CN1856448A - System and method for treatment of acidic wastewater - Google Patents
System and method for treatment of acidic wastewater Download PDFInfo
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- CN1856448A CN1856448A CN 200480027830 CN200480027830A CN1856448A CN 1856448 A CN1856448 A CN 1856448A CN 200480027830 CN200480027830 CN 200480027830 CN 200480027830 A CN200480027830 A CN 200480027830A CN 1856448 A CN1856448 A CN 1856448A
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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
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 separation system l8 can comprise one or more reverse osmosis units with separatory membrane (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, second separation system 20 can comprise one or more reverse osmosis units 20 with separatory membrane (not shown), is suitable for providing wastewater treatment, for example the brackish water of about 6-of pH about 7 and the about 20GFD of the about 15-of flow velocity.The same with the reverse osmosis system of first separation 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 first or second separation 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 FiimTec, FilmTec is The Dow
TMChemical Corporation, Midland, the Subsidiary Company of Michigan.First separation system is turned round handle pH to be lower than about 3.5 waste water, with the formation that promotes the hydrosulfate material and/or remove, with formation that suppresses sulfate species and the trend that reduces calcium sulfate scaling.First separation system is turned round handle pH to be lower than about 3.5 waste water, to promote the formation and/or the removal of silicofluoric acid material, to reduce the trend of silicon oxide and Calcium Fluoride (Fluorspan) or the two fouling.First separation system is turned round handle pH to be lower than about 3.5 waste water, to promote the formation and/or the removal of phosphoric acid substance, to reduce the trend of calcium phosphate fouling.First separation system is turned round handle pH to be lower than about 3.5 waste water, to reduce the trend of metal fouling.First separation system is turned round handle pH to be lower than about 3.5 waste water, to promote the formation and/or the removal of ammonium material, to improve the escape velocity of ammonia.Second separation system is turned round handle the waste water of the about 6-of pH about 7, promote the formation of fluorochemical material and/or remove, to promote the removal of this class material.Second separation system is turned round handle 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.Second separation system is turned round handle the waste water of the about 6-of pH about 7, promote the formation of phosphoric acid salt material and/or remove, to promote the removal of this class material.Second separation system is turned round handle 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 first and second separation systems, can adopt other technology to remove pollutent or other material of not expecting, include but not limited to electrodialysis, electric deionize, micro-filtration and evaporation/concentrate.In some situations, Waste Water Treatment can further comprise scale inhibitor and/or the condensing agent source that is configured to introduce scale inhibitor and/or condensing agent in the waste water of the upstream of pretreatment system or any separation system.Any suitable scale inhibitor that suppresses fouling formation in various unit operations according to the present invention can use.Scale inhibitor can still use with the concentration of the about 4ppm of about 3-usually with the use of each manufacturer recommendation.Whole treatment system 22 can comprise one or more unit operations, and described operation further reduces any pollutent 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 negatively charged ion and Zeo-karb 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 TheDow
TMChemical Corporation, Midland, the DOWEX that Michigan obtains
TMMARATHON
TMResin series and can be from Rohm and Hass Company, Philadelphia, the AMBERLITE that Pennsylvania obtains
TMResin series.Waste Water Treatment 10 further comprises acid source 26 and alkali source 28 usually.Acid source 26 is connected with the inlet stream of first separation system 18 usually, and alkali source 28 is connected with the inlet stream of second separation system 20 usually.In this arrangement, can regulate one or more chemical property of pending waste water in first separation system 18 from the acid of acid source 26.For example, the pH that can regulate pending waste water in first separation system 18 inlet 30 is with control and/or keep the solubleness or the balance of one or more chemical substances, for example comprises by for example improving formation that this class solubility of substances and/or promotion comprise this class otherwise complexing material that can sedimentary material suppressing the formation of sedimentable matter.
