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WO2001034523A1 - Traitement d'eaux usees contaminees - Google Patents

Traitement d'eaux usees contaminees Download PDF

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Publication number
WO2001034523A1
WO2001034523A1 PCT/US1999/026345 US9926345W WO0134523A1 WO 2001034523 A1 WO2001034523 A1 WO 2001034523A1 US 9926345 W US9926345 W US 9926345W WO 0134523 A1 WO0134523 A1 WO 0134523A1
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WIPO (PCT)
Prior art keywords
species
electrodes
aqueous solution
ions
solution
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Application number
PCT/US1999/026345
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English (en)
Inventor
Stephen Ray Wurzburger
James Michael Overton
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Priority to AU24734/00A priority Critical patent/AU2473400A/en
Priority to PCT/US1999/026345 priority patent/WO2001034523A1/fr
Publication of WO2001034523A1 publication Critical patent/WO2001034523A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/463—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrocoagulation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
    • C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds

Definitions

  • This invention relates to a method and process for the removal of contaminants such as heavy or light metals from waste water, particularly such are discharged from various processing operations and particularly to a method which incorporates magnetic, electrolytic and chemical techniques.
  • Electrolytic Hydroxide precipitation
  • Oxidation state modification Low voltage electrolysis
  • High voltage electrolysis High voltage electrolysis
  • U. S. Patent 3,901,781 to Passino et al discloses pretreatment of water utilizing ion exchange followed by a dialysis process. Ion exchange resins are expensive and must be periodically reconditioned.
  • U. S. Patent 4,006,067 to Gussack discloses a process for changing the oxidation state of a dissolved ionic species using porous electrodes. Porous electrodes are subject to degradation by accumulation of scum in pores.
  • U. S. Patent 4,011,151 to Ho et al discloses a processs for purifying water in two steps.
  • the electrolysis is effected by dipping an iron anode and a carbon cathode in the waste water, filtering the water, adjusting the pH to 14 by electrolysis with a carbon
  • U. S. Patent 4,123,339 to Gale et al discloses a plurality of closely spaced parallel electrodes, using hydrochloric acid cleaning system to keep the iron electrodes free from oxides coating. Removal of the chloride ions requires an additional step.
  • U. S. Patent 4,338,178 to Vyacheslav et al discloses a nozzle which, together with gas formed on the surface of the electrode carry the sludge away from the electrodes.
  • U. S. patent 4,655,895 to Feofanov et al discloses dissolving a metal anode in the presence of a nonsoluble cathode and precipitating nonsoluble inorganic and organic impurities, the electrodes being alternately brought into contact with the air, oxygen and liquor being treated.
  • the patent clearly states that calcium is a problem and requires a preprocessing step not disclosed.
  • a magnetic field is positioned to remove iron particl;es.
  • U. S. patent 4,810,344 to Okazaki discloses a plurality of electrolysis vessels, each having an anode and cathode and an electrolysis diaphragm partitioning the space between them with an alkaline water discharge conduit connected to the cathode side and an acidic discharge conduit connected to the anode side of the diaphragm.
  • a magnetic supply unit may be disposed to the vessels to exert a magnetic effect.
  • a diaphragm tends to have a limited life in the field.
  • U. S. Patent 5,045,214 to Walker discloses coprecipitating non-volatile contaminants with a carrier precipitate formed in situ in the solution. This system is essentially a batch process and requires long treatment times. The primary drawback of this type of system is that, as contaminant levels decrease, the law of "Mass Action" predicts a slowing of the reactions then takes place in these batch processes.
  • the data presented shows a final concentration of Se to be 22 mg/1 of Se in water which issignificantly greater than the levels permitted by the present EPA Water Standard for Se allowance which is 0.05 mg/1
  • the most plentiful ionic species of metallic selenium in aqueous solution is a +4 valent ion, a strong reducing agent that readily combines with oxygen to form Se ⁇ 2, a colorless solid that is readily soluble in water.
  • Hydrolysis of water is the disassociation of the water molecule into ions.
  • the disassociation is given by:
  • This invention is directed toward a process of steps including putting the solution through "ion state modification " chambers where ions that would normally and naturally form soluble hydroxides are converted to species that form insoluble hydroxides.
  • Exemplary steps of the method include:
  • a significant feature of the invention is the enhancement of the ion state modification step by the impositon of the magnetic field on the solution while it is undergoing treatment between the electrodes of the ion state modification cell.
  • Another significant feature of the invention is the selection of the appropriate electrodes and voltage applied between the electrodes of the ion state modification cell such as to raise the valence to a value where the resultant hydroxide formed is more insoluble.
  • Fig. 1 shows the steps in the process of this invention.
  • Fig. 2 shows the steps for preparing the first chemical agent.
  • Fig. 3 shows the apparatus for carrying out the invention.
  • Fig. 1 shows the steps in carrying out the process of this invention for removing contaminating metal ions from aqueous waste solutions, particularly magnesium and calcium from brines.
  • a first chemical agent is added to the aqueous waste water to be purified and mixed in the presence of a magnetic field in a sufficient amount to raise the pH to about 7.5 to about 9.5 depending on the level of calcium contamination.
  • a preferred first agent is prepared according to steps listed in following paragraphs.
  • step 2 the mixture is passed serially through at least one "ion state modification" cell.
  • Each cell has a pair of electrodes, across which an electric field is applied. The voltage between the electrodes in each cell is selected to induce change of valency of the ions.
  • step 2 A principle result of step 2 is to cause the precipitaion of ions such as Ca having a low ionization potential.
  • ions such as Ca having a low ionization potential.
  • step 3 the mixture is allowed to digest so that a sludge of Ca(OH)3 forms.
  • step 4 the metal hydroxide sludge (often calcium) is drawn out by settling and/or filtering and the sludge is further dewatered by passage through a filter press. At this point in the process most light metal ions that might have originally been in the waste water have been removed.
  • step 5 steps 1 through 4 are repeated.
  • Mg (OH) 2 is typically used to adjust pH and mixed into the solution, preferably in the presence of a magnetic field.
  • the "ion state modification" cell is operated at 78 to 82 volts where the Mg is oxidized according to the reaction:
  • Mg +++ forms large crystal of insoluble Mg(OH)3 precipitate with most heavy metal ions that might originally have been in the water and which are easily filtered out in the final step.
  • Fig. 2 shows the steps for preparing the first chemical agent applied in step 1.
  • step 1 40 ml of concentrated sulfuric acid (Be 12°) is added to one liter of water.
  • step 2 Ca(OH) 2 is added to bring the solution up to a range of 12.1 to 13.1.
  • step 3 the solution is passed through an eleven micron filter thereby removing any CaSO 4 precipitates larger than eleven microns.
  • step 4 sufficient potassium hydroxide is added to bring the pH to a range of 13.8 to 14 thereby producing a base solution.
  • step 5 magnesia is added in the amount of 10 grams per one liter of base solution thereby formulating the first chemical agent.
  • Fig. 3 shows a schematic diagram of the apparatus for performing the steps of the process.
  • the mixer 12 is subject to a magnetic field provided by a magnet 14.
  • the first chemical agent is admitted to the mixer 12 from reservoir 16.
  • the solution is allowed to digest and is then passed through two series connected "ion state modification cells" 17 and 18.
  • Each cell has a pair of electrodes across which pair a voltage is impressed from power supply 20.
  • the electtodes are preferably tin .
  • the cells are preferably subjected to a magnetic field imposed by externally positioned magnets 15.
  • the calcium and light metal hydroxides precipitate out and these precipitates are removed in the clarifier 22.
  • the solution is then passed to a chemical mixer 24 where it is mixed with Mg(OH) 2 from reservoir 26.
  • the solution is then passed through another "ion state modification" cell 27 where Mg(OH)3 is formed, the electrodes of the second stage cell are preferably iron,, carbon or titanium. . This precipitate is filtered out in the clarifier 30.
  • the power supply 28 for applying power to the "ions state modification" cell 27 is shown.
  • the process of this invention overcomes a problem encountered in using Ca(OH) 2 in state of the art processes to raise the pH to a value high enough to precipitate metal hydroxide precipitates
  • the problem is that the Ca(OH) 2 precipitates thus formed have very low density and consequently poor properties for filtering.
  • U. S. Patent 4,054,516 very plainly shows that a solution of Cu-Zn mixture can be removed by adjusting the pH to 9 + whereas a five metal mixture of Cu-Ni-Pb- Co-Mn ions requires a pH above 10.5 to remove the ions.
  • a solution with a pH above 10.5 requires an excessive amount of acid for reducing the liquid back to 7.0 to 8.0 range required for dumping.
  • the amount of cations added to the waste water for pH reduction may render the water unfit for dumping.
  • the present invention overcomes this problem by converting the Ca ++ to Ca +++ in the first two ion state modification cells as discussed above.
  • Magnesium hydroxide ⁇ Mg(OH) 2 is also used for water treatment in state of the art processes.
  • Mg(OH) 2 has several advantages in that it is not a toxic metal and it has excellent filtering characteristics in terms of the its coagulant properties.
  • this hydroxide is not effective for removing multiple metals primarily because it is self buffering in a pH range of 9.0 to 9.2.
  • the present invention overcomes this problem by converting the Mg(OH) 2 to Mg(OH)3 in the third "ion state modification " cell discussed above. With the problem calcium removed, the magnesium ions are converted from Mg + ⁇ to Mg +++ in the ion state modification cell using iron, titanium or carbon electrodes.
  • the Mg(OH)3 is self flocculating and does not require additive chemical flocculating agents for precipitation and filtering.
  • the pH needs to be reduced to a pH range from 7.0 to 8.2.
  • the pH may be reduced using a strong acid.
  • EXAMPLE I A sample of contaminated cooling tower water was obtained from a Mojave Desert industrial site. The contaminants include significant amounts of Cr, Cu, and Zn and as such constitute a toxic hazard that requires treatment as a toxic waste material.
  • a 650 ml of sample was placed in a stage one reactor (tin anodes) and was treated for two minutes. After the initial treatment, the sample was allowed a digestion time of 2 hours. A 50 ml sub sample was taken from the initial sample and sent to a certified lab for analysis. The remainder was treated in a stage 2 laboratory "ion state modification" cell for an additional one min with no additional digestion time. Total treatment time (including time for digestion) was 2 hr. 4 min. Table I summarizes results of the above procedure:
  • a sample of contaminated water was taken from a Mojave desert industrial site.
  • the water from which the sample was obtained was used in steam generation as well as in a cooling water application.
  • a small amount of HCl had been added as an algicide.
  • the combination of silicates and arsenic together posed a major disposal problem.
  • a 650 ml sample was placed in a stage 1 cell and was treated for four minutes After the initial treatment the sample was allowed to digest for 1 hour.
  • a 50 ml sub sample was taken from the the initial sample and sent to a certified laboratory for analysis. The remainder (approximately 600 ml) was treated in a stage 2 "ion state modification cell" for an additional one minute with no additional digestion time. Total treatment time was therefore 1 hr, 5 min. Table 2 summarizes the results of the above procedure.
  • stage 1 + digest. 7.6 3.9 13.0 ⁇ 0.14 3.8
  • a sample of contaminated water was taken from a well on a Northern California industrial site. The site has been in continuous service for over 40 years. The sample was highly alkaline and contained a measurable concentration of several heavy metal contaminants.
  • a 650 ml sample was placed in a stage one cell and treated for 4 min after which a 25 ml sample was extracted. The sample was allowed a digestion time of 1 hour. A second 25 ml sample was taken. Both extracted samples were sent to a certified lab for analysis. The remainder was placed in a stage two laboratory cell and treated for an additional minute with no additional digestion time. Total treatment time (including digestion time ) was 1 hour 5 min. TABLE III summarizes the results of the treatment.
  • Selenium exhibits multiple valence states -2, +4, +6.
  • the multi valence selenium as a contaminant requires a multistage ion state modification cell to deal with the multiple ionic states that are present.
  • the initial treatment is accomplished using two cells.
  • the stage 1 cell leaves residual electrode material in the solution.
  • the stage 2 cell is used to remove the residual stage 1 electrode material from the solution and naturally occurring magnesium. This resulted in a significant reduction of selenium levels. Results of the treatment are presented in TABLE IV.
  • an embodiment of this invention includes a preparatory step of removing Ca by any of the procedures discussed above in situations where the presence of Ca requires such a step.
  • EXAMPLE V A waste effluent was obtained from a circuit board and electroplating operation in Northern California. The solution was analyzed and the primary constituent was determined to be copper, but in multiple oxidation states. The predominant species was Cu ++ with lower levels of Cu + .
  • a long ion state modification cell was constructed.
  • the cell was essentially a parallel plate reaction chamber (trough) with iron electrodes which modified the Cu + oxidation state to Cu ++ oxidation state prior to passing thr solution through laboratory cells which are more costly and less simple to maintain.
  • the pH was then raised to neutral ( 7.0 + 0.5 ) by the addition of bicarbonate of soda
  • the concenration was again analyzed and found to contain 1130 ppm copper.
  • the treatment time in the laboratory cell was 15 minutes. During the 15 minute period, considerable precipitate formed.
  • the copper collected during the operation was collected as "metallic copper concentrate" and was commercially maiketable as a high grade ore concentrate.
  • the spent etching solution was analyzed and found to contain 1800 ppm copper.
  • Initial processing modified the Cu + state to CU++.
  • the pH shift was achieved by the addition of bicarbonate of soda.
  • the solution was now allowed 1 hr of undisturbed digestion time. An additional drop in copper concentration to 920 ppm was observed.
  • the solution was allowed an additional 1 hr digestion resulting in a further reduction of Cu to 910 ppm.
  • the results are summarized in TABLE VA TABLE V.A
  • the solution was allowed to digest for one hr and again analyzed.
  • the copper level had decreased further to 120 ppm.
  • the filtrate at this point was high grade copper ore having commercial value.
  • the residue was a high grade metal hydroxide concentrate.
  • An important embodiment of this invention is based on our observation that when the ion state of the ions are undergoing modification in the cell (contiOlled oxidation) , the presence of a very strong magnetic field enhances and accelerates the process;
  • the magnetic field is preferably a strong gradient field generated by the presence of the north magnetic pole. To illustrate this effect the following tests are presented.
  • EXAMPLE VI 650 ml of a well water sample was treated under identical conditions using a cell with and without a magnetic field. Each sample was treated for 2 min under identical conditions.in a cell having a type 3 stannite cell. The pH was measured before treatment, immediately after treatment and again 1 hr after passive digestion time. . The results are tabulated in TABLE VI
  • This invention has wide application for removal of contaminating heavy and light metal ions from waste water and particularly for providing an efficient process for removing large concentrations of calcium and magnesium such as are found in desert waters in brines created from operations used in processing olives.
  • the invention is particularly useful for removing from water impurities such as selenium and arsenic (metallic and non metallic forms) which pose a hazard even when present in small concentrations.
  • the method and apparatus of the present invention is less complex in terms of required steps and additives required and consequently less costly.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)
  • Removal Of Specific Substances (AREA)

Abstract

L'invention se rapporte à un procédé et à un appareil permettant d'extraire d'une solution aqueuse à purifier un ensemble d'espèces d'ions métalliques. Ledit procédé consiste à effectuer, pour chaque espèce, (1) l'ajustement du pH de la solution aqueuse sur une valeur où les précipités hydroxydes de ladite espèce dans son état de plus grande valence sont insolubles, puis (2) à faire passer la solution aqueuse par une cellule de modification de l'état ionique en présence d'un champ magnétique de manière à accroître la valence de l'espèce respective jusqu'à son état de valence le plus grand et (3) à digérer l'espèce ionique de manière à former l'hydroxyde insoluble, puis (4) à extraire l'hydroxyde précipité de la solution aqueuse par des étapes appropriées de sédimentation et de filtrage au filtre-presse, et enfin (5) à répéter les étapes (1) à (4) à une tension supérieure au cours de l'étape de modification de l'état ionique. Le champ magnétique imposé entre les électrodes améliore l'efficacité de l'étape de modification de l'état ionique.
PCT/US1999/026345 1999-11-06 1999-11-06 Traitement d'eaux usees contaminees Ceased WO2001034523A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU24734/00A AU2473400A (en) 1999-11-06 1999-11-06 Treatment of contaminated waste water
PCT/US1999/026345 WO2001034523A1 (fr) 1999-11-06 1999-11-06 Traitement d'eaux usees contaminees

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US1999/026345 WO2001034523A1 (fr) 1999-11-06 1999-11-06 Traitement d'eaux usees contaminees

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113277654A (zh) * 2021-05-28 2021-08-20 金川集团股份有限公司 一种利用电化学方法处理电积高纯锰废液的方法及装置
CN113717916A (zh) * 2021-09-30 2021-11-30 苏州水星环保工业系统有限公司 一种用于处理凉果废水的复合菌剂的制备方法及应用

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4011151A (en) * 1973-07-06 1977-03-08 Nippon Risui Kagaku Kenkyusho Process for purifying waste water by electrolysis
US5401420A (en) * 1993-03-08 1995-03-28 Nalco Chemical Company Sulfide ion-selective electrodes for control of chemical feed of organic sulfide products for metal ion precipitation from waste water
US5423962A (en) * 1994-04-18 1995-06-13 Herbst; Robert Electrolytic treatment apparatus
US5427691A (en) * 1992-12-02 1995-06-27 Noranda, Inc. Lime neutralization process for treating acidic waters
US5443719A (en) * 1994-02-23 1995-08-22 Aqua-Ion Systems, Inc. System and reactor for mixing coagulating agents into a contaminated water flow, and for removing contaminants therefrom

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4011151A (en) * 1973-07-06 1977-03-08 Nippon Risui Kagaku Kenkyusho Process for purifying waste water by electrolysis
US5427691A (en) * 1992-12-02 1995-06-27 Noranda, Inc. Lime neutralization process for treating acidic waters
US5401420A (en) * 1993-03-08 1995-03-28 Nalco Chemical Company Sulfide ion-selective electrodes for control of chemical feed of organic sulfide products for metal ion precipitation from waste water
US5443719A (en) * 1994-02-23 1995-08-22 Aqua-Ion Systems, Inc. System and reactor for mixing coagulating agents into a contaminated water flow, and for removing contaminants therefrom
US5423962A (en) * 1994-04-18 1995-06-13 Herbst; Robert Electrolytic treatment apparatus

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113277654A (zh) * 2021-05-28 2021-08-20 金川集团股份有限公司 一种利用电化学方法处理电积高纯锰废液的方法及装置
CN113717916A (zh) * 2021-09-30 2021-11-30 苏州水星环保工业系统有限公司 一种用于处理凉果废水的复合菌剂的制备方法及应用

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Publication number Publication date
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