TW200812916A - Process for treatment of water to reduce fluoride levels - Google Patents

Abstract

Improved methods for removal of fluoride from waste water, particularly from waste water generated through semiconductor manufacture. In one aspect, an improved fluoride precipitation method is provided in which fluoride is immobilized in the solid generated. In this method the precipitated fluoride is adsorbed or complexed into a cation exchange resin. In another aspect, waste water containing fluoride is treated with a macroporous anion exchange resin to improve the efficiency of fluoride removal by the improved fluoride precipitation method. After treatment with macroporous anion exchange resin waste water is subjected to fluoride precipitation employing cation exchange resin alone or in combination with addition of a water-soluble calcium salt. The methods herein can be applied to mixed acid waste water containing various species including mixed acid etchant, dissolved silica species and buffered oxide etchant and having fluoride levels up to 40,000 ppm. The methods of this invention are optionally combined with reverse osmosis to provided additional reductions in fluoride. Fluoride levels below 10 ppm or preferably 1-3 ppm or less can be obtained employing these methods.

Description

200812916

V IX. DESCRIPTION OF THE INVENTION: TECHNICAL FIELD The present invention relates to a process for treating fluoride-containing wastewater to reduce fluoride content in wastewater and to form a solid comprising fixed fluoride. [Prior Art] Gases in the form of hydrofluoric acid or fluoride salts are widely used in various industrial applications. For example, the semiconductor industry uses large amounts of fluoride compounds in etching and cleaning processes to produce large amounts of fluoride-containing wastewater, which represents an important disposal issue. Fluoride has a low urban emission limit, usually 3 ppm. In addition, many municipalities have imposed a total pound/day limit on fluoride emissions. The fluoride content in the wastewater from such plants must be significantly reduced before the water can be released into the municipal wastewater treatment system. The methods currently used to reduce fluoride in this industrial wastewater are mostly calcium chloride or other calcium species to produce calcium fluoride, followed by agglomeration and / or precipitation steps to precipitate calcium fluoride based precipitation method . However, the effluent-containing wastewater is often a complex mixture of some components, including mixed acids such as sulfuric acid, citric acid and acetic acid (for example, mixed acid, mea); soluble and colloidal oxidation; ^, and can inhibit or prevent normal Wastewater treatment steps such as buffering: buffers for effective use of PH, such as buffered oxide etching including components such as gasification, buffer d, and surfactant. In another method, a large amount of chlorinated and/or ferric chloride, sodium hydroxide and other chemicals are consumed. Adding a large amount of fluoride to an acceptable level 6 200812916 The required vapors and other salts also produce vapors or other regulated species that are too high for urban emissions. The methods currently used to reduce fluoride are generally poorly performing, time intensive, expensive, not sufficiently reducing the fluoride content and producing a large amount of residual fluoride and other unacceptable chemical species, making the slurry a dangerous Waste shows an expensive off-site disposal problem. The present invention provides a method for improving the use of fluoride in wastewater to improve one or more of these difficulties.

A variety of methods have been reported for treating water to reduce fluoride levels, using sinks, ion exchange, membrane separation, or different combinations of such steps: Eight Precipitation U.S. Patent 6,436,297 is directed to a method for degassing wastewater, which is neutralized in a base. An acid neutralization step is included between the step and the decanting step. More specifically, the initial use of burnt lime (Ca(0H)2) adjusts the pH of the wastewater to 6.5 'and then' in the second step, by adding super-burned lime to adjust the yang to 8? The pH of the solution is adjusted to between 5.5 and 7 by adding an acid other than hydrogen peroxide (e.g., sulfuric acid). Then, the formed solid was discharged. Can be decanted, pounding water. The step of continuously extracting solids is also mentioned. It has been reported that a fluoride content ranging from ''''''''''''' U.S. Patent ΜΗ, for example, relates to a method for transferring a effluent from wastewater, which comprises adding calcium calcium to the reagent. Before the addition of calcium, the calcium fluoride " seed granules formed by the fluorinated lamp calcium sulphate are added to the fluoridation mother to form and kill. This patent also reports that the wastewater containing the calcium test 7 200812916 and the seed granules, which are added to the 3 所 促 以 以 以 以 以 2008 2008 2008 2008 2008 、 、 、 、 、 、 、 反应 反应 反应 反应 反应 反应 反应 反应 反应 反应 反应 反应 反应 反应 反应 反应 反应 反应 反应 反应 反应 反应The formation of a granule that can be removed from the water by the Mingha~h 增大 increases the velocity of the particles through a tubular reactor. U.S. Patent 6,267,892 discloses a method of treating vaporized wastewater to reduce fluoride levels comprising the steps of - (d) adding a compound to wastewater to produce calcium telluride and using a device comprising a reaction vessel and a settling vessel. A polymer solution, described as a high molecular weight aggregating agent, can be added to the reaction vessel.

Wu Guo Patent 5,403,495 relates to a multi-stage method for removing dissolved gasification from wastewater, which comprises first forming a precipitate of calcium or magnesium fluoride by repeating the precipitate with about or magnesium ion source and gas. The circulation of ions (ie, in wastewater) contacts to form a so-called "increased fluorine (four) or gasification>children" It has been reported that contacting this increased precipitate with other ruthenium or town ions and with the fluoride waste water (iv) recycles the gas from the wastewater and increases the particle size of the increased sinking matter. The enlarged precipitate is finally separated from the treated water by precipitation or filtration. U.S. Patent 5,215,632 is directed to a two-step cup method for the removal of fluoride and sulfate ion impurities from aqueous sodium chlorate in the manufacture of sodium chlorate crystals. The hydrazine method involves first adding calcium chloride and a phosphate source to form a removed first precipitate. Then, money salt ions are added to the T liquid to form a second precipitate. Removal of the second precipitate indicated 99% fluoride and sulfate ion impurities. U.S. Patent No. 4,808,316 is directed to a treatment comprising both uranium and fluorine. The first step is to add slaked lime to the wastewater and then remove the sink (2008 and the sinking step). Then, the supernatant liquid from the neutralization precipitation step is contacted with a first chelating resin capable of selectively adsorbing fluoride ions and a second chelating resin capable of selectively adsorbing uranyl sulfhydryl ions to adsorb and remove residual liquid in the supernatant layer. Ions in the middle. The resin is washed and regenerated and the liquid used to wash and regenerate the resin is returned to the neutralization precipitation step. The use of a sulphuric acid type s-framaline chelating resin as a chelating resin for adsorbing fluoride has been described. It has been reported that the fluoride is eluted by the resin by washing with an aqueous sodium hydroxide solution. A decarburization step is provided to decompose the carbonate ions prior to the neutralization precipitation step. U.S. Patent 4,028,237 is directed to a process for the removal of fluorine from a fluorine-containing wastewater wherein the first addition of aluminum ions to the wastewater is reported to convert fluorine to a low solubility hydroxy fluoride complex. Phosphoric acid or phosphate and calcium compounds are then added to form fluoride apatite. The solid formed is removed and the residual fluoride is decanted in water. More particularly, the method includes separating wastewater into concentrated and dilute fluoride containing wastewater portions, adding calcium compounds to the concentrated fluoride containing wastewater to form calcium fluoride, and adding aluminum ions to the dilute fluoride wastewater to convert the fluorine The compound is converted to a low solubility complex. The separated treated wastewater is then mixed and calcium ions are added to the mixture to form fluoride apatite and to remove solids. Ion Exchange The US Published Patent Application 2005/0145572 (July 7, 2007), and U.S. Patent No. 6,998, 〇54, disclose two methods for the removal of fluoride from industrial wastewater. The first method uses a series of four ion exchange steps in which the wastewater successively passes through (1) a strong acid cation resin (exchanges hydrogen ions with cations); (2) a strong base anion resin in the form of sulfate (9

U.S. Patent No. 5,876,685, the disclosure of which is incorporated herein by reference to the entire entire entire entire entire entire entire entire entire entire entire content It has been reported in this method that "substantially all fluoride ion" is removed from a solution containing a mixture of fluoride ions greater than 10 ppm and other anions and several forms of ruthenium. In this method, the pH of the solution containing the fluoride ion is adjusted to the testability ρΗ (ρΗ 8·9) to hydrolyze the gas 矽S夂 and any metal fluoride complex, after which the alkaline solution is passed through the lining. A strong base anion exchange resin column in the form of a hydroxide (〇Η·). Fluoride and other anions (nitrates) have been reported to be adsorbed while the dissolved and colloidal cerium oxide tends to pass through the column. The fluoride is then released from the column and a number of additional steps are applied to produce purified hydrofluoric acid. In tests of simulated wastewater containing fluoride, nitric acid and sulphuric acid, it has been reported that the fluoride content in the column effluent is less than 5 ppm. 200812916 removes hexafluoride); (3) weak base anion exchange resin with a tertiary amine group in a free form (to remove acid); and W a weak anion exchange in the form of a free base Resin (to remove hydrofluoric acid). A second method reported in the published application requires dissolution with an aluminum salt: initial treatment of a strong acid cation exchange resin containing hydrogen ions, exchange of aluminum ions with hydrogen ions, followed by passing the waste water through the exchanged aluminum Strong acid cation = change the resin tower to remove ions from wastewater. The cation exchange of the cations is described as having all the cation capacity that can be filled by the ions. It has been reported that this resin can promote the mismatch reaction between the ionic ions and the fluorine materials in the reactive matrix of the ion exchange resin. The fluoride content that can be successfully removed is not reported. This method indicates that it is suitable for use in wastewater that is discharged from a conventional fluoride precipitation system such as neutral or semi-inorganic. 200812916 v US Patent 5,707,514 and 5,772,891 relates to a multi-step process for treating wastewater from the semiconductor manufacturing industry, which comprises a precipitation and ion exchange step and a water treatment device for carrying out the method. This patent mentions the addition of a large amount of chemicals (eg 'slaked lime, Corrosion soda, polychlorine: Ming, polymer aggregating agent, etc.) to treat acidic wastewater from semiconductor plants to achieve fluoride and sulfate removal by precipitation. The residual water after this precipitation step has a relatively high conductivity And for its own sake, it cannot be recycled immediately. In the method reported in this patent, let the temple and solid solution The water treated in the separation step passes through the cation exchange resin to remove the (tetra) (in other ions) and reduce the conductivity. The used cation exchange resin is contacted with the acidic wastewater entering the treatment unit to release the (iv) into the wastewater. Regenerated. The 'regenerated cation exchange resin is then separated from the wastewater and reused. The released trans ions indicate a reaction with the vapor in the acidic wastewater to form some CaF2' but after contact with the cation exchange resin, The wastewater is subjected to several of the above mentioned sinking and separation steps and the resulting reduced sulphate and sulphate water is passed through the regenerated cation exchange resin. In this cycle, 'cation exchange resin is used to reduce the treated The conductivity of the water does not seem to remove any substantial amount of fluoride or sulfur salts. Wu Guo Patent 4,734,200 reports a treatment of acid waste water produced in the sulphuric acid plant of the Cheng method to be contaminated with consumables and/or phosphorus. Method of treatment. The treated water packet has been reported as 2. It has been indicated that it is loaded into the tree when passing the forced anion exchange tower. It is removed from the wastewater. This step indicates that the pH of the wastewater is between 55 $ p p, 仓 , , , : I·5 to 2. It has been reported that fluoride can be released from the cation 200812916 ion exchange material. Prepared as a useful substance. It has been reported that phosphate ions are increased from pH to 5 to 7 and the pH-adjusted wastewater is contacted with a strong anion exchange resin to allow phosphate ions to be loaded onto the resin from the wastewater. In the related method, U.S. Patent No. 4,965, 〇 61, discloses a method for recovering fluoride from a waste fluoroantimonic acid solution and converting waste fluoroantimonic acid into a nitrogenous acid. This method is used to treat wastewater. The alkali anion exchange material releases SiF, and SiF62· produces hydrofluoric acid as (NH4)2SiF"; i^^ and from the precipitated salt. U.S. Patent 4,952,386 is directed to a method of purifying hydrofluoric acid by removing ions from hydrofluoric acid by passing an acid through a cation exchange material and an anion exchange material. Film Fence US Pat. No. 5,043,072 is directed to a method of treating fluoride containing water using a reaction step to form a suspension, a membrane separation step to form a concentrated suspension and a permeate having reduced fluoride, and a recycle step At least a portion of the concentrated suspension separated by the membrane is introduced into the reaction step to act as a seed crystal for precipitation of the fluoride and to introduce the residual concentrated suspension into the circulation tank. The calcium and/or aluminum compound is added to the water together with a portion of the concentrated suspension while the pH of the liquid suspension is adjusted to the heart 8. The resulting suspension is introduced into a circulation tank where it is mixed with the residual concentrated suspension. The suspension from the circulation tank is treated by membrane separation (microfiltration membrane or ultrafiltration membrane) to separate it into an osmotic solution and a concentrated suspension. The solids precipitated and enlarged in the % tank were removed. In a particularly exemplified process, raw water comprising 370 gram per liter of fluoride is treated to produce a permeate comprising 17-25 mg/liter of fluorine 12 200812916. The permeate is further treated as needed by passing it through a fluoride ion adsorbate. Fluoride ion adsorbing substances are indicated as yttrium, arsenic, titanium or yttrium type cation exchange resins, strong or weakly acidic cation exchange resins, dentate alkyl type adsorption resins, weak base anion exchange resins, rare earth metal oxide hydrate type chelation Resin, aluminum salt type chelate resin and similar adsorption resin' and activated alumina or magnesia type adsorbent. The permeate may also be treated by a COD adsorbing substance (which is indicated to include a gel type or MR (macro, periplasmic) type weak, medium or strong anion exchange resin and activated carbon). COD (Chemical Oxygen Demand) refers to the amount of dissolved oxygen required for complete chemical oxidation of organic and inorganic materials in water, expressed in milligrams per liter. U.S. Patent No. 6,338,803 discloses the use of reverse osmosis to treat wastewater containing hydrogen halide, mixed acid etchant waste, dissolved cerium oxide and solid particles. The pH of the wastewater is adjusted to about 7 or above, the solid matter is removed by filtration, and the filtered wastewater feed is passed through a reverse osmosis membrane to produce a permeate stream of treated water having a reduced fluoride content. A scale inhibitor can be added prior to the application of reverse osmosis to prevent the film from becoming dirty. This patent has been reported to be best applied to contain 2 ppm ppm or less of fluoride, MO Pim or less calcium, 1 〇 ppm or less of magnesium, 2 〇〇 or less of cerium oxide, 1 〇 Phenol or less of iron or aluminum, 75 〇〇 or less of combined nitrate and nitrite, and 5 〇〇〇 ppm or less of acetic acid wastewater. =^ has been reported to derive such methods, in this technique it is possible to reduce the amount of contaminated solid waste with a minimum of process steps = a reduction in the amount of contaminated solid waste (which must in turn be properly treated and hazardous waste) At 13 200812916, there is still a need to reduce the amount of fluoride in wastewater by reducing costs. The present invention is directed to an improved process that provides one or more of these benefits = reducing fluoride levels in wastewater. SUMMARY OF THE INVENTION The present invention relates to a method for reducing fluoride in a liquid waste stream to be distinguished from industrial wastewater and more particularly to include hydrofluoric acid (hf), mixed acid etching solution (MAE, HF, A mixture of nitric acid and acetic acid) and dissolved cerium dioxide (as produced by the enamel wafer manufacturer). Wastewater treated by the methods herein may also include a buffered oxide etchant (7) 〇e) component and may further comprise colloidal cerium oxide. The process of the invention is useful in the presence of mixed acids (including, for example, sulfuric acid, nitric acid, and optionally acetic acid), dissolved cerium oxide, peroxides, and/or BOE chemicals (including, for example, ammonium fluoride, hydrazine) Reduce fluoride content. The process herein can be particularly useful for reducing the fluoride content in wastewater and for wastewater containing more than 1 〇〇 ppm of fluoride. The method can also be used to reduce fluoride levels in wastewaters containing more than 1 000 ppm of fluoride. The process can also be used to reduce fluoride levels in wastewaters having a fluoride content greater than 3000 ppm. In certain embodiments, the method of the invention can be applied to reduce the fluoride content in the wastewater to 50% or more, 75 〇 / 0 or more, 9 〇 % or more, 99% or More or 99.99% or more. In certain embodiments, the methods herein can be used to reduce fluoride levels from 40-40, 〇〇〇ppm to ί 0 ppm or lower, and preferred applications to reduce fluoride containing 200812916 『 to μ Ppm or less to meet city emission limits. #Understanding that the process of the present invention can be repeated more than once over the batch of wastewater provided to achieve the desired reduction in gasification content. Compared with the current (4), coagulation and clarification method for removing fluoride, the method of the invention can provide efficient fluoride reduction in a shorter process time and at a lower cost, and the method does not require full-scale control of wastewater. PH. The methods herein can reduce the addition of ionic species such as chlorides. In the specific embodiment of the invention, the method of the present invention can significantly reduce the amount of residual residue produced compared to the method currently used (a reduction in residual solid waste exceeding 50% of the conventional physical/chemical method can be obtained, In a preferred embodiment, the solid solids-containing waste produced in the process herein is primarily a low water solids rather than a colloidal slurry typically produced by conventional precipitation methods. The present invention provides a method of immobilizing fluoride removed from wastewater in a solid, from which only a relatively low gas content can be dissolved. In a particular embodiment, produced by the methods herein The solid fluoride waste waste is leached out of less than about 35 〇〇 ppm as measured by the TCLP (毋 characteristic dissolution procedure) method. In a specific embodiment, the solid waste produced in the method herein Has a sufficiently low soluble fluoride content that meets local and/or federal regulatory requirements in a non-hazardous landfill treatment. In a particular embodiment, An improved precipitation method for reducing the fluoride content in wastewater, which produces, for example, a percentage of water in a solid of 50% by weight or less, a relatively low water content containing gasification 15 200812916 solids (residual waste Solids), ie, in the form of a solid state of the kidney, which reduces the cost of treatment. In a specific implementation - the volume of residual waste solids is the total volume of treated liquid waste < 10 / ° or less Or preferably 5% or less. In a particular embodiment, ^ the waste solid produced is a large amount of insoluble filtration (eg, no greater than 3500 ppm for individuals, as measured by the TCLp method). Low water content solid.

In a specific embodiment of the improved precipitation process, a water-soluble (tetra) salt such as chlorine (tetra) is added to the wastewater and the wastewater is contacted with a cation exchange resin, particularly a cation exchange resin in the form of sodium or calcium (chemical form).乂 y 氟化 fluoride containing l and production - only soluble in the relatively low vaporization of the oral cavity 胄 Generally, the water-soluble salt and cation exchange tree 曰 2 into the wastewater 'and the mixed group added Divide until the desired fluoride 3 is achieved or until the fluoride content is stable. In a preferred embodiment, the water/salt calcium salt is added to the wastewater, and the treated water is thoroughly mixed to allow the cation exchange resin to be added thereto. Once the fluoride reduction is achieved, the solid is separated from the treated water. The addition of calcium ions at least to some extent removes the fluoride by producing low solubility calcium fluoride (CaF2). The calcium treated wastewater is thoroughly mixed to allow the component to react. When the fluoride content measured in the mixture is stable, the reaction is completed. Typically, the treated wastewater is 15-30 minutes or longer. Generally, an amount of calcium ions sufficient to reduce the desired amount of fluoride in the wastewater is added. Typically, the amount of cation exchange resin added to the 4' is sufficient to achieve the desired residual fluorinated ink. For example, a cation exchange resin can be added incrementally to the calcium treated wastewater while periodically monitoring the fluoride concentration to achieve the desired fluoride 16 200812916 content. In a particular embodiment, prior to any solids that have been formed, the # ion is removed and contacted from the wastewater using a conventional method of separation from the wastewater = cation exchange resin. The solid and cation exchange resin formed is precipitated with = ions and/or in particular embodiments, such solids are - low water solids. The content is leached. /, Low fluorination as mentioned above In a specific embodiment, the counterfeit is formed in / > and 2, adding a relative stoichiometry of the mouse compound. The amount of 2+ (i.e., rCa is 50 / of the vapor present or expected to be present in the wastewater). In other embodiments, 'Zu's, a substoichiometric amount of Ca2+ is added. : In particular, the amount of sub-stoichiometric amount of 5% from the 5% of the fluoride present in the wastewater to less than 5 %. In its particular embodiment, the amount of feed in the wastewater can range from (10) to less than the amount of moles present in the t-form of the wastewater. In a preferred embodiment, the amount of sub-stoichiometric amount of Ca 2+ present in the amount of fluoranthide of the fluorene is from 10% to 25%. The water soluble salt can be added to the mill water in a (four) or more typically aqueous solution. The soluble salt solution is rather concentrated, and for example, contains 20% by weight or more of a salt. In a specific embodiment, a 30% by weight aqueous solution of calcium chloride is used. The cation exchange resin is preferably a strong acid cation exchange resin in the form of sodium or calcium. In a more specific embodiment, the (iv) ion exchange resin is a cation exchange resin other than in the form of a proton (acid) or aluminum (i.e., a cation having a majority of 17 200812916 in the resin is A1+3).

Rt 匕 匕 杂 杂 交换 交换 交换 交换 交换 交换 交换 交换 交换 交换 交换 交换 交换 交换 交换 交换 交换 交换 交换 交换 交换 交换The amount of cationic parental resin added is usually determined by the amount of soluble salt added to the person (1 depending on the amount of fluoride in the wastewater). In a particular embodiment, the volume of cation exchange resin added is from 〇5% to as high as 10% of the treated wastewater volume. In the specific concrete 》T joined the yang

