IL322288A - Combined slurry copper waste and concentrated copper waste for the treatment of azoles, metals, and silica solids in wastewater - Google Patents

Description

COMBINED SLURRY COPPER WASTE AND CONCENTRATED COPPER WASTE FOR THE TREATMENT OF AZOLES. METALS, AND SILICA SOLIDS IN WASTEWATER FIELD OF TECHNOLOGYAspects and embodiments disclosed herein relate to systems and methods for the treatment of wastewater, for example, copper chemical-mechanical polishing (CMP) wastewater including organic contaminants such as azoles. The methods disclosed herein provide for the destruction of organic contaminants in the wastewater utilizing a modified Fenton’s reagent utilizing copper from combined waste streams of a semiconductor manufacturing facility as a catalyzing agent.

SUMMARYIn accordance with one aspect, there is provided a method for removing organic compounds from a copper-containing solution. The method comprises producing the copper- containing solution from a mixture of wastewater from a copper chemical mechanical polishing (CMP) operation of a semiconductor manufacturing facility and a concentrated copper waste stream (CCW) from the semiconductor manufacturing facility', and introducing an oxidizer into the copper-containing solution, the copper catalyzing production of hydroxyl radicals from the oxidizer that react with the organic compounds.In some embodiments, the method further comprises maintaining a pH of the copper- containing solution in the vessel at a level at which the copper catalyzes the production of the hydroxyl radicals from the oxidizer.In some embodiments, the method further comprises maintaining the pH of the copper- containing solution in the vessel between about 2 and about 4.In some embodiments, the method further comprises maintaining a temperature of the copper-containing solution in the vessel at between about 55°C and about 650C.In some embodiments, introducing the oxidizer into the copper-containing solution includes introducing hydrogen peroxide into the copper-containing solution.In some embodiments, the method further comprises maintaining a concentration of hydrogen peroxide in the copper-containing solution in the vessel of 250 mg/L or more.In some embodiments, the method further comprises obtaining the hydrogen peroxide from a waste stream from the semiconductor manufacturing facility.

In some embodiments, producing the copper-containing solution includes mixing at least one part of the CCW with 25 parts of the CMP wastewater or at least one part of the CCW with parts of the CMP wastewater.In some embodiments, removing the organic compounds from the copper-containing solution includes removing one or more azole compounds from the copper-containing solution.In some embodiments, producing the copper-containing solution includes mixing the CCW with the CMP wastewater in an amount sufficient to provide 20 parts by weight copper per part by weight of the one or more azole compounds.In some embodiments, removing the organic compounds from the copper-containing solution includes removing one or more of 1,2,4-Triazole, IH-Benzotriazole pyrazole. Benzotriazole, 5-methyl IH-benzotriazole (Tolutriazole), or 3-amino 1.2.4-triazole from the copper-containing solution.In accordance with another aspect, there is provided a system for removing organic compounds from wastewater from a semiconductor manufacturing facility. The system comprises a vessel fluidly connectable to a source of the wastewater, a source of copper configured to introduce copper into the wastewater in the vessel, the source of copper including a concentrated copper waste stream from the semiconductor manufacturing facility; a source of oxidizer configured to introduce the oxidizer into the wastewater in the vessel, and a source of pH adjustment chemical configured to introduce the pH adjustment chemical into the wastewater in the vessel.In some embodiments, the system further comprises a pH monitor disposed within the vessel, and a controller configured to control the source of pH adjustment chemical to introduce the pH adjustment chemical into the wastewater in the vessel at a quantity' and rate sufficient to maintain the pH of the wastewater at a level at which the copper catalyzes production of hydroxyl radicals from the oxidizer.In some embodiments, the controller is configured to control the source of pH adjustment chemical to introduce the pH adjustment chemical into the wastewater in the vessel at a quantity and rate sufficient to maintain the pH of the wastewater at between about 2 and about 4.In some embodiments, the system further comprises a heater, the controller further configured to control the heater to maintain a temperature of the wastewater in the vessel at between about 55°C and about 650C.In some embodiments, the source of oxidizer is a source of hy drogen peroxide, and the controller is further configured to control the source of oxidizer to maintain a concentration of hydrogen peroxide in the wastewater in the vessel at 250 mg/L or more.2 In some embodiments, the source of hydrogen peroxide includes a waste stream of the semiconductor manufacturing facility.In some embodiments, the wastewater includes one or more anti-corrosives for copper and the system is configured to decompose the anti-corrosives for copper with hydroxyl radicals produced from the oxidizer with the copper acting as a catalyst from the production of the hydroxyl radicals.In some embodiments, the wastewater includes one or more azole compounds and the system is configured to decompose the one or more azoles with hydroxyl radicals produced from the oxidizer with the copper acting as a catalyst from the production of the hydroxyl radicals.In some embodiments, the wastewater includes one or more of 1,2,4-Triazole, 1H- Benzotriazole pyrazole, Benzotriazole, 5-methyl IH-benzotriazole (Tolutriazole), or 3-amino 1,2,4-triazole and the system is configured to decompose the one or more of 1,2,4-Triazole, 1H- Benzotriazole pyrazole, Benzotriazole, Tolutriazole, or 3-amino 1,2,4-triazole with hydroxyl radicals produced from the oxidizer with the copper acting as a catalyst from the production of the hydroxyl radicals.In some embodiments, the source of wastewater is a unit operation at the semiconductor manufacturing facility.In some embodiments, the source of wastewater is a copper CMP operation at the semiconductor manufacturing facility.In some embodiments, the source of copper includes a copper plating operation at the semiconductor manufacturing facility.

BRIEF DESCRIPTION OF THE DRAWINGThe accompanying drawing is not intended to be drawn to scale. In the drawing, each identical or nearly identical component that is illustrated is represented by a like numeral. For purposes of clarity, not every component may be labeled. In the drawings:FIG. 1 illustrates an example of a system as disclosed herein.

DETAILED DESCRIPTIONThe chemical mechanical polishing (CMP) planarization process involves a polishing slurry comprising an oxidant, and abrasive, complexing agents, and additional additives to remove and/or etch semiconducting wafers during the manufacturing process. The polishing is performed with a polishing pad to remove excess copper from the semiconductor wafers. Silicon, copper, and various trace metals are removed from the silicon structure via the 3 polishing slurry'. The polishing slurry is introduced to the silicon wafer on a planarization table in conjunction with polishing pads. Oxidizing agents and etching solutions are introduced to control the removal of material. Deionized water rinses are generally employed to remove debris from the silicon wafer. UPW from reverse osmosis (RO), demineralized, and polished water may also be used in the semiconductor fabrication facility tools to rinse the silicon wafer.An oxidizer of hydrogen peroxide (H2O2) typically is used to help dissolve the copper from the microchip. Accordingly, hydrogen peroxide (H2O2) at a level of about 300 ppm and higher also can be present in the byproduct polishing slurry wastewater.In fabrication processes of semiconductor devices, large amounts of wastewater containing anticorrosives for copper are discharged from CMP steps for performing surface polishing of copper when copper wiring is installed. Therefore, treatment of the wastewater is desirable to prevent discharge of undesirable contaminants to the environment.Among anticorrosives for copper, in particular, azole-type anticorrosives for copper have an excellent anticorrosive effect. However, the azole-type anticorrosives for copper typically have a chemically stable structure and are not easily biodegraded. Thus, conventionally, in treating wastewater containing an azole-type anticorrosive for copper discharged from the process, the azole-type anticorrosive for copper is decomposed using an oxidizing agent having high oxidizing power, such as ozone, ultraviolet light, or hy drogen peroxide, or by an advanced oxidation process in which these oxidizing agents are combined, and then treated water is discharged or collected.However, as described above, since the azole-type anticorrosives for copper are chemically stable, even when using of an oxidizing agent having high oxidizing power, such as ozone, addition of a large amount thereof is required for oxidative decomposition of the azole- type anti corrosives for copper, thus posing a large problem in terms of cost. In particular, in recent years, with the increase in the degree of integration in semiconductor devices, the number of fine polishing steps has been increasing, and along with this, the amount of polishing wastewater discharged has been increasing. Therefore, the increase in cost due to an increase in the capacity' of wastewater treatment equipment has become a problem.Fenton’s reagent is often used for the treatment of organic compounds. Fenton’s reagent may be produced by adding 10 parts of peroxide to 1 part of ferrous iron (ferrous sulfate) for every7 0.3 parts of organic compounds.Fenton’s reagent is effective when treating some azoles, such as pyrazole. However, lab tests have shown that other forms of azoles such as 1,2,4-Triazole are not decomposed when exposed to Fenton’s reagent.4 As discussed above, azoles are often used in facilities that manufacture computer chips as an anticorrosive additive. These facilities also generally have high strength copper bearing wastewaters from the CMP process that, once spent, are treated and disposed of at a cost to the facility. In one embodiment, the use of a waste copper stream in place of iron in Fenton’s reagent (a Fenton’s-like reagent) is used to treat and degrade azole compounds in wastewater. Testing has shown that 1,2,4-Triazole. IH-Benzotriazole, and Methylbenzotriazole: 4,Tolytriazole can all be treated using copper-substituted Fenton’s reagent. In one test waste hydrogen peroxide (which contained the azole to be treated), and waste copper sulfate, which can be used in place of iron sulfate in the Fenton’s reaction w as found to produce an oxidant- containing solution which successfully degraded the azole.In some embodiments, copper is substituted for iron in a modified Fenton’s reaction, referred to herein as a Fenton’s-like reaction. A waste copper stream from a semiconductor production facility may be used as the source of the copper. The w aste copper may be present in the effluent of a copper CMP process, referred to as slurry copper w aste (SCW) herein. More specifically, in some aspects and embodiments, a combined SCW and concentrated copper waste (CCW) stream may be used as a source of copper for producing a Fenton’s-like reagent (using Cu as a catalyst for the production of hydroxy radicals from H2O2 instead of iron as in a traditional Fenton’s reagent) for the treatment of azoles, metals (e.g., copper, cobalt, andiron), and silica solids in wastewater. In some embodiments, the two wastewaters are blended at a 1:ratio (CCW: SCW) or greater, for example, a 1:10 ratio (CCW: SCW) or greater. In some embodiments, additional copper, for example, in the form of a copper sulfate solution, may be added to the combined CCW/SCW to provide additional copper to act as a catalyst in the Fenton’s-like reaction. In some embodiments, the combined CCW/SCW or the combined CCW/SCW after dosing with additional copper may include 5,000 mg/L of dissolved copper or more, for example, 6,000 mg/L or 7,000 mg/L or more of dissolved copper or a ratio of up to 10:1, 15:1, or 20:1 copper: azoles by weight or more in the wastewater to be treated.As noted above, the wastewater from semiconductor manufacturing facilities or other industrial sources may include high levels of azoles, for example, from about 20 mg/l up to about 200 mg/l total azoles or greater, that are used as anticorrosive agents for copper during the wafer planarization and polishing process. The wastewater from these processes may also include heavy metals, additional organic compounds, for example, alcohols, and/or surfactants such as ammonium salts, and inorganic abrasives, such as colloidal silica, all of w hich should be removed prior to discharge of the wastewater. These additional contaminants may be present at levels from about 0.01 wl% up to about 1 wt%. The wastewater may further have a high 5 background total organic carbon (TOC) concentration, with the total azoles comprising a portion of the TOC. For example, oxidizers such as hydrogen peroxide (H2O2) are generally used to assist in dissolving copper from microchips and may be present in CMP wastewater at concentrations exceeding 1,000 mg/L or 0.1 sNt%.Azoles are not currently regulated for maximum contaminant levels (MCL) by regulatory authorities in the United States but are believed to have a negative impact on the environment upon discharge into open waterways. Recent evidence has indicated bioaccumulation of azoles in fish and incidences of toxicity of naturally occurring algae blooms, necessitating their removal from process w ater before discharge.As described in US Patent No. 8,801,937, the disclosure of which is herein incorporated by reference in its entirety for all purposes, azole compounds are widely used in the semiconductor industry as anticorrosive agents for copper during silicon wafer processing. Examples of such azole compounds include, but are not limited to, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, selenazole, 1,2,3-triazole, 1,2,4-triazole, 1,2,5- oxadiazole. 1,3,4-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,3,4-thiadiazole, tetrazole, 1,2,3,4-thiatriazole, any derivatives thereof, amine salts thereof, and metal salts thereof. Examples of azole derivatives include compounds having a fused ring of an azole ring and a benzene ring or the like, such as indazole, benzimidazole, benzotri azole, and benzothiazole, and further include derivatives thereof, such as alkylbenzotriazoles (e.g., benzotriazole, o-tolyl tri azole. «7-tolyl tri azole. /7-tolyltri azole. 5-ethylbenzotriazole, 5-n- propylbenzotriazole, 5-isobutylbenzotriazole, and 4-methylbenzotriazole), alkoxybenzotriazoles (e.g., 5-methoxy benzotriazole), alkylaminobenzotriazoles, alkylaminosulfonylbenzotriazoles, mercaptobenzotriazoles, hy dr oxybenzotri azoles, nitrobenzotriazoles (e.g., 4-nitrobenzotriazole), halobenzotriazoles (e.g., 5-chlorobenzotriazole), hydroxyalkylbenzotriazoles, hydrobenzotriazoles, aminobenzotriazoles, (substituted aminomethyl)-tolyltriazole, carboxybenzotriazole, N-alkylbenzotriazoles, bisbenzotriazole, naphthotriazole, mercaptobenzothiazoles, aminobenzothiazole, amine salts thereof, and metal salts thereof.One embodiment of a system for treating azole-containing wastewater from a semiconductor manufacturing facility is shown schematically in FIG. 1. A semiconductor manufacturing facility 110 typically includes hundreds of unit operations, three of which are identified in FIG. 1. The unit operations identified in FIG. 1 are a copper CMP unit operation 120, a unit operation 130 that produces wastewater with a high concentration of dissolved copper, for example, a copper plating operation, and a unit operation 140 that produces wastewater having a high concentration of hydrogen peroxide, for example, one of the wafer 6 cleaning unit operations within the semiconductor manufacturing facility 110. The disclosed system is utilized to decompose organic contaminants such as azoles present in wastewater from the copper CMP unit operation 120 utilizing a Fenton’s-like reaction in which copper is utilized to catalyze the production of hydroxyl radicals from hydrogen peroxide. The hydroxyl radicals decompose the organic contaminants by oxidation into less objectional byproducts such as nitrogen oxides (NO2/NO3), carbon dioxide, and water.Wastewater from the CMP unit operation 120 is directed into a vessel 150, for example, by a pump Pl. An oxidizer, for example, hydrogen peroxide from a source of oxidizer 160 is added to the wastew ater in the vessel 150, for example, using another pump P4 in an amount and at a rate sufficient to maintain a concentration of hydrogen peroxide in the vessel at a desired level, for example, 300 mg/L or greater, to facilitate reactions resulting in decomposition of organic compounds in the wastewater. In some embodiments, the addition of oxidizer from the source of oxidizer 160 may be supplemented by the addition of hydrogen peroxide-containing wastewater from the unit operation 140, for example, using pump P3. If the hy drogen peroxide- containing wastewater from the unit operation 140 includes sufficient hydrogen peroxide, it may be utilized as the sole source of hydrogen peroxide added to the wastewater in the vessel 150.In other embodiments, a persulfate salt such as ammonium persulfate, potassium persulfate, and/or sodium persulfate, may be utilized as the oxidizer. Aspects and embodiments disclosed herein are not limited by the type of oxidant added in the treatment system. Peroxides produce hydroxyl and hydroperoxyl radicals and persulfates produce persulfate radicals when reacting with dissolved copper in the vessel 150.A source of pH adjustment chemical 170, for example, a source of sulfuric acid and/or sodium hydroxide may add pH adjustment agent into the wastewater in the vessel 150 in an amount and at a rate sufficient to maintain the pH of the wastewater in the vessel at a desired level, for example, between 2 and 4 or about 3 to facilitate reactions resulting in decomposition of organic compounds in the wastew ater.A heater or heat exchanger 210 may also be present in the vessel and may be used to maintain the temperature of the wastew ater in the vessel at a temperature suitable to facilitate decomposition of organic compounds such as azoles in the wastewater via a Fenton’s-like reaction within a desired timeframe. This temperature may be, for example, between 550C and 650C or about 60°C.The wastewater from the CMP unit operation 120 may include sufficient copper, for example, in the form of copper sulfate, to catalyze production of hydroxyl radicals from the hydrogen peroxide in the vessel 150 in a Fenton’s-like reaction which will decompose one or 7 more organic species in the wastewater in the vessel 150. Byproducts of the decomposition of the organic contaminants such as nitrogen oxides (NO2/NO3) and carbon dioxide may exit the vessel 150 through a vent V. The one or more organic species may include one or more azoles, for example, one or more of 1,2,4-Triazole, IH-Benzotriazole, or Methylbenzotriazole: 4,Tolytriazole which may have been present in the wastewater from the CMP unit operation 120. The Fenton’s-like reagent used for the decomposition of the azoles may be formed by adding about 500 mg/1 to about 3.000 mg/1 of an oxidant, such as hydrogen peroxide or a persulfate salt, to about 50 mg/1 to about 300 mg/1 of a soluble copper compound (e g., copper (Cu 2+) sulfate).The Fenton’s-like reaction may occur in accordance with chemical equations (l)-(3): Cu2+H2O2^Cu3+HO* + OH (1) Cu 3+ + H2O2 Cu 2+ + HOO* + H+ (2) Cu 2+ + S20s2 Cu 3+ + SO4• + SO42 (3) The persulfate salt and the hydroxyl, hydroperoxyl, and persulfate radicals formed by the oxidation of Cu 2+ or the reduction of Cu 3+ may react with and decompose the azoles in the CMP wastewater into primarily nitrogen oxides (NO2/NO3), carbon dioxide, and water. Without wishing to be bound by any particular theory, the decomposition of a nitrogenous organic molecule, such as an azole, may occur by the reaction illustrated in equation 4: CxNyHz + OH• CO2 + NO3 + H2O (4) One or more sensors or monitors, for example, temperature, pH, ORP, chemical concentration sensors, etc., collectively indicated at "S" may be present in the vessel 150 in contact with the wastewater in the vessel. The one or more sensors S may be in communication with a controller 190. The controller 190 may be a conventional computer including a conventional processor, for example, a Core® processor from the Intel Corporation and running a conventional operating system such as one of the versions of Windows® from the Microsoft Corporation and programmed to perform the functions disclosed herein. The controller may optionally be or include a specially programmed controller such as an Application Specific Integrated Circuit (ASIC) programmed to perform the functions disclosed herein. The controller 190 is programmed or otherwise configured to control the source of pH adjustment chemical 170 to introduce the pH adjustment chemical into the wastewater in the vessel 150 at a quantity and rate sufficient to maintain the pH of the wastewater at a level at which the copper catalyzes production of hydroxyl radicals from the oxidizer. The controller 190 may also control operation of the heat exchanger or heater 210 and any of the pumps P1-P7 to control, e.g., introduction of wastewater from the CMP unit operation 120, oxidizer from the source of oxidizer 160, CCW from the unit operation 130, hydrogen peroxide-containing wastewater from the unit operationl40, supplemental copper solution from the source 200, and removal of treated wastewater from the vessel 150.In some embodiments, the wastewater from the CMP unit operation 120 (the SCW) may not contain sufficient copper to catalyze production of sufficient hydroxyl radicals for decomposition of organic contaminants in the wastewater from the CMP unit operation 120 to levels that are as low as might be desired. Accordingly, additional copper may be added to the wastewater in the vessel 150 from, for example, the unit operation 130 that produces the wastewater with the high concentration of dissolved copper (the CCW) through a pump Poperated by the controller 190. As noted above, in some embodiments, the two wastewaters may be blended or introduced into the vessel 150 at a 1:25 ratio (CCW:SCW) or greater, for example, a 1:10 ratio (CCW:SCW) or greater. In some embodiments, additional copper, for example, in the form of a copper sulfate solution, may be added to the combined CCW/SCW from a source 200 of supplemental copper solution through, for example, another pump P7 to provide additional copper to act as a catalyst in the Fenton’s-like reaction. In some embodiments, the combined CCW/SCW or the combined CCW/SCW after dosing with additional copper may include 5,000 mg/L of dissolved copper or more, for example, 6,000 mg/L or 7,000 mg/L or more of dissolved copper or a ratio of up to 10:1, 15:1, or 20:1 copper: azoles by weight or more in the wastewater to be treated.Wastewater from which organic compounds have been removed by decomposition by a Fentons’s-like reaction as disclosed herein in the vessel 150 may exit the vessel and be directed, for example, by a pump P6 into a post-treatment system 180. The post-treatment system 1may be used to remove residual copper and other undesired components from the partially treated wastewater exiting the vessel 150 using methods known in the art and may produce treated water that may be discharged to the environment, recycled, or sent for further treatment or disposal.Aspects and embodiments disclosed herein are also directed to a method for removing organic compounds, for example, one or more azoles from a copper-containing solution, for example, wastewater from a chemical mechanical polishing unit operation of a semiconductor manufacturing facility utilizing a Fenton’s-like reagent. The copper-containing solution may be 9 produced from a mixture of wastewater from a copper chemical mechanical polishing (CMP) operation of the semiconductor manufacturing facility and a concentrated copper waste stream (CCW) from the semiconductor manufacturing facility. The method may include introducing an oxidizer into the copper-containing solution, the copper catalyzing production of hydroxyl radicals from the oxidizer that react with the organic compounds. The pH of the copper- containing solution in the vessel may be maintained at a level at which the copper catalyzes the production of the hydroxyl radicals from the oxidizer, for example between 2 and 4. The temperature of the copper-containing solution in the vessel may be maintained at between about 55°C and about 650C. Introducing the oxidizer into the copper-containing solution may include introducing hydrogen peroxide into the copper-containing solution. The concentration of hydrogen peroxide in the copper-containing solution in the vessel may be maintained at 2mg/L or more. The hydrogen peroxide may be obtained from a waste stream from the semiconductor manufacturing facility. Producing the copper-containing solution may includes mixing at least one part of the CCW with 25 parts of the CMP wastewater or at least one part of the CCW with 10 parts of the CMP wastewater. Producing the copper-containing solution may include combining the CCW with the CMP wastewater in an amount sufficient to provide parts by weight copper per part by w eight of the one or more azole compounds. Removing the organic compounds from the copper-containing solution may include removing one or more of 1,2,4-Triazole, IH-Benzotriazole, or Methylbenzotriazole: 4,5 Tolytriazole from the copper- containing solution.Example 1CMP slurry wastewater (Slurry ׳ Copper Waste - SCW) and wastewater having a high concentration of Cu (Concentrated Copper Waste - CCW), as w ell as a 25:1 mixture of the SCW and CCW from a semiconductor production facility was analyzed and found to include the contaminants listed in Table 1 below׳: Table 1 - SCW and CCW Wastewater AnalysisParameter Units Slurry Copper Waste (SCW)Concentrated Copper Waste (CCW)Blended Sample (25:SCW:CCW)Aluminum mg/L <5.40 <5.40 -Ammonia mg/LNH3-N 56.5 <0.35 41.9Calcium mg/L 0.02 4.00 -Cobalt mg/L 0.14 0.09 - Copper mg/L 20.0 22,000 Not analyzedMagnesium mg/L 0.03 0.98 -Potassium mg/L 42.0 <2.20 -Sodium mg/L 0.37 12.0 -Chloride mg/L -Fluoride mg/L -Nitrate mg/L -Phosphate mg/L -Sulfate mg/L -1,2,4-Triazole mg/L 32.8 - 33.1Hydrogen Peroxide (H202)mg/L < 8.0 1,210 41 PH- 7.6 1.1 1.9Total Kjeldahl Nitrogen (TKN)mg/L Total Organic Carbon (TOC)mg/L 130 67 106 Total Solids (TS) mg/L -Total Suspended Solids (TSS)mg/L 25 - 44 Turbidity NTU 23 5.8 52 Testing was performed to determine if the copper was present in the 25:1 mixture of the SCW and CCW in amount sufficient to catalyze production of sufficient hydroxyl radical to decompose the 1,2,4-Triazole present in the mixture. Details of the test conditions and resultsare presented in Table 2 below: Table 2 - Azole decomposition using Fenton-like reaction in SCW:CCW mixtureUnit Blended 962 mL SCW and 38 mL CCW (25:1) at pH 3.0Chemical Added Before ReactionNaOH mg/L 1,142Test ConditionsReactionTimeMins 0 30 60 90 120 Temp. °C 60 60 60 60 61pH- 3.0 3.0 3.0 3.0 3.0 ResidualH2O2mg/L 0 522 743 596 400 H2O2 Dose mg/L 0 910 1,400 1,540 1,680H2SO4 mg/L 91 46 46 23 -NaOH mg/L - - 1,300 - 1,450SBS1 mg/L - - 800 - 1,650Test ResultsTOC mg/L 106 - 24 - 11TOCRemoval% - - 77% - 90% 1,2,4-Tri azolemg/L 33.9 - - - 0.38 1,2,4- Tri azole Removal % 99% 1 Sodium Bisulfate - decomposes H2O2The pH of the blended sample (962 mL SCW + 38 mL CCW) was 3.0. A cumulative dose of 1,680 mg/L H2O2 over the 120-minute reaction time yielded 90% TOC removal and 0.5 mg/1 azole residual (99% removal). These results were achieved without adding iron and show that copper already present in wastewater streams from a semiconduction production facility may be utilized as catalyst for a Fenton‘ s-like reaction to successfully remove organic contaminants, including azoles, from those same wastewater streams.

Example 2Further testing was performed to evaluate whether a Fenton’s like reaction as disclosed herein could successfully decompose organic compounds such as azoles from wastewater from a semiconductor manufacturing facility under a simulated worst case scenario for concentration of contaminants in the wastewater. 25:1 SCW:CCW and 10:1 SCW:CCW wastewater mixtureswere spiked with additional 1,2,4-Triazole to result in wastewater mixtures with the copper and azole concentrations shown in Table 3 below.

Table 3 - Simulated worst case wastewater mixturesApproximate Concentrations 25:1 Test 10:1 TestCopper (mg/L) 670 1,659Azoles (mg/L) 350 350 The test conditions and results for TOC removal from the simulated worst case wastewaters are shown in Table 4 below.

Table 4 - Test conditions and results for TOC removal from simulated worst case wastewatersParameter Unit Blended SCW CCW (25:1) Blended SCW:CCW (10:1)Chemical Added Before ReactionNaOH mg/L 780 3,145Test ConditionsReaction Time mins 0 30 60 90 120 0 30 60 90 120Temp. °C 60 60 61 60 60 59 60 62 61 60pH-3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0ResidualH2O2 mg/L 1,483 1,799 1,566 1,316 782 740 629 604H2Dose mg/L-1,650 2,250 2,250 2,250-900 1,300 1,450 1,600H2SO4mg/L- - - -- - - -340fest ResultsTOC mg/L 827-690-653 790-594-538TOC Removal % 17% 21% 25% 32% The 10:1 blend removed more TOC than the 25:1 blend but still only removed 32% TOC. One more Fenton’s-like reaction test was conducted to determine the ratio of copper to azolerequired to get around 70% TOC removal, which should correspond to more than 90% azole removal. The copper to azole ratio versus TOC removal was extrapolated from the results above, and it was determined that the concentration of copper required would be -7,000 mg/L. a ratio of about 20 copper/azoles by weight.This Fenton’s-like reaction test was performed by spiking the 25:1 blend, whichcontained around 690 mg/L Cu with 6,330 mg/L Cu (9,582 mg/L CuSO4). The results are shown in Table 5 along with the same blend sample with no copper spiked for comparison.

Table 5 - TOC removal from simulated worst case wastewaters with supplemental Cu Parameter Unit Blended SCW:CCW (25:1)Blended SCW:CCW (25:1) + 6.g/L CuApprox.Cu Cone. mg/L 670 670Chemical Added Before ReactionNaOH mg/L 780 1,305Cu mg/L-6,330Test ConditionsReaction Time mins 0 30 60 90 120 0 30 60 90 120Temp. °C 60 60 61 60 60 61 62 63 61 61pH-3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0ResidualH2O2 mg/L 1,483 1,799 1,566 1,316 538 416 468 490H2O2Dose mg/L-1,650 2,250 2,250 2,250-1,000 1,600 2,100 2,500HSO4 mg/L - - - - 60 - - - - 820fest ResultsTOC mg/L 827 - 690 - 653 850 - 483 - 371TOCRemoval % - - 17% - 21% - - 43% - 56% The TOC removal was greatly improved with the addition of copper at the beginning of the test suggesting that a ratio of 20 copper/azoles or higher may provide for successfuldecomposition of organic compounds in a combined SCW:CCW wastewater by a Fenton’s- like reaction.

The phraseology and terminology used herein is for the purpose of description and should not be regarded as limiting. As used herein, the term "plurality" refers to two or more items orcomponents. The terms "comprising," "including, " "earn ing," "having," "containing," and "involving." whether in the written description or the claims and the like, are open-ended terms, i.e.. to mean "including but not limited to." Thus, the use of such terms is meant to encompass the items listed thereafter, and equivalents thereof, as well as additional items. Only the transitional phrases "consisting of’ and "consisting essentially of," are closed or semi-closedtransitional phrases, respectively, with respect to the claims. Use of ordinal terms such as "first," "second," "third." and the like in the claims to modify a claim element does not by itself connote any priority, precedence, or order of one claim element over another or the temporal order in which acts of a method are performed, but are used merely as labels to distinguish one claim element having a certain name from another element having a same name (but for use of the ordinal term) to distinguish the claim elements.

Claims (23)

What is claimed is: CLAIMS

1. A method for removing organic compounds from a copper-containing solution, themethod comprising:producing the copper-containing solution from a mixture of wastewater from a copper chemical mechanical polishing (CMP) operation of a semiconductor manufacturing facility and a concentrated copper waste stream (CCW) from the semiconductor manufacturing facility; andintroducing an oxidizer into the copper-containing solution, the copper catalyzing production of hydroxyl radicals from the oxidizer that react with the organic compounds.

2. The method of claim 1, further comprising maintaining a pH of the copper-containing solution in the vessel at a level at which the copper catalyzes the production of the hydroxyl radicals from the oxidizer.

3. The method of claim 2, further comprising maintaining the pH of the copper- containing solution in the vessel between about 2 and about 4.

4. The method of claim 1, further comprising maintaining a temperature of the copper- containing solution in the vessel at between about 55OC and about 650C.

5. The method of claim 1, wherein introducing the oxidizer into the copper-containing solution includes introducing hydrogen peroxide into the copper-containing solution.

6. The method of claim 5, further comprising maintaining a concentration of hydrogen peroxide in the copper-containing solution in the vessel of 250 mg/L or more.

7. The method of claim 5, further comprising obtaining the hydrogen peroxide from a waste stream from the semiconductor manufacturing facility.

8. The method of claim 1, wherein producing the copper-containing solution includes mixing at least one part of the CCW with 25 parts of the CMP wastewater.

9. The method of claim 1, wherein removing the organic compounds from the copper- containing solution includes removing one or more azole compounds from the copper- containing solution.

10. The method of claim 9, wherein producing the copper-containing solution includes mixing the CCW with the CMP wastewater in an amount sufficient to provide 20 parts by weight copper per part by weight of the one or more azole compounds.

11. The method of claim 9, wherein removing the organic compounds from the copper- containing solution includes removing one or more of 1,2,4-Triazole, IH-Benzotriazole pyrazole. Benzotriazole, 5-methyl IH-benzotriazole (Tolutriazole), or 3-amino 1,2,4-triazole from the copper-containing solution.

12. A system for removing organic compounds from wastewater from a semiconductor manufacturing facility, the system comprising:a vessel fluidly connectable to a source of the wastewater;a source of copper configured to introduce copper into the wastewater in the vessel, the source of copper including a concentrated copper waste stream from the semiconductor manufacturing facility:a source of oxidizer configured to introduce the oxidizer into the wastewater in the vessel; anda source of pH adjustment chemical configured to introduce the pH adjustment chemical into the wastewater in the vessel.

13. The system of claim 12, further comprising:a pH monitor disposed within the vessel; anda controller configured to control the source of pH adjustment chemical to introduce the pH adjustment chemical into the wastewater in the vessel at a quantity and rate sufficient to maintain the pH of the wastewater at a level at which the copper catalyzes production of hydroxyl radicals from the oxidizer.

14. The system of claim 13, wherein the controller is configured to control the source of pH adjustment chemical to introduce the pH adjustment chemical into the wastewater in the vessel at a quantity and rate sufficient to maintain the pH of the wastewater at between about and about 4.

15. The system of claim 13, further comprising a heater, the controller further configured to control the heater to maintain a temperature of the wastewater in the vessel at between about 55°C and about 65°C.

16. The system of claim 13, wherein the source of oxidizer is a source of hydrogen peroxide, and the controller is further configured to control the source of oxidizer to maintain a concentration of hydrogen peroxide in the wastewater in the vessel at 250 mg/L or more.

17. The system of claim 16, wherein the source of hydrogen peroxide includes a waste stream of the semiconductor manufacturing facility.

18. The system of claim 12, wherein the wastewater includes one or more anti-corrosives for copper and the system is configured to decompose the anti-corrosives for copper with hydroxyl radicals produced from the oxidizer with the copper acting as a catalyst from the production of the hydroxyl radicals.

19. The system of claim 12, wherein the wastewater includes one or more azole compounds and the system is configured to decompose the one or more azoles with hydroxyl radicals produced from the oxidizer with the copper acting as a catalyst from the production of the hydroxyl radicals.

20. The system of claim 12, wherein the wastewater includes one or more of 1,2,4- Triazole, IH-Benzotriazole pyrazole. Benzotriazole, 5-methyl IH-benzotriazole (Tolutriazole), or 3-amino 1,2,4-triazole and the system is configured to decompose the one or more of 1,2,4-Triazole, IH-Benzotriazole pyrazole, Benzotriazole, Tolutriazole, or 3- amino 1,2,4-triazole with hydroxyl radicals produced from the oxidizer with the copper acting as a catalyst from the production of the hydroxyl radicals.

21. The system of claim 12, wherein the source of w astew ater is a unit operation at the semiconductor manufacturing facility.

22. The system of claim 12, wherein the source of w astew ater is a copper CMP operation at the semiconductor manufacturing facility.

23. The system of claim 12, wherein the source of copper includes a copper platingoperation at the semiconductor manufacturing facility .