According to one or more embodiments of the present invention, acid can be introduced inlet 30 and mixes to promote, also to keep or to change equilibrium conditions with pending waste water, suppress any vitriol (SO
4 2-) material formation and/or promote any hydrosulfate (HSO
4) formation of material.As shown in Figure 3, the equilibrium phase of vitriol and hydrosulfate material is to forming the function as pH.Lower pH condition can promote the formation of hydrosulfate material, and higher pH condition can promote the formation of sulfate species.Therefore, control pH can influence the availability of sulfate species, and this material is easy to precipitate in separation system of the present invention usually.
In other embodiments, adopt interpolation acid also to promote, keep or the change equilibrium conditions, with the formation of promotion silicofluoric acid and/or the precipitation of inhibited oxidation silicon and fluorochemical material.As shown in Figure 4, the equilibrium phase of hydrofluoric acid and fluorochemical 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 fluorochemical material.Therefore, control pH can influence the availability of hydrofluoric acid material, this so that influence the formation of silicofluoric 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 conditions, with the solubleness of raising phosphoric acid salt material such as but not limited to calcium phosphate.For example the pH that waits to introduce the waste water in the inlet 30 of first separation system 18 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 is depended on some solid plain, includes but not limited to the factor that supplies property and cost and other processing to consider.For example, hydrochloric acid may be more preferred than sulfuric acid, avoids the rising of any sulfate species concentration.
Same, can be from the alkali of alkali source 28 in order to regulate one or more chemical property of pending waste water in second separation system 20.As the situation that adopts acid to add, can will add alkali advantageously in order to control and/or to keep the solubleness or the balance of one or more chemical substances.For example, the pH that can regulate from the treated waste water of first separation system 18 promotes silicate or fluorochemical material or the formation of the two, is beneficial in second separation system 20 it be removed from waste water stream.Similarly, can regulate this pH, be beneficial in second separation system 20, it be removed from waste water stream to facilitate the formation of phosphoric acid salt and ammoniacal substance.Therefore,, the pH of waste water in the inlet 32 of second separation system 20 can be promoted at least about 6 according to one or more embodiments of the present invention, 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 second separation 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 first separation system.In addition, as shown in Figure 6, the equilibrium phase of phosphoric acid and phosphoric acid salt material is to forming the function as pH.Can control the pH condition and promote H
2PO
4 -The formation of material, this can promote its removal in second separation 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 sodium hydroxide, Ke Xingjia 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 " pollutent " and " material of not expecting " are meant in the waste water or have the material of the concentration limit of qualification in the treated waste water.Pollutent comprises the material that for example comprises calcium, magnesium, sodium, potassium, aluminium, barium, ammonium, supercarbonate, vitriol, muriate, phosphoric acid salt, nitrate, fluorochemical, silicon oxide, iron and manganese.As used herein, the term organism can comprise bacterium, microorganism, algae and the suspended solids that comprises this class material.Also as used herein, " to make ... inactivation " be to instigate organism 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 the figure l 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 can be from the ACTIFLO of OTV SA acquisition
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 (42)
1. method of removing pollutent from waste water comprises:
A. waste water is introduced first reverse osmosis system, removed pollutent from waste water;
B. before waste water is introduced first reverse osmosis system, the pH of control water so that the pH of waste water remain in the selected scope;
C. will introduce second reverse osmosis system from the waste water of first reverse osmosis system, remove pollutent from waste water; And
D. the processing of having experienced in first reverse osmosis system at waste water before handling in second reverse osmosis system, is heightened its pH afterwards.
2. the method for claim 1 is included in waste water is introduced before first reverse osmosis system, and the pH that regulates waste water is to being lower than about 3.5.
3. the method for claim 2 is included in the waste water guiding by before second reverse osmosis system, and the pH that regulates waste water is at least about 6 or higher.
4. the method for claim 3 is included in guiding waste water by before second reverse osmosis system, will be maintained at about 6 or higher from the waste water effluent of first reverse osmosis system.
