CN100422092C - System and method for treatment of acidic wastewater - Google Patents
System and method for treatment of acidic wastewater Download PDFInfo
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- CN100422092C CN100422092C CNB2004800278308A CN200480027830A CN100422092C CN 100422092 C CN100422092 C CN 100422092C CN B2004800278308 A CNB2004800278308 A CN B2004800278308A CN 200480027830 A CN200480027830 A CN 200480027830A CN 100422092 C CN100422092 C CN 100422092C
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Abstract
A wastewater treatment system comprising separation unit operations inhibits or promotes the formation and precipitation of species by controlling the pH of wastewater to be treated entering into the separation unit operations. The separation unit operations include first and second reverse osmosis devices. The first reverse osmosis device treats wastewater having pH that is less than about 3.5 and the second reverse osmosis device treats wastewater, from the first reverse osmosis device, having a pH that is about 6 or higher.
Description
The cross reference of related application
The application requires following U.S. Provisional Application No. according to U.S.C. § 119 (e): the sequence number of submitting on July 24th, 2003 is 60/489,853 application.This application is incorporated herein by reference in full herein.
Background technology
1. technical field
Present invention relates in general to the processing of acidic industrial effluent, in particular to making precipitation minimize in order in the reverse osmosis system of handling waste water.
2. the content of correlation technique
Follow the waste water of phosphate production operation to be generally acid, and have fluorochemical, ammonia, silicon-dioxide, vitriol, calcium, heavy metal and phosphoric acid salt material usually.With the content of multiple technologies in order to this pollutant of reduction before can discharging at waste water.For example, two limings and subsequently gas to carry be a kind of common technology.This method adopts adds the precipitation that lime promotes fluorochemical material and phosphoric acid salt material in two stages, with after high pH air stripping removes deammoniation.In another kind of technology, with the technical finesse waste water that comprises reverse osmosis after the chemical precipitation.Similar with two limings, this technology improve the pH that flows into waste water with before reverse osmosis step, promote precipitation and solids constituent from.Usually follow the high chemical cost of rising waste water ph that these class methods are had no attraction economically.
Summary of the invention
The invention provides a kind of method of removing fluorochemical, comprise from influent waste water:
A. waste water is introduced first reverse osmosis system, removed fluorochemical from waste water;
B. before waste water enters first reverse osmosis system, regulate or keep the pH of waste water to be lower than 3.5, with the pH of waste water remain on 3.5 or under, leave first reverse osmosis system until waste water;
C. will guide second reverse osmosis system into from the waste water of first reverse osmosis system, remove fluorochemical from waste water;
D. before after waste water has experienced processing in first reverse osmosis system and in second reverse osmosis system, handling, the pH of waste water is heightened; And
E. remove at least 90% fluorochemical from waste water with first and second reverse osmosis systems.
The present invention also provides a kind of Waste Water Treatment that is used to remove pollutent, comprises:
A. sand ballast formula flocculation system has one or morely in order to the mixing tank of ballast weight and pending waste water blended be arranged on the slurry tank in one or more mixing tanks downstream, and this slurry tank generates clarifying effluent and slurry;
B. first reverse osmosis system is arranged on sand ballast formula flocculation system downstream, in order to handle the clarification effluent that ballast formula flocculation system generates;
C. second reverse osmosis system is arranged on the downstream of first reverse osmosis system, in order to handle the effluent from first reverse osmosis;
D. sour inlet is arranged on the upstream of first reverse osmosis system and is used for being operably connected with acid source optionally waste water was injected in acid before arriving first reverse osmosis system at waste water; And
E. alkali inlet is arranged between first and second reverse osmosis systems and is used for being operably connected optionally alkali is injected the waste water effluent from first reverse osmosis system, to regulate the pH from the waste water effluent of first reverse osmosis system with alkali source.
According to one or more embodiments, the invention provides a kind of Waste Water Treatment, comprise the influent source, this influent source comprises pH and is lower than about 3.5 pending waste water; First reverse osmosis system that is connected with the influent source fluid; Be arranged in the first reverse osmosis system downstream and introduce the alkali source of alkali; Second reverse osmosis system that is connected with the downstream and the alkali source fluid of first reverse osmosis system.
According to one or more embodiments, the invention provides the method that a kind of pH of processing is lower than about 3.5 waste water.The method includes the steps of: remove to the small part all contaminations from waste water in first separation system; In first separation system, remove to the small part all contaminations, the pH regulator of the first separation system effluent is at least about 6 or higher from waste water; And with the pH regulator of the first separation system effluent be at least about 6 or higher after, in second separation system, remove to the small part all contaminations from waste water.
According to one or more embodiments, the invention provides a kind of method of handling waste water.The method includes the steps of: be suppressed at the condition that promotes fluoride ion and at least a formation of silicate ion in the waste water; In first separation system, remove all contaminations from waste water; Promote fluoride ion and at least a formation of silicate ion; After promoting fluoride ion and at least a formation of silicate ion, remove the effluent that any pollutent industry in next life is handled from waste water.
According to one or more embodiments, the invention provides a kind of method of handling waste water.The method includes the steps of: the equilibrium conditions that keeps any deposit fouling thing in the waste water; Remove phosphoric acid salt, dissolved solid, ammonia, organically reach the colloidal materials any from waste water; Remove from waste water dissolved solid, ammonia, organically reach the colloidal materials any after, the equilibrium conditions of regulating at least a deposit fouling thing in the waste water; Regulate after the equilibrium conditions of at least a deposit fouling thing in the waste water, remove the effluent that any remaining fluorochemical, ammonia or dissolved solid industry in next life handled from waste water.
The invention provides a kind of method of removing fluorochemical and silicon-dioxide from waste water with reverse osmosis system, this method reduces the trend of fouling in the reverse osmosis system.In the situation of this mode of the present invention, this method can promote the waste water that is beneficial to the condition of silicofluoric acid formation in the waste water and will contains silicofluoric acid to guide reverse osmosis system into.When waste water passes reverse osmosis system, from waste water, remove the fluorochemical and the silicon-dioxide of silicofluoric acid form.The subordinate phase reverse osmosis system can be used for removing other fluorochemical and silicon-dioxide.In this situation, keep being beneficial in the waste water effluent of first reverse osmosis system condition that fluorochemical and silicate ion form.Thus, when waste water passed second reverse osmosis system, the other fluorochemical and the silicon-dioxide of fluorochemical and silicate ion form were removed.
In addition, the present invention can realize removing algae from waste water.In a kind of specific embodiments, waste water is acid.For removing algae, chlorine or chlorine by product are added in the waste water to kill algae from waste water.In addition, after having experienced with chlorine or chlorine byproduct for treatment, add wilkinite, algae is by wilkinite absorption and or unstability.Available then conventional treatment method is removed algae.
In a specific embodiments of the present invention, algae and/or suspended substance are removed by system by ballast formula (ballasted) flocculation separation.In this method, algae that is adsorbed and wilkinite form solid in waste water.In ballast formula flucculation process, flocculation agent and insoluble particles thing are added in the waste water to form the flocculation mixture.Flocculation mixture formation is adsorbed algae and bentonitic floss from comprising of wastewater sedimentation.
When considered in conjunction with the accompanying drawings, other advantage of the present invention, new feature and target will become obviously from following detailed description of the present invention, and some in the accompanying drawing are schematically, and be not intended to drafting in proportion.Among the figure, the single numeral of each assembly identical or much at one that several picture in pictures are separated.For clarity sake, when not needing diagram that those of ordinary skills are understood when of the present invention, both each assembly of mark in every width of cloth figure did not mark each assembly shown in every kind of embodiment of the present invention yet.
The accompanying drawing summary
By embodiment non-limiting embodiments of the present invention is described with reference to accompanying drawing, wherein:
Fig. 1 is the process flow sheet of expression Waste Water Treatment of one or more embodiments according to the present invention;
Fig. 2 is the synoptic diagram of the ballast formula separation system of one or more embodiments according to the present invention;
Fig. 3 is that a width of cloth represents that one or more embodiments are as the vitriol of pH function and the figure of equilibrium phase to forming of hydrosulfate material according to the present invention;
Fig. 4 is that a width of cloth represents that one or more embodiments are as the hydrofluoric acid of pH function and the figure of equilibrium phase to forming of fluorochemical material according to the present invention;
Fig. 5 is that a width of cloth is represented as the ammonium of pH function and the figure of equilibrium phase to forming of ammoniacal substance;
Fig. 6 is that a width of cloth is represented as the phosphoric acid of pH function and the chart of equilibrium phase to forming of phosphoric acid salt material.
Detailed Description Of The Invention
There is the problem of fouling in the wastewater treatment that contains silica, calcium sulfate, calcium phosphate, calcirm-fluoride and any material that other can precipitate under neutrality or near-neutral pH condition. For example, when this class waste water therefrom passed through, reverse osmosis units operation or system formed fouling. Other potential fouling problem comprise those follow solvable organic compound and from the problem of organic substance. Therefore, the operating cost that this systems face is very large is such as but not limited to film cleaning and/or displacement and high chemical depletion. Thereby, the invention provides the system and method for processing waste water, utilize stage by stage chemical balance character to produce to be suitable for the effluent that in the drainage of regulation, discharges. For example, system and a method according to the invention can be produced effluent, i.e. treated waste water, and this effluent has dissolved solid, fluoride, ammonia, phosphate and the sulfate species of the low concentration that can satisfy drainage requirement. Thus, according to one or more embodiments, the invention provides a kind of Waste Water Treatment, comprise inflow liquid source, this inflow liquid source comprises pH and is lower than about 3.5 pending waste water; The first counter-infiltration system that is connected with inflow liquid source fluid; Be arranged in the first counter-infiltration system downstream and introduce the alkali source of alkali; The second counter-infiltration system that is connected with the alkali source fluid with the first counter-infiltration system downstream. This Waste Water Treatment further comprises fluid and is connected to the clarifier that flows between liquid source and the first counter-infiltration system. This Waste Water Treatment can further comprise fluid and be connected to the medium type that flows between liquid source and the first counter-infiltration system or the filter of other type. This Waste Water Treatment can comprise further that also being arranged in the first counter-infiltration system waste water upstream adds sour acid source. This Waste Water Treatment can comprise that also fluid connects the mixed bed demineralizer in the downstream of the second counter-infiltration 25 systems. According to another embodiment, the invention provides the method that a kind of pH of processing is lower than about 3.5 waste water. The method can comprise following steps: remove at least part of any material of not expecting from waste water in the first piece-rate system; In the first piece-rate system, after waste water is removed at least part of any material of not expecting, the pH of the first piece-rate system effluent is adjusted at least about 6; And the pH of the first piece-rate system effluent is adjusted at least about after 6, in second system, remove at least part of various material of not expecting from waste water. The method can further be included in carries out removing before at least part of any step of not expecting material the step of clarified wastewater in the first separation unit operation. The method can further be included in carries out removing in the first piece-rate system before at least part of any step of not expecting material, removes various organic steps from waste water. Removing any organic step can comprise to waste water interpolation bactericide, coagulating agent and flocculant. The method can further be included in carries out removing before at least part of any step of not expecting material the step of removing various trickle solids from waste water in the first piece-rate system. The method can further be included in carries out removing in the first piece-rate system before at least part of any step of not expecting material, and the pH that regulates waste water is about 3 step. The method can further comprise from any is reduced to the step of deferring to the level that the EPA that sets up requires in ammonia and the phosphate in the treated waste water of the second piece-rate system.
