.
Utilize above-mentioned magnetic valve, the acid effluent that imported is handled by drain treatment apparatus according to the order of first anion exchanger of first anion exchanger of water injection pipe, first anion exchange tower, first storagetank, pipe connecting, second anion exchange tower, second storagetank, water shoot.
In addition, after the processing of above-mentioned acid effluent begins, such shown in time 0～a among Fig. 2, in first anion exchanger of first anion exchange tower, make nitrate ion, phosphate ion, acetic acid ion all carry out ion-exchange, discharge pure water from first water shoot.Like this, can all become very low value by TOC, the EC that observes first water shoot, for example TOC＜0.1ppm, EC＜1 μ S/cm judges that whole ions have carried out ion-exchange in first anion exchange tower.
Then, when time a, the ion exchange resin of equipping in first anion exchanger of first anion exchange tower is saturated by nitrate ion, phosphate ion and acetic acid ion.During ensuing time a～b, in first anion exchange tower, carry out ion-exchange by making acid effluent, make the low ion of ion-exchange selectivity to replace, and become the state that is discharged from the high ion of ion-exchange selectivity.Promptly, utilize the nitrate ion and the phosphate ion that contain in the acid effluent, the acetic acid ion that ion-exchange has taken place with above-mentioned anionite-exchange resin is broken away from, replace, the anionite-exchange resin that nitrate ion and phosphate ion and acetic acid ion have been broken away from carries out ion-exchange.
Like this, owing to from first water shoot, discharge acetic acid ion that contains in the original acid effluent and the acetic acid ion that from anionite-exchange resin, detaches, so the TOC of first water shoot is in case than the TOC height of water injection pipe, very fast when time b, acetic acid ion breaks away from from anionite-exchange resin when finishing, and the TOC of the two demonstrates identical value again.
At this moment, can rise a little since the value of TOC, the EC of first water shoot and judge that acetic acid discharges (for example TOC=0.7ppm, EC=4 μ S/cm).But,, therefore can discharge pure water from vent pipe because the acetic acid ion of discharging from first anion exchange tower can carry out ion-exchange second ion exchange tower.
And then, after time b, equally, proceeding draining handles, the phosphate ion that the nitrate ion that contains in acid effluent makes the anionite-exchange resin that utilizes first anion exchange tower carry out ion-exchange breaks away from, replace, make the nitrate ion and the anionite-exchange resin that contain in the acid effluent carry out ion-exchange.
At this moment, owing to discharge phosphate ion and acetic acid ion,, for example be EC=100 μ S/cm so acetic acid ion and phosphate ion rise the EC value of first water shoot greatly from first anion exchange tower.
In addition, this moment is also owing to discharging phosphate ion that contains in the original acid effluent and the phosphate ion that detaches from anionite-exchange resin, so flow out than the higher draining of phosphate ion concentration in the acid effluent from first water shoot.
In addition, also owing to the phosphate ion of discharging from first anion exchange tower, can carry out ion-exchange with acetic acid ion this moment in second anion exchange tower, therefore still can discharge pure water from vent pipe.
And then, when reaching time c proceeding the draining processing, the ion exchange resin of second anion exchange tower can form by phosphate ion and the satisfied state of acetic acid ion, being directed into acetic acid ion second anion exchange tower from pipe connecting can form by second anion exchange tower and be expelled to state in second water shoot, further, proceeding draining handles, can make the acetic acid ion disengaging of having carried out ion-exchange with the anionite-exchange resin of second anion exchange tower, replace, make phosphate ion carry out ion-exchange.
At this moment, also owing to from second water shoot, discharge acetic acid ion that contains in the original acid effluent and the acetic acid ion that breaks away from from anionite-exchange resin, so the TOC of second water shoot is in case at the TOC height than first water shoot, very fast at time d place, acetic acid ion breaks away from from anionite-exchange resin when finishing, and the TOC of the two becomes again and demonstrates identical value.
That is, at time d place, first anion exchanger of second anion exchange tower can be regarded as and is in by the satisfied state of phosphate ion, by reclaiming this anion exchanger, phosphate ion can be carried out selective recovery.
In addition, during this time c～d, also exist with acetic acid ion and discharge small amounts of phosphoric acid ionic situation, but if desired, then can be by switching the electromagnetic valve switch of the vent pipe and second return line, make the draining of second storagetank not flow to vent pipe and in second anion exchange tower, carry out ion-exchange once more, phosphate ion is not discharged to outside the system reclaims.In addition, for the acetic acid ion of being discharged, the nutrition source that can be used as biological processes uses.
In addition, the optionally recovery of the such phosphate ion in second anion exchange tower, in during till the anion exchanger to first anion exchange tower carries out saturated time e with nitrate ion, can be by using the magnetic valve of second anion exchange tower, switch in and make draining carry out the anion exchanger of ion-exchange in second anion exchange tower, thereby can implement repeatedly.
Promptly, at t2 shown in Figure 3, t4, t6, it is indicated that the time point of t8 switches the chart of ionic concn of the draining of discharging from second water shoot under the situation of anion exchanger of second anion exchange tower, by switching anion exchanger, can be at 0～t1, t2～t3, t4～t5, reclaim pure water during t6～t7, and at t2, t4, t6, the time point of t8, to be replaced by new interchanger by the satisfied anion exchanger of phosphate ion, perhaps phosphate ion is broken away from from anionite-exchange resin, come phosphate ion is reclaimed with alkaline aqueous solution etc.
Here, during t1～t2, t3～t4, t5～t6, t7～t8, phosphate ion and acetic acid ion are discharged from, but in this case, the water vent of second storagetank does not flow into vent pipe, but in second ion exchange tower, carry out ion-exchange once more, can not make phosphate ion be expelled to that system is external to be reclaimed thus.
If during the time e in reaching Fig. 2, the anion exchanger that will carry out the acid effluent processing in first anion exchange tower switches, and (0～t8), interrupt handling is not carried out the successive draining and handled then can to implement above-mentioned a series of processing repeatedly.
In addition, be provided for the TOC, the EC that confirm in the present embodiment, but the above-mentioned switching of the actual anion exchanger in first anion exchange tower can be determined according to each ionic ionic concn and water-flowing amount in the draining that determines in advance.But be not limited only to this method, if desired, also can determine above-mentioned switching time with reference to the value of EC and TOC.For example, can also make water-flowing amount remain certain value in advance, judge the time b that arrival is shown in Figure 2 according to the EC value of first water shoot, then, with timing register etc., before the state that reaches time e, switch and make draining carry out the anion exchanger of ion-exchange in first anion exchange tower, suppress nitrate ion and flow in first storagetank or second anion exchange tower.
In addition, same, the switching time of the anion exchanger in second anion exchange tower, also can after being remained certain value, water-flowing amount determine by timing register.
In addition, the phosphate ion that has carried out ion-exchange with the anionite-exchange resin of second anion exchange tower, can be in above-mentioned resin, come to reclaim with the alkaline aqueous solution that contains any metal ion in sodium, potassium, the magnesium with the form of the aqueous phosphatic that contains high concentrations of phosphoric acid salt, for example, can also use the aqueous solution of sodium hydroxide, potassium hydroxide, magnesium hydroxide to wait to make anionite-exchange resin regeneration, reclaim with the form of the aqueous solution of the phosphate metal salt that contains the phosphate ion that detaches to some extent and above-mentioned metal ion.
At this moment, contain the alkaline aqueous solution of the metal ion of greater concn, can improve the concentration of phosphate aqueous solution, conveying or the required expense of phosphatic dry solidification that can cut down aqueous phosphatic by use.
In addition, like this in the phosphoric acid salt of Huo Deing, as sodium phosphate salt, usually with the form recovery of the mixture of SODIUM PHOSPHATE, MONOBASIC and Sodium phosphate dibasic, by adjusting the pH of the sodium phosphate aqueous solution that will reclaim, can improve the containing ratio of SODIUM PHOSPHATE, MONOBASIC, Sodium phosphate dibasic or tertiary sodium phosphate.
More specifically, be 4.3～4.9 by making pH, can reclaim with the form of SODIUM PHOSPHATE, MONOBASIC, be 9.0～9.6 by making pH, can reclaim with the form of Sodium phosphate dibasic, be 11.5～12.5 by making pH, can reclaim with the form of tertiary sodium phosphate.
Especially, the amount of the sodium hydroxide that uses during recovery can be seldom, and from the viewpoint that can reclaim more at an easy rate and the phosphoric acid that is reclaimed is utilized with the form of foodstuff additive, preferably the form with SODIUM PHOSPHATE, MONOBASIC and Sodium phosphate dibasic reclaims.
In addition, because Sodium phosphate dibasic separates out than SODIUM PHOSPHATE, MONOBASIC is easier, so from can greater concn reclaiming the viewpoint of phosphoric acid, preferably the form with SODIUM PHOSPHATE, MONOBASIC reclaims.
That is, the recovery of sodium phosphate aqueous solution is preferably implemented in pH is 4.3～4.9 scope, reclaims with the form of the aqueous solution of SODIUM PHOSPHATE, MONOBASIC.
In addition, in the recovery of Sodium phosphate dibasic and tertiary sodium phosphate, can wait by the addition of adjusting sodium hydroxide and regulate pH, and then, than reclaiming under the required more situation of theoretical amount of sodium phosphate, can carry out the regeneration of anionite-exchange resin at sodium hydroxide, therefore be fit to.
In addition, equally, in the phosphoric acid salt that under utilizing the situation of potassium hydroxide, obtains, as potassium phosphate salt, usually can potassium primary phosphate and the form of the mixture of dipotassium hydrogen phosphate reclaim, and, can improve the containing ratio of potassium primary phosphate, dipotassium hydrogen phosphate or Tripotassium phosphate by adjusting the pH of the potassiumphosphate aqueous solution that will reclaim.
More specifically saying so, is 4.4～4.9 by making pH, can reclaim with the form of potassium primary phosphate, and be 8.7～9.3 by making pH, can reclaim with the form of dipotassium hydrogen phosphate, be 11.5～12.5 by making pH, can reclaim with the form of Tripotassium phosphate.
In addition, in the recovery of SODIUM PHOSPHATE, MONOBASIC, as shown in Figure 4, temporarily regenerated liquid is stored in the accumulator tank 100, then, uses pump 101 that above-mentioned regenerated liquid is directed in the cation exchanger 103, carry out the ion-exchange of sodium.Thus,, the pH of regenerated liquid becomes the stage of 4.3～4.9 scopes in that being reduced, by closing magnetic valve 102, stopping cationic exchange, can further suppress in the regenerated liquid of accumulator tank 100, to sneak into Sodium phosphate dibasic, can make the purity of the biphosphate sodium water solution that is reclaimed very high.
In such regeneration, with using hydrochloric acid, sulfuric acid and salt thereof etc. the situation of pH in 4.3～4.9 scope of regenerated liquid compared, it can prevent to sneak into impurity such as chlorine, sulphur in SODIUM PHOSPHATE, MONOBASIC.
Below, based on Fig. 5 second embodiment is described.
This second embodiment is compared with above-mentioned first embodiment, in the drain treatment apparatus of second embodiment, do not have first storagetank 13, second storagetank 23 that first embodiment is possessed, but first anion exchange tower 1 and second anion exchange tower 2 are directly by pipe coupling, the draining of discharging from second anion exchange tower 2 directly is discharged to the system outside from water shoot 5, is different in these areas.In addition, do not possess yet so-called first return line 14 and second return line 24, make the device that refluxes from the draining of first, second storagetank.That is, the drain treatment apparatus of second embodiment, its first water shoot 15 directly is connected with pipe connecting 4, and second water shoot 25 directly is connected with water shoot 5.But, in each anion exchange tower of first anion exchange tower 1, second anion exchange tower, 2 these two anion exchange towers, respectively having on 2 anion exchanger this point, this second embodiment is identical with above-mentioned first embodiment.In addition, two anion exchangers that anion exchange tower possessed can be switched that to use also be identical on this point being constituted as.In addition, although it is not shown, but in water injection pipe 3, first water shoot 15 and second water shoot 25, be equipped with total organic carbon (TOC) tester, in first water shoot 15 and second water shoot 25, further be equipped with specific conductivity (EC) tester, measure the ion that draining that the TOC of the draining flow through pipe and EC be used for confirming flowing through each pipe contains; And by measuring each ionic concn in the draining in advance, calculate to the influx of ion exchange tower according to this measured value and draining, carry out the switching of the ion-exchanger in each ion exchange tower, also the drain treatment apparatus with first embodiment is identical in these areas.
The drain treatment apparatus of this second embodiment further constitutes, and can come the anion exchanger of first, second anion exchange tower of counter flow washing with pure water, and is different with first embodiment in this.In addition, further be constituted as, in the anion exchanger of first, second anion exchange tower, the aqueous solution that contains any metal ion in sodium, potassium, the magnesium passed through, make anionite-exchange resin regeneration.
The equipment of using as above-mentioned counter flow washing, it possesses the counter flow washing pure water groove 16 of storing the pure water that is used for counter flow washing, 26, with this counter flow washing pure water groove 16, pure water in 26 is directed into each anion exchanger 11,12,21, counter flow washing water ingress pipe 17a in 22,27a, and then be used for from each anion exchanger 11,12,21, discharge the counter flow washing water discharge pipe 17b of counter flow washing water in 22,27b, and store via this counter flow washing pipe 17b, 27b is from each anion exchanger 11,12,21, the counter flow washing draining storagetank 18 of the counter flow washing draining of discharging in 22,28.
Be constituted as in addition, above-mentioned counter flow washing water ingress pipe 17a, 27a are connected the downstream side (draining oral-lateral) of each anion exchanger 11,12,21,22, above-mentioned counter flow washing water discharge pipe 17b, 27b are connected the upstream side (water filling oral-lateral) of each anion exchanger 11,12,21,22, can be in each anion exchanger 11,12,21,22 from the downstream side upstream the logical washing water of effluent wash.
In addition, as being used for anionite-exchange resin is carried out above-mentioned regenerated equipment, have alkali reclaim liquid storagetank 19,29, its storage is used for the anionite-exchange resin of ion-exchange is carried out the regenerated alkaline aqueous solution; Pure water storagetank 110,210, it stores pure water, and this pure water is used for that the alkali reclaim liquid that remains in each ion- exchanger 11,12,21,22 after this alkali reclaim liquid regeneration is carried out stream and washes; Regenerated liquid ingress pipe 111a, 211a, it is directed into each anion exchanger 11,12,21,22 with alkali reclaim liquid or pure water from these alkali reclaim liquid storagetanks 19,29 and pure water storagetank 110,210; Regenerated liquid vent pipe 111b, 211b, it is used for discharging alkali reclaim liquid or pure water from each anion exchanger 11,12,21,22; Regeneration draining storagetank 112,212, it stores the alkali reclaim liquid or the pure water of discharging from each anion exchanger 11,12,21,22 via this regenerated liquid vent pipe 111b, 211b.
Be constituted as in addition, above-mentioned regenerated liquid ingress pipe 111a, 211a are connected the upstream side (water filling oral-lateral) of each anion exchanger 11,12,21,22, above-mentioned regenerated liquid vent pipe 111b, 211b are connected the downstream side (draining oral-lateral) of each anion exchanger 11,12,21,22, in each anion exchanger 11,12,21,22 can from upstream side downstream the logical regenerated liquid of effluent or pure water, the anionite-exchange resin of anion exchanger is regenerated or the regenerated liquid the anion exchanger is washed with regenerated liquid with pure water.
Below, being that example comes following method is described as the situation of alkali reclaim liquid with aqueous sodium hydroxide solution, this method is to use such drain treatment apparatus, the acid effluent that comes crystal liquid substrate that etch processes is crossed to produce with the pure water washing carries out ion-exchange with anionite-exchange resin, simultaneously with alkali reclaim liquid to by anionite-exchange resin ion-exchange phosphate ion regenerate, reclaim phosphatic method.
Here, except not carrying out following operation, carry out order till saturated up to anion exchanger 21 usefulness phosphate ions with second anion exchange tower 2, all identical with above-mentioned first embodiment, described operation of not carrying out is, the draining temporary storage that will discharge from first, second anion exchange tower is first storagetank 13 or second storagetank 23; The draining that is stored in this first, second storagetank is refluxed in first, second return line respectively.
At an anion exchanger 21 of this second anion exchange tower 2 by phosphate ion under the satisfied situation, by closing the water filling oral-lateral that is arranged on this satisfied anion exchanger 21, the magnetic valve at draining oral-lateral place, open the water filling oral-lateral of another anion exchanger 22, the magnetic valve of draining oral-lateral simultaneously, the stream of the draining that imports from pipe connecting 4 can be switched to another anion exchanger 22, proceed ion-exchange with this anion exchanger 22.Then, in with the satisfied anion exchanger 21 of phosphate ion, open the magnetic valve that is arranged on counter flow washing pipe 27a and counter flow washing water discharge pipe 27b place, when making the pump running that is arranged in the counter flow washing usefulness pure water groove 26, open the magnetic valve at this pump discharge place, come in anion exchanger 21, to supply with the pure water that counter flow washing is used, the draining that residues in the anion exchanger 21 is discharged, and be stored in the counter flow washing draining storagetank 28.
After this counter flow washing is finished, stop the pump of counter flow washing with pure water groove 26, close the magnetic valve of the magnetic valve at this pump discharge place and counter flow washing pipe 27a, these two pipes of counter flow washing water discharge pipe 27b, in the pump running that makes alkali reclaim liquid storagetank 29, open the magnetic valve that is arranged on this pump discharge place and the magnetic valve of regenerated liquid ingress pipe 211a, regenerated liquid vent pipe 211b, 211a is directed into aqueous sodium hydroxide solution in the anion exchanger 21 by the regenerated liquid ingress pipe.Then, the anionite-exchange resin of anion exchanger 21 is regenerated, make the phosphate ion disengaging of having carried out ion-exchange with this anionite-exchange resin simultaneously, and discharge by regenerated liquid vent pipe 211b from anion exchanger 21 with the form of sodium phosphate, be stored in the regeneration draining storagetank 212 with the form of sodium phosphate aqueous solution.
After the regeneration of this anionite-exchange resin is finished, stop the pump of alkali reclaim liquid storagetank 29, close the magnetic valve that is arranged on this pump discharge place, replace, in the pump of running pure water storagetank 210, open the magnetic valve that is arranged on this pump discharge place, in anion exchanger 21, import pure water.Then, discharge the aqueous sodium hydroxide solution that remains in the anion exchanger 21, make and recover the preceding state (A-stage) of phosphate ion generation ion-exchange in the anion exchanger 21, stop the pump of pure water storagetank 210.Then, close the magnetic valve at the pump discharge place that is arranged on pure water storagetank 210 and be arranged on the magnetic valve at each pipe place of regenerated liquid ingress pipe 211a, regenerated liquid vent pipe 211b.In addition, utilize this pure water to make the aqueous sodium hydroxide solution of discharging also pass through regenerated liquid vent pipe 211b, be stored in the regeneration draining storagetank 212 from anion exchanger 21.
As mentioned above, because at these anion exchanger 21 regeneration periods, by the ion-exchange of another anion exchanger 22 enforcement phosphate ions, so can interruptedly not implement the processing of acid effluent continuously.
In addition, the regeneration of anion exchanger 21, when all anionite-exchange resin has carried out regeneration with aqueous sodium hydroxide solution, finish, but all whether for anionite-exchange resin is regenerated by aqueous sodium hydroxide solution, can judge according to the ion-exchange capacity of anionite-exchange resin and the concentration and the amount of the employed aqueous sodium hydroxide solution of regeneration.
In addition, when the anionite-exchange resin of anion exchanger 21 being regenerated with aqueous sodium hydroxide solution, can also adopt such method:, come the regeneration situation of the anionite-exchange resin in the anion exchanger 21 is judged in more detail by measuring from the temperature of the aqueous sodium hydroxide solution (sodium phosphate aqueous solution) of anion exchanger 21 discharges.Promptly, because aqueous sodium hydroxide solution, thermopositive reaction takes place under the situation that phosphate ion is broken away from from anionite-exchange resin, so the temperature of the aqueous sodium hydroxide solution of discharging from anion exchanger 21 rises, but it is very fast, along with phosphate ion breaks away from from anionite-exchange resin, the temperature of the aqueous sodium hydroxide solution of discharging from anion exchanger 21 reduces.Therefore, by measuring, can judge in more detail the regeneration situation of the anionite-exchange resin in the anion exchanger 21 from the temperature of the aqueous sodium hydroxide solution of anion exchanger 21 discharges.
For the temperature measuring of the aqueous sodium hydroxide solution of discharging, by the regenerated liquid vent pipe 211b place after being next to anion exchanger 21 water port thermopair etc. is set and gets final product from this anion exchanger 21.As the temperature tester that is used for this temperature measuring, usually,, just can be used to judge anionite-exchange resin regenerated situation as long as precision is about 0.1K.
In addition, under the satisfied situation, also can be operated the recovery of carrying out sodium phosphate equally by phosphate ion at the anionite-exchange resin of another anion exchanger 22.
And then, in this second embodiment, owing in first anion exchange tower 1, also be equipped with the equipment of counter flow washing and anionite-exchange resin regeneration usefulness, therefore also the anion exchanger with second anion exchange tower 2 is the same by the saturated situation of phosphate ion by the saturated situation of nitrate ion for the anion exchanger of first anion exchange tower 1, can when implementing the acid effluent processing, implement the regeneration of anion exchanger.In addition, the sodium nitrate aqueous solution that is stored in by the regeneration of the anionite-exchange resin of this first anion exchange tower 1 in the regeneration draining storagetank 112 carries out waste treatment by other approach.In addition, in this waste treatment, wait by evaporation concentration sodium nitrate aqueous solution is carried out concentration, this can make, and the process object object is long-pending to be reduced, and sees it is preferred from this aspect.
In addition, in above-mentioned first and second embodiments, though use and to utilize etching solution to carry out acid effluent that crystal liquid substrate that etch processes crosses produces with the pure water washing to carry out draining and handle, this drainage processing method has following advantage, promptly, drainage water is except nitrate ion, phosphate ion, outside the acetic acid ion, substantially do not contain seston and positively charged ion etc., before in vent pipe, discharging acetic acid ion, the drainage water that is discharged from all can be used as pure water and utilizes, such crystal liquid substrate is washed and the acid effluent that produces but not only be defined in the present invention.
In addition, in being the tart draining, contain as carrying out the draining of the ionic nitrate ion of ion-exchange with anionite-exchange resin, in the present invention than phosphate ion is easier though use, except above-mentioned nitrate ion, can also use the draining that contains sulfate ion, iodide ion.
And then, can suppress more effectively nitrate ion be directed in the second negatively charged ion tower aspect, with when the drainage water with second anion exchange tower utilizes as pure water again, can suppress acetic acid ion sneak into aspect, though each ionic ionic concn of having carried out containing in the prior mensuration draining, the value of the ionic concn that goes out according to said determination and the amount of anionite-exchange resin, obtain the processing water yield of the anion exchanger in switching first anion exchange tower or the processing in treatment time, but, can not implement the mensuration of ionic concn in advance yet, use TOC tester or EC tester to judge, if desired, can also utilize pH meter that pH is measured, judge the ion situation of the draining at this place, place.
