Patent Application
20080245742
1. Technical Field
The present invention relates to wastewater treatment methods and wastewater treatment systems, and more specifically relates to a wastewater treatment method wastewater treatment system for treating wastewater containing oxidizing substances and arsenic.
2. Description of the Related Art
In order to remove arsenic from arsenic-containing wastewater, one technique known to date is to add to the wastewater a metal salt to flocculate/precipitate the arsenic, and then separate the solid matter from the wastewater to remove the arsenic. (Cf. Japanese Unexamined Pat. App. Pub. No. H11-333468, for example.)
One conceivable way of employing the above-described technique as a way to dispose of arsenic-containing wastewater is as follows. Namely: Initially, calcium hydroxide (Ca(OH)2) is introduced into the wastewater to render the pH of the wastewater highly alkaline. Subsequently, a specific amount of a metal salt—for example, ferric chloride (FeCl3)—is introduced as a flocculant into the wastewater to lower its pH to near neutral and to coprecipitate the arsenic, and then a flocculation aid is introduced into the wastewater to flocculate/precipitate the arsenic-containing solid matter, and the precipitated solid (precipitate) is eliminated. A technique of this sort makes it possible to remove the arsenic from arsenic-containing wastewater as a precipitate (sludge).
Nevertheless, in employing the above-described method, in some cases the precipitation in the wastewater retards, such that the arsenic cannot be substantially eliminated from the wastewater. One conventional approach to dealing with such situations has been to dilute by several times the wastewater being treated, and then apply the above-described treatment method to remove the arsenic. The present inventors investigated wastewater in instances in which removing arsenic in this way was not possible. Their results revealed that with wastewater containing a large amount of polishing agents and other oxidizing substances in the slurry, arsenic removal in the manner described above will not prove successful.
An object of the present invention, brought about to resolve the problems noted above, is to make available a method and system for treating arsenic-containing wastewater that enable the reliable removal of the arsenic as a precipitate even in instances in which the wastewater includes oxidizing substances.
As a result of investigating the phenomenon in which precipitation retards in wastewater including an oxidizing substance, the inventors came to the realization that if the oxidizing substance in the wastewater can be reduced, the arsenic can be removed from the wastewater by a flocculation/precipitation technique employing a flocculant (FeCl3 for example) like those that are traditional. Furthermore, if a ferrous salt is utilized in order to reduce the oxidizing substance, the reduction of the oxidizing substance transforms (oxidizes) the ferrous salt containing bivalent iron into a ferric salt containing trivalent iron. Then this ferric salt, acting as a flocculant, is needed also in precipitating the arsenic.
The inventors also studied other substances, apart from ferrous salts, as reducing agents for reducing oxidizing substances in wastewater. For example, hydrogen peroxide (H2O2) was added as a reducing agent, in which case the hydrogen peroxide made reduction of the oxidizing substances possible. The problem with adding hydrogen peroxide, however, was that it generated bubbles in the wastewater, and consequently flocculated solid matter was prevented by the bubbles from precipitating. In another instance, sodium thiosulfate was added as a reducing agent to the wastewater, in which case reduction of the oxidizing substances was also made possible. The problem with adding sodium thiosulfate, however, was that it increased the total ion count within the wastewater, lowering the precipitability of the flocculated solid matter in the wastewater. Consequently, employing sodium thiosulfate as a reducing agent required introducing into the wastewater a greater amount of flocculation aid. Thus it was concluded that, as reducing agents for reducing oxidizing substances in wastewater, ferrous salts are best suited as materials that can be utilized without causing the problems discussed above (the problems of bubble generation and compromised precipitability).
Based on findings such as noted above, a wastewater treatment method in accordance with one aspect of the present invention is a method of treating wastewater containing an oxidizing substance and arsenic, and is provided with: a step of preparing the wastewater containing an oxidizing substance and arsenic; a treatment step; a precipitation step; and a separation step. In the treatment step, an amount of ferrous salt necessary to reduce the oxidizing substance is introduced into the wastewater. In the precipitation step, the arsenic is precipitated out from the wastewater as a precipitate utilizing, as at least a part of the flocculent, ferric salt transformed from the ferrous salt by the reduction of the oxidizing substance. In the separation step, the precipitate is separated from the wastewater.
Thus designed, the method promotes precipitation of arsenic because oxidizing substances that are a factor inhibiting arsenic precipitation can be reduced by the ferrous salt. Furthermore, the ferric salt crated by the ferrous salt being oxidized by reducing the oxidizing substances acts as a flocculant in the flocculation-precipitation process for removing the arsenic. On this account, the amount of material introduced as a flocculant can be reduced over the situation in which a flocculant is added to the wastewater separately from the reducing agent for reducing oxidizing substances—as in the situation in which another substance (not utilizable as a flocculant) is employed in order to reduce the oxidizing substances.
It should be understood that in a wastewater treatment method of the present invention, FeCl2 can be utilized as ferrous salt, and FeCl3 as the ferric salt. Alternatively, FeSO4 can be utilized as the ferrous salt.
In the treatment step of the foregoing wastewater treatment method, the oxidation-reduction potential of the wastewater may be assayed to determine, based on the assay results from measuring the oxidation-reduction potential of the wastewater, whether the amount of ferrous salt introduced has reached the level necessary to reduce the oxidizing substance. Herein, wastewater containing an oxidizing substance will indicate a relatively high oxidation-reduction potential, on the plus side, but after reduction of the oxidizing substance in the wastewater by the ferrous salt is complete, the oxidation-reduction potential will go to being zero or on the minus side. Therefore, measuring the wastewater oxidation-reduction potential makes it possible to check whether or not reduction of the oxidizing substance has completed. That is, whether the amount of ferrous salt necessary to reduce the oxidizing substance has been introduced into the wastewater is determined from the measurement result. The determination thus enables introducing into the wastewater ferrous salt in the sufficient quantity needed for reduction of the oxidizing substance. In turn, reducing the oxidizing substance in the wastewater with dependable certainty ensures precipitation of the solid matter, as a result allowing removal of arsenic from the wastewater to be carried out assuredly.
What is more, excessive introduction of ferrous salt into the wastewater can be prevented, making it possible to prevent ferrous salt from remaining in excess in the post-processed effluent (that is, in the wastewater after the precipitate has been removed).
In accordance with another aspect of the present invention, a wastewater treatment system is a system for treating wastewater containing an oxidizing substance and arsenic, and is provided with a reaction vessel, a measuring device, and a feeding device. The reaction vessel holds the wastewater. The measuring device measures the oxidation-reduction potential of the wastewater held in the reaction vessel. The feeding device introduces ferrous salt into the reaction vessel, based on the output from the measuring device.
Designed in this way, the wastewater treatment system makes it possible to determine, according to the output from the measuring device, whether or not the amount of ferrous salt necessary to reduce the oxidizing substance has been introduced into the wastewater. As a result, ferrous salt can be introduced into the wastewater in the sufficient quantity needed for reduction of the oxidizing substance. In turn, reducing the oxidizing substance in the wastewater with dependable certainty allows precipitation of the solid matter within the wastewater to take place reliably. As a result, removal of arsenic from the wastewater can be carried out assuredly.
According to the present invention, even in situations in which an oxidizing substance is included in wastewater containing arsenic, the arsenic can be dependably removed from the wastewater by a flocculation-precipitation technique.
From the following detailed description in conjunction with the accompanying drawings, the foregoing and other objects, features, aspects and advantages of the present invention will become readily apparent to those skilled in the art.
Hereinafter, referring to the accompanying drawings, an explanation of embodiments of the present invention will be made in detail. It should be understood that in the following description, with the same reference marks being used for identical or equivalent features, reduplicating description will be omitted.
With reference to
Next, in order to control the wastewater pH, a Ca(OH)2 introducing step (S20) as a pH adjusting step of introducing calcium hydroxide (Ca(OH)2) into the wastewater to control the wastewater pH so as to be the predetermined value is carried out. The wastewater pH is controlled to fall within the range, for example, of from 11.5 to 11.8, inclusive, by this step (S20).
Successively, a FeCl3 and FeCl2 introducing step (S30) is carried out. In this step (S30), specifically, the predetermined fixed amount of FeCl3 and the only amount of FeCl2 necessary to reduce the oxidizing substances in the wastewater are introduced into the wastewater. A specific example of the step (S30) will be described with reference to
As represented in
Next, an ORP measuring step (S32) is carried out. In this step (S32), oxidation-reduction potential of the wastewater is measured, for example, with any measuring device conventionally well known.
