CN102417259A - Method for removing iron and manganese from water body in membrane combination process - Google Patents
Method for removing iron and manganese from water body in membrane combination process Download PDFInfo
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- CN102417259A CN102417259A CN2011104041350A CN201110404135A CN102417259A CN 102417259 A CN102417259 A CN 102417259A CN 2011104041350 A CN2011104041350 A CN 2011104041350A CN 201110404135 A CN201110404135 A CN 201110404135A CN 102417259 A CN102417259 A CN 102417259A
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Abstract
The invention relates to a method for removing iron and manganese from a water body in a membrane combination process. The method is characterized by comprising the following steps of: performing aerated oxidation on the water body; and feeding the water which is subjected to aerated oxidation into a continