TW200812915A - System and method of slurry treatment - Google Patents

Abstract

Wastewater streams from semiconductor processing operations are treated to reduce the concentration therein of one or more metal species to a satisfactory level. The disclosed systems and technique utilize complexing ion exchange media to treat the wastewater streams having a significant concentration of oxidizing species and high solids concentration.

Description

200812915 IX. DESCRIPTION OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to systems and methods for reducing the concentration of one or more metal species from a waste stream, particularly for use in self-chemical/mechanical planarization waste honing A system and apparatus for removing one or more metal species from a stream of agents. [Prior Art] Various techniques can be employed for reducing the concentration of one or more of the target species from the waste stream. For example, in U.S. Patent No. 3,3,01,542, Medford et al. disclose a system for treating an acidic etching solution. In U.S. Patent No. 3,428,449, Swanson et al. disclose the use of phenolic hydrazine to extract copper from an acidic liquid. In U.S. Patent No. 3,440,036, Spinney discloses a solution with copper: copper is recovered. In U.S. Patent No. 3,912,810, Stephens discloses the use of a cyclic alkylene carbonate feed solvent to extract metals. In U.S. Patent No. 3,914,374, Koehler et al. disclose the removal of residual copper from a nickel solution. In U.S. Patent No. 3,923,74, Asano et al. discloses the refining of an aqueous solution of acrylamide. Asano et al., in U.S. Patent No. 3,941,83, discloses a process for treating an aqueous solution of acrylamide. In U.S. Patent No. 4,010,099, Leach et al. disclose a settler for a copper liquid extraction system. In U.S. Patent No. 4,2,10,5,0, Etzel et al. disclose the use of an unexpanded vermiculite cation exchange column to treat metallized waste. In U.S. Patent No. 4,231,8,8, Dalton discloses the use of a composition for extracting copper from aqueous copper salts. In U.S. Patent No. 4,23,2,10, Merchant et al. discloses a method of regenerating an etchant and recovering the etched metal. Brown et al. disclose a method for removing copper from a solution of a chelating agent and copper, in U.S. Patent No. 4,666,683. In U.S. Patent No. 5,25,1,8,7,0,028,129, Gefvart discloses the use of an ion exchange procedure to separate precious metals. In U.S. Patent No. 5,298,1, Guess discloses a ferrous ferrous sulfite process and composition for removing dissolved heavy metals from water. Siefert et al. disclose a method for removing metals from a fluid stream in U.S. Patent No. 5,3,46,627. In U.S. Patent No. 5,344,712, Marquis et al. disclose the use of carbonates in metal ion extraction. Hayden discloses a method for decomposing and removing peroxides in U.S. Patent No. 5,464,605. Abe et al. disclose a process for the manufacture of acrylamide from purified acrylonitrile in U.S. Patent No. 5,476,883. In U.S. Patent No. 5,5,99,5,5, Misira et al. disclose a method for removing mercury from a solution. In U.S. Patent No. 6, 3, 5, 90, Sassaman et al. disclose the removal of metal ions from wastewater. U.S. Patent No. 6,3,46,1, 95, to Filson et al. discloses the removal of metals from ion exchange in wastewater. In US Patent No. 6,8 1 8,1 2 9 , K e m p and the like similarly disclose the removal of metal ions from ion exchange in wastewater. However, in U.S. Patent No. 6,818,129, Kemp et al. indicate that if hydrogen peroxide is present, certain resin methods will not be present because of its incompatibility. Kemp et al. further indicate that ion exchange can be used to attach copper ions, but because of the presence and amount of solid particles present therein (solid particles are typically in the form of vermiculite, alumina slurry), for polishing the honing agent stream Most likely invalid. SUMMARY OF THE INVENTION In accordance with one or more embodiments, the present invention is a method of treating a flow of a honing agent. The method can include the steps of providing a honing agent stream comprising at least one metal and at least one oxidizing agent having a concentration of at least about 50 mg/L and introducing the honing agent stream into an ion exchange column. -6- 200812915 In accordance with one or more embodiments, the present invention is directed to a method of treating a chemical mechanical polishing honing agent stream. The method can include the step of introducing the blush agent stream into a processing system consisting essentially of at least one ion exchange unit comprising a chelating ion exchange resin. According to a further embodiment, the invention relates to a method of manufacturing an electronic component. The method can include chemically polishing the electronic component using a honing agent and introducing at least a portion of the honing agent to a processing system consisting essentially of an ion exchange column comprising an ion exchange material comprising an iminodiacetate functional group. In accordance with one or more embodiments, the present invention is directed to a treatment system for treating a honing agent stream, the honing agent stream comprising a population selected from the group consisting of: at least one metal: copper, lead, nickel, zinc And cobalt, cadmium, iron, manganese and tungsten, and comprising at least one oxidizing species selected from the group consisting of nitric acid having a concentration of at least about 50 m/L, hydrogen peroxide, ferric nitrate, and persulfuric acid, ammonium. The processing system can include a fluid inlet connected to a source of the honing agent stream and an apparatus for reducing the concentration of at least one metal from the honing agent stream. In accordance with one or more embodiments, the present invention has A method of at least one metal type of honing agent stream. The method includes the steps of providing a processing system consisting essentially of an ion exchange column having an ion exchange medium contained therein. The ion exchange medium includes at least one pendant functional group capable of forming a complex with at least one metal species. [Embodiment] In terms of its application, the present invention is not limited to the details of -7 « 200812915 disclosed in the following description. This is to be carried out. Should not be considered 1, "including π and its equivalents at least or at least reduced. In some cases one or several kinds of fluidic species, such as in addition to or at least reduce the particulate material) to remove metal ions, or to system and technical wastewater In the case where the copper is honed by the by-products, the wording "environment: discharge flow, to > 5 ppm) of the copper or the construction and configuration of the components illustrated in the drawings, etc., have other embodiments and can The words and terms used herein are intended to be limiting in terms of a variety of ways. The use of "including "," includes π, "has π, π contains." The variations herein are meant to include the items listed thereafter and the other items. In accordance with one or more embodiments, the present invention provides for removal. In systems and techniques for the concentration of metal ions from a solution or stream, the method and system of the present invention can be utilized to remove one or more non-metal ions from a body stream, typically one or more wastewater streams. By way of example, the present