In addition, as anionite-exchange resin, can use any in weak base anion-exchange resin, the strongly basic anion exchange resin.
In addition, from preventing the viewpoint of the interruption that draining is handled, adopted the method for in first, second anion exchange tower, respectively using two anion exchangers, but in the present invention, also can use an anion exchanger, adopt the draining that utilizes delayed time system to handle.In addition, also can use the above anion exchanger of three or its to implement.
And then, to anion exchange tower, also not only be defined in two towers, also can be the multistage tower that has more than or equal to 2 towers.
If desired, also can after the ion exchange tower that uses 1 tower is removed than the higher ion of the ion selectivity of phosphate ion in advance, make the anionite-exchange resin regeneration of this anion exchange tower, then, carry out the ion-exchange of phosphate ion.
The change that the quantity of these anion exchangers, anion exchange tower and size etc. can suit according to the water displacement that will handle.
In addition, anionite-exchange resin being equipped under the situation of multistage more, can more only reclaim effectively phosphate ion.
In addition, though used magnetic valve for the stream that switches draining,, in the present invention, be not limited only to magnetic valve, also can adopt the device that is used to switch general stream, in addition, also can not use this sampling device.
In addition, if desired, also can equip and be used for making in advance draining to carry out the cation exchanger of cationic exchange, be used to remove the membrane separation unit etc. of particulate etc. of swimming, carry out draining and handle.
State in the use under the situation of Zeo-karb, can remove positively charged ions such as aluminum ion, titanium ion, indium ion, molybdenum ion.
In addition, though phosphate ion is reclaimed with the form of sodium phosphate salt etc., in the present invention, the recovery of phosphate ion not only is defined in such recovery.
In addition, the salt of sodium phosphate salt etc. can utilize precipitin reaction to reclaim, and from the viewpoint that can reclaim easily, it is preferred.
Embodiment
Below, the present invention will be described in more detail to exemplify embodiment, but the invention is not restricted to these embodiment.
The recovery of＜draining processing and sodium phosphate salt 〉
First, " the レ バ チ Star ト MP62WS " that dispose バ イ エ Le ケ ミ カ Le ズ society in second anion exchange tower respectively is as anionite-exchange resin, and make separately superficial velocity SV=(treatment capacity/amount of resin)=10[1/h], as draining to be processed, make and contain the 300ppm phosphate ion, the 25ppm acetic acid ion, the acid effluent of 8ppm nitrate ion passes through first continuously with the flow that 3L/ divides, behind second anion exchange tower, carry out the pure water washing, and then, aqueous sodium hydroxide solution with 2 times of normal 10wt% carries out manipulation of regeneration, obtains sodium phosphate aqueous solution.
＜result 〉
By above-mentioned recovery, can be with the phosphate ion in the draining with the form recovery 80% of the sodium phosphate salt aqueous solution of 8wt% or more than it.In addition, above-mentioned sodium phosphate salt is utilized chromatography of ions analysis, measure the mol ratio of phosphorus and sodium, the result is 1.5 substantially, can confirm that thus the sodium phosphate salt that is reclaimed is the mixture of SODIUM PHOSPHATE, MONOBASIC and Sodium phosphate dibasic.
And then, regenerated liquid is stored in the regeneration tank, use the pump of circulation usefulness, and use ダ ウ ケ ミ カ Le ズ society " 650C-H " to carry out ion-exchange as Zeo-karb, when pH reaches 4.5, recycle pump is stopped, the above-mentioned sodium phosphate salt that is reclaimed is utilized chromatography of ions analysis, measure the mol ratio of phosphorus and sodium, the result is 1 substantially, can confirm that thus sodium phosphate salt can reclaim with the state of SODIUM PHOSPHATE, MONOBASIC.
The recovery of＜draining processing and sodium phosphate salt 〉
Except make aqueous sodium hydroxide solution that regeneration the time is used as 25wt%, all carry out the recovery of draining processing and sodium phosphate similarly to Example 1.
＜result 〉
By above-mentioned recovery, can make that the phosphate ion in the draining reclaims 80% or more than it with the form of the sodium phosphate salt aqueous solution of 15wt%.
In addition, with above-mentioned to make regenerated liquid contact Zeo-karb equally and form pH be 4.5 sodium phosphate salt, it is utilized chromatography of ions analysis, measure the mol ratio of phosphorus and sodium, the result is 1 substantially, can confirm that thus the sodium phosphate salt that is reclaimed is a SODIUM PHOSPHATE, MONOBASIC.