Subsequently, a step (S33) of determining whether or not the measured ORP reaches a criterion level is carried out. In the step (S33), the measured ORP is compared with the predetermined criterion level to decide whether or not the measured ORP and the criterion level are equal. As the criterion level, the ORP at which all the oxidizing substances in the wastewater are reduced is utilized. If it was decided in the step (S33) that the measured ORP and criterion level are equal, all the oxidizing substances in the wastewater are believed to be reduced by the FeCl3. Therefore, the step (S30) is finished. On the other hand, if it was decided in the step (S33) that they are not equal, a part of the oxidizing substances remaining to be reduced is believed to be present in the wastewater, and thus a step (S34) of introducing the predetermined amount of FeCl2 into the wastewater is carried out. In the step (S34), the predetermined foxed amount of FeCl2 is introduced into the wastewater. After the step (S34) is finished, the step (S32) is carried out again. As just described, the steps (S32 through S34) are repeated until the measured ORP reaches the criterion level in the step (S33).
Herein, although the step (S31) of introducing a fixed amount of FeCl3 is carried out in the flow chart represented in
Next, a flocculation-aid introducing step (S40) is carried out as represented in
Successively, a precipitation step (S50) is carried out. In the precipitation step (S50), specifically, with the wastewater into which the flocculation aid has been introduced being stored in, for example, a precipitation vessel, solid matter flocculated in the wastewater is precipitated as described above. The solid matter contains arsenic.
After the solid matter is precipitated, a post-treatment step (S60) including a process of removing from the wastewater the solid matter (precipitates) precipitated in the wastewater (for example, a process of discharging from the precipitation vessel a treated solution left after the solid matter is precipitated, and of taking out from the precipitation vessel to the outside the precipitates accumulated on the bottom of the precipitation vessel) is carried out. Removing the solid matter from the wastewater means that arsenic is removed as a precipitate from the wastewater, making it possible to decrease arsenic concentration in the treated solution.
As described above, in the wastewater treatment method, the wastewater ORP is measured in order to decide the amount of introduced FeCl2. A relationship between the wastewater ORP and pH in the wastewater treatment method will be briefly described with reference to
As demonstrated in
Then, carrying out the step (S20) in
Next, carrying out the step (S30) in
Successively, referring to
With reference to
In the reaction vessel 3, a supply pipe for from the pH adjusting vessel 2, as represented with an arrow 12, supplying the wastewater whose pH has been adjusted is disposed. The pH-adjusted wastewater supply pipe is provided with a not-illustrated transferring member (for example, a pump). Furthermore, in the reaction vessel 3, the feeding device 25 for introducing FeCl3, and feeding device 24 for introducing FeCl2, into the reaction vessel 3 are disposed. Also, the measuring device 22 for measuring oxidation-reduction potential (ORP) of the wastewater stored inside the reaction vessel 3 is disposed in the reaction vessel 3. Moreover, measurement result from the measuring device 22 is input in the control section 23 connected to the measuring device 22. The control section 23 controls the FeCl2 feeding device 24, based on the input measurement result data. As to what the control section 23 controls, for example, the amount of introduced FeCl2 can be controlled based on the flow chart represented in
In the flocculation vessel 4, a supply pipe for from the reaction vessel 3, as represented with an arrow 13, supplying the wastewater into which FeCl2 has been introduced is disposed. The FeCl2-introduced wastewater supply pipe is provided with a not-illustrated pump for transferring the wastewater. In the flocculation vessel 4, the charging device 26 for introducing a flocculation aid into the flocculation vessel 4 is disposed. The step (S40) represented in
In the precipitation vessel 5, a supply pipe for from the flocculation vessel 4, as represented with an arrow 14, supplying the wastewater into which the flocculation aid has been introduced is disposed. The flocculation aid-introduced wastewater supply pipe is provided with a not-illustrated pump for transferring the wastewater. On the bottom of the precipitation vessel 5, a discharging mechanism (such as a discharge pipe as represented with an arrow 16) for discharging the precipitates (sludge) that are the solid matter accumulated on the bottom of the precipitation vessel 5 is disposed. Also, a pipe for discharging a (treated) solution other than the precipitates, as represented with an arrow 15, from the precipitation vessel 5 to the outside. The treated-solution discharge pipe is provided with a pump. Furthermore, the pH adjusting vessel 2, reaction vessel 3, and flocculation vessel 4 are provided with a propeller or other stirring members rotatable on a motor, because the wastewater that these vessels each store is stirred. The steps (S50 and S60) represented in
Although partially overlapped with above embodiment, a characteristic structure of the present invention is summarized below: the wastewater treatment method of the present invention is the method of treating wastewater containing oxidizing substances and arsenic, and is provided with a preparation step (S10) of preparing the wastewater containing oxidizing substances and arsenic, the step (S30) as the treatment step, the precipitation step (S50), and the post-treatment step (S60) as separation step. In the step (S30), the amount of FeCl2 as the ferrous salt necessary to reduce the oxidizing substances such as polishing agents is introduced into the wastewater. In the precipitation step (S50), FeCl3 as the ferric salt transformed from the FeCl2 by its reducing the oxidizing substances is utilized as at least a part of flocculant to precipitate the arsenic out from the wastewater as a precipitate. In the post-treatment step (S60), the precipitates are separated from the wastewater.