invention provides for the removal of systems and techniques from high concentrations of suspended solids (also referred to herein as solutions and/or quenching streams, such as one or more concentrations of the honing agent stream. In the present case, the present invention provides for a reduction in the concentration of copper ions from one or more honing agent streams. For example, the method and system of the present invention can be removed from a chemical mechanical honing (CMP) complex. A honing agent for a circuit by attaching a metal ion or immobilizing a metal ion therein, thereby producing an environmentally clean discharge water product cleansing system and a waste that can be directed to an urban wastewater treatment plant. } The wastewater discharge stream is contained at a concentration of less than about 0.5 mg/L (about < ion. According to still further embodiments, the treatment systems and techniques of the present invention may comprise, consist essentially of, or comprise one or more ion exchanges Unit Operation It may remove one or more of the target species from one or more of the honing agent streams and may cause the one or more honing agent streams to be suitable for discharge to the outside. According to other embodiments, the processing system of the present invention And techniques can include, consist essentially of, or comprise an ion exchange system and a carbon branch system. The ion exchange system can utilize one or more ion exchange columns and the carbon system can utilize one or more carbon beds. For example, the treatment systems and techniques of the present invention may utilize an ion exchange column, a carbon bed, or a combination thereof, without any unit operation that reduces or otherwise alters the solids concentration of the honing agent stream being processed. The ion exchange column, carbon bed, or a combination thereof, the system and technique of the present invention can process a CMP honing agent stream without substantially altering the solids concentration of the CMP honing agent stream, As used herein, the wording "does not substantially change" may describe the concentration of solid particles in the treated CMP honing agent stream relative to the concentration of solid particles in the treated honing agent stream produced, such that the concentration The same or because the concentration of solid particles associated with solid particles that are not intentionally maintained in the processing system is reduced by about 5% or 10%. As used herein, the wording "suitable for emissions" is described and processed. A flow wherein the concentration of one or more of the regulated species contained therein is at a level not greater than the limits of government control or instruction. Thus, the systems and techniques of the present invention can be utilized to meet or exceed one or more of the imposed regulations. Constraining the dischargeable honing agent stream to facilitate fabrication of one or more semiconductor devices and/or one or more types of semiconductor devices. In accordance with one or more embodiments, the systems and techniques of the present invention may be removed or at least reduced by one The concentration of the various standard metal species to the extent or concentration that meets environmental emission limits and/or guidelines. In accordance with certain features of one or more embodiments of the present invention, the systems and techniques disclosed in 200812915 may include one or more processing systems, in some cases including substantially one or more unit operations in contact with a honing agent. The stream removes one or more of the target categories. Contaminant concentrations can also be utilized using the systems and techniques of the present invention, such as, but not limited to, transition metals from one or more streams comprising particulate materials. Solid Particles or Particulate Materials Definition herein Total solids dried (1 998, 廿) at 1300-105 °C using standard method 2540B. In accordance with one or more embodiments, the systems and techniques of the present invention self-deplete, for example, by-product polishing honing agent streams, during one or more chemical mechanical planarization processes, during the manufacturing operation of the free-oriented integrated circuit microchips The genus ions are, for example, but not limited to, copper metal ions. In semiconductor processes, one or more metals are typically utilized, for example, limited to aluminum and/or transition metals such as copper and tungsten during one or more operations during a microchip device or group fabrication operation. Chemical mechanical planarization or a technique that can be utilized during the fabrication of such devices, operations can be utilized to create a smooth surface on such semiconductor devices. Typical CMP utilizes one or several honed honing agents to facilitate the planarization process. Typically, honing honing agents and honing pads are used to move the unwanted metal material on the semiconductor device. In order to further or facilitate the planarization process, the abrasive honing agent typically comprises one or more honing materials and, in some cases, one or several agents that facilitate the planarization process. During the C ΜΡ process, bismuth and other metals are typically removed from the semiconductor package and transferred into the chemical mechanical honing honing agent stream. In particular, in practice, the self-degrading liquid is used to remove the gold from the particle water flow device, but the grinding is performed in the amount of the CMP process or in the crucible, and is applied to the copper-based microchip of -10-200812915. The CMP planarization operation on the device can produce a by-product "honing &" honing agent wastewater stream typically comprising a metal species, typically having a concentration ranging from about 1 mg/L to about 100 mg/L. A typical CMP tool may produce a chemical mechanical honing agent stream at a flow rate of about 1 Ogpm, typically including a wash stream. However, because of the typical operation of the manufacturing facilities of such tools, a sufficient amount of one or several metallic coppers may be present in the aggregate honing agent stream, which may be discharged without further processing, in a concentration, amount or volume. Form environmental concerns. For example, a plurality of copper CMP tool clusters can produce about 100 g of pm of wastewater. The stream being treated may include one or more oxidizing agents or oxidizing agents as additives. The oxidizing agent may be any species that promotes the dissolution of metal species such as copper. For example, the oxidizing agent may be nitric acid, hydrogen peroxide (H202), iron nitrate, and ammonium persulfate, and mixtures or combinations thereof. Other non-limiting examples of oxidizing agents or precursors include iodate, periodate, bromate, perbromate, chlorate, perchlorate, peroxy compound, nitrate compound, persulfate compound , permanganate compounds and chromate compounds. The oxidizing agent may be present in the honing agent stream at a concentration sufficient to promote dissolution of the metal, e.g., the dissolution of the transition metal. For example, the concentration of - or several oxidizing agents may be at least about 50 mg/L, typically in the range of from about 50 mg/L to about 10,000 mg/L. One or more chelating agents such as citric acid or ammonia may also be present in the by-product honing agent stream being treated, typically functioning to promote maintenance of one or more of the transition metals in solution. The honing agent wastewater stream can also have solid particles or granules, typically ranging in size from about 〇·0 01 to about 1 μm and 200812915 having from about 500 to about 5,000 mg/L (about 500 to about 5,000 ppm) or even up to 20,000 ppm in content or concentration. Mixing agents, such as gluconate, tartrate, citrate, and ammonium hydroxide, which promote etching or enhance the rate of corrosion of transition metals such as copper, may also be present in the CMP honing agent stream. Table 1 lists the general CMP honing agent stream components and their typical concentrations. Table 1 Typical CMP honing agent composition concentration dissolved copper 5-100mg / L total solid particles 5 0 0 - 5,0 0 0 mg / L oxidant 5 0 -1,0 0 0 mg / L etchant 2 0 0 mg/L Miscellaneous Agent 1 0-400mg/LDI Water Background 9 9 % + pH値6 to 7

It is important to note that ion exchange media and equipment manufacturers support advanced φ removal of particulate materials, ie upstream of systems such as ion exchange and carbon, and emphasizes that solid particle removal operations form a major feature of pretreatment systems because The particles may stick and clog the active medium and operate as a particulate filter. Therefore, if it is not removed, these unwanted suspended solid particles accumulate resulting in an increase in pressure drop across the resin and/or carbon bed. The increased pressure drop typically results in a channeling phenomenon in which the fluid stream being processed is directed to the least resistive flow path, effectively avoiding at least a portion of the bed, limiting access to the overall process fluid. This phenomenon leads to high contaminant leakage and insufficient bed capacity. Suspended solid particles and colloidal substances may also cover -12-

One or more functional groups may have any or several of the target species, thus self-removing, or at least reducing the concentration of one or more of the target species through a fastening to the ion exchange media material or including ion exchange media ion exchange media It may include an ion exchange medium with 200812915 to reduce the rate at which ion species diffuse to (media) and self-intermediate. In fact, ion exchange media manufacturers further reject the stream to be treated to remove or neutralize the ion exchange medium degradation components. By way of example, such species include oxygen, ozone, chlorine, peroxides, and other oxidizing agents or oxidizing species or agents. Thus prior art systems utilizing ion exchange include the removal of such particles and/or oxidation species by a number of pretreatment unit operations. In contrast, the systems and techniques of the present invention are uniquely eliminated and are reduced. For processing particle streams, such additional complexity may also contain one or more oxidized species. In accordance with one or more features, the ion exchange media of the systems and techniques of the present invention comprise, consisting essentially of or comprising one or more materials forming or promoting the formation of one or more chelating species with one or more of the target species. For example, the plasma exchange medium can include one or several jobs and one or more metal species can form one or several ligands or mismatches. According to certain features of the invention, the ion exchange medium includes a A part of a body or chelation, typically a side group on a substrate, with a suitable degree of functionality, which can be bonded or dispensed with a fluid or treated stream. Therefore, during processing operations or several functional groups are combined or used . One or more of the side support materials may be supported on other support media. The first area of the functional level of the younger brother and the soluble diffusion pretreatment of one of the soluble hydrogen peroxide exchange media or if it is not good, the material it uses can be a compound. Because · or a few. These fixed-body implementations can be combined in a method of polymerization, thus having a second region of degree -13-200812915. In addition, ion exchange media can include any number or type of such functional groups at different concentrations or densities that provide the desired load capacity. Thus, for example, an ion exchange medium can have a first region comprising a functional group having a first density or concentration, typically based on volume, and one or more second regions including a second functional group in the second region, or Other density or concentration. The first region and the second region may differ in one or more features to provide for the scalability of capturing one or more of the target categories but may include the same functional groups. In accordance with one or more embodiments, the systems and techniques of the present invention can provide a honing agent treatment system and method or a method of at least reducing copper ion concentration. The method includes contacting a stream containing copper ions with a processing system comprising 'substantially comprising or comprising an ion exchange medium comprising a mismatched ion exchange medium' preferably not performing prior removal of solid particles or particles And/or previously oxidizing species are removed or reduced via catalytic exposure to carbon. Contacting the liquid stream can include introducing the liquid stream into one or more ion exchange beds in a downward flow direction or in an upward flow direction. The invention may be related to a pretreatment system that does not involve chemical addition. For example, the pretreatment system can neutralize, remove or at least reduce the concentration of any oxidant that may be present in the liquid stream being treated. For example, the pretreatment system can introduce energy to promote reduction of the oxidant. Non-limiting examples of such pretreatment systems include, but are not limited to, electro-optic and photochemical and thermochemical techniques. Electrochemical techniques can utilize one or several electrochemical cells including an anode and a cathode (electrode) connected to a power source to direct current into the liquid. The cell -14-200812915 can be configured to be in a bulk tank, flow through a tube or other configuration in which a solution containing an oxidant is in electrical communication with the electrode. In this configuration, one or more of the electrodes deplete the electrons and are transferred to the other electrodes via an external connection. The reduction reaction can occur at the cathode and the oxidation reaction can occur correspondingly at the anode. The current supplied, for example, is typically controlled by a rectifier. The amount of current used, the amperage can be determined by several factors or conditions, such as the concentration and type of solution characteristics and/or related chemical species. And the rate at which the reduction is performed or the rate required. Photochemical techniques typically provide actinic radiation that promotes one or several reactions. For example, photochemical techniques can utilize ultraviolet radiation to promote one or more reduction reactions. Thermochemical techniques can include heating a solution containing an oxidizing agent to a temperature that promotes decomposition of the oxidized species. For example, in the case of copper CMP honing agent wastewater, the temperature may be as high as and including the boiling point of water (about 1000 ° C). At elevated temperatures, the rate of various reactions, including reduction or decomposition, typically increases, as this promotes the destruction of one or more oxidized species. Mismatched ion exchange media typically include at least one mismatch or chelation function. The degree of functionality includes any group, typically a polyligand group, which forms a complex with the target species. For example, the plasma exchange medium can include a functional group of imine diacetate on the polymeric backbone. Other functional groups that may be utilized in accordance with one or more embodiments of the invention include, but are not limited to, polyamines, bispyridylmethylamines, and aminophosphinyl groups. The choice of functional groups can be based on several factors, including, for example, the affinity for the target species. Thus, for example, the choice of one or more of the functional groups utilized may be based on the metal species of -15-200812915, such as a transition metal which may be any one or more of the following elements: copper, lead, nickel , zinc, cobalt, cadmium, iron, giant, silver, gold, uranium, palladium, rhodium, ruthenium, osmium, manganese, tungsten, and/or gallium. As illustrated in Figure 1, one or more of the streams may be collected from one or more CMP systems 20 using one or more collection tanks 30 prior to processing in processing system 40. An acid or a base (not shown) may be introduced (tank 30) as needed to adjust the p Η値 of the treated liquid stream. In certain embodiments, the processing system can include two or more ion exchange beds in parallel or in series, or a combination thereof. For example, the processing system can include two series of second ion exchange beds each comprising a first ion exchange bed and a downstream of the first bed. The first ion exchange bed can be considered a primary bed, typically removing or reducing the concentration of the metal species in the honing agent stream and the second, downstream ion exchange bed can be considered a honing bed which removes any residual target species. The main bed and the honing machine can be interchanged as necessary. For example, the primary pump can be replaced after a predetermined period of time or when an unacceptable condition or concentration of one or more of the target species is detected in the flow of the outlet. The honing machine can then be placed in the main position and the newly regenerated column can be placed in the polished position. The spent ion exchange bed can be repaired and/or regenerated. Ion exchange media typically comprise a pendant functional group pendant on the crosslinked polymer backbone. The support matrix or backbone of most ion exchange resins typically consists of a long chain of polystyrene. Resin manufacturers typically improve the strength and render the resin insoluble in water and/or non-aqueous solvents, and polystyrene chains typically react with a crosslinking agent such as divinylbenzene (D V Β ). The reaction is linked together by a plurality of chains of typically linked polystyrene. The oxidant erodes and destroys not only the functional side groups on the tree but also erodes and destroys the D V B bond. Both functional groups and DVB cross-linking. When more DVB water is used, the resin absorbs and expands to soften. When in use, expanding and squeezing together prevents or inhibits the fluidized species from being more aggressive and higher in oxygen species than others. Other conditions, such as low or high pH, also accelerate the rate of deterioration. In some cases, the transitional resin is oxidatively degraded, especially under acidic conditions. A typical change medium can have an operating volume that ranges from more metal per cubic foot. Ion exchange media typically have a maximum of about 1.7 ion exchange resin screening of the methods and apparatus of the present invention. The ion exchange resin of the method and apparatus of the present invention may be of a nature. The treated honing agent stream is self-treated in a state suitable for discharge as discussed above. Further, in one or several aftertreatment systems (not shown), the solid particles may be removed in one or more filtration unit operations, typically in ion exchange and/or carbon unit operations. Seeds, such as coagulants and/or flocculation aftertreatment. Embodiments that can be utilized in an aftertreatment system include, but are not limited to, the degree of reverse osmosis and other systems and techniques that can be used to reduce other target categories. When all oxidant intrusion is destroyed, the softened resin can be used. Some oxidant concentrations accelerate the heating and the presence of the catalyst is, for example, copper catalyzed, chelated ions having an exchange weight of 1.5 to 2.0 pounds or a uniformity factor. The size of the ball will be controlled in the future with the system exit listed in Table 2, which handles the processed stream. For example or in the system from after or downstream of it. : Agents to improve one or several other unit operations can be carried out from the liquid stream. -17- 200812915 Table 2 Typical properties of ion exchange resin 値 Bead size, mi η, 90% 0.4-1.23mm Effective size 〇.55mm Uniformity coefficient 1.7 Overall weight ( + /-5%) 800g/L Density 1 · 1 8 g / m 1 Water retention. 5 0 - 5 5 wt % pH値 range 0-1 4 Functional imine diacetate structure Giant polycrystalline matrix crosslinked polystyrene minimum capacity 2.2 eq / L amount H + form

Under load, regeneration of a generally saturated ion exchange medium can be carried out by using one or more mineral acids, such as sulfuric acid, to remove the mismatched metal species. Hydrochloric acid can be used in some cases. The functions and advantages of the present invention and other embodiments of the present invention are further understood from the following examples, which illustrate the advantages and/or advantages of one or more systems and techniques of the present invention but are not intended to limit the scope of the present invention. . In each of the examples, the copper in the solution is according to the standard method 3丨20B, the metal via the inductively coupled plasma (ICP) method or the 3125B, inductively affinity plasma/mass spectrometry (ICP/MS) method (1 998, The second edition) is to be measured. -18- 200812915. The solids content is measured according to U.S. EPA Method 160.3. The hydrogen peroxide concentration is quantified by direct titration using a standardized potassium permanganate reagent. The ion exchange resin utilized was a LEWATIT & TP207 weakly acidic, macroscopic porous ion exchange resin having a chelated iminodiacetic acid group available from Sybron Chemical Co., Ltd., LANXESS, Birmingham, NJ. EXAMPLE 1 Properties of an ion exchange resin exposed to an oxidizing agent ^ In this example, a treatment system according to one or several embodiments of the present invention comprising an ion exchange column utilizing a chelated ion exchange resin is exposed to an oxidizing agent. The effective volume of the exposed ion exchange resin is used to characterize the deterioration and its effect on its performance. The processing system is shown schematically in Figure 2. The system consists essentially of an ion exchange column 210 comprising an ion exchange resin therein. The copper-containing solution was taken from the source of the feed tank 2 1 2 using a pump 214 and introduced into the ion exchange column 2 1 0 . The I treated fluid from the ion exchange column 210 is collected using the effluent storage tank 2 16 . The circulation of the solution was not carried out to expose the ion exchange material to a solution having the same initial and final copper concentrations. Prior to the first run, the resin was preconditioned by hydrating it in deionized water for at least 24 hours and then converted to an acid form by exposure to about 10% hydrochloric acid solution. The ion parent column has a resin bed which is about 1 · 5 c m in diameter and about 16 c ηι deep. Several operations were performed by exposing the resin bed to various oxidizing agent-containing solutions -19-200812915. The solution was also composed of about 40 mg/L of copper species (salt salts). The exposure is carried out by passing various solutions through an ion exchange column for about 8 hours and maintaining a static, non-flowing condition for about 16 hours per day. The pH of the solution was adjusted to about 3 pH units by the addition of sufficient sulfuric acid. The oxidizing agents used were hydrogen peroxide at various concentration levels indicated in Table 3. Table 3 further lists the volume of the ion exchange bed measured after exposure at different time intervals during exposure. The volume of the bed is calibrated relative to the unexposed resin. Specifically, the ion exchange resin not exposed to the oxidizing agent is designated to have a volume of 1 · 〇 and the resin volume during the exposure is specified relative to the unexposed volume. Thus, for example, an ion exchange resin having an oxidant exposed to a volume of about half of the unexposed resin is designated to have a volume of about 〇·5. The determination of the resin volume can be carried out via relative saturation. For example, the resin can be removed by regeneration using a solution of about 1% hydrochloric acid. A solution of 2 liters of copper sulfate containing about 3,000 mg of Cu/L was passed through about 25 ml of the resin to completely deplete the ion exchange site with the copper species. Excess copper solution was rinsed away from the resin. Approximately 10% of a hydrochloric acid solution of about 5 L was used to remove copper from the resin. This removal solution was retained and analyzed for total copper content. The amount of copper measured is directly related to the number of exchangeable parts per unit volume of the ion exchange resin which can be used (the original resin is designated as having a 〇 of 〇). Exposure to oxidizing species or reagents renders some exchange sites unusable, so the amount of copper per unit volume of resin that can be loaded is typically reduced with degradation. 〇。 Therefore, compared with the original resin, the oxidizing agent exposed resin, the enthalpy is less than 1. 〇. The data in Table 3 shows that the volume of the ion exchange resin can be reduced with extended exposure -20-200812915. In addition, the rate of degradation accelerates at higher oxidant concentrations

Table 3 Effect of oxidant exposure on iminodiacetate resin H202 Concentration (mg/L) Exposure time (hours) 0 50 100 500 1,000 0 1 1 1 1 1 264 1 1 3 84 1 1 1 552 1 0.94 672 0.99 0.97 0.89 936 1.03 0.86 0.77 1056 0.99 0.99 1320 1 0.94 0.91 0.82 0.71 1560 0.99 0.7 0.58 1584 0.94 0.88 1776 1.01 0.95 0.91 0.66 0.5 1 1968 0.92 0.88 2016 0.98 0.58 0.43 2256 0.52 0.38 2280 0.92 0.86 2496 0.87 0.83 2784 0.89 0.82 3144 0.88 0.80 3 3 84 0.82 0.75 Example 2 Properties of ion exchange resin when chemically neutralized with oxidant In this example, 'evaluation of an ion exchange column comprising a chemically neutralized oxidant according to one or several embodiments of the invention is evaluated The metal handling capacity of the system. The processing system is shown schematically in Figure 2 and is generally described in Example 1 -21-200812915. The neutralizing or reducing agent is sodium metabisulfite. However, other reducing agents such as sodium hydrogen sulfite and sodium sulfite may be used. Neutralization of hydrogen peroxide with sodium sulfite, sodium hydrogen sulfite or sodium metabisulfite results in the formation of sodium sulfate (Na2S04). The initial concentrations of hydrogen peroxide in the treated solution prior to neutralization are listed in Table 4. The concentration of the sodium sulfate product produced is also listed. The initial concentration of the metal species and copper (sulfate) was about 40 mg/L for each test operation solution. The initial pH of each solution is about 3 pH units. The ion exchange column has a resin bed having a diameter of about 1.5 cm and a depth of about 16 cm. Citric acid is included as an organic chelating agent for copper and is typically used in copper CMP honing formulations. The organic chelating agent typically mates the copper ions produced during the copper CMP process to inhibit precipitation and/or reabsorption of such species onto the semiconductor surface. The organic chelating agent binds copper to varying degrees. Typically, the stronger the strength of the combined copper in the chelating agent, the more difficult it is for the ion exchange resin to remove copper from the chelating agent and collect it on the ion exchange resin. The high salt background also reduces copper sorption from the solution onto the resin, in this case via a high ion background. When ® uses a chemical reducing agent such as sodium bisulfite to chemically decompose an oxidizing agent, such as hydrogen peroxide, the chemical reaction increases the total solution ion background. Specifically, the reaction between sodium hydrogen sulfite and hydrogen peroxide produces sodium and sulfate ions in solution. The higher the oxidant concentration, the more sulfite is needed for neutralization, and as a result, the resulting ion background is greater. Table 4 lists the number of equivalent bed volumes (BV) through the resin bed prior to effluent therefrom, which was found to be about 30 mg/L, designated as a breakthrough condition, or a fluidized metal concentration of about 75%. Table 4 compares copper negatives on ion exchange in three cases -22- 200812915. A "blank" or baseline condition shows the copper loading when a chelating agent (e.g., citric acid) is absent and has only a small ion background loading. The "citric acid" condition shows a copper loading when the amount of chelating agent, citric acid, is added to the baseline in the typical copper CMP wastewater. In this case, because citric acid is only partially ionized In the solution, a little additional ion background is produced. The "sulphate" condition shows the copper loading when the ionic background is significantly increased when no citric acid is present. The amount of sodium sulphate is equivalent to the amount formed if about 1,100 ppm of hydrogen peroxide is removed via sodium bisulfite (in both cases, this amount is equal to removing about 200 ppm of hydrogen peroxide). The results show that both citric acid and sodium sulphate are essentially the same as the baseline and that increasing the background ionic loading by using a chemical reducing agent has no appreciable negative effect on copper removal by the ion exchange resin, whether or not citric acid is present. Table 4 Effect of High Sulfate Exposure Test Solution Composition Copper (mg/L) 40 40 40 BTA (mg/L) 5 00 500 500 Na2S04 (mg/L) 800 800 4500 Citric Acid (mg/L) 0 500 0 pH値3 3 3 H2〇2 before treatment (mg/L) 200 200 1,000 Operation BV breakthrough (to approximately 30mg/L) “Blank ""Citrate""Sulphate" 1 2,000 1,920 2,140 2 1,900 1,640 2,320 3 2,080 -23- 200812915 BTA is 1,2,3-benzotriazole. BTA is a typical "alkyl/aryl/triazole rust" component of current copper CMP honing formulations. BTA typically prevents copper oxide formation from remaining on the polished copper on the semiconductor device during and after the CMP process. Example 3 High Total Solids Flow This example shows the performance of a processing system in accordance with one or more embodiments of the present invention when processing a honing agent stream from a CMP process. Implementation evaluation takes about 20 days. This test also shows the effectiveness of absorption through the resin, copper, and even the presence of an oxidizing agent. The system illustrated in Fig. 3 is schematically illustrated by an ion exchange column 3 1 0 downstream of the carbon column 311. The CMP solution from the feed tank 3 1 4 is driven by the pump 3 1 2 through the carbon column 31 1 and the ion exchange column 3 10 . A sample point 3 1 6 is disposed between the carbon column 3 1 1 and the ion exchange column 3 10 . The treated fluid from the ion exchange column 310 is collected in a collection tank 318. The system was operated for about 8 to 12 hours per day, and was restarted the next day when the operation was terminated every day. After 1 2 days, the ion exchange test was stopped and the hydrogen peroxide was removed with carbon for a continuous period of 8 days. The honing agent feed solution flows through the carbon bath and the ion exchange tank uniformly and stably throughout the test, indicating that no solid particles accumulate on either medium. At the end of the test, each medium was examined to show that no honing agent solids accumulate on either medium. A simulated copper CMP honing agent wastewater was prepared. The entire commercially produced copper CMP honing agent concentrate was diluted to the solid particle test condition. The honing agent solution was prepared by diluting a commercially available copper CMP honing agent with the addition of hydrogen peroxide and copper sulfate to simulate copper CMP honing agent wastewater. Calculated quantities of copper sulphate (systematic technical grade ^11804-51120) from De-24-200812915, Houston, Chem, and from Ashland Specialty Chemicals, Dublin, Ohio Hydrogen peroxide (about 30% H2O2, electronic grade) is added to the inflowing honing agent solution. The hydrogen peroxide concentrations of the honing agent streams entering and exiting the ion exchange resin bed per day are listed in Table 5. Similarly, the import and export copper concentrations are also listed in conjunction with the solids inlet concentration. The pH was adjusted to 3 pH units via the addition of sulfuric acid. The particle size of the solid particles is in the range of from about 0·0 0 1 μm to about 1 μm. The ion exchange column 310 has a resin bed having a diameter of about 8 inches and a depth of about 40 inches. The diameter of the carbon column 31 is about 14 inches and about 40 inches deep. The carbon used is CENTAUR® granular activated carbon available from Calgon Carbon, Pennsylvania. The samples were taken at the hours listed in Table 5, retrieved and analyzed. The data in Table 5 shows that even with a total solids loading of up to about 4,500 mg/L, copper can still be removed. Moreover, in the case of effective copper removal, the removal of hydrogen peroxide is not required as shown by the results of the operations performed on days 4, 5 and 7. The total solids in the test of Table 5 are mainly derived from honing agent particles. The solid particles themselves, i.e., used in honing and polishing of vermiculite and alumina. Very few solid particles come from dissolved ions like copper and sulfate. -25- 200812915 Table 5 Effect of high total solid particles

Days of operation time (hours) Cumulative operation time (hours) Hydrogen peroxide concentration (mg/L) Copper concentration (mg/L) Solid particle concentration (mg/L) IN POST CARBON IN OUT 1 1 8 524 <0.3 26.2 0.052 3,370 8 ΝΑ <0.3 26 0.033 3,680 2 1 16 ΝΑ 28.6 0.024 3,450 . 8 520 <0.3 29.8 0.046 4,515 3 1 24.5 450 27.6 0.032 3,360 8.5 520 <0.3 27.2 0.027 3,180 4 1 32.5 384 29 0.025 4,000 8 ΝΑ 17 28.5 0.027 3,750 5 1 40.5 428 4 29.3 <0.04 3,785 8 410 16.4 31 < 0.04 3,980 6 1 48.5 377 <0.3 27.1 0.114 3,870 8 402 <0.3 27.7 <0.04 3,420 7 1 60.5 610 3,5 28.6 <;0.04 3,930 12 493 <0.3 25.4 < 0.04 3,580 8 1 72.5 503 <0.3 25 < 0.04 3,540 12 463 <0.3 31.5 0.053 4,090 9 1 84.5 510 <0.3 28.7 < 0.04 3,760 12 517 < 0.2 26.9 0.156 3,400 10 1 96.5 500 <0.3 27.1 0.079 3,350 12 524 <0.2 23.2 0.124 2,840 11 1 108.5 525 <0.3 27.1 0.127 3,420 12 502 <0.2 27.1 0.167 3,790 12 1 120.5 563 <0.2 27.6 0.08 3,800 12 510 <0.2 25.1 1.61 3,480 13 1 129 428 4 to 3,500 8.5 410 16.4 to 3,500 14 1 137.3 377 <0.3 to 3,500 8.3 402 <0.3 -3,500 15 1 146.1 610 3.5 to 3,500 8.8 493 <0.3 to 3,500 16 1 155.1 503 <0.3 -3,500 9 463 <0.3 〜3,500 17 1 163.6 510 <0.3 〜3,500 8.5 517 <0.2 〜3,500 18 1 171.8 500 <0.3 -3,500 8.2 524 <0.2 〜3,500 19 1 180.6 525 <0.3 〜3,500 8.8 502 < 0.2 to 3,500 20 1 1 Ο Π /C 563 < 0.2 〜 3,500 9 i 〇 y 〇 510 < 0.2 〜 3,500 -26 - 200812915 Example 4 uses carbon and a filter medium to remove hydrogen peroxide in this embodiment Processing from the processing system of the waste honing agent treatment branch system of the CMP process. The general system in Fig. 3 consists of a pretreatment system 31 which is a carbon column or a filter medium exchange column 310. The pump 3 1 2 is used to direct the particles from the feed tank, the oxidant and the solution containing copper. The treated honing tank is immersed in the tank 3 1 8 and sampled. The hydrogen peroxide in the honing agent stream is pretreated by the C 1 ack company of Pends, New Jersey, using the CENTAUR® granular activity available from Calgon Carbon Company, Penn. The system is removed and/or neutralized. The granular activated carbon system is mainly composed of a diameter of about 8 inches and a depth of about 40%. The BIRM® Granular Filter Media Branch System consists primarily of columns approximately 20 inches in diameter. Off Each operation corresponds to the same order as the respective carbon column or filter media column. The concentrations of the influent and post-treated copper solids in the honing agent stream are listed in Tables 6 and 7. This data shows two pretreatment or removal of hydrogen peroxide concentrations and shows that copper species are removed via ion exchange. The flow is included in the column including the pre-display, and the solid agent of the ion 3 14 is collected in the collection, the carbon of the Fortune City, or the column of the BIRM® CENTAUR® inch column 8 inches and deep ionized column and peroxidation Hydrogen system can reduce column efficiency -27- 200812915 Table 6 Time to pass oxidant sample removal via granular activated carbon (hours) Copper concentration (mg/L) Total solid particles (mg/L) H2〇2 (mg/L IN POST RESIN IN POST CARBON POST RESIN IN POST CARBON 1 0 30.8 0.018 2,920 2,100 1,600 204 <1 2 1.5 31.8 0.043 2,810 3,170 2,580 198 <2.6 3 3.5 32.5 <0.016 2,520 2,605 2,400 204 <1.3 4 5.5 31.4 0.021 2,510 2,550 2,390 185 <1.4 5 7.5 34.6 0.021 2,680 2,640 2,550 209 <1