According to another embodiment, the invention provides a kind of method of processing waste water. The method includes the steps of: be suppressed at the condition that promotes fluoride ion and at least a formation of silicate ion in the waste water; Promote to form or keep in the waste water condition of the complexing material of silica and fluoride; In the condition of the complexing material that promotes formation or maintenance silica and fluoride, from waste water, remove at least a material of not expecting; After from waste water, removing at least a material of not expecting, regulate the condition of waste water to suppress the formation of complexing material. The method can further be included in the first piece-rate system to remove from waste water anyly not to be expected to remove at least part of any organic step before the material.
According to other embodiment, the invention provides a kind of method of processing waste water. The method includes the steps of: the equilibrium condition that keeps any deposit in the waste water; Remove the solid, ammonia of dissolving, organically reach the colloidal materials any from waste water; At the solid of removing dissolving from waste water, ammonia, organically reach the colloidal materials after any equilibrium condition of regulating at least a deposit in the waste water; Regulate after the equilibrium condition of at least a deposit in the waste water, remove the effluent that the solid material industry in next life of any remaining fluoride, ammonia or dissolving is processed from waste water. Remove the solid, ammonia of dissolving, organically reach the colloidal materials any step and can be in keeping waste water carry out in the equilibrium condition of any deposit from waste water. According to another embodiment of the present invention, the invention provides a kind of method of processing waste water. The method can comprise following steps: the condition that promotes to form or keep in the waste water complexing material of silica and fluoride; In the condition of the complexing material that promotes formation or maintenance silica and fluoride, from waste water, remove at least a material of not expecting; Remove at least a material of not expecting from waste water after, adjusting condition is with the formation of the complexing material of inhibition silica and fluoride; And after adjusting condition suppresses the formation of complexing material, remove the effluent that any remaining material industry in next life of not expecting is processed from waste water. According to one or more embodiments of the present invention, Fig. 1 represents Waste Water Treatment 10, this system can comprise with waste water source 14 in waste water flow into the first pretreatment system 12 that the liquid fluid is connected. Waste Water Treatment 10 can further comprise the second pretreatment system 16 that is connected with the first pretreatment system 12 fluids. The first piece-rate system 18 and the second piece-rate system 20 common fluids are connected to the first and/or second pretreatment system 12 and 16 downstreams. Send to discharging 24 before, in whole treatment system 22 further process usually by experience for treated waste water effluent.
Flowing into liquid can be the waste water that is suitable for according to any source of the present invention's processing. For example, suitable inflow liquid waste water can be the collected waste water with meta-acid pH, those waste water that for example operate from phosphate production.
The first pretreatment system can comprise one or more unit operations, and described operation is removed such as the organic matter of algae and reduced and flows into the turbidity of liquid wastewater streams under its pH value. Suitable pretreatment system can comprise the clarifier with ballast formula flocculation subsystem. Fig. 2 represents a kind of this type of exemplary unit, has the section of condensing, slaking section, settling section and waterpower swirling flow section. Clarifier 30 can use bactericide, such as clorox, makes any microorganism or organic matter inactivation in the wastewater streams; Coagulating agent such as but not limited to bentonite, aluminum sulfate and iron chloride, promotes condensing of inactivation material; And flocculant, such as but not limited to nonionic, cationic and anionic polymer or its combination, promote the flocculation of material inactivation, that condense. This clarifier can adopt fine sand to strengthen sedimentation and waterpower swirling flow technology is come separating slurry or solid from rich liquid stream. This type systematic preferably is brought down below about 3NTU with the turbidity of wastewater streams.
The second pretreatment system comprises one or more unit operations, and described operation is removed trickle solid and/or improved the turbidity of wastewater streams. Suitable system can comprise the medium filter that adopts in anthracite, sand and the garnet any. This type systematic preferably the turbidity of waste water is brought down below about 2NTU and SDI is brought down below about 4, to reduce the possibility of downstream dirt.
The first and second piece-rate systems are removed pollutant or do not expected from waste water material makes it be suitable for draining into water body. As used herein, phrase " is suitable for discharging " and refers to that treated waste water has the pollutant levels that meet or surpass United States EPA emission request. For example, the first and second piece-rate systems can comprise one or more reverse osmosis equipments of turning round of being suitable under the waste water condition. Treated waste water effluent has usually such as pollutant levels listed in the table 1.