5. the process of claim 1 wherein that pending waste water comprises fluorochemical, silicon oxide, phosphoric acid salt, metal, calcium and vitriol; And wherein this method can be regulated its pH before waste water enters first reverse osmosis system, thereby waste water is adjusted to the complexing material that is beneficial to formation silicon oxide and fluorochemical, it further is beneficial to the formation hydrosulfate, thereby reduces in first reverse osmosis system trend because of silicon oxide, Calcium Fluoride (Fluorspan), calcium sulfate, calcium phosphate or metal fouling.
6. the method for claim 5 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.
7. the method for claim 6, the waste water of wherein handling also comprises ammonia, phosphoric acid salt or metal; And wherein before waste water enters first reverse osmosis system, the control of its pH is adjusted to waste water to be beneficial to and forms phosphoric acid and ammonium ion, this form to reduce in first reverse osmosis system the 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 common raising, thereby be beneficial to organic removal in second reverse osmosis system.
8. the method for claim 1 is included in before first reverse osmosis system, waste water is clarified by ballast formula flocculation system by guiding waste water.
9. the method for claim 8 is included in waste water is introduced before first reverse osmosis system, guiding from the waste water effluent of ballast formula flocculation system by multiple medium type filter.
10. the process of claim 1 wherein that waste water comprises algae, and wherein this method makes chlorine or chlorine by product mix with waste water to kill algae, and wilkinite is mixed adsorb or make the algae unstability with waste water.
11. the method for claim 10, wherein algae is removed in being arranged at the ballast formula flocculation system of the first reverse osmosis system upstream.
12. the process of claim 1 wherein that its pH of control comprises to the interpolation acid of waste water selective ground before waste water enters first reverse osmosis system; And wherein the pH from the waste water effluent of first reverse osmosis system is heightened and comprise to waste water selective ground and add alkali.
13. a method of removing fluorochemical and silicon oxide from waste water that comprises at least one reverse osmosis system comprises:
A. before waste water is introduced reverse osmosis system, the pH of waste water is remained below about 3.5;
B. wherein keeping pH to be lower than about 3.5 makes at least some fluorochemicals and silicon oxide present the form of silicofluoric acid; And
C. guide the waste water that has silicofluoric acid by reverse osmosis system, fluorochemical and silicate are removed with the silicofluoric acid form in this system.
14. the method for claim 13 comprises that adding acid to waste water selective ground keeps its pH to be lower than about 3.5.
15. the method for claim 14, wherein waste water comprises calcium, and this method comprises by the trend that reduce to form Calcium Fluoride (Fluorspan), calcium phosphate or lime carbonate and reduce fouling in the reverse osmosis system, and further reduces the fouling that the scaling tendency because of silicon oxide causes.
16. the method for claim 15 comprises:
A. will heighten from the pH of the waste water effluent of first reverse osmosis system and guide this waste water into second reverse osmosis system with heightening pH; And
B. the pH that wherein heightens makes fluorochemical and silicon oxide take the form of fluorochemical and silicate ion, and it is removed from waste water in second reverse osmosis system.
17. the method for claim 16, the pH level of control waste water is beneficial to the formation of hydrosulfate, phosphoric acid and ammonium ion under low pH level before and after wherein handling in first reverse osmosis system; And wherein higher pH level is beneficial to the formation of phosphate ion and improves some organic solubleness usually, and it is beneficial to phosphoric acid salt and the removal of ammonia from waste water.
18. a method of removing algae from waste water comprises:
A. add chlorine or chlorine by product to waste water, kill algae;
B. add wilkinite to waste water, absorb or make the algae unstability with wilkinite; And
C. remove algae from waste water.
19. the method for claim 18 comprises with ballast formula flocculation process and handles waste water and wherein remove the algae and the wilkinite of absorption by ballast formula flocculation process from waste water.
20. the method for claim 19 comprises that flocculation agent and insoluble microparticle material are mixed with waste water forms the flocculation mixture, thereby forms algae and bentonitic throw out and the sedimentation from waste water that comprises absorption on microparticle material.
21. the method for claim 18, the waste water that wherein comprises algae is for acid.
22. one kind is lower than about 3 waste water from pH and removes method such as fluorochemical, silicon oxide, vitriol, ammonia and phosphatic pollutent, comprises:
A. in first separation system, remove to the small part all contaminations from waste water;
B. before guiding first separation system into, the pH of waste water is remained below about 3;
C. in first separation system, remove to the small part all contaminations from waste water, will be from the pH regulator of the effluent of first separation system at least about 6 or higher; And
D. will from the pH regulator of the effluent of first separation system to after, in second separation system, remove to the small part all contaminations from waste water at least about 6.
23. the method for claim 22 further is included in and guides waste water into first separation system step of clarified wastewater before.
24. the method for claim 23 is included in clarified wastewater in the ballast formula flocculation system.
25. the method for claim 22 is included in waste water guided into and removes organism from waste water before first separation system.
26. the method for claim 25 comprises by add sterilant, condensing agent or flocculation agent in waste water and removes organic step.
27. the method for claim 22 is included in waste water guided into and fluorochemical in the waste water and silicon oxide is converted into silicofluoric acid before first separation system, and fluorochemical and the silicon oxide of removing the silicofluoric acid form by first separation system.
28. the method for claim 27, wherein first separation system is a reverse osmosis system.
29. the method for claim 27, thereby thereby comprise by enter before first separation system pH with waste water at waste water and remain below the formation that vitriol in about 3 waste water presents the form of hydrosulfate and suppress calcium sulfate and come to remove vitriol from waste water.
30. the method for claim 29, wherein about 3 by before entering first separation system pH of waste water being remained below, the phosphoric acid salt in the waste water tends to present the form of phosphoric acid, and ammonia tends to present the form of ammonium ion; Wherein hydrosulfate, silicofluoric acid, phosphoric acid and ammonium ion can be removed in first separation system efficiently.
31. the method for claim 30, wherein pH is transferred at least about 6 and in waste water, set up such condition: be beneficial to the form that fluorochemical and silicon oxide present fluorochemical and silicate ion, further be beneficial to the form that phosphoric acid salt presents phosphate ion, and improved organic solubleness in the waste water, all these pollutents all will experience in second separation system to be removed.
32. the method handling waste water and remove fluorochemical and silicon oxide from waste water comprises:
A. suppress in the waste water to promote the condition that fluoride ion or silicate ion form one of at least;
B. promote to be beneficial in the waste water condition that silicofluoric acid forms;
C. remove the fluorochemical and the silicon oxide of silicofluoric acid form by guiding waste water from waste water by first separation system;
D. after waste water has been handled, promote to be beneficial to the condition of fluorochemical and silicate ion formation in first separation system; And
E. the waste water of direct packets fluoride and silicate ion passes through second separation system and remove fluorochemical and silicate ion from waste water.
33. the method for claim 32, wherein first and second separation systems comprise first and second reverse osmosis systems.
34. the method for claim 32 is wherein controlled condition in the waste water by the control wastewater pH before and after first reverse osmosis system.
35. the method for claim 34 wherein was controlled to be the pH of waste water before waste water enters first reverse osmosis system and is lower than about 3; And wherein will be controlled to be at least about 6 or higher from the pH of the waste water effluent of first reverse osmosis system.
36. the method for claim 33, wherein waste water comprises other pollutent of ammonia, phosphoric acid salt and vitriol; And wherein by before entering first reverse osmosis system, controlling the pH of waste water, phosphoric acid salt tends to present the form of phosphoric acid, reduce the scaling tendency that rises because of calcium phosphate thus, ammonia tends to present the form of ammonium ion, and this form can be removed efficiently by first reverse osmosis system.
37. the method for claim 36, the pH that wherein improves from the waste water effluent of first reverse osmosis system causes phosphoric acid salt to present the form of phosphate ion, and generally improve organic solubleness in the waste water, and wherein phosphate ion and organism can both be removed in second reverse osmosis system.