Table 7 Time (hours) for removal of oxidant sample via granular filter medium Copper concentration (mg/L) Total solid particles (mg/L) H2〇2 (mg/L) IN POST RESIN IN POST BIRM8 POST RESIN IN POST BIRM 8 1 0 28.3 0.186 2,920 3,430 2,510 214 95 2 1·5 29.2 0.322 2,750 2,910 2,750 NA 88 3 3.5 29.5 0.844 2,870 2,890 2,840 NA 108 4 5.75 30.6 2.87 2,820 2,895 2,840 NA 161 5 7.75 30.5 2.84 2,790 2,810 2,840 201 170 ( NA = not analyzed) The performance of the total solids and hydrogen peroxide concentration of the ion exchange modification of Example 5 was evaluated using a refractory wastewater obtained from a commercially available copper CMP process via a pretreatment branch with a carbon bed. The system and the oxidant and metal removal of the treatment system with two ion exchange beds are illustrated in Figure 4, -28-200812915. The carbon bed 510 is composed of about 3.6 cubic centimeters of CENTAUR^: activated carbon and the ion exchange beds 5 1 2 and 5 1 4 each consist of about 3.6 of chelated iminodiacetate groups. Cubic 呎 LEW ATI T® TP2 0 7 weakly acidic giant porous ion exchange resin. The honing agent system is introduced into the system from the feed tank 5 16 using a pump 5 1 8 . Using the supplied copper honing agent, approximately 30% hydrogen peroxide from Ashland Specialty Chemical Company and copper sulfate pentahydrate from Chem One Company adjusted the concentrations of total solid particles, hydrogen peroxide and copper to Table 8 Show it. The pH was adjusted to the level shown in Table 8 by adding about 25% sulfuric acid solution diluted with a ratio of about 1:1 using deionized water. The system fluid streams from the ion exchange columns 5 1 2 and 5 14 are collected in a collection tank 520. The sample for analysis is retrieved at sample point 522 and at collection tank 520. Table 8 lists the inlets and various properties of the honing fluid for various test operations. This data shows that copper is effectively removed or not removed via the activated carbon branch system, as shown in Runs Nos. 2, 4, 5 and 10. The data also shows that the treatment can be carried out even for a blister stream having solid particles up to about 20,000 ppm. In fact, when nearly 20, 〇〇〇ppm of solid particles are loaded, the effective removal of the metal is still more than 90%, so the data indicates that for a honing agent flow greater than 2 〇, 0 0 0 ppm, the present invention It can still be implemented. -29- 200812915 Table 8 Removal of hydrogen peroxide and copper Test number pH turbulence rate (gpm) Total solid particles (mg/L) Copper (mg/L) H2〇2 (mg/L) Removed copper ( %) H2〇2 (%) removed 1 3 3.5 12,795 54.9 64.6 99.6 100 2 4 5.4 6,044 8.98 ;43.8 99.4 8.7 3 2 1.6 8,532 9.02 1,632 98.1 94.6 4 4 1.6 4,932 97.6 672 100 88.6 5 4 5.4 15,240 84.5 2,074 99.3 51.6 6 2 5.4 6,140 87.3 663 99.5 100 7 3 3.5 10,305 42.8 1,887 99.5 100 8 3 3.5 10,630 45.3 1,802 99.2 100 9 2 1.6 17,750 83 476 99.7 96.4 10 2 5.4 19,180 7.39 2,142 96.3 74.9 11 4 1.6 18,240 8.86 536 99.1 100

Example 6 Photochemical Pre-System via Electromagnetic Irradiation In this example, the removal or reduction of hydrogen peroxide from a typical C Μ P honing agent stream was carried out by a technique that did not have a chemical addition. The non-chemical substrate oxidant reduction is carried out by an actinic reduction based pretreatment system comprising exposure to ultraviolet (U V ) electromagnetic radiation, as generally illustrated in Table 5. The pretreatment system 610 utilizes the #AMD150B1/3T model UV assembly from Aquionics, Inc. of Erlanger, Kentucky, using a volume capacity of about 1.6 gallons, UV unit 612 having a wavelength of 185 nm, #130027- -30- 200812915 1001 Type, medium pressure UV lamp 613. The lamp is operated at approximately 1 kW and is powered by a power source 161. The treated solution prepared as generally described below was pumped from the feed tank 61 to the medium pressure UV unit 612 using a pump 618 at a flow rate of about 0.75 gpm. The dose of UV radiation applied at this flow rate is about 4,00 micro watt-seconds per cubic centimeter. The irradiated fluid is collected in the collection tank 620. The honing agent flow system is a mixture of commercially available copper CMP honing agent concentrates which are diluted in deionized with a vermiculite base and alumina-based base at a ratio of about 1: 1: 40. Composition. The pH of the honing agent stream is adjusted to about 3 pH units using sulfuric acid. The metal species, copper sulfate pentahydrate, is added to the enamel stream. About 30% of the electronic grade hydrogen peroxide of the calculated aliquot was added to the solution as an oxidant. The concentrations of oxidant and metal species were listed in Table 9 prior to treatment. This data shows that a pretreatment system including UV radiation technology can reduce the oxidant concentration. Instead of using ion exchange resins, these tests focused on photochemical removal or reduced oxidation species. However, as shown in the experiments of the various embodiments described above, metal species, copper, may have been effectively removed via the use of one or more embodiments of the processing system of the present invention. It is expected that the higher the UV dose level, the longer the UV unit residence time, and other techniques may further improve the reduction of the oxidant species; however, as specified in the above examples, particularly with respect to Examples 4 and 5, All oxidant species must be removed to achieve metal removal. -31- 200812915 Table 9 Hydrogen peroxide decomposition test by irradiation, pH turbulence rate (gpm) Total solid particles (mg/L) Inflow of H2〇2 (mg/L) Inflow of copper (mg/L) H2〇2 Reduction (%) 1 6.6 0.75 3,500 470 30 15 2 3 0.75 3,500 300 30 33 3 3 0,75 3,500 200 30 18 Although the invention has been described in connection with several embodiments, it should be understood that many alternatives and modifications are And the changes will be apparent to those skilled in the art. Accordingly, the present invention is intended to embrace all such alternatives, modifications, and variations, which are within the scope and scope of the appended claims. The exemplified embodiments of the present invention have been described by way of example only. Numerous modifications and other embodiments are within the scope of the present invention and are considered to be within the scope of the present invention. In particular, although many of the embodiments set forth herein include specific combinations of procedural regulations or system components, it should be understood that those provisions and those may be combined in other ways. For example, the present invention contemplates utilizing a fluidized bed or similar unit operation in which the ion exchange medium is effectively fluidized by appropriately directing the fluid being treated at one or more bottom ports at a sufficient flow rate. Moreover, only the regulations, components, and features discussed in connection with an embodiment are not intended to be excluded from the like tasks in other embodiments. It is to be understood that the various changes, modifications, and improvements of the present invention are intended to be apparent to those skilled in the art and that such changes, modifications, and improvements are intended to be part of the disclosed invention and are within the spirit and scope of the invention. Moreover, it should be understood that the present invention is directed to any feature, system, branch system or technology described herein, and any combination and two or more features of two or more features, systems, systems or techniques described herein. Any combination of systems, subsystems, and/or