The volume of the ion-parent resin ranges from 25% to 1% by volume of the treated wastewater. In a specific embodiment of the feed, the cation exchange resin having a volume equal to 1% by weight or less of the total volume of the wastewater and 2 additions is added. In a more specific embodiment, the addition volume is equal to the total bead cation exchange resin of the treated wastewater volume or less. In other specific embodiments, a cation exchange resin having a volume ranging from from 04% to 5% by volume of the treated wastewater is added. In a particular embodiment, the cation exchange resin can be added incrementally. In this particular embodiment, the initial addition range is from 0.25 of the treated wastewater volume. /. To a cation exchange resin of 53⁄4, and optionally, other cation exchange resins may be added to reduce the fluoride content in the treated 2 water to a minimum and reduce the processing time as needed. It is preferred to add a cation exchange resin having a content of less than 5% by volume of the treated wastewater to minimize the amount of solid waste produced. In another specific specific embodiment, a powdered cation exchange resin having a volume equal to 2 to 25% of the total volume is added. In a particular embodiment, the cation exchange resin has an average particle size between 30-1 and 〇〇〇 microns. In a particular embodiment, the cation exchange resin has an average particle size between 3 Å and 3 Å microns. In the specific shell example of 200812916, the cation exchange resin is powdered and has an average particle size of between 3 μm and micron. Powdered cation exchanges are particularly preferred for faster water treatment. The hydrophobic and the additive comprising the cation exchange resin are combined for a sufficient period of time to obtain a stable reduced I content. The water and the combined additive 2 are contacted and σ in a suitably sized container equipped with a dispensing or mixing device to promote the interaction of the additive and the resin and wastewater components. It is preferred that the ampere used for % is an open-ended container. Typically, the combined materials are mixed for 1 5 30 minutes or more. After thorough mixing, the treated aqueous supernatant is separated from the solid (any precipitate and resin) to provide treated water having a reduced fluorinated content. Fluoride content in the treated water can be measured using any suitable method well known in the art. The treated water is separated from the solid knife in a particular embodiment, and the treated and solid are separated by filtration. In a specific embodiment, the isolated solid, the f-cation parent-replacement resin and any precipitated salt, do not dissolve the high-I ion containing:: (ie, insoluble filtration is greater than about 35 〇〇 ppm, as by The TCLp method measures =)' and in a particular embodiment this solid does not filter out the fluoride content required to classify this solid as hazardous waste. The sinful use of the modified cation exchange resin as described above to provide a significantly reduced gasification content in the treated wastewater can be achieved by using the modified cation exchange resin as described above. . This method, for example, can be used to reduce the amount of I compounds in semiconductor wastewater from more than 2 〇, _ ppm to 2, _ ppm or less. This improved precipitation method can be combined with other fluoride removal methods such as reverse osmosis, and the upper layer of the good/infantile method is subjected to reverse osmosis to provide significant additional 200812916 vapor removal and to provide treated water with fluorine. The content of the compound is less than (7) ppm and preferably the amount of the compound is less than or equal to that of the melon. This modified sinker can be combined with other steps as described herein to provide treated water with this desired low fluoride content. The wastewater treated by the modified precipitation method is subjected to a pH adjustment step as needed to pH 4 or higher, pH between 5 and 6, pH 8 or above, or pH 10 or above. In another aspect of the invention, the fluoride containing wastewater is contacted with a cationic parent resin in the form of calcium, wherein the function of the resin is to remove significant il species from the wastewater and produce a low water solid (ie a solid (a fluoride-containing resin) that is not a gel or a slurry, and in a particular embodiment it is - has a relatively low vapor content leaching (ie, less than 3 5 〇〇) Fluoride-containing solid. In this regard, it is not necessary to previously add soluble about salt to promote fluoride removal. The cation exchange resin is preferably a strong acid cation exchange resin in the form of calcium. The cation exchange resin may be in the physical form of φ in whole beads or in powder form. The amount of cation exchange resin added is usually determined by the amount of the unsaturation in the wastewater. Most commonly, the amount of cationic ion exchange resin added ranges from 25% to 1% by volume of the treated wastewater. More specifically, the amount of cation exchange resin added ranges from 0.5% to 5% by volume of the treated wastewater. In a particular embodiment, the volume of the cation exchange resin is equal to 1% or less of the volume of the wastewater. In a more specific embodiment, a total bead cation exchange resin having a volume equal to 5% or less of the volume of the wastewater is added. As mentioned above, the ion exchange resin in the form of calcium can be gradually added to the wastewater while monitoring the fluoride content until 20 200812916 to obtain the desired reduced content of the compound. After the initial addition, other cation exchange resins in the form of a mother may be added if necessary to reduce the fluoride content in the produced wastewater to a minimum and reduce the treatment time as needed. In another specific embodiment, a powdered cation exchange resin having a volume equal to the volume of the wastewater is added. In a particular embodiment of the material, the cation exchange resin has an average particle size between 3 (m, 〇〇〇 microns). In a particular embodiment, the cation exchange resin has an average 瘫 particle size of 30 to microns. In a specific embodiment, the cation exchange resin is powdered and has an average particle size between "to _ U meters. Xiao is faster & water treatment 纟 said, umbrella points & cation + It is better to exchange the tree and the mixture. The mixed wastewater and the cation + exchange resin are sufficient for a period of time. (4) to obtain a stable reduction of the IU content of the IU. In a container of appropriate size equipped with a mobilization or mixing device, the water and the resin are allowed. Contact and mixing to promote the interaction of additives and resin and wastewater components. The container used is preferably a lidded container. Typically, the combined additive is mixed for 15-30 minutes or more. _ After thorough mixing, let the The treated water overlayer is separated from the solid (resin) to provide treated water having a reduced fluoride content. The fluoride content in the treated water can be measured. The treated water and solids are divided. In a particular embodiment, the treated water and solids are separated by filtration. The residual solids are preferably a low water content solid (less than 50% by weight water). In a particular embodiment, The volume of residual waste solids produced is 10% or less or less or less of the total volume of the treated liquid. In a particular embodiment, the separated solids comprising fluoride and cation exchange resin Insoluble in high fluoride content ions (ie, insoluble 21 200812916 filtered out greater than about 3500 ppm, as measured by the TCLp method), and in the special two =: embodiment, this solid insoluble filtrate will be classified as hazardous waste Fluoride content of the substance/mouth. The vaporized wastewater is contacted with the (%) form of the % ion exchange resin without the previously added 30 salts to provide a significant reduction in fluoride content in the treated wastewater. This method can be combined with other fluoride removal methods such as reverse osmosis, in which the supernatant liquid separating the resin is subjected to a counter-feed to provide significant additional fluoride removal and supply.

The rational water has a residual content of 1 G ppm and a preferred vapor content of 1-3 ppm or less. The wastewater is treated with a cation exchange resin in the form of calcium as needed to carry out a pH adjustment step to pH 4 or above, or above or pH 1 〇 or above.

pH between 5 and 6, pH In another aspect of the invention, the mixed acid wastewater containing fluoride, mixed acid and/or dissolved ceria and/or B〇E is contacted with a macroporous anion exchange resin , wherein the resin increases the efficiency of fluoride removal and at least to some extent removes one or more chemical species that interfere with the removal of fluoride (one or more interferents) (except fluoride itself) ). In a specific embodiment, the fluoride containing wastewater is contacted with an anion exchange resin and subjected to calcium addition, calcium addition and contact with a cation exchange resin, or contact with a cation exchange resin in the form of 壬#5 as described above. In a particular embodiment, the volume is added from 〇·5% of the volume of the wastewater to the macroporous anion parent resin and mixed with the wastewater. The volume of the macroporous anion exchange resin to be added is preferably less than 2% by volume of the wastewater to be treated. In a particular embodiment, the volume of macroporous anion exchange resin added is between m and 12 of the volume of wastewater to be treated. In the above (4) of the present invention, a pH adjustment step is carried out before or after treatment with an anion exchange resin, to pH 4 or above, PH at 5 to 6, F 曰 1, PH 8 or above or pH 1 (). or above. The macroporous anion exchange resin preferably contains iron. The macroporous anion exchange resin is preferably a magnetic resin. In a preferred embodiment, the pH of the wastewater is adjusted to a pH between 5 and 6. In a specific embodiment, the fluoride-containing wastewater is firstly associated with a large hole

The ion exchange resin is contacted and thereafter a water-soluble calcium salt or an aqueous solution containing the salt is added to the wastewater. This embodiment is preferred for treating fluoride-containing wastewater which also contains B〇E. Thereafter, the wastewater is brought into contact with the cation exchange resin as described above. In an alternative embodiment, calcium is added to the wastewater simultaneously with or prior to contacting the wastewater with the macroporous anion parent. The calcium content added to the wastewater in these embodiments is such that the calcium content in the wastewater is equal to or less than 5% of the molar amount of fluoride in the wastewater (stoichiometric or substoichiometric as described above). In a particular embodiment, the calcium content in the wastewater is adjusted to between 5% and 50 Å/mol of the amount of fluoride present in the wastewater. between. In other embodiments, the calcium content in the wastewater is adjusted to between 25% and 25% of the amount of fluoride present in the wastewater. In these embodiments, the pH of the wastewater is adjusted as needed prior to treatment to pH 4 or above, pH between 5 and 6, pH 8 or above, or pH 10. In a preferred embodiment, the wastewater is adjusted to between $ and 6. In a more preferred embodiment, the macroporous anion exchange resin is a strong base anion exchange resin in the form of a vapor and more preferably a type 1 strong base anion 23 200812916 2 sub-exchange resin. Preferably, the anion exchange resin is in the form of a hydrophilic polymer. :: In a particular embodiment, the anion exchange resin has an average of between ^ ^ wood and more particularly an average particle size of between 30 1 μm. In other specific embodiments, the 2-well anion exchange resin comprises iron (III) oxide which has been dispersed in the resin. In other specific examples of the teeth, the macroporous anion exchange tree is a resin. In still other specific embodiments, the anion parent replaces the resin to have been dispersed

The macroporous strong base anion exchange resin of iron oxide (III) in the resin and having an average particle size of between 3...00 microns. The treatment of this anion exchange resin at least to some extent is removed or reduced - or the amount of chemical species that would interfere with the removal of the gas in the subsequent process steps in the wastewater (except for the fluoride ion itself). The wastewater is contacted with a macroporous anion exchange resin and other treatment components in an appropriately sized vessel equipped with an actuating or agitating device to promote the interaction of the anion exchange resin with the wastewater. When the wastewater is initially treated with a macroporous anion exchange resin, the _ or difficult mixture is sufficient to achieve the time to remove the interfering species. Typically, the addition of mixed combinations is 5·3 () minutes or more. The anion exchange resin should be separated from the water prior to further processing (i.e., prior to the addition of each contact with the cation + parent resin) and reused for further processing. When the anion exchange resin is a magnetic resin, the separation can be made into a magnetic device. "In the case of (4) time, the anion exchange resin is not separated from water prior to further processing. In this particular embodiment of the invention, after initial treatment with macroporous anionic fat, this can be applied as described above Improved precipitation method borrows 24 200812916

A water-soluble calcium salt such as a chlorinated feed is added to the wastewater to promote the fluoride to precipitate with fluorine (tetra). Typically, the addition of a soluble (tetra) salt results in a molar concentration of good ion content in the wastewater equal to or less than 50% of the amount of fluoride present in the wastewater. Again, the addition of the soluble (tetra) salt is carried out in a suitable container equipped with (d) or agitated (d). If the anion exchange resin is not dehydrated from the water, it is added to the same vessel used to contact the anion exchange resin fish wastewater. After the addition of the (d) sub-component, the waste mixture tray is contacted with a cation exchange resin in the form of sodium or feed (chemical form) as described above. The cation exchange resin can be simply added to the thief in which the aforementioned steps are carried out. The mixed water and the additive comprising the cation exchange resin are combined for a sufficient period of time to obtain a stable reduced fluoride content. Typically, the combined additive is mixed for 15·3 () minutes or more. After thorough mixing, the treated water, the supernatant liquid' is separated from the solids (any condensate and resin) to provide treated water having a reduced fluoride content. The fluoride content in the treated water can be measured. In a preferred embodiment, the fluoride containing cerium can be reduced to 10 ppm or better or less. The treated water is separated from the solid. In a particular embodiment, the treated water is separated from the (iv) by a transition. In a particular embodiment, the separated: fluorine: solid comprises an anion exchange resin, a cation exchange resin, and any precipitated salt that does not dissolve the oxime content of the ions, & in a preferred embodiment: fluoride ion The solubility of the content is low enough that the solid is not classified as hazardous waste. In general, lower fluoride levels can be achieved by increasing the contact time of the wastewater treatment mixture with the cation exchange resin or by increasing the amount of cation exchange resin added. Faster ion exchange resins are generally preferred. When using ^儿泰(四) volume or increasing contact time to achieve on fluoride =: Use: powder to compare. In the - or more addition steps: , 'The cation exchange resin used in the cation exchange resin body to be added depends on the amount of the resin, m/inch and the cation exchange or a cation exchange treatment step A rat with a rat content of 1 〇p or a lesser amount of positive ppm or less. It is generally preferred to use a lower body filbert 1% ion parent for resin production. In order to produce lower-solid waste, in another embodiment of this aspect of the invention, after contact with the anion exchange treatment, the wastewater can be in direct contact with the cation exchange resin of formula (IV) without the above A previously added water-soluble feed salt. The cation exchange resin of the formula is contacted with the pretreated wastewater in a suitable valley equipped with a stirring or dialing device. If the anion exchange resin is not separated from water in the first step, the cation exchange resin of the formula (IV) is simply added to the same vessel used to contact the anion exchange resin with the wastewater. The mixed water and the additive comprising the cation exchange resin are combined for a sufficient period of time to obtain a stable reduced fluoride content. Typically, mix and combine • add d 15-30 minutes or more. After thorough mixing, the treated water overlayer is separated from the solids (any precipitate and resin) to provide treated water having a reduced fluoride content. The amount of rat compound in the treated water can be measured. In a preferred embodiment, the fluoride content can be reduced to 10 ppm or better to u ppm or less. Allow treated water and solids 26 200812916

V separation. In a particular embodiment, the treated water and solids are separated by filtration. In a particular embodiment, the isolated ruthenium-containing solid comprising an anion exchange resin, a cation exchange resin, and any sink salt is insoluble in a high fluoride ion content, and in a preferred embodiment, leaching out the vapor The content ions are low enough that the solid is not classified as hazardous waste. Mixed acid, fluoride-containing wastewater is typically very acidic with a pH below 4 and often with a pH below 1. The process of the present invention has been found to act to remove the gas' without adjusting the initial pH of the wastewater. However, this method can be carried out at ρΗι or above at pH 4 or above, at alkaline pH 8 or above, and at a very pH at 10-12. Thus, in a related embodiment [if desired, wastewater containing a salt, mixed acid, soluble cerium oxide and/or BOE is initially adjusted to pH 4 by the addition of a base such as a hydroxide or higher. ΡΗγ is adjusted by adding a solid alkali salt such as Na〇H to the wastewater. P can also be adjusted by adding a / test solution. Alternatively, the pH can be adjusted to a pH of 8 or higher. For the other option, the wastewater can be initially adjusted to a high pH of 1〇_12 before the “step treatment.” After the initial pH adjustment, there is no need to further adjust or control the pH of the water. The wastewater is treated with a modified sink as described above or contacted with a cation exchange resin of the form of calcium as described above. The pH-adjusted wastewater is also contacted with an anion exchange resin as described above followed by a modified precipitate or 14 Passing on the cation exchange resin of the formula. In its specific embodiment, the wastewater containing fluoride, mixed acid, "spoon oxide and/or 首先0Ε is firstly used with 27 as described above

Right to taste the waste of the sulphate 200812916 Anion exchange resin is contacted to handle. Thereafter, the pH is adjusted to pH 4 or above by adding a base such as a hydroxide. The pH can be adjusted by adding a solid base such as NaOH to the wastewater. The pH can also be adjusted by adding a concentrated alkali solution. Alternatively, the pH can be adjusted to a more alkaline pH of 8 or above. As for the pH of the other wastewater, it can be initially adjusted to a high of 10-12 before further processing. After the initial pH adjustment, there is no need to further adjust or control the pH of the water as the treatment continues. The pH adjusted wastewater is then subjected to a modified precipitate as described above or contacted with a cation exchange resin in the form of calcium as described above and subjected to further processing steps as described above.

π, 〇 〇 〇 半 J J J J J 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的If the fluoride-containing wastewater is known to also contain ammonium ions, the pH should be initially adjusted to a pH of 1 (between M2 and degassed ammonia. The presence of money ions is used to measure fluoride by some methods, therefore, Further processing waste: 刖 reducing the ammonium ion content or removing it as desired. The wastewater may initially contain particulate matter. The particulate matter of the present invention may be removed. However, by the method of the present invention = as needed The particulate matter is removed by filtration. For example, before the presence of the colloidal oxidized bismuth is required to be treated by the filtration method, it is removed by filtration. After treatment to reduce the fluoride content, local regulations or this Additional use of water for the intended use of water: membrane filtration, reverse osmosis and/or ρΗ adjustment. ^, including 28 200812916 [Embodiment] The present invention relates to reducing gas in wastewater produced by industrial processes Content, wherein the wastewater may contain other anions, particularly anions such as salts, sulfates, and other acidic species such as acetates and other buffer anions; dissolved cerium oxide, Silicate containing fluorine and other fluorinated silicate stone dioxide Xi species; and / or may include ammonia, ammonium fluoride, or ammonium ions.

In general, the method herein can be applied to any water stream that requires removal or dialysis of fluoride. The method herein is particularly beneficial for applications where the initial fluoride content is greater than 100 ppm, greater than 1000 ppm, greater than 10,000, or greater than 30,000 ppm. In a particular embodiment, the invention is directed to reducing fluoride in the wastewater produced by semiconductors, such as from cleaning and etching processes. These wastewaters are complex mixtures and may include mixed acid engraving components such as nitrates, sulfates and/or acetates and other organic anions, dissolved and/or colloidal oxygen cuts, various metal ions, metal oxides, various volatilizations) Raw organic species, multiple dissolved organic species, and buffered oxide surnames such as ammonium hydroxide, ammonia and ammonium fluoride, and surfactants. The presence or absence of components in the waste Jc may interfere with the use of conventional precipitation methods to remove fluoride, such as the use of added water-soluble dance salts to form low solubility calcium carbonate. Typically, wastewater streams from several different semiconductor manufacturing or cleaning steps or processes can be treated to remove fluoride, and the wastewater produced is typically one that may contain one or more of these interferent species. Complex because specific manufacturing equipment is available at 29

200812916 Process, the composition of the fluoride-containing wastewater + and the fluoride content itself can vary significantly with time. The fluoride content in a particular wastewater batch can be measured prior to treatment to reduce the enthalpy of the flow, = lj. However, because it is difficult to track all of the components containing strontium that may be present and interfere with fluoride removal by any practical method, the material may be adjusted according to the fluoride content of the present invention - and when the interference is present, Substantial reduction or removal of interferents to achieve a fluoride content of less than 10 ppm can provide significant benefits. The wastewater is typically acidic with an initial pH of less than 4, and the wastewater is more blood type and has an initial pH of less than 3 and in many instances has an initial pH of less than] and the resulting fluoride-containing wastewater can also be discarded, for example, by mixing mixed acid. The logistics is alkaline with the waste stream containing the test. The process of the invention can be applied to fluoride containing waste streams of varying initial pH. The fluoride content in this wastewater typically ranges from several tens of mils up to tens of thousands of ppm of I compounds. Fluoride can exist in free-state ionic form, in more complex species such as ton or SiF6, or in some way with organic or inorganic species (such as dissolved organics or dissolved inorganic species or polymer species containing dioxide) . "Fluoride" - the term generally refers to fluoride ion (F·), hydrofluoric acid (hf) or any other chemical species containing fluorine and which can produce or release fluoride in wastewater streams, including fluoride salts and more complex I-containing anions such as sulphuric acid salts, transbasic fluorides, and cerium fluoride. The process herein is particularly useful in wastewaters containing mixed acid water having an acidic pH, typically less than at least one anion, fluoride. This waste PH 4, and in addition to fluoride and chloride ions and more typically in addition to fluoride and chloride ions 30 200812916

Two or more anions are also included. The mixed acid wastewater may include one or more of nitrate (nitrate), acidate (phosphoric acid), acetate (acetic acid) or other Wei (usually), or two or more Wastewater that can be treated by the method of the present invention may include dissolved cerium oxide species, which may be S1 〇2, Si(0H)4, SiF(OH)3, SiF2(〇H)2, SiF3, among others. (OH) and SlF4 forms, either in the form of neutral or anionic species and SiF6· and soluble polymeric silicates and fluoroantimonates (eg species containing more than one ruthenium atom). Wastewater may also include buffered Oxide etchant components, such as antimony telluride, ammonium A and ammonia, and surfactants, dispersants, and the like wastewater can also include a variety of organic species (eg, solvents), metal ions, and a variety of other Complex anions of fluorine - the name used again "stoichiometry, its use in the art - refers to the relative atomic or ionic number in a particular chemical species. This name is used to refer to a specific atom. Or the relative molar number of ions, which combine to form a chemical species of a chemical formula. For example, - Mo Er ^ 2 : 2: Ear F-bonded to form a salt called salt, thus a fluoride ion per mole. F combines to form a stoichiometric Ca2+ amount of Cah Calcium ion for " This name is used herein to mean "," and assumes the formation of CaF2. The name used in this article is deducted to less than a stoichiometric atom or ion molar amount, which is specific. The chemical species is used to remove sores; it is used to form a reference atom or ion to the species. Therefore, the amount of the ear is less than 1/2 of the molar amount of fluoride. For example, a hypothesis is formed. In one aspect, the present invention provides an improved fluoride precipitation method 31 200812916, in which the fluoride of the ten sinks is substantially immobilized on the residual solid that has been separated from the treated water. If the 帛pti 7 compound is less than 靡mg, the fluorinated material is smear of the bristles/open %, and the fluoride is substantially fixed. In the improved sinking method, the soluble (tetra) salt is added. To the wastewater to introduce the word ions into the water I, the amount of converted ions is typically in the wastewater. The molar amount of about 50% of the fluoride (ie, relative to the equivalent of the compound - should be reacted with the two-mole fluoride to form < Μ). Depending on the presence of interfering substances present in the water and Depending on the amount, additional calcium ions may be required to achieve the desired reduction in fluoride content. However, it is generally preferred to avoid the amount of calcium ions in excess of the amount required to achieve the desired fluoride reduction. It is a water-soluble salt which can cause the production of a solid which remains liquid or in the form of a gel. It is more difficult and expensive to handle and dispose of. After the addition of the salt, the mixture is mixed or batched to promote interaction of the combined additives and to obtain a stable measured fluoride ion content. It has been found that the addition of salt to the sulphate-containing wastewater results in an initial wide variation in ion content as measured in water, as measured using a fluoride-selective ion probe. These changes can be caused by the I (I) and the incomplete mixture caused by the I ion measurement. Continue mixing until the nominal measured fluoride content is stable. This is a symbol of complete reaction and uniform mixing of the additive. Mix this combination-segment time range, which can be longer from i, minutes or if necessary, more typically 5, using 15_3 minutes or longer mixing time. However, the usual example is that the process time (i.e., mixing time) can be reduced by adding a higher amount of calcium ions. Thus, the amount of calcium ion added can be adjusted to meet the needs of a particular application to achieve the desired fluoride reduction using a convenient processing time at an acceptable processing cost. Although the fluorinated | bow is in the water and has a six-processing (four) low reading degree, it is not found in the economical version. In the method of the present invention, the fluorinated handle which has been added and promoted to adsorb and/or precipitate out in the treated wastewater, and the cation of the fluoride content is reduced. : The father changed the resin to contact. The amount of cation exchange resin added is in the range of about 4% of the total volume of water to be treated, about G.G5%s of treated water.

— 疋 depending on the fluoride content present and/or the amount of soluble calcium salt added. The amount of cation exchange resin added ranges from about 1% to about 5% of the volume of treated water. Using this improved sinking method, it is possible to achieve more or less, 75% or more, 9% or more, 99% or more, 99 or more vapors in the wastewater. The precipitation process is particularly useful for reducing fluoride levels in wastewater including vapor content greater than 1.0 ppm, in wastewater including fluoride levels above 1000 ppm, and in wastewater including fluoride levels above 1 M (10) ppm. In a particular embodiment, when the calcium chloride added is 30 weight percent of the aqueous solution, the volume of cation exchange resin added is equal to the volume of calcium chloride solution added. The combined additive is mixed or agitated until a stable reduced fluoride content is obtained for 1-30 minutes or longer. Other calcium salt addition steps may be followed, if desired or desired, followed by cation exchange resin to provide reduced fluoride levels or reduced processing time. Thereafter, the treated water and solid having a reduced fluoride content are separated. The precipitated material formed in this method is a low water content solid rather than a colloidal 33 200812916. The TCLP (Toxic Characteristic Dissolution Procedure) method can be used to measure the fluoride content that can be filtered from the solids separated from the treated water. The benefits of certain embodiments of the method of the method are as follows: during the treatment process, the residual solids are formed, the unacceptable fluoride content is insoluble and the fluorinated content can be classified as non-hazardous waste. The residual gas-containing solids produced in the demonstration application of the method have been shown to meet the requirements for non-hazardous waste disposal (sub-heading classification D TCTC method.) ❿ TCLP test procedure described in us EpA · (d) towel, rod used to evaluate the solid waste test method, physical / chemical method ^ and fine method 2510 or 3520, using TCLp solute filter which has been extracted with solvent by chlorohydrin in ρΗ > ι and PH < . Although not intended to be limited by any particular theory, the salt transfer from the wastewater is mainly on or in the cation exchange resin (possibly combined with strontium or sodium ions) and immobilized on solids and cannot be easily granulated. Out. The fluoride may also precipitate calcium fluoride, such as calcium pentoxide, and may be sodium fluoride, or may precipitate in or on the resin. The amount of water-soluble calcium salt added to the wastewater in the method of the month is usually based on the amount of vaporized water in the luxury water or estimated in the wastewater. The amount of fluoride in the wastewater can be measured or estimated by any method well known in the art prior to application to the steps of the process to select the amount of water soluble salt to be added. A special fast fluoride measurement method is the spads ion-specific electrode water, one-h'L〇Veland, CO). It can be directly in the wastewater or treated waste fluoride ion. The accuracy of this direct fluoride measurement on wastewater 34 200812916 2 has been obtained by ^p =. When the higher vapor content is present, the second is also == sample. However, it is preferred that the "fourth" system is used in the "fluoride probe" of the wastewater sample. The use of the liquid is well known in the art (Ms- and Shuangzhong Mr (1968)) 'Using total ionic strength adjustment Buffer (TISAB) ^ measure the vapor in the water supply '' (such as Researeh, v〇i. 4〇,

ο. 7). Depending on the other components present in the wastewater, the _ sub-measurement without buffer can provide a reading of the fluoride concentration of the virtual high. When the amount of fluoride in the produced wastewater remains fairly constant over time (or for each desired batch:: water batch), the fluorine in a particular batch can be estimated based on the well-known range of measured analytes in the wastewater. The amount of the compound. : Shi:: The compound temperature has been known from previous measurements or can be based on the estimated material 'measurement of vaporization does not need to be followed by the method of this article: Second: the amount of soluble salt added can be Depending on the maximum amount of sucrose in the wastewater to be treated from a particular source, it is not necessary to make a large excess (iv) to achieve a fluoride shift in %. It is possible to add about the amount of vapor to the amount of valence that can be present. 50% (the amount required to form a post relative to fluoride) will not cause unnecessary addition to other unacceptable negatives, such as chloride ions entering wastewater or solid waste. The best is to reduce Add X water-soluble dance salt to provide the desired amount of Duns content, and the treatment time can be reduced by adding excess #5 salt. Therefore, it is better to limit the addition of any excess salt to the highest level. Exceeding Chemistry 35 200812916 3 I In particular embodiments of the methods herein, it has been found that sub-input: stoichiometric amounts of calcium ions can cause efficient removal of fluorine-separated salts from wastewater in specific embodiments, Avoid adding too much water Solubility

: Ben: In another view of Ming, the gasification in the wastewater has been reduced by direct contact of the fluoride-containing wastewater with the cation exchange resin in the form of calcium. This method does not require adding any water-soluble salt to the wastewater. After separation from the treated water, the residual fluoride-containing resin produced in this treatment step can be used to immobilize the fluoride on the I babe as described above in the modified sinking method. The amount of cation exchange resin added in the form of calcium can generally range from about q to about 1% by volume of the total volume of water to be treated, depending on the fluoride content present in the water. The amount of cation exchange resin added to the crucible of the alumina ranges from _ 1% to about 5% of the volume of water. The cation exchange resin can be added as a series of separable samples with agitation to achieve the desired reduction in fluoride content. Fluoride reduction of 5% or more, 75% or more, 9% or more, or 99% or more can be achieved using this method. This method reduces the fluoride content in wastewater containing fluoride content higher than 100 ppm, in wastewater containing fluoride content higher than 1000 ppm, and in wastewater containing fluoride content higher than 1 〇, 〇〇〇 ppm. Particularly useful. Generally, any type of cation exchange resin in the form of calcium can be used. Preferably, the cation exchange resin is a strong acid cation exchange resin. The cation exchange resin, as is well known in the art, can be prepared from a cation exchange resin in acid form or in a sodium form by contacting the cation exchange resin with a solution comprising calcium from 36 200812916. Although not intended to be limited by the special theory of Ren Kesheng 2 f, salty and calcium-containing cation exchanges && s 猎L hunting by direct major #入/阳杂 | , =1) and the second resin is in the resin or in the upper lip and cannot be easily filtered out from the resin. Also referred to as "column, when sodium ions are present in the wastewater, some of the calcium ions in the cation exchange resin are precipitated in or on the resin from the sodium/sodium difluoride content. Some of the Si: The improved method of sinking can be used to remove the separation. It is also known by the technique to reduce the vapor content by directly contacting the wastewater with the cation exchange resin of the formula (IV). A method of degassing ions such as reverse osmosis bonding, for example, may be followed by one or more reverse osmosis steps via a modified/infantastic method herein or after treatment with wastewater in contact with a calcium-containing cation exchange resin. In other methods provided, the mixed acid wastewater containing the a compound is pretreated to remove or reduce one or more dry species content prior to removal of the large amount of fluoride, and thereafter by (iv) and/or cation exchange steps Treatment to reduce fluoride content in wastewater. Interferants can generally be organic or inorganic species and they can be ionic or neutral species. It is not intended to be limited by any particular theoretical practice. Anions other than fluorine, such as sulfates and/or phosphates; and/or dissolved cerium oxide-containing species such as citrate, fluoroantimonate, cesium fluoride, and polymeric dioxides containing soluble or dispersed Alfalfa species, which may additionally contain fluorine. Interfering substances may additionally contain organic species. One or more interfering substances prevent fluoride from reacting efficiently with calcium and are mismatched 37 200812916 Fluoride and its removal from wastewater' Less than 1 〇ρριη and preferably reduced to a content of 1-3 ppm or less. Interfering substances may adversely affect the ionization of fluoride (ie, fluoride species decomposition to form fluoride), and may adversely affect chlorine Ionization and / or inhibition of insoluble fluoride salts, especially calcium fluoride formation. The function of reducing the content of such interferences is to promote the reduction of fluoride content in wastewater. In an embodiment, the wastewater is removed or reduced in contact with the anion exchange resin to remove or reduce the content of one or more of such interferers. The anion parent exchange resin is preferably a macroporous anion exchange resin. The ion exchange resin is preferably in the form of a main chloride ion. The anion exchange resin preferably comprises a polymer having a hydrophilic backbone. In a particular embodiment, the macroporous anion parent exchange resin is formed from a hydrophilic polymer and comprises Dispersed species include macroporous anion exchange resins which oxidize Fe(III) such as -Fe2〇3 (magnetic hematite), such as those described in U.S. Patents 5,9,146 and 6, i7i,489 It is a magnetic ion exchange resin. The macroporous anion exchange tree can be a strong base anion exchange resin in which about 10% to about 50% of iron oxide (πι) (based on the total weight of the resin) is dispersed therein. Can be _

FhO3' is dispersed as a solid dispersant such as a pigment dispersant during resin preparation. Without wishing to be bound by any particular theory, it is now known that the anion exchange tree is known to be a macroporous anion exchange resin by anion exchange, adsorption or a combination of these methods to remove or reduce one or more of the above. Interfering substance, amount: In a specific embodiment, when an anionic parent-replacement resin is formed from a hydrophilic polymer, adsorption of an organic or inorganic hydrophilic species promotes the function of the resin. In other embodiments, if the anion exchange resin comprises dispersed Fe(III) oxide, the mismatch reaction of Fe(III) with an organic or inorganic species and/or the adsorption of Fe(III) oxide may promote the resin. Features. In a specific embodiment of the 4-inch crucible, the macroporous anion exchange resin is a copolymerization of glycidyl methacrylate and divinylbenzene (also known as divinylbenzene) and other monomers are used as needed. The triammonium quaternized chloride functionalization is described in U.S. Patent Nos. 5,900,146 and 6,171,489. In a specific embodiment of t, the anion exchange resin is a copolymer of methyl acrylic acid, K glycerol I oxime, monovinyl benzene, and vinyl ethyl benzene (also known as ethyl vinyl benzene). It is functionalized with a chloride that is quaternized with trimethylamine. In a still more specific embodiment, the anion exchange resin is a copolymer of glycidyl methacrylate, divinyl benzene, and vinyl ethyl styrene, and a quaternized chloride of dimethylamine. The functionalization, and 50% or more of the monomers incorporated into the copolymer, are glycidyl methacrylate. In another more specific embodiment, the anion exchange resin is a copolymer of methacrylic acid decyl methacrylate, diethyl benzene benzene, and vinyl ethyl benzene, which is quaternized with an If amine. The compound functionalized and the monomer in which the copolymer is exchanged is between 50% and 80% of glycidyl methacrylate. The macroporous magnetic anion exchange resin which can be prepared in the method of this month and which is substantially as described in U.S. Patent (10), I" and 6,171,489 is now available under the trade name MIEX®HW1201 (〇rica Australia pty , Ud,

AuStralia) is commercially available. The macroporous anion exchange resin preferably has an average particle size of from 30 to 10,000,000 μm and an average particle size of 3 (10) μm or less. In a more specific embodiment, the anion is replaced by a macroporous magnetic anion exchange resin comprising ~Fe2?3 in the form of a chloride. After the J is removed or the interferent is removed, for example, after contact with the anion exchange resin, the soluble 35 salt and cation exchange resin as described above are used to precipitate the fluoride. The amount of calcium ions added is typically about 5 G% of the molars of the fluoride in the wastewater (one mole should react with the two moles of fluoride to form CaF2). It has been found that in comparison to the precipitation method of the prior art, it is not necessary to add an excess of soluble calcium salt in the process herein. However, adding excess calcium ions reduces the processing time required to achieve the desired reduction in fluoride content. The above mentioned to ij ‘but it is not intended to be made by any theory, and the removal of interferents promotes the use of fewer words. After the addition of (iv), the mixture is mixed or stirred to promote the interaction of the bound additives. The (IV)-containing water is then contacted with a cation exchange resin in a particular neat or about form which promotes calcium fluoride adsorption and/or precipitation and functions to reduce the fluoride content in the treated wastewater to 10 ppm or less. The amount of cation exchange resin added ranges from about GG of 5% of the total volume of water to be treated to about 10% of the volume of treated water, the amount of sucrose present, the amount of soluble salt added. And processing time. Depending on the amount of resin added and, more importantly, the particle size of the cation exchange resin used, this method can be used to achieve the fluoride content of & Mix or mix the additions of the mixture ", minutes or more until a stable reduction in fluoride content is obtained. Thereafter, the treated water having a reduced fluoride content is separated from the solid. As widely used herein, the name cation exchange resin, as understood and used in 40 200812916 f * refers to the exchange of cations in the solution: the cation exchange, the cation exchange The resin can function in the methods herein except for the tree scorpion in the form of hydrogen. More specifically, a cationic exchange resin in the form of a king sodium ion or a calcium ion can be used in the method of the present invention. Both gel-based and macroporous resins can be used. A full bead resin or a crushed resin can be used. Strong acid cation exchange resins are preferred over weak acid cation exchange resins. In a specific embodiment, a strong acid cation exchange resin having a minimum capacity of 2.Oeq/L in a sodium form on a gel basis, such as IR-120 (Rohm and Haas), can be used. In another embodiment, a powdered strong acid cation exchange resin which is ground to a nominal average particle size of 3 〇〇 (4) in a nano-form can be used. In particular, it is possible to use a styrofoam functional group and a powdered styrene DVB gel-based cationic resin having an average particle size of micron in the form of nano, which is now available under the trade name MIEX@HW3251 (〇rica Australia Pty. Ltd, Australia) ^# As mentioned above, in the improved precipitation process, a cation exchange resin is added after the calcium has been added to the wastewater, this addition promotes reduction of the fluoride content in the water and immobilization of the fluoride on the solid. The efficiency and extent of fluoride reduction in wastewater is at least somewhat dependent on the particle size of the resin, the amount of resin added, and the contact time. In the presently preferred method of the present invention, the cation exchange resin separated from the treated water having a reduced vapor content and the adsorbed or precipitated salt are not regenerated. Collect this solid material and dispose of it under appropriate conditions. Separated solids include: to remove dry (four) and not separated from water), cation exchange resin and any vaporized salt of the sink (for example, and may be called 200812916 ▲ has been found to be used in the method of this article A form of cation exchange resin. The name "in the form of calcium" refers to a cation exchange resin in which calcium is at least dominant in the resin. The preferred cation in the form of calcium ions is known to be in contact with excess calcium ions. To remove any other cation content that can be measured. A cation exchange resin in ionic form can be prepared using techniques well known in the art. In a particular embodiment, the cation exchange resin in the form of ruthenium can be rendered by Proton or Na form

The cations are prepared by contacting the resin with a saturated calcium chloride solution. More particularly, the cation exchange resin in the form of calcium is obtained by allowing 300 ml of IR_12 形式 form (Rohm & Haas) with an excess of saturated calcium chloride solution (25 〇

=1 〇〇 / q calcium is dissolved in 4 liters of deionized water. The contact is prepared by rinsing with deionized water. The vapor-containing mixed acid wastewater may include ammonium ions, peroxides or a compound thereof. These species can be reduced or removed in the wastewater treated by the process herein. For example, ammonium can be removed from P = by taking the pH of the wastewater as PH 1 〇 12 (by adding the test as described later) and deaeration of ammonia. Peroxides and other volatiles can be treated as described herein. Two: The effluent is removed by passing the air through the air for a sufficient period of time. Others known to remove ammonium ions and/or remove peroxides or other volatiles 2 can be used in the present invention without being incompatible with subsequent ion exchange steps and removal of fluoride. S fluoride mixed acid wastewater blood spleen, "a /, type will have a pH of less than 4, although in the treatment of the 'mixed waste Hua ^, ^ Lai /), L can produce higher pH wastewater. In a specific embodiment of 4 inches, the pH of the U T water is initially adjusted to 4 or greater. 42 200812916 pH adjustment is not required, but can be beneficial for the design of a particular water treatment system. The method herein acts to reduce fluoride in wastewater having an initial pH ranging from less than 1 to over J 。 . However, as mentioned above, initial adjustment of the wastewater to pH 10-12 can be used to reduce or remove ammonium ions such as ammonia. Furthermore, it has been found that initially adjusting the pH of the wastewater to an alkaline pH, such as pH 8 or above, facilitates the removal of fluoride by the methods herein, at least to some extent, because when the initial pH of the wastewater is alkaline, The floc formed during the process is usually large. The pH of the fluorine-containing wastewater can be adjusted to pH 4 or above by adding a test, which can be added to the wastewater by adding an alkali salt (for example, NaOH is preferred, but K〇H can also be used) or by adding an alkali salt. The aqueous solution is achieved. It is not preferable to increase the volume of water to be treated, so it is preferred to adjust the pH of the wastewater by adding a selected amount of solid alkali salt or by adding a relatively concentrated aqueous alkali salt solution (for example, 20% by weight or more). . It is preferred to use an alkali salt other than the basic calcium salt. It is preferred not to introduce calcium ions into the wastewater prior to the anion exchange step of the process. For example, the use of calcium hydroxide (which can be provided in various forms of lime) is less than ¥. In the first step, the wastewater is contacted with an anion exchange resin used to remove the interferent, and the vaporization is not substantially removed directly. In the wastewater as described in Figure 4, the fluoride is removed to the eve of the evening by exchange or adsorption in the first treatment step. After the wastewater and the anion as described herein were contacted, no significant decrease in fluoride ion was observed, as measured using a fluoride ion selective electrode (Hach). The methods herein are particularly suitable for including moderate (4〇ppm to ^00 43 200812916 ppm), moderately high (!, 〇〇〇 to 5,000), high (5,000 to 1 〇〇〇〇ppm) or very high fluoride ( Wastewater at a concentration of 10,000 ppm or higher. The method herein may optionally be combined with a reverse osmosis process to further reduce the fluoride content in the water that has been separated from the solids of the sink. U.S. Patent 6,338,803 describes a reverse osmosis process that can be used in combination with the method of the present invention. For example, a multi-channel reverse osmosis method can be used. The waste stream from the fluoride-containing reverse osmosis membrane can be recycled back and mixed with the incoming fluoride-containing wastewater to be reprocessed to remove fluoride. In general, any reverse osmosis method for reducing the fluoride content can be used. A reverse osmosis polishing step can be applied to 1-3 ppm of treated water to further reduce the fluoride content to less than ppm. If this step is used, the concentrate from the reverse osmosis unit can be recycled back to the initial wastewater stream for continuous processing because it will be considerably more dilute on the fluoride than the original wastewater stream. After treatment to reduce the fluoride content, the treated water can be subjected to other purification steps, including film over-pressure, reverse osmosis, and/or pH adjustment, depending on the intended use of the water or the intended use of the water. For example, 'If you want to reduce chloride, the treated water can be combined with an anion exchange resin in the form of (7) 3• (for example, macroporous anion exchange resin MIEX_W12G1 (trademark, 〇Hea Aus^a,

Pty., Australia) contact. The resin used to reduce the chloride will be in the form of chloride and, if necessary, recycled for use in the initial pretreatment of the wastewater, as described herein below. Care In some embodiments, the wastewater is initially treated with an anion exchange resin of macroporous anion exchange grease. As used herein, % 44 200812916, "anion exchange resin, as it is understood and used in the art, refers to a resin that acts to exchange anions in solution. In general, any anion parent exchange resin (except for inclusion) Those of the fluoride ion may function in the methods herein. More particularly, the anion exchange tree in the form of chloride ions, especially those which remove potentially interfering sulfates and/or phosphate ions, It is useful in the method of the present invention. A strong base anion-replacement resin in the form of chloride ions is preferred. Both type 丨 and type 2 strong base and weak base anion ion exchange resins can be used. • Anion exchange resin is a macroporous resin Preferably, the term "large pores" as used herein, as it is used broadly in the art and generally used, refers to a solid or polymer comprising macropores having a large diameter diameter ranging from about 50 nanometers to about megameters. Macroporous resins have a generally increased total surface area for contact with liquids (e.g., wastewater) as compared to non-macroporous resins. The anion exchange resin has an average particle size of 300 μm or less, preferably. This resin can be used in the physical form of the whole bead or in the form of crushed beads or powder. A wide variety of macroporous strong base anion exchange resins in the form of chlorides of Form 1 and Form 2 can be used and the effect is at least partially related to the size of the resin particles having a smaller particle size which results in a faster reaction rate (exchange rate). The less preferred anion exchange tree Moonbee includes a type 2 weak base anion exchange resin and a non-macroporous resin such as a gel based resin. In a particular embodiment, the anion exchange resin is a magnetic macroporous type 1 strong base anion exchange resin having an average particle size of 300 microns or less in the form of a chloride. The name, the type j and the type 2 anion exchange resin are each referred to as a resin each containing a trimethylammonium group and a dimethylethanolamine group on the resin. 45 200812916 Preferably, the anion exchange resin comprises a hydrophilic polymerization. As used herein, the term "polymeric" refers to a polymer that is at least partially hydrophilic, and the name "hydrophilic" is generally a molecular species that exhibits affinity for water or In part, it is often due to the formation of chlorine bonds. Hydrophilic species are recorded < contain polar enthalpies and tendencies (4) 纟 its polar species show affinity. For example, hydrophilic polymers can be linked to other hydrophilic species or polar species For example, hydrophilic polymers can adsorb hydrophilic or polar species. The resin polymers herein are more hydrophilic than conventional acrylic and styrene-ion exchange resins. Polymers used in anion exchange resins Generally described as having a polymer backbone comprising one or more pendant groups attached to the backbone for crosslinking and one or more attachments The polymer backbone carries a spacer group that has been (or can) interact with the anionic parent for a position such as a pendant group of a quaternary ammonium group. Additional 1, these polymers may further comprise no interaction to crosslink and no carry VS a thiol backbone monomer. In a particular embodiment herein, the spacer group between the agglomerate backbone and the anion exchange site of the functionalized monomer is hydrophilic and is typically in acrylic acid or It is more hydrophilic to find in the styrene polymer. In addition, the hydrophilic side group can be incorporated into a polymer backbone monomer that is hydrophilic or carries one or more hydrophilic groups. In a particular embodiment, the hydrophilic polymer comprises a polymer carrying a hydrophilic side group. Examples of certain hydrophilic monomers that can function with anion exchange sites include, in particular, glycidyl methacrylate, dialkyl. Aminoalkyl methacrylate, dimethylaminoethylmercapto hydrazide, 2_vinyl-4,4-dialkyl oxazolone, 2_vinyl _4,4•dimethyl 46 200812916 ki-5-oxazolidinone, acetamidine acetone Enamines, vinyl benzoate, vinyl benzoate halides and vinyl benzoate chlorides. Hydrophilic spacers, pendant groups and monomers include, in particular, one or more ester linkages, one or more a hydroxide group, one or more guanamine groups, one or more Dai group, one or more amine or imine groups or a combination of such groups. In particular embodiments herein, The macroporous anion parent-replaceable resin useful in the present invention comprises a copolymer comprising glycidyl methacrylate and a crosslinked polymer and a copolymer comprising glycidyl methacrylate and a crosslinked polymer and a backbone polymer. In a particular embodiment, the macroporous anion exchange resin useful in the present invention comprises a monomer comprising 50% or more copolymer of glycidyl methacrylate monomer. In other specific embodiments, The macroporous anion exchange resin useful in the present invention comprises a monomer comprising a 75% or more copolymer of a glycidyl methacrylate monomer. In other specific embodiments, the macroporous anion parent-replaceable resin useful in the present invention comprises a monomer of a copolymer of mercapto acrylate glycidol having a monomer comprised between 〇% and 80%. The cross-linking monomers can be selected from a wide range of monomers, including divinyl monomers such as diethylbenzene, ethylene glycol dimethacrylate or polydiethylene, as described in U.S. Patent Nos. 5,900,146 and 6,171,489. Acryl methacrylate or methylene bis acrylamide, ethylene glycol divinyl ether, and a polyvinyl ester compound having two or more double bonds. A wide range of functional monomers can also be used' in many others including glycidyl methacrylate, vinyl hexyl chloride, decylaminoethyl methacrylate, N,N-dimethylaminopropyl Acrylamine, and mercapto acrylamide, vinyl hydrazine, diallyl 47 200812916 amine and its quaternized derivatives, and N-vinylformamide and its hydrolyzed derivatives, And methyl acrylate and its derivatives. The backbone monomer includes any monomer that can be polymerized by free radicals, such as styrene, vinyl toluene, methyl methacrylate, and other acrylates and methacrylates, particularly substituted and carried one or more Hydrophilic group.

In a particular embodiment, the macroporous anion exchange resin is a magnetic anion exchange resin comprising dispersed iron oxide. The magnetic anion exchange resin is used to produce a secondary agglomeration of the resin for rapid precipitation, or the resin can be removed or separated from the liquid phase by magnetic removal. The resin (magnetic resin) doped with magnetic particles is rapidly agglomerated and precipitated due to magnetic attraction. Magnetic polymer beads, in particular magnetic polymer beads of the type of alkaloid anion exchange resin in the form of a chloride, are described in U.S. Patent No. 6,171,489, the disclosure of which is incorporated herein by reference. Into this article. The term "contact" as used in the description of the method herein is used broadly to mean any method of bringing a liquid waste stream (e.g., a waste water stream) into contact with a solid such as an ion exchange resin. The solid or resin is added to a certain volume of waste water. Further, waste water may be added to the solid or resin. The waste water may pass through to accommodate the solid or resin, and may be used in the "contact" step of the present invention. Any method of contacting the solids herein with a liquid, such as the wastewater herein, is well known in the art. Depending on the method used to achieve the contact, the method of mixing the solid and liquid components combined with the mouth can be used to ensure The liquid has sufficient S-contact with the solid particles. In a specific embodiment, the solid, the resin, and the hydrazine and its hydrazine additive are substantially added to the wastewater in the batch-human process by separating the /, U body, for example, using a certain 48. 200812916, Filtration method to remove treated water. In this particular embodiment, any resin, solids, and other additives are contacted with the wastewater in a lidded container. In this embodiment, the macroporous anion exchange resin is selectively separated from water prior to the addition of the calcium salt and the cation exchange resin.

Those skilled in the art will be aware that the contact step will cause heat or gas release, which will be required in the case of the use of the #container and its 匕η. The process of the present invention is carried out at any convenient temperature and does not require heating or cooling of the wastewater. This method can typically range from 5_4〇. It is carried out at ambient temperature, but more typically at temperatures from 2〇 to 25. Take it down. This method is most conveniently carried out in open-capped vessels, tanks or columns under weekly pressure to avoid the accumulation of gas by the released gas during processing. The method herein can be carried out without applying external cooling, however, depending on the components present in the wastewater and the heat that can be released during processing, the process vessel or tank can be cooled to maintain the desired in the vessel or tank. temperature. θ In a specific embodiment, the anion and cationic parent-replacement resin are combined with any precipitate during the treatment, and the combined solids are separated from the treated wastewater. The @(四) residue is dried and suitable. Disposition. In another embodiment, the anion exchange resin that removes the interfering material during the pretreatment step is separated from the wastewater prior to contacting the sink source and/or contacting the cation exchange resin. When a magnetic anion exchange resin is used, magnetic separation can be used to separate the resin from the treated water. The anion exchange resin that has been separated can repeat more than one batch of wastewater. Further, the separated anion exchange resin can be regenerated by treatment with brine and reused for other treatments. In this example, the extract from the anion exchange resin 49 200812916 must be disposed of properly. In a preferred embodiment, the anion exchange resin is not regenerated. In a particular embodiment, the step of contacting the wastewater with the resin or other solid may be carried out in _ or a plurality of open tops, wherein the resin or solid has been packed into the column and passed through the tower. The wastewater is in contact with the resin or solid. If desired, the wastewater can be recycled through a single column or through a series of columns to achieve a desired reduction in vapor content. Specifically implemented herein: <<>> using a resin-containing column until it is depleted by removing the interfering or fluoride. In the specific embodiment of the feed, the __ series of this column can be used for continuous wastewater treatment, and the depleted resin-containing column in the crucible can be switched to the new column without significantly interrupting the treatment process. The depleted resin column can be, for example, capped and suitably disposed of. The method of the present invention optionally includes a step of adjusting the cation, for example, a pretreatment step prior to the contact of the pen anion parent-replacement resin or at the anion exchange = or after. The name, adjustment, and use are emphasized to allow the 2 step to be added (or acid) to select (ie, adjust) the pH of the wastewater. In the implementation of wealth, before the exchange of money with the yin (four) at the beginning of the fluorine ^: as needed to adjust the yang. In another specific embodiment, the pH is adjusted as needed during or after the == treatment. In yet another fat, the pH adjustment step is used in the addition of a soluble calcium salt followed by addition to a cation exchange tree. In a further embodiment, a pH adjustment step is required as needed prior to contacting the cation exchange resin in the form of _fI#^. In an alternative embodiment of the invention, when more than about 20, 〇〇〇ppm fluoride is present in the wastewater in the water 50 200812916, the wastewater may be water or more prior to treatment as described herein above. It is diluted with wastewater containing a lower fluoride content. In particular embodiments, the methods of the present invention may each exclude the following: (two or more) pH adjustment steps during wastewater treatment; extraction of continuous solid precipitates;

Adding calcium fluoride seed particles to promote calcium fluoride formation and precipitation; adding agglomerating agents, especially polymer solutions; recycling the sediments to other wastewater containing dance or magnesium ions and vapors; adding phosphate Adding carbonate; adding phenolic type phenol_formalin chelating resin; adding aluminum ion; using cation exchange resin in the form of ing; using cation exchange resin of yttrium, zirconium, titanium or ytterbium type; using i-based - decane type adsorption resin; using rare earth metal oxide hydrate type chelate resin; using Ming salt type chelate resin; cation exchange resin and multiple use for continuously contacting wastewater with more than one cation exchange resin The step of using a strong anion resin in the form of a sulfate with a strong acid cation resin (exchanged as a cation with a cation) (to remove the hexafluoride acid 51 200812916 salt), having a tertiary amine group as a free base a form of weak base anion exchange resin (to remove acid) and a weak base anion exchange resin in free form (to remove a continuous step of contacting with hydrofluoric acid; using a strong acid cation exchange resin exchanged with aluminum; or adjusting the wastewater to an alkaline pH (pH 8-9) to hydrolyze fluoroantimonic acid and miscible metal fluoride, followed by hydroxide ( 〇ίΓ) Form 2 strong base anion exchange resin column. In a particular embodiment of the method of the present invention, one or more of the following may be further included: one or more reverse osmosis steps are applied to the wastewater treated to reduce the fluoride content by the methods used herein to further reduce the fluoride content or To remove or reduce the content of other undesired components; or to treat the wastewater obtained by the process herein and to separate the fluoride-reducing wastewater from the added resin and the solids added or formed during the period with the macroporous anion parent The step of changing the resin or contacting the cation exchange resin. The Fig. ® formula illustrates the processing system for carrying out the method of the present invention. This system is clarified for batch processing. Suitable size open lid containers or tanks (10) are equipped with certain mixing or mixing equipment. This container is illustrated as having a mechanical agitator (12), but may again be provided - a gas (e.g., air) supply for mixing. In general, any mixing or mixing equipment can be used. A wastewater flow liquid connector (I4) is provided to the tank. Provide - introduce a sigh of selected anion exchange resin volume (16). Also provided is a device that introduces a selected volume of soluble salt solution (e.g., Cad, 18). In addition, an apparatus for adding a Kolo salt in a solid form is provided. Furthermore, an introduction of a selected cation exchange tree is provided 52 200812916

Device or volume of fat (20). Any use that introduces a solid or liquid into the middle can be used. In the illustrated system, all components are added to a single vessel or tank and mixed. The combined solids and fruits (2 2) are passed through a liquid-solid separator (24) after the force is introduced and mixed as described herein to provide treated water (25) separated from the solids. Any equipment for separating treated water and solids can be used, including various types of filtration devices, including pressure filters and centrifuges. In addition, large solids may be allowed to settle in the tank, the shape of which may be selected to provide a solid precipitation zone, and then the treated water may be withdrawn from the tank leaving the precipitated solid behind. The illustrated system may further provide an apparatus for introducing an alkali (or acid) to adjust the pH of the wastewater before or during treatment. In another embodiment, the anion exchange resin used to remove the interferent can be separated from the treated water prior to the incorporation of the calcium and cation exchange resin. A variety of system configurations are available to remove this resin or solid. Specially, when the resin or solid used is magnetic, it will polymerize when the transfer is stopped. The treated water can be separated from the agglomerates (4) and transferred to a second tank for subsequent processing steps. In this particular embodiment, the resin or other solids can be reused to treat other wastewater. Further, a magnetic separator or a transitioner can be used to remove the magnetic resin or solid. In order to avoid the possibility of releasing dangerous substances, it is better not to regenerate this Xie Dan. Finally, the resin or solid used is preferably disposed of in situ. The solid formed by the heart combines with the system that is suitable for use in Fig. 1 to improve the sinking method without a pretreatment step. Here, there is no need to introduce an anion 53 200812916 and replace the resin equipment. Further, the water separated from the solids may be directed to a retrograde membrane wherein the dialysis provides treated water and the waste stream is recycled for mixing with the incoming wastewater stream. Further, the system illustrated in Fig. 1 can be subjected to wastewater treatment by being used in contact with a cation exchange resin in the form of calcium. In this example, equipment for introducing an anion exchange resin and a phosphonium salt is not required. Further, the water separated from the solid may be directed to the reverse osmosis membrane, and the permeate provided by the permeate and the waste stream are recycled to be mixed with the incoming wastewater stream. When the J J system is used for the initial treatment using an anion exchange resin, and then treated with a cation exchange resin of the ruthenium (IV) type, there is no need to introduce a device for dissolving the calcium salt. Water with reduced fluoride content (25) and already with resin and other solids = can be purified according to local regulations and the intended use or purpose of the water. For example, 'If you want to reduce the chloride content in water, you can remove the interference with the anion exchange resin in the form of bicarbonate:::= in the anion exchange resin in the form of chloride. Things. In a specific embodiment: a two-hole macroporous anion exchange resin such as in the order of HC0 :::: can be used to remove chlorides and: to pretreat fluoride-containing wastewater. Equipment that would adversely affect the process steps and provide any mixing of the resin in the wastewater: ... force. Typical equipment used for mixing and transfer includes multi-port = body agitator, aeration or jet, and especially cyclone: °. In the method 54 200812916, when using magnetic ion exchange beads, let the beads The beads are dispersed in the wastewater by combining with the fluoride-containing wastewater and applying agitation (or mixing) of sufficient strength to break the magnetic agglomerates of the resin beads. Removal of agitation or mixing results in rapid agglomeration and precipitation of the magnetic beads.

When a Markush group or other cluster is used herein, all individual members of the group and all combinations and possible sub-combinations of the group are intended to be included in the disclosure. Each of the formulations or combinations of the agents or components described or exemplified herein can be used in the practice of the invention unless otherwise stated. It will be apparent to those skilled in the art that the present invention may be carried out using methods, apparatus, and methods other than the specifically illustrated methods, device components, and materials, without undue experimentation. It is intended in the present invention to encompass any such methods, device components, and materials that are well known in the art: equivalent. Whenever a range, such as temperature range, frequency range, inter-day range or composition range, all intermediate ranges and all sub-ranges and all individual equivalent packages included in the ranges provided are provided in the patent specification: Not revealing. The patentable system may be excluded from the scope of the invention or any one or more of the individual members disclosed herein. This meal is clearly described in the same paragraph of the Bank, and can be properly carried out in the absence of any early warnings and restrictions without special disclosure.怯 怯 汝 汝 本文 本文 本文 本文 本文 本文 本文 本文 本文 本文 本文 本文 本文 本文 本文 本文 本文 本文 本文 本文 本文 本文 本文 本文 本文 本文 本文 本文 本文 本文 本文 本文 本文 本文l The unit has a unit or system that has not been described. If used in this article, where I private, t H consists of .., and, and excludes any unit that is not specified in the patent application. Dry circumference / im 乂 乡 or ingredients. If used too, "substantially by the group does not exclude substances or steps that do not significantly affect the basic and novel characteristics of patent application 55 200812916 :. Name = cite, especially in the description of the fraction of the composition or in the case of the attack - can be composed of "substantially composed of" or, consisting of "exchange. However, the description herein includes many specificities, which should not be construed as being limited to the scope of the invention, but rather as merely providing some of the inventions. Each of the references cited herein is hereby incorporated by reference in its entirety. However, the fish right in the cited reference materials

The present disclosure has precedents when any misalignment occurs between the present disclosure. Some of the references provided herein are hereby incorporated by reference in their entirety to the extent that the disclosure of the disclosures A specific embodiment of the prior art::. Other references may be cited to provide a buccal or additional device component, additional or additional material f, additional or analytical or application methods. The US (4) request filed by May 15th, 2006, 6〇m7’266 ’, the full text of which is hereby incorporated by reference. " instance

Fluoride Removal (Sample J Wastewater treated in this example includes: Component Fluoride Sulfate Chloride Ammonia Concentration 2,900 ppm 4,500 ppm 1,800 ppm 0.28 ppm 56 200812916 25 ppm 1.5 ppm A1

Cr Low VOC This is a partial list of wastewater components measured using standard analytical techniques. The dissolved cerium oxide was not measured, but its existence is well known because of the source of the wastewater.

Sample 1 was treated as follows: pH was not adjusted before treatment and was less than pH 2. Will be about 1/2 volume / 〇 (relative to the total water volume) from the hydrophilic polymer (MIEx@HW12〇1, 〇rica

Australia Pty, Ltd., Australia) formed a large pore type i strong alkali anion ion replacement magnetic father to the waste water and mixed this mixture for 1 minute to allow the tree sorghum to react with the components in the wastewater. Then, calcium chloride is added to the water-anion exchange resin combination (3)·6 gallons/125 gallons of waste water with 30% water/liquid mixture. The volume of 3% calcium chloride added is treated water. A total volume of about 0.5 volume. /0. ^ Mix the combined calcium chloride, anion exchange resin and water up to a nominal fluoride of 3 疋 (i.e., about 5 minutes) as measured by fluoride selective probe (Hach, Loveland, co). Then 'will be a gel-based strong acid cation exchange resin with a sulfonic acid functional group in sodium form (iR_i2〇, R〇hm = added to this water treatment mixture. The volume of the cation exchange resin added is equal to the addition of people# • Gasification (iv) of this treatment mixture for 3 minutes. Then, the second two 57 200812916 is separated from the water by a pressure regulator to provide treated water and solid waste. The treated water has the following measured component content. :

Component Concentration Fluoride 3.7 ppm Sulfate 2,500 ppm Chloride 14,000 ppm Ammonia 7.7 ppm Aluminum <200ug/L Chromium 710 ug/L Measured solid waste collected, including: Component Concentration Fluoride (Soluble) 2700mg/Kg Sulfate (soluble) 2600 mg/Kg Chloride (soluble) 4900 mg/Kg Sulfide, Reactive <50 mg/Kg A1 Not measured Cr <0.20 mg/L PH 10.8 Moisture% 46% 58 200812916 Example 2 ···································································· Ppm