38. a Waste Water Treatment, design is in order to remove such as the pollutent of fluorochemical, silicon oxide, phosphoric acid salt, vitriol, ammonia and not remove these pollutents with not generating fouling, and this system comprises:
A. first reverse osmosis system;
B. second reverse osmosis system is arranged on the downstream of first reverse osmosis system;
C. 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, thereby can control the pH of the waste water that enters first reverse osmosis system; And
D. alkali inlet, the waste water effluent that is arranged between first and second reverse osmosis systems and is operably connected with alkali source and optionally alkali is injected before second reverse osmosis system from first reverse osmosis system to enter at waste water is with the pH of control waste water.
39. the Waste Water Treatment of claim 38 further comprises the settler that is arranged on the first reverse osmosis system upstream.
40. the Waste Water Treatment of claim 39, wherein settler constitutes the parts of ballast formula flocculation system.
41. the Waste Water Treatment of claim 39 further comprises the multiple medium type filter that is arranged on the first reverse osmosis system upstream.
42. the Waste Water Treatment of claim 38 further comprises the mixed bed demineralizer that is arranged on the second reverse osmosis system downstream.
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 true CN1856448A (en) | 2006-11-01 |
| CN100422092C 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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| ZA (1) | ZA200600753B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN105142763A (en) * | 2013-04-25 | 2015-12-09 | 索尔维公司 | Reverse osmosis for purifying mixtures of hydrofluoric acid and nitric acid |
| CN105498545A (en) * | 2008-11-17 | 2016-04-20 | 罗克伍德锂公司 | Recovery of lithium from aqueous solutions |
| 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 |
| CN111252873A (en) * | 2020-02-20 | 2020-06-09 | 中国科学院过程工程研究所 | Source inhibition method for acid mine wastewater |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US5766479A (en) * | 1995-08-07 | 1998-06-16 | Zenon Environmental Inc. | Production of high purity water using reverse osmosis |
| CA2186963C (en) * | 1996-10-01 | 1999-03-30 | Riad A. Al-Samadi | High water recovery membrane purification process |
| US6398965B1 (en) * | 1998-03-31 | 2002-06-04 | United States Filter Corporation | Water treatment system and process |
| US6071413A (en) * | 1999-01-13 | 2000-06-06 | Texaco Inc. | Process for removing organic and inorganic contaminants from phenolic stripped sour water employing reverse omosis |
| US6338803B1 (en) * | 1999-08-30 | 2002-01-15 | Koch Microelectronic Service Co., Inc. | Process for treating waste water containing hydrofluoric acid and mixed acid etchant waste |
| IL141642A (en) * | 2001-02-26 | 2003-01-12 | Ide Technologies Ltd | Method of boron removal in presence of magnesium ions |
| AU2002322559A1 (en) * | 2001-07-20 | 2003-03-03 | Microbar, Inc. | Reverse osmosis pretreatment using low pressure filtration |
| US6758976B2 (en) * | 2001-10-25 | 2004-07-06 | Imc Global Operations Inc. | Simplified purification of phosphoric acid plant pond water |
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2004
- 2004-07-26 ZA ZA200600753A patent/ZA200600753B/en unknown
- 2004-07-26 CN CNB2004800278308A patent/CN100422092C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105498545A (en) * | 2008-11-17 | 2016-04-20 | 罗克伍德锂公司 | 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 |
| CN105142763A (en) * | 2013-04-25 | 2015-12-09 | 索尔维公司 | 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 |
| CN111252873A (en) * | 2020-02-20 | 2020-06-09 | 中国科学院过程工程研究所 | Source inhibition method for acid mine wastewater |
| 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 |
Also Published As
| Publication number | Publication date |
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| CN100422092C (en) | 2008-10-01 |
| ZA200600753B (en) | 2007-05-30 |
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