The recovery of＜draining processing and sodium phosphate salt 〉
Except make aqueous sodium hydroxide solution that regeneration the time is used as 40wt%, all carry out the recovery of draining processing and sodium phosphate similarly to Example 1.
＜result 〉
By above-mentioned recovery, the phosphate ion in the draining is reclaimed with the form of the sodium phosphate salt aqueous solution of 17wt%.
But, to observe, the heat release during owing to interpolation sodium hydroxide make ion exchange resin reach 70～80 ℃, and Sodium phosphate dibasic is very easy to separate out.
The recovery of＜draining processing and potassium phosphate salt 〉
Using potassium hydroxide except replacing sodium hydroxide, is that 20wt%, 2.5 times of equivalents carry out all reclaiming similarly to Example 1 beyond the manipulation of regeneration with concentration.
＜result 〉
By above-mentioned recovery, can make the phosphate ion in the draining reclaim about 80% with the form of the potassium phosphate salt aqueous solution of 15wt%.
In addition, utilize chromatography of ions to come the potassium phosphate salt that is obtained is analyzed, measure the mol ratio (potassium/phosphoric acid) of phosphoric acid and potassium, the result is 2 or more than it.
Claims (21)
1. drainage processing method, it is the drainage processing method that from the draining that contains a kind of ion being selected from nitrate ion, sulfate ion, the iodide ion and phosphate ion, reclaims phosphate ion at least, it is characterized in that, be under the tart state, draining is contacted with anionite-exchange resin, make the ion in the nitrate ion that contains in the above-mentioned draining, sulfate ion, the iodide ion carry out ion-exchange, and then contact with anionite-exchange resin, make phosphate ion and anionite-exchange resin carry out ion-exchange, reclaim phosphate ion.
2. drainage processing method as claimed in claim 1, the phosphate ion concentration of wherein said draining is below 1%.
3. drainage processing method as claimed in claim 1, it is characterized in that, by making the anionite-exchange resin of above-mentioned draining by the multistage configuration, draining is contacted continuously with this anionite-exchange resin, make phosphate ion and be configured in the 2nd section or its later anionite-exchange resin and carry out ion-exchange.
4. drainage processing method as claimed in claim 3 is characterized in that, before the anionite-exchange resin that makes above-mentioned draining with the multistage configuration contacts, each the ionic ionic concn that contains in the above-mentioned draining is measured.
5. drainage processing method as claimed in claim 1 is characterized in that, above-mentioned draining is the tart draining that generates with the pure water washing with the crystal liquid substrate that the etching solution etch processes that contains nitric acid and phosphoric acid is crossed.
6. drainage processing method as claimed in claim 5, it is characterized in that, the anionite-exchange resin that disposes by multistage by the tart draining that the crystal liquid substrate that utilizes the etching solution etch processes contain nitric acid and phosphoric acid to cross is generated with the pure water washing, make this draining contact continuously with above-mentioned anionite-exchange resin, in the total organic carbon concentration and specific conductivity of measuring draining that imports from the upstream side that is configured in the 2nd section or its later anionite-exchange resin and these two kinds of drainings of draining of discharging, make phosphate ion carry out ion-exchange from the downstream side.
7. drainage processing method as claimed in claim 3 is characterized in that, above-mentioned draining is the tart draining that generates with the pure water washing with the crystal liquid substrate that the etching solution etch processes that contains nitric acid and phosphoric acid is crossed.
8. drainage processing method as claimed in claim 7, it is characterized in that, the anionite-exchange resin that disposes by multistage by the tart draining that the crystal liquid substrate that utilizes the etching solution etch processes contain nitric acid and phosphoric acid to cross is generated with the pure water washing, make this draining contact continuously with above-mentioned anionite-exchange resin, in the total organic carbon concentration and specific conductivity of measuring draining that imports from the upstream side that is configured in the 2nd section or its later anionite-exchange resin and these two kinds of drainings of draining of discharging, make phosphate ion carry out ion-exchange from the downstream side.
9. drainage processing method as claimed in claim 4 is characterized in that, above-mentioned draining is the tart draining that generates with the pure water washing with the crystal liquid substrate that the etching solution etch processes that contains nitric acid and phosphoric acid is crossed.
10. drainage processing method as claimed in claim 9, it is characterized in that, the anionite-exchange resin that disposes by multistage by the tart draining that the crystal liquid substrate that utilizes the etching solution etch processes contain nitric acid and phosphoric acid to cross is generated with the pure water washing, make this draining contact continuously with above-mentioned anionite-exchange resin, in the total organic carbon concentration and specific conductivity of measuring draining that imports from the upstream side that is configured in the 2nd section or its later anionite-exchange resin and these two kinds of drainings of draining of discharging, make phosphate ion carry out ion-exchange from the downstream side.