A1 Cr Higher voc 5.8 ppm 0.13 ppm 280 ug/L Acetone + 4.4 Ug/L Toluene This is a partial list of wastewater components measured using standard analytical techniques. The cerium oxide in the solution is not measured, but it is well known because of the source of the wastewater. Sample II was treated as follows: pH unadjusted and salty than pH 2.0; MIEX® HWl2〇l (〇rica Australia pty, Ltd, Australia) was added to the wastewater (total volume of water · 2% by volume). The mixed anion exchanges the tree sap and the water is 15 minutes for the resin to react with the components in the water. Then, the calcium chloride is, for example, 30 ° /. The aqueous solution was added to this water-anion exchange resin combination (2 gallons / 125 gallons of wastewater). Mixed combined calcium chloride, anion 59 200812916 Exchange resin and water until the measured fluoride content is stable (about 5 minutes). Then, a strong acid cation parent resin (IR-120 Rohm & HaSs) having a sulfonic acid functional group in sodium form on a gel basis was added to the water treatment mixture. The volume of cation exchange resin added is equal to the volume of the 3 〇 % chlorinated solution added. This treatment mixture was then mixed for 3 minutes. The combined solids are then separated from the water by a filter press to provide treated water and solid waste. The treated water has the following measured component contents. Component Concentration Fluoride 8.6 ppm Sulfate 5 80 ppm Chloride 25,000 ppm Ammonia 2100 ppm

Aluminum

710ug/L <10ug/L

VOC

Acetone 31 ug/L + benzene 9.5 ug/L Measure the solid waste collected, including: Concentration fluoride (soluble) Sulfate (soluble) Chloride (soluble) 3100mg/Kg 160mg/Kg 6800mg/Kg 200812916 Sulfide 'reactive' 5〇mg/Kg not measured

<0.20 mg/L

pH 8.93 48% Moisture% Plate Exchange Resin Fluoride-containing wastewater was contacted with a powdered cation exchange resin similarly as treated in Examples 1 & The resin is a powdery strong acid cationic resin, / a sulphate functional group in sodium form based on a stupid ethylene DVB gel and ground to a nominal 2 〇〇 micron particle size of 4·8 milliequivalents/dry, 〇 4〇 60/. Water is a resin containing $ and 95% ion conversion (now available under the name MlEX® HW3251 (Orica Australia Pty5 Ltd, Australia) ^ ^ .3⁄4). The volume of the powdered cation exchange resin added is 50% of the volume of the aqueous calcium chloride solution that has been added! Let water be mixed with powdered cations; the resin is mixed for 30 minutes. With this treatment, an acceptable low fluoride ion concentration as low as 3 ppm or less can be achieved. Width A 4 : Demonstration of the bottle 訧 Give mixed acid with 30,000 ppm of fluoride and appropriate B〇E content. 61 200812916 « A series of bottle tests (200 ml of wastewater) on waste. In Test 1, the pH of the sample was adjusted from pH 1 · 75 to pH 12·1 by adding the test. The pH adjusted sample was stirred for 45 minutes, after which 3 ml of solid CaC! 2 (anhydrous) was added and the sample was mixed for an additional 15 minutes. Then join MIEX®HW3251 (trademark, Orica Australia Pty, Ltd

Australia) Powdered cation exchange resin (6 ml) and re-mixed the mixture for 30 minutes. The solid was then precipitated (2-Art 3 min) before measuring the fluoride content using the SPANDS fluoride ion selective probe method (Hach, Loveland, CO). This treatment reduces the fluoride content in the wastewater to 3 〇〇 ppm (1 减少 reduction). In Trial 2, MIEX®HW1201 (〇rica Australia Pty,

Ltd., Australia) macroporous anion exchange resin (6 ml) was added to the sample and the sample was stirred for 15 minutes. Then, the pH of the sample was adjusted from pH 1.75 to 11.8 and stirred for another 30 minutes. Solid caCl2 (anhydrous, 3 ml) was added and the sample was mixed for an additional 15 minutes. Then, add MIEX® HW3251 (trademark,

Onca Australia Pty, Ltd., Australia) Powdered cation exchange resin (3 ® mL) and stirred for another 30 minutes. The fluoride content was measured after 2 to 3 minutes of precipitation and was below the detection limit (less than 1 ppm). Test 3 was carried out as in Test 2, and 5 % by volume (1.5 ml) of the volume of the powdery cation exchange resin used in Test 2 was used. The fluoride content was again reduced to less than 1 ppm. Test 4 was carried out as measured 2 and 3, except that 6 ml of a gel-based cationic parent resin (IR_12〇, R〇hm & Η_) was substituted for the powdery cation exchange resin. The fluoride content was again reduced to less than 1 ppm. 62 200812916 Test 5 was carried out as in Test 2, without adjustment # and after adding a large hole anion exchange resin (four) for 30 minutes. The fluoride content is reduced by i ppm. Test 6 was carried out as in Test 2, and 6 ml of a different macroporous anion exchange resin was added. Shaw ResinTech SBMpi, a strong base type 1 macroporous anion resin having a particle size in the form of chloride having a particle size between 42 Å and 12 Å and a capacity of 1.15 meq/ml. Fluoride content reduced to 2〇〇 ppm 〇

Test 7 was carried out as in Test 6, and the macroporous anion exchange resin was replaced with a gel-based resin rti_ 1245. The fluoride content is reduced to 3 〇〇 ppm. The foregoing examples are illustrative and are not intended to limit the scope of the invention. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic diagram showing a process system for removing fluoride and/or interference from wastewater. [Main component symbol description] Benefit 4 63

Claims (1)

200812916 X. Patent application scope: 1 · A method for treating fluoride-containing wastewater to reduce fluoride content in wastewater and forming a solid containing fixed fluoride, comprising the following steps: (a) adding a certain amount of water to dissolve The calcium salt to the wastewater is such that the added calcium is 50% or less of the amount of fluoride in the wastewater; (b) the cation exchange resin in the form of sodium or calcium is added to the wastewater; and (4) from the treated Separating the solids added, formed or both in the water. For example, the method of adding the water-soluble calcium salt to the resin of the first aspect of the invention, wherein the cation exchange resin is in the form of sodium. 4. The method of any of claims 3, further comprising the step of contacting the cesium fluoride hydrazine with the macroporous anion exchange resin prior to the addition of the water soluble (iv) bow salt. Κ 5 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ - Process for the treatment of fluoride-containing wastewater to reduce the amount of fluorine in the wastewater and to form a solid comprising a fixed surface compound. Steps: , 匕栝下64 200812916 (a) Exchange of wastewater with cations in the form of calcium The resin is contacted; and thereafter (b) the resin and any solids formed are separated from the treated water. 7. The method of claim 6, further comprising the step of contacting the fluoride-containing wastewater with the macroporous anion exchange resin prior to contacting the wastewater with the cation-form cation exchange resin. 8. The method of claim 6, further comprising the step of contacting the wastewater with the macroporous anion exchange resin after contacting the wastewater with the cationic parent resin. The method of any one of the preceding claims, wherein the pH of the wastewater is adjusted to pH 5 or above prior to treatment. The method of any one of the preceding claims, wherein the pH of the wastewater is adjusted to pH 8 or above prior to treatment. 11. The method of any one of the preceding claims, wherein the pH of the wastewater is adjusted to at least pH 在 prior to treatment. 12. The method of any one of claims 4, 5, 7 or 8 wherein the pH of the wastewater is adjusted to pH 5 or above after first contacting the wastewater with the macroporous anion exchange resin. 13. The method of claim 4, wherein the pH of the wastewater is adjusted to pH 8 or above after first contacting the wastewater with the macroporous anion exchange resin. 14. The method of any one of claims 帛N13, further comprising the step of subjecting the treated water to reverse osmosis. 15. A method as claimed in any one of the claims of claim 14 - the step comprising contacting the treated water separated from the resin and the solid with a macroporous anion 65 200812916 exchange resin. The method of any one of the claims of the invention, wherein the water-soluble calcium salt is calcium carbonate. 〉, 1 basin 7. The amount of the water-soluble 33 salt of any of the items in the patent range w &amp; 9_16, the amount of water-soluble 33 salt added in the treated wastewater is relative to the amount of the word in the treated wastewater The amount of fluoride in the wastewater is sub-stoichiometric. ... method, ^·如巾, please refer to the scope of the patent, the amount of water-soluble calcium salt added in the second paragraph of Item 9_16, so that the amount of calcium in the treated wastewater is fluoride in the wastewater. Between 5% and 50% of the molar amount: Method, ^If the towel please patent range 1_5 &amp; 9·16 of any item of the item &8; add 5 Hai water-soluble calcium salt to make the treated wastewater The amount of vapor in the middle of the calcium pen is 5% to 25 〇/. between. Method::. Applying for the patent range of any of the items (1), adding the water-soluble calcium salt to make the amount of vapor in the treated wastewater in the treated wastewater to the daytime . The method of the compound of the formula 帛 1-5 or 9-16 of the method of the remedy + ° month == soluble dance salt to contain 2 ❻ weight ^ more salt water, please call the method of the 21st patent range, The water-soluble aqueous solution containing 30% by weight of a salt is added to the wastewater. Method, if the scope of the patent application is 5, the party of any of items 9-16, the water-soluble calcium salt is added as solid to the wastewater. In the process of any of the above-mentioned claims, the cation exchange resin volume of the treated wastewater is between 0.05% and 10% by volume of the treated wastewater of 2008 200812916. The method of any one of claims -23, wherein the cation exchange resin volume added to the treated wastewater is between 0.5% and 5 Torr/0 of the treated wastewater volume. The method of any one of claims 1 to 23, wherein the volume of the cation exchange resin added to the treated wastewater is between 5% and 2.5% of the treated wastewater volume. , The method of any one of the preceding claims, wherein the cation exchange resin is a strong acid cation exchange resin. The method of applying any of the patents (4), wherein the cation exchange resin is in the form of a powder. /, 29. The method of claim 28, wherein the cation exchange resin has a large pore. /, /a〇. The method of any of the items (7) of claim 11, wherein the cationic parent resin has an average particle size of micrometers or less. The method of any one of the preceding claims, wherein the cation exchange resin is a gel-based resin. &amp; </ RTI> as claimed in any one of claims 4, 5, 7 or 8 to 31, wherein the macroporous anion exchange resin comprises iron. The method of any one of claims 4, 5, ..., wherein the macroporous anion exchange resin is magnetic. Any of the methods wherein the macroporous anion, t 乂 树 is known as a strong base anion exchange resin. The method of any one of the claims 4, 5, 7, ..., wherein the macroporous anion exchange resin is a chlorinated strong base anion exchange resin. The formula 36, such as any one of the claims 4, 5, aa ^ ^ 7 or 8-35, wherein the macroporous anion exchange tree hetero-exchange resin. $ "1 strong alkali yin 3 into any of the patent application scope 4, 5 zh, ** / or 8_36 to make. Further, the method of changing the shape of the hydrophilic polymer is described in any one of the claims 4, 5, and 4, Α 8.36, wherein the macroporous anion is exchanged, and a copolymer of divinylbenzene. τ m 39. The method of any one of claims 4, 5, wherein the macroporous anion is exchanged, and the tree is also J-Ethyloxyethyl ester, one a copolymer of vinyl benzene and ethyl vinyl benzene. Hungry as a patent application (4) Any of items 4, 5, 7 or 8_39. The method of the macroporous anion exchange resin has an average of between 3 Å and 1000 μm. j. For example, any of the two methods of claim 4, 5, 7 or 8, wherein the macroporous anion exchange resin has an average particle size of between 30 and 300 microns. Any of 4% of the 41 items has been dispersed in the resin. 42. The method of claim 4, 5, 7 or 8 wherein the macroporous anion exchange resin comprises iron (III) oxide. 68 200812916 Μ The method of applying the method of claim 4, 5, 7 or 8_42, wherein the macroporous anion exchange resin is added to the wastewater: from 0.5 to 5% by volume of the treated wastewater. 44. The method of claim 43, wherein the macroporous anion exchange resin added to waste 7 has a volume less than the volume of the treated wastewater. 45. The method of applying patent _43, wherein The volume of the macroporous anion exchange resin to the second is between 2 〇/〇 of the treated wastewater. The initial fluoride content in the wastewater is 1 〇〇 ppm or more in the method of any one of the following claims. 47. The method according to any one of the preceding claims, wherein the initial amount of the dendrite in the wastewater is _ or more. The initial I compound content in the wastewater in the method of any one of the claims of the scope of claim μ is! Hey, _PPm or more. 49. If the scope of patent application 帛i, any one of the items includes the measurement of the presence in the wastewater, 'initial. The initial steps of the chaotic compound, such as; ^ please apply any of the items in the scope of the patent, including the treated leeches? The step of contacting the anion exchange resin of the formula -^ , ^ 3 &gt; to reduce the vapor content. XI. Schema: as the next page 69