methods, if such features, systems, subsystems, and Φ techniques are not mutually inconsistent, are considered to be within the scope of the invention as set forth in the appended claims. The use of ordinal terms such as "first", "second", etc. to modify a patentable scope component does not imply any preference, lead or order, or temporary order of one component for another component. The steps or rules of a method are implemented in order, but only as a mark to distinguish between a component having a certain name and another component having the same name (if no ordinal term is used) to distinguish the components. Those skilled in the art will also appreciate that the parameters and groups described herein can be exemplified and that actual parameters and/or configurations will be based on the particular application in which the systems and techniques of the present invention are used. Those skilled in the art do not use For the purposes of routine experimentation, specific embodiments equivalent to the present invention are also identified or can be determined. Accordingly, it should be understood that the embodiments described herein are set forth by way of example only. Within the scope of the patent scope and its synonyms; in addition to the special description, the hair may be implemented in other cases Ming. -33- 200812915 [Simple description]

The accompanying drawings are not intended to be drawn to scale. In the drawings, the same or similar elements are denoted by the same numerals. For the sake of clarity, not every component in the drawings may be labeled. In the drawings: FIG. 1 is a schematic illustration of a processing system in accordance with one or more embodiments of the present invention; FIG. 2 is a diagram of one or more embodiments of the present invention as described in Embodiments 1 and 2 Schematic illustration of a processing system; ^ Figure 3 is a schematic illustration of the processing system described in Embodiments 3 and 4; Figure 4 is a schematic illustration of an additional processing system described in Embodiment 5; Figure 5 is a schematic illustration of the pretreatment system described in Example 6. [Main component symbol description] 20 CMP system 30, 3 18> 520 collection tank 40 treatment system 2 10, 3 1 0 ion exchange column 2 12, 3 14, 5 16 feed tank 214, 3 12, 618 pump 2 16 outflow Storage tank 3 11 Carbon column 3 16 Sample point • 34- 200812915 5 10 Carbon bed 512, 514 Ion exchange bed 5 1 6、6 1 6 Feed tank 5 18 Pump used 5 22 Sample point 6 10 Pretreatment system 6 12 UV unit 613 UV lamp 6 14 Power supply 62 0 Collection tank -35-

Claims (1)

200812915 X. Patent Application Range: 1. A method of treating a honing agent stream, comprising: providing a honing agent stream comprising at least one metal and at least one oxidizing agent at a concentration of at least about 50 mg/liter; and directing the honing The agent flows into the ion exchange column. 2. The method of claim 1, wherein the ion exchange column comprises an ion exchange material comprising at least one miscible group. 3. The method of claim 1, wherein the ion exchange column comprises an ion exchange material comprising at least one side functionality selected from the group consisting of iminodiacetate, polyamine, bispyridylmethyl Amines and aminophosphonic acids. 4. The method of claim 2, wherein the ion exchange material comprises an imidodiacetate functional group. The method of any one of claims 1 to 4, wherein the oxidant concentration is less than 1,500 mg/L. The method of any one of claims 1 to 5, wherein the oxidizing agent comprises at least one selected from the group consisting of iodate, periodate, bromate, perbromate Chlorate, perchlorate, peroxy compound, nitrate compound, persulfate compound, permanganate compound and chromate compound. The method of any one of claims 1 to 5, wherein the oxidizing agent comprises at least one compound selected from the group consisting of nitric acid, hydrogen peroxide, iron nitrate, and ammonium persulfate. 8. The method of any one of claims 1 to 7, wherein at least -36-200812915 A metal includes copper selected from the following, nickel, zinc, cobalt, cadmium, iron, nail, gallium, antimony, tungsten, and the like. 1 G · If the patent application range is 1 to 8, the material has 〇·〇〇丨μπι to 丨μιη 1 1 · The concentration of the material in the first paragraph of the patent application is 50 mg/L 3 12♦ as claimed in the patent scope The step of at least one oxidation-column in the carbon removal column of the first item is carried out before the step of the oxidizing agent as in the first aspect of the patent application. 1 4 · As in the scope of patent application, item i 3, add at least one reducing species to 硏 1 5 · Chemical, electrochemical, photochemical or characterization as in Article 13 of the patent application. 1 6 · Before the introduction of the flow of the first paragraph of the patent scope into the ion exchange column, a metal used to treat the honing agent stream at a concentration of at least 50 mg/L: copper, group , silver, gold, platinum, rhodium, ruthenium, and mixtures thereof. The method, wherein the at least one metal is the method of any one of the items, wherein the diameter is within the range of the particles. The method wherein the particles in the honing agent stream are in the range of 20,000 mg/L. The method wherein there is no pretreatment step to transfer the honing agent stream to the ion exchange, the method further comprising neutralizing at least the method, wherein the step of neutralizing comprises adding a grinding agent stream. The method wherein the step of neutralizing comprises causing the oxidizing agent to be inerted by thermochemical means or the like: the method further comprising the step of treating the honing agent into the carbon column by a honing agent, comprising at least one metal at least one oxidizing species And a concentration of a honing agent concentration of solid particles ranging from -37 to 200812915 50 mg/L to 20,00 mg/L, wherein the treatment system comprises: an inlet fluidly connected to a source of the honing agent stream; Apparatus for reducing the concentration of at least one metal from a honing agent stream. 1 8 The processing system of claim 17 wherein at least one of the metals is selected from the group consisting of copper, lead, nickel, zinc, cobalt, cadmium, iron, giant, silver, gold , platinum, palladium, rhodium, ruthenium, osmium, gallium, table, give and crane. A treatment system according to claim 17 wherein at least one oxidizing agent is one selected from the group consisting of hydrogen peroxide, iron nitrate and ammonium persulfate. 20. A processing system as claimed in claim 6 further comprising means for neutralizing at least one oxidizing agent. A treatment system according to claim 20, wherein the apparatus for neutralizing at least one oxidant reduces the concentration of the at least one oxidant in an electrochemical, photochemical and/or thermochemical manner. A treatment system according to any one of claims 6 to 21 wherein the apparatus for reducing the concentration of at least one metal from the honing agent stream comprises an ion exchange column having a medium which is capable of At least one metal forms at least one functional group of the complex. The treatment system of any one of claims 16 to 2, further comprising a carbon bed disposed upstream of the apparatus for reducing the concentration of at least one metal from the honing agent stream. -38·