11. each described drainage processing method as claim 1～10, it is characterized in that, after making phosphate ion and anionite-exchange resin carry out ion-exchange, contact with above-mentioned anionite-exchange resin by the alkaline aqueous solution that makes any metal ion that contains sodium ion, potassium ion and magnesium ion, make phosphate ion reclaim from above-mentioned anionite-exchange resin disengaging and as the phosphate metal salt brine solution.
12. drainage processing method as claimed in claim 11 is characterized in that, the alkaline aqueous solution that contains sodium ion by use makes phosphate ion reclaim as sodium phosphate aqueous solution as above-mentioned alkaline aqueous solution.
13. drainage processing method as claimed in claim 12 is characterized in that, when the pH of above-mentioned sodium phosphate aqueous solution is adjusted, carries out above-mentioned recovery.
14. drainage processing method as claimed in claim 11 is characterized in that, uses the alkaline aqueous solution that contains potassium ion as above-mentioned alkaline aqueous solution, and phosphate ion is reclaimed as the potassiumphosphate aqueous solution.
15. drainage processing method as claimed in claim 14 is characterized in that, when adjusting the pH of the above-mentioned potassiumphosphate aqueous solution, carries out above-mentioned recovery.
16. drain treatment apparatus, be from containing at least a kind of ion being selected from nitrate ion, sulfate ion, the iodide ion and phosphate ion and being the drain treatment apparatus that reclaims phosphate ion in the draining of acid state, it is characterized in that, for make above-mentioned draining by and can implement 2 times or anionresin more than it 2 of series arrangement or its above anion exchanger that is equipped with anionite-exchange resin.
17. drain treatment apparatus as claimed in claim 16 is used for reclaiming phosphate ion from the above-mentioned draining that contains phosphate ion with the concentration below 1%.
18. drain treatment apparatus as claimed in claim 16 is characterized in that, this device is used for containing the processing of the acid effluent that crystal liquid substrate that the etching solution etch processes of nitric acid and phosphoric acid crosses generates with the pure water washing.
19. drain treatment apparatus as claimed in claim 18, it is characterized in that, the upstream side and downstream survey place of at least 1 anion exchanger in the anion exchanger of enforcement the 2nd time or its later anionresin further are equipped with the total organic carbon concentration of the above-mentioned draining of mensuration and the total organic carbon density measuring device and the mhometer of specific conductivity.
20. as each described drain treatment apparatus of claim 16～19, it is characterized in that, implement the 2nd time or the anion exchanger of its later anionresin at least 1 anion exchanger be constituted as, make above-mentioned draining by and carry out anionresin after, can contact with the alkaline aqueous solution of any metal ion that contains sodium ion, potassium ion and magnesium ion and it is passed through.
21. drain treatment apparatus as claimed in claim 20, it is characterized in that, implement the 2nd time or the anion exchanger of its later anionresin at least 1 anion exchanger be constituted as, make above-mentioned draining by and carry out anionresin after, can contact with the alkaline aqueous solution of any metal ion that contains sodium ion, potassium ion and magnesium ion and it is passed through, and further be provided with the temperature tester so that the temperature of the above-mentioned alkaline aqueous solution after can measuring this and passing through.
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| JP2004233543 | 2004-08-10 | ||
| JP233543/2004 | 2004-08-10 | ||
| JP186376/2005 | 2005-06-27 |
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| CN100389075C true CN100389075C (en) | 2008-05-21 |
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| CN110054315A (en) * | 2019-03-28 | 2019-07-26 | 浙江理工大学 | A kind of method that quick adsorption removes ammonia nitrogen in dyeing waste water |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0760135A (en) * | 1993-08-26 | 1995-03-07 | Sumitomo Metal Mining Co Ltd | Method for regenerating anion exchange resin for adsorbing rhenium |
| JP2828496B2 (en) * | 1990-09-17 | 1998-11-25 | オルガノ株式会社 | Method for recovering phosphoric acid from acid waste liquid |
| US6670505B1 (en) * | 2000-03-07 | 2003-12-30 | Eastman Chemical Company | Process for the recovery of organic acids from aqueous solutions |
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2005
- 2005-08-10 CN CNB2005100902410A patent/CN100389075C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2828496B2 (en) * | 1990-09-17 | 1998-11-25 | オルガノ株式会社 | Method for recovering phosphoric acid from acid waste liquid |
| JPH0760135A (en) * | 1993-08-26 | 1995-03-07 | Sumitomo Metal Mining Co Ltd | Method for regenerating anion exchange resin for adsorbing rhenium |
| US6670505B1 (en) * | 2000-03-07 | 2003-12-30 | Eastman Chemical Company | Process for the recovery of organic acids from aqueous solutions |
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