Table 1 effluent quality standard (mg/l)
| Form | Concentration |
| pH | 6.5-8.5 |
| Fluoride | ＜5.0 |
| Ammonia | ＜1.0 |
| Total nitrogen | ＜2.0 |
| Phosphorus | ＜0.5 |
| TDS | ＜50 |
Thereby, according to one or more embodiments of the present invention, the first piece-rate system 18 can comprise one or more reverse osmosis units with diffusion barrier (not shown), be suitable for providing wastewater treatment, for example pH is lower than about 3 and the brackish water of the about 12GFD of the about 6-of flow velocity, because it is believed that high flow rate greater than about 12GFD can cause dirt and can to cause permeating quality less than the flow velocity of about 6GFD low. Similarly, the second piece-rate system 20 can comprise one or more reverse osmosis units 20 with diffusion barrier (not shown), is suitable for providing wastewater treatment, for example the brackish water of the about 6-of pH about 7 and the about 20GFD of the about 15-of flow velocity. The same with the counter-infiltration system of the first piece-rate system, higher flow velocity can cause unacceptable dirt, and lower flow can make the infiltration quality become bad. Any reverse osmosis unit all can be used in the first or second piece-rate system. Suitable example comprises that those can be from United States Filter Corporation, Milton, Ontario, the commercial device that obtains of Canada. Be suitable for being used in according to the film in the reverse osmosis unit of the present invention and comprise the FILMTEC BW30-365 film that can obtain from FilmTec, FilmTec is The DowTMChemical Corporation, Midland, the subsidiary of Michigan. Can make the first piece-rate system turn round to process pH and be lower than about 3.5 waste water, with the formation that promotes the disulfate material and/or remove, with the formation that suppresses sulfate species and the trend that reduces calcium sulfate scaling. Also can make the first piece-rate system turn round to process pH and be lower than about 3.5 waste water, to promote formation and/or the removal of fluosilicic acid material, to reduce the trend of silica and calcirm-fluoride or the two fouling. Also can make the first piece-rate system turn round to process pH and be lower than about 3.5 waste water, to promote formation and/or the removal of phosphoric acid substance, to reduce the trend of calcium phosphate fouling. Also can make the first piece-rate system turn round to process pH and be lower than about 3.5 waste water, to reduce the trend of metal fouling. Also can make the first piece-rate system turn round to process pH and be lower than about 3.5 waste water, to promote formation and/or the removal of ammonium material, to improve the escape velocity of ammonia. Can make the second piece-rate system turn round to process the waste water of the about 6-of pH about 7, promote the formation of fluoride material and/or remove, to promote the removal of this class material. Can make the second piece-rate system turn round to process the waste water of the about 6-of pH about 7, promote the formation of silicate material and/or remove, to promote the removal of this class material. Can make the second piece-rate system turn round to process the waste water of the about 6-of pH about 7, promote the formation of phosphate material and/or remove, to promote the removal of this class material. Can make the second piece-rate system turn round to process the waste water of the about 6-of pH about 7, promote the formation of organic substance and/or remove, to promote the removal of this class material. In the first and second piece-rate systems, can adopt other technology to remove pollutant or other material of not expecting, include but not limited to electrodialysis, electric deionization, micro-filtration and evaporation/concentrated. In some situations, Waste Water Treatment can further comprise scale preventative and/or the coagulating agent source that is configured to introduce scale preventative and/or coagulating agent in the waste water of the upstream of pretreatment system or any piece-rate system. Any suitable scale preventative that suppresses fouling formation in various unit operations according to the present invention can use. Scale preventative can with the use of each manufacturer recommendation, still use with the concentration of the about 4ppm of about 3-usually. Whole treatment system 22 can comprise one or more unit operations, and described operation further reduces any pollutant or the material of not expecting and makes it be suitable for discharging from treated waste water. For example, whole treatment system 22 can comprise one or more mixed bed demineralizers, and ammonia content is brought down below about 1mg/l. Mixed bed 15 can comprise one or more anion and cationic ion-exchange resin usually, attracts and in conjunction with the remaining charge species in the treated waste water. Ion exchange resin can be present in the mixed bed with any suitable arrangement, with the treated waste water of further purification. The example of suitable ion exchange resin comprises can be from The DowTMChemical Corporation, Midland, the DOWEX that Michigan obtainsTM
MARATHON
TMResin series and can be from Rohm and Hass Company, Philadelphia, the AMBERLITE that Pennsylvania obtainsTMResin series. Waste Water Treatment 10 further comprises acid source 26 and alkali source 28 usually. Acid source 26 is connected with the inlet streams of the first piece-rate system 18 usually, and alkali source 28 is connected with the inlet streams of the second piece-rate system 20 usually. In this arrangement, can regulate one or more chemical property of pending waste water in the first piece-rate system 18 from the acid of acid source 26. For example, the pH that can regulate pending waste water in the first piece-rate system 18 entrances 30 is with control and/or keep solubility or the balance of one or more chemical substances, for example comprises that solubility by for example improving this class material and/or promotion comprise this class otherwise the formation of the complexing material of the material that can precipitate suppresses the formation of deposit.
According to one or more embodiments of the present invention, acid can be introduced entrance 30 and mix to promote, also keep with pending waste water or change equilibrium condition, suppress any sulfate (SO4 2-) material formation and/or promote any disulfate (HSO4) formation of material. As shown in Figure 3, the equilibrium phase of sulfate and disulfate material is to forming the function as pH. Lower pH condition can promote the formation of disulfate material, and higher pH condition can promote the formation of sulfate species. Therefore, control pH can affect the availability of sulfate species, and this material is easy to precipitate in piece-rate system of the present invention usually.
In other embodiments, adopt interpolation acid also to promote, keep or the change equilibrium condition, with the formation that promotes fluosilicic acid and/or the precipitation that suppresses silica and fluoride material. As shown in Figure 4, the equilibrium phase of hydrofluoric acid and fluoride material is to forming the function as pH. Lower pH condition can promote the formation of hydrofluoric acid material, and higher pH condition can promote the formation of fluoride material. Therefore, control pH can affect the availability of hydrofluoric acid material, this so that affect the formation of fluosilicic acid material and the availability of reduction precipitated silica or silicate material.
In some embodiments again, adopt and add acid and also promote, keep or the change equilibrium condition, with the solubility of raising phosphate material such as but not limited to calcium phosphate. For example the pH of the waste water in the entrance 30 of the first piece-rate system 18 to be introduced can be remained on or is adjusted to and be lower than approximately 3, be usually less than approximately 2.8, be lower than approximately 2.5 under some situation, other has in some situations to about 2.
According to the present invention, can use any acid that the pH of stream can be reduced to or remain on the pH scope of expectation. Suitable example comprises hydrochloric acid, sulfuric acid or its mixture. The selection of specific acid depends on a number of factors, and includes but not limited to the factor that available and cost and other processing will be considered. For example, hydrochloric acid may be more preferred than sulfuric acid, avoids the rising of any sulfate species concentration.
Same, can be in order to regulate one or more chemical property of pending waste water in the second piece-rate system 20 from the alkali of alkali source 28. As the situation that adopts acid to add, can will add alkali advantageously in order to control and/or to keep solubility or the balance of one or more chemical substances. For example, the pH that can regulate from the treated waste water of the first piece-rate system 18 promotes silicate or fluoride material or the formation of the two, is beneficial in the second piece-rate system 20 it be removed from wastewater streams. Similarly, can regulate this pH to facilitate the formation of phosphate and ammoniacal substance, be beneficial in the second piece-rate system 20, it be removed from wastewater streams. Therefore, according to one or more embodiments of the present invention, the pH of waste water in the entrance 32 of the second piece-rate system 20 can be promoted at least about 6, in some cases at least about 6.5, in the other situation between about 6 and about 7. PH raises and also can promote formation and their removals in the second piece-rate system 20 of organic salt, to improve the TOC quality of effluent. As shown in Figure 5, the equilibrium phase of ammonium and ammoniacal substance is to forming the function as pH. Lower pH condition can promote the formation of ammoniacal substance, and this can promote its removal in the first piece-rate system. In addition, as shown in Figure 6, the equilibrium phase of phosphoric acid and phosphate material is to forming the function as pH. Can control the pH condition and promote H2PO
4 -The formation of material, this can promote its removal in the second piece-rate system. According to the present invention, can use any alkali that the pH of stream can be promoted to the pH scope of expectation. The example that is suitable for use as alkali comprises caustic soda or NaOH, caustic potash or potassium hydroxide. Preferably, bronsted lowry acids and bases bronsted lowry comprises the material that is suitable for being discharged into water body. As used herein, term " pollutant " and " material of not expecting " refer in the waste water or have the material of the concentration limit of restriction in the treated waste water. Pollutant comprises the material that for example comprises calcium, magnesium, sodium, potassium, aluminium, barium, ammonium, bicarbonate, sulfate, chloride, phosphate, nitrate, fluoride, silica, iron and manganese. As used herein, the term organic matter can comprise bacterium, microorganism, algae and the suspended solid that comprises this class material. Also as used herein, " to make ... inactivation " be to instigate organic matter to be suitable for condensing and/or flocculating to term. The function of these and other embodiment of the present invention and advantage will be understood more fully from following examples. Following examples want to illustrate Li Chu of the present invention, but illustration four corner of the present invention not.
Embodiment
This embodiment represents the running of the Waste Water Treatment of one or more embodiments according to the present invention.Particularly, the Waste Water Treatment 10 that schematically shows among Fig. 1 has the pretreatment system 14 and 16 that comprises settler and multiple medium type filter respectively.This Waste Water Treatment further comprises first separation system 18 that comprises first reverse osmosis unit and second separation system 20 that comprises second reverse osmosis unit.This treatment system also comprises the whole treatment system 22 of mixed bed demineralizer.
Settler comprises and can obtain from OTV SA
Treatment system makes to any organic substance inactivation of small part with NaOCl.The wilkinite of the about 250mg/l of the also available about 80-of settler promotes that inactivation is organic and condenses, and depends on the organism required amount of condensing that makes.Also can be with from Betz Dearborn, Downers Grove, the high-molecular weight polymer P1142 of Illinois, promptly a kind of non-ionic type polymerizing agent is used for settler to promote the organic flocculation of agglomerative inactivation.This flocculation agent is introduced with the concentration of about 1mg/l.The effluent of settler has the turbidity that is lower than about 3NTU.Make slurry and other semi-solid waste materials of settler return the gathering pond, or process in addition.
Multiple medium type filter adopts and comprises and hard coal, sand and garnet medium are brought down below about 2NTU and SDI is brought down below about 4 with the turbidity with waste water.
Mixed bed demineralizer adopts DOWEX
TMMARATHON
TMA and DOWEX
TMMARATHON
TMThe mixed bed of C ion exchange resin, every kind can be from The Dow
TMChemical Corporation, Midland, Michigan obtains.Mixed bed demineralizer is used for further with NH
3Concentration be controlled at and be lower than about 1mg/l, with PO
4The concentration of material is brought down below about 0.5mg/l.
First reverse osmosis unit adopts the FILMTEC that obtains from FilmTec company
TMBW30-365 film, FilmTec are The Dow
TMChemical Corporation, Midland, the Subsidiary Company of Michigan.It turns round under the mean flow rate of the working pressure of about 250-300psig and about 10GFD.Second reverse osmosis unit also adopts FILMTEC
TMThe BW30-365 film.It is operated under the mean flow rate of about 8GFD.If desired, from acid source acid (hydrochloric acid) is added to the influent waste water stream before handling in first reverse osmosis unit, pH is lower than about 3 with control.After first reverse osmosis unit and before introducing second reverse osmosis unit, be sodium hydroxide, add in the waste water stream, pH is promoted between about 6-about 7 with alkali.Replenish influent waste water from the gathering pond of phosphate production factory.This waste water contains usually just like Pollutant levels listed in the table 2.With enter first reverse osmosis unit the waste water influent pH regulator or be maintained at about between the 2-2.8, to keep or promotes oxidn silicon and fluorochemical complexing formation silicofluoric acid material, reduce the trend of the fouling that comes with silicon oxide and Calcium Fluoride (Fluorspan) thus.This pH condition also helps balance to move to promote the formation of phosphoric acid, calcium bisulfate and ammonium material, thereby reduces the scaling tendency that comes with calcium phosphate and calcium sulfate in the removal that promotes ammonia.Table 2 has been listed the character that comprises Pollutant levels (infiltration of first road is formed) from the permeate stream of first reverse osmosis unit.Table 2 has also been listed from the character of the permeate stream of second reverse osmosis unit and Pollutant levels (infiltration of second road is formed).Data show that system and method for the present invention can be used for handling waste water, produce the effluent that is suitable for discharging that meets or exceed the EPA drainage requirement.The purposes of Waste Water Treatment that this embodiment has gone back illustration, this system has the cost lower with respect to legacy system, has avoided the disposal to lime slurry and other pre-treatment chemical simultaneously.
Table 2 waste water composition (mg/l of unit, except as otherwise noted)
| Component | Influent is formed | The infiltration of first road is formed | The infiltration of second road is formed |
| Calcium | 551 | 0.25 | 0.1 |
| Magnesium | 229 | 0.074 | 0.025 |
| Sodium | 1,290 | 50.7 | 1.4 |
| Potassium | 196 | 0.86 | 0.021 |
| Aluminium | 8.4 | 0.05 | 0.05 |
| Barium | 0.02 | 0.001 | 0.001 |
| Ammonium | 600 | 5.2 | 0.27 |
| Supercarbonate | 0.78 | - | 2.4 |
| Vitriol | 5,200 | 5.5 | 0.2 |
| |
100 | 14 | 0.26 |
| Phosphoric acid salt | 1,600 | 1.1 | 0.004 |
| Nitrate | 0.26 | 0.16 | 0.014 |
| Fluorochemical | 150 | 35 | 0.54 |
| Silicon oxide | 200 | 0.61 | 0.3 |
| Iron | 5.6 | 0.02 | 0.025 |
| Manganese | 2.9 | 0.006 | 0.005 |
| TDS | 11,500 | 111 | 15 |
| |
24 | 4 | - |
| BOD | 17 | 0.74 | 0.2 |
| TOC | 66 | 1.0 | 0.55 |
| TKN | 650 | 5.9 | 1 |
| pH | 2.8 | 2.9 | 6.3 |
| Turbidity (NTU) | 14 | 0.25 | 0.05 |
| Colourity (PCU) | 110 | 5 | 5 |
Although describe and exemplified of the present invention in the literary composition as if an embodiment, but those of ordinary skills will be easy to predict various other systems and the structure of implementing function described in the literary composition and/or obtaining described result or advantage, and every kind of this class changes or changes to be doomed within the scope of the invention.In general, those skilled in the art understand that all parameters, size, material and structure are exemplary described in the easy to understand literary composition, and actual parameter, size, material and structure depend on the concrete application of using the present invention's instruction.Thereby the size of every kind of unit operation and turnout will depend on the some factors vary in concrete installation.And the certain material that makes up container, pump and other member of system of the present invention also will depend on specific concrete installation factor, but the selection of this class A of geometric unitA and system, structure and design will be in the technology of the present invention personnel's limits of power.For example, those skilled in the art generally acknowledge that stainless steel should be as the material of tectonic element operation, and this unit operation is used to be not suitable for adopting the use or the application of carbon steel.Those skilled in the art only adopt normal experiment just can recognize or definite literary composition described in the equivalent of specific embodiments of the present invention.Thereby, be appreciated that embodiment described in the literary composition only proposes with by way of example, in the scope of the claim of appendix and equivalent thereof, the present invention can differ from and specifically describe and implement.The present invention relates to the independent feature of each described in the literary composition, system, material and/or method.In addition, if this category feature, system, material and/or method are not conflicting, the arbitrary combination of two or more these category features, system, material and/or method is also contained in the scope of the present invention.As used herein, all cambic phrases are open as " comprising ", " comprising ", " having ", " containing ", " comprising " and similar phrase, promptly mean and include but not limited to, only have cambic phrase " by ... constitute ", " basically by ... constitute " be only sealing or semi-enclosed cambic phrase respectively, set as the § 2111.03 of United States Patent Office (USPO) patent examination guide.
Claims (25)
1. method of removing fluorochemical from influent waste water comprises:
A. waste water is introduced first reverse osmosis system, removed fluorochemical from waste water;
B. before waste water enters first reverse osmosis system, regulate or keep the pH of waste water to be lower than 3.5, with the pH of waste water remain on 3.5 or under, leave first reverse osmosis system until waste water;
C. will guide second reverse osmosis system into from the waste water of first reverse osmosis system, remove fluorochemical from waste water;
D. before after waste water has experienced processing in first reverse osmosis system and in second reverse osmosis system, handling, the pH of waste water is heightened; And
E. remove at least 90% fluorochemical from waste water with first and second reverse osmosis systems.
2. the process of claim 1 wherein that influent waste water also comprises calcium, vitriol, phosphoric acid salt and silicon oxide, and wherein at least 90% calcium, vitriol, phosphoric acid salt and silicon oxide are removed by first and second reverse osmosis systems.
3. the method for claim 1 is included in and guides waste water into first reverse osmosis system before with waste water filtering.
4. the method for claim 1 is included in and guides waste water to pass through sand ballast formula flocculation system before guiding waste water into first reverse osmosis system.
5. the method for claim 4, wherein sand ballast formula flocculation system generates clarifying effluent, and this method comprises and will filter from the clarification effluent of sand ballast formula flocculation system and will guide first reverse osmosis system into from the effluent after filtration of ballast formula flocculation system.
6. the process of claim 1 wherein that to comprise pH be 3.5 to influent waste water or be lower than 3.5, and wherein this method comprises that pH with waste water remains on or is lower than 3.5, till having been handled by first reverse osmosis system to waste water at least.
7. the method for claim 1 is included in guiding waste water and before the pH of waste water is heightened at least 6 by second reverse osmosis system.
8. the process of claim 1 wherein that waste water comprises silicon oxide, phosphoric acid salt, calcium and vitriol; And wherein this method is included in waste water and enters and regulate its pH before first reverse osmosis system, thereby waste water is adjusted to the complex compound that is beneficial to formation silicon oxide and fluorochemical, it further is beneficial to the formation hydrosulfate, thereby reduces the trend because of silicon oxide, Calcium Fluoride (Fluorspan), lime carbonate, calcium sulfate, calcium phosphate or metal fouling fouling in first reverse osmosis system.
9. the method for claim 8 wherein forms in waste water from heightening of the waste water effluent pH of first reverse osmosis system and is beneficial to the condition that fluorochemical and silicate ion form, and perhaps various light current is converted into the form of salt from acid.
10. the process of claim 1 wherein that waste water comprises calcium, ammonia and phosphoric acid salt or metal; And wherein this method is included in waste water and enters before first reverse osmosis system control to its pH and waste water is adjusted to be beneficial to forms phosphoric acid and ammonium ion, this reduces in first reverse osmosis system trend because of the calcium phosphate fouling, and improves the removal of ammonia in first reverse osmosis system; And wherein waste water is adjusted to and is beneficial to the formation phosphate ion from the raising of the waste water effluent pH of first reverse osmosis system, it is beneficial to phosphatic removal in second reverse osmosis system, and further waste water is adjusted to the organic solubleness of raising, thereby be beneficial to organic removal in second reverse osmosis system.
11. the process of claim 1 wherein that waste water comprises algae, and this method comprises that chlorine or chlorine by product are mixed with waste water kills algae, and wilkinite mixed absorb or make the algae unstability with waste water.
12. the method for claim 1, being included in waste water guided into guides waste water to pass through sand ballast formula flocculation system before first reverse osmosis system, and wherein waste water comprises algae, and this method makes chlorine or chlorine by product mix with waste water and kills algae, and wherein removes described algae in described ballast formula flocculation system.
13. the process of claim 1 wherein that waste water comprises silicon oxide and this method and is included in guiding waste water and forms silicofluoric acid by before first reverse osmosis system in waste water, and remove fluorochemical and silicate with first reverse osmosis system.
14. the method for claim 1, wherein waste water comprises calcium, phosphoric acid salt and vitriol, comprise by the trend that reduce to form Calcium Fluoride (Fluorspan), calcium phosphate, lime carbonate and calcium sulfate with this method and to reduce fouling in the reverse osmosis system, and further reduce the fouling that the scaling tendency because of silicon oxide causes.
15. the method for claim 13 is wherein heightened the form that pH from the waste water effluent of first reverse osmosis system causes fluorochemical in the waste water and silicon oxide to present fluorochemical and silicate ion, it is removed from waste water in second reverse osmosis system.
16. the method for claim 13, wherein waste water also comprises vitriol, phosphoric acid salt and ammonia, wherein the pH level of control waste water is beneficial in the formation of hanging down hydrosulfate, phosphoric acid and ammonium ion under the pH level before entering first reverse osmosis system, wherein heighten pH from the waste water effluent of first reverse osmosis system and waste water is adjusted to be beneficial to forms phosphate ion and improve some organic ionization, this is beneficial to and removes phosphoric acid salt, organism and ammonia from waste water.
17. the process of claim 1 wherein that first time of wastewater pH is heightened after waste water leaves first reverse osmosis system carries out.
18. the process of claim 1 wherein the pH from the waste water effluent of first reverse osmosis system is heightened to 6 or higher.
19. the method for claim 1, wherein said waste water source is from having 3.5 or the influent waste water stream of lower pH, the wherein pre-treatment of one step of waste water experience or the multistep first reverse osmosis system upstream, wherein this method comprise when waste water go on foot through one or the pH of waste water remained on during the multistep pre-treatment and before waste water enters first reverse osmosis system 3.5 or under.
20. the method for claim 19 is wherein heightened after waste water leaves first reverse osmosis system and carry out the first time of wastewater pH.
21. a Waste Water Treatment that is used to remove pollutent comprises:
A. sand ballast formula flocculation system has one or morely in order to the mixing tank of ballast weight and pending waste water blended be arranged on the slurry tank in one or more mixing tanks downstream, and this slurry tank generates clarifying effluent and slurry;
B. first reverse osmosis system is arranged on sand ballast formula flocculation system downstream, in order to handle the clarification effluent that ballast formula flocculation system generates;
C. second reverse osmosis system is arranged on the downstream of first reverse osmosis system, in order to handle the effluent from first reverse osmosis;
D. sour inlet is arranged on the upstream of first reverse osmosis system and is used for being operably connected with acid source optionally waste water was injected in acid before arriving first reverse osmosis system at waste water; And
E. alkali inlet is arranged between first and second reverse osmosis systems and is used for being operably connected optionally alkali is injected the waste water effluent from first reverse osmosis system, to regulate the pH from the waste water effluent of first reverse osmosis system with alkali source.
22. the Waste Water Treatment of claim 21, comprise the strainer that is arranged between the sand ballast formula flocculation system and first reverse osmosis system, in order to filter clarification effluent before entering first reverse osmosis system at the clarification effluent from sand ballast formula flocculation system.
23. the Waste Water Treatment of claim 21 further comprises the mixed bed ion exchange demineralizer that is arranged on the second reverse osmosis system downstream.
24. the Waste Water Treatment of claim 22, its middle filtrator are multiple medium type filters.
25. the Waste Water Treatment of claim 21, wherein said pollutent is selected from the pollutent of fluorochemical, silicon oxide, phosphoric acid salt, vitriol, ammonia and metal.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US48985303P | 2003-07-24 | 2003-07-24 | |
| US60/489,853 | 2003-07-24 | ||
| US10/899,326 | 2004-07-26 |
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| CN1856448A CN1856448A (en) | 2006-11-01 |
| CN100422092C true CN100422092C (en) | 2008-10-01 |
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| CNB2004800278308A Expired - Fee Related CN100422092C (en) | 2003-07-24 | 2004-07-26 | System and method for treatment of acidic wastewater |
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| CN (1) | CN100422092C (en) |
| ZA (1) | ZA200600753B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101433086B1 (en) * | 2008-11-17 | 2014-08-25 | 록우드 리튬 잉크 | Recovery of lithium from aqueous solutions |
| CN101602560B (en) * | 2009-07-09 | 2011-12-28 | 天津荣翔正达环保科技有限责任公司 | Method and device for concentrating and reclaiming low-concentration industrial waste acid water |
| US9840667B2 (en) * | 2013-04-25 | 2017-12-12 | Solvay Sa | Reverse osmosis for purifying mixtures of hydrofluoric acid and nitric acid |
| CN106645290A (en) * | 2016-10-11 | 2017-05-10 | 广西大学 | System for pre-warning destabilization of microstickies by utilizing pH value change of white water |
| CN108128933A (en) * | 2018-01-16 | 2018-06-08 | 四川大学 | Silicon-containing wastewater treatment technology in a kind of silicon process |
| CN110304695A (en) * | 2019-06-28 | 2019-10-08 | 南方汇通股份有限公司 | A kind of reclaiming system and method for the high fluorine waste water of high phosphorus |
| CN111252873B (en) * | 2020-02-20 | 2021-06-08 | 中国科学院过程工程研究所 | Source inhibition method for acid mine wastewater |
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| US5766479A (en) * | 1995-08-07 | 1998-06-16 | Zenon Environmental Inc. | Production of high purity water using reverse osmosis |
| US6113797A (en) * | 1996-10-01 | 2000-09-05 | Al-Samadi; Riad A. | High water recovery membrane purification process |
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| US20030080067A1 (en) * | 2001-10-25 | 2003-05-01 | Michalski Dennis H. | Purification of phosphoric acid plant pond water |
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| CN1856448A (en) | 2006-11-01 |
| ZA200600753B (en) | 2007-05-30 |
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