In such a wastewater treatment method, the oxidizing substances that are a factor inhibiting the arsenic precipitation are reduced by the FeCl2, and thus the arsenic precipitation can be prompted. Furthermore, FeCl3 generated by reducing the oxidizing substances acts as flocculant in the flocculation-precipitation process for removing arsenic. For this reason, the wastewater treatment method makes the amount of a substance introduced as flocculant smaller than adding, separately from a reducing agent for reducing oxidizing substances, a flocculant to wastewater as employing another substance (not utilizable as flocculent) in order to reduce the oxidizing substances.
In the step (S30) of the wastewater treatment method, as represented in
Herein, the ORP of the wastewater containing oxidizing substances is relatively higher on the plus side, but after the reduction of the oxidizing substances in the wastewater by FeCl2 is completed, the ORP changes to 0 or to on the minus side. Therefore, measuring the wastewater ORP makes it possible to check whether or not the oxidizing-substance reduction is completed. That is, whether or not the amount of FeCl2 necessary to reduce the oxidizing substances is determined from the measurement result. Consequently, such a determination enables introducing into the wastewater as much FeCl2 as necessary enough to reduce the oxidizing substances. And, completely reducing the oxidizing substances in the wastewater ensures precipitation of the solid matter, resulting in that the arsenic is reliably removed from the wastewater.
Moreover, excessive introduction of FeCl2 can be prevented, which means that the FeCl2 is prevented from excessively remaining in solution discharged after the treatment (that is, in the wastewater from which the precipitates have been removed).
Herein, in the wastewater treatment method described above, FeCl2 as ferrous salt may alone be introduced into the wastewater in the step (S30) corresponding to the treatment step. Alternatively, in addition to introducing a preestablished amount of FeCl3 as a ferric salt into the wastewater, FeCl2 as a ferrous salt may be introduced into the wastewater, as described above.
A wastewater treatment system 1 of the present invention is a system for treating the wastewater containing oxidizing substances and arsenic, and as illustrated in
Such a wastewater treatment system 1 makes it possible to determine, based on the output from the measuring device 22, whether or not the amount of FeCl2 necessary to reduce the oxidizing substances has been introduced into the wastewater. As a result of this determination, as much FeCl2 as necessary enough to reduce the oxidizing substances can be introduced into the wastewater. Furthermore, completely reducing the oxidizing substances in the wastewater ensures precipitation of the solid matter in the wastewater. Consequently, the arsenic can be reliably removed from the wastewater. Herein, in the wastewater treatment system 1 described above, the reaction vessel 3 may be equipped solely with the feeding device 24 for introducing FeCl2 as a ferrous salt.
In order to confirm advantages of the present invention, the experiment in which a precipitation rate of the flocculated solid matter (sludge) in adding as flocculate only FeCl3 to the wastewater is compared with that in charging FeCl2 and FeCl3 into the wastewater was conducted. The experiment will be described below.
First, arsenic-containing wastewater including a polishing agent as oxidizing substance was prepared. The wastewater was produced as a result of GaAs wafer polishing process, with INSEC® (from Fujimi Incorporated) being contained as polishing agent. Furthermore, the wastewater pH and ORP were respectively 7.1 and 630 mV. Moreover, concentration of the arsenic contained in the wastewater was 37 ppm.
A liter of the wastewater was poured in beakers as test samples for the comparative example and embodiment. Furthermore, into one of the beakers into which the wastewater as the embodiment test sample was poured, 50 cc solution containing 5% Ca(OH)2 as pH adjuster, and then 2 cc solution containing 33% FeCl2 and additionally only 4 cc solution containing 0.1% flocculation aid were introduced.
On the other hand, into the other of the beakers into which the wastewater as comparative example test sample was poured, 50 cc solution containing 5% Ca(OH)2 as pH adjuster, and then 2 cc solution containing 38% FeCl3 and only 4 cc solution containing 0.1% flocculation aid were introduced.
Subsequently, the wastewater was stirred for a fixed period of time after the flocculation aid was introduced, and from when the stirring was completed, precipitated level of the solid matter (sludge) flocculated in the wastewater in accordance with the passage of time was visually measured. Specifically, the most upper boundary position of where the sludge was present in the wastewater (the boundary between the solution region in which only solution is present with no sludge and the region in which the sludge is present) was visually checked, and a ratio of the interval from the beaker bottom wall to the boundary position with respect to the distance (wastewater depth) from the beaker bottom wall to the wastewater surface was measured. The measurement was carried out several times whenever a fixed period of time passed from when the stirring was completed.
As to the comparative example test sample, above ratio was 90% two minutes after the stirring was completed, and was 70% even when 5 minutes passed. And, the ratio was approximately 55% when 10 minutes passed. On the other hand, as to the embodiment test sample, the ratio becomes about 40% approximately one minute after the stirring was completed, and dropped to 30% two minutes later. Furthermore, as to the embodiment test sample, arsenic concentration of the treated solution from which the precipitates had been removed was 0.034 ppm, which meant that arsenic was removed sufficiently.
Such a measurement result proves that the embodiment of the present invention has a faster precipitate precipitation rate in the wastewater than the comparative example. The possible cause is that FeCl2 introduced into the wastewater in the embodiment reduces the oxidizing substances to heighten precipitability of the flocculated solid matter, and with the reduction of the oxidizing substances, bivalent iron ions of which FeCl2 is composed changed into trivalent iron ions, which acted as flocculant.
Next, arsenic-containing wastewater discharged from a plant was treated by the wastewater treatment method of the present invention. Specifically, wastewater in GaAs wafer polishing process was subjected to the following wastewater treatment. Herein, undiluted solution of the wastewater had arsenic concentration of 40 ppm, ORP of 650 mV, and pH of 6.8. Furthermore, the wastewater was subjected to the conventional flocculation-precipitation method in which only FeCl3 was employed, but flocculated solid matter could not sufficiently precipitated with the wastewater being undiluted. Therefore, the undiluted solution was diluted to two times lower concentration, and then was subjected to the treatment.
First, as in the step (S20) in
Next, as in the step (S30) in
Subsequently, as in the step (S40) in
After the introduction of acrylamide-sodium acrylate copolymer, in the wastewater, the flocculated solid matter were precipitated. The precipitate precipitation rate sufficiently fastened. Subsequently, the precipitates and the residual solution (treated solution) were separated. The treated solution had arsenic concentration of 0.05 ppm. As just described, the wastewater treatment method of the present invention made it possible to subject the wastewater that could not be conventionally treated without dilution to the treatment in which arsenic was removed with the wastewater being undiluted.
The presently disclosed embodiments and implementation examples should in all respects be considered to be illustrative and not limiting. The scope of the present invention is set forth not by the foregoing description but by the scope of the patent claims, and is intended to include meanings equivalent to the scope of the patent claims and all modifications within the scope.
The present invention is applied to treatment of arsenic-containing wastewater, and particularly, is applied advantageously to treatment of arsenic-containing wastewater including oxidizing substances.
Only selected embodiments have been chosen to illustrate the present invention. To those skilled in the art, however, it will be apparent from the foregoing disclosure that various changes and modifications can be made herein without departing from the scope of the invention as defined in the appended claims. Furthermore, the foregoing description of the embodiments according to the present invention is provided for illustration only, and not for limiting the invention as defined by the appended claims and their equivalents.
| Number | Date | Country | Kind |
|---|---|---|---|
| JP-2007-100811 | Apr 2007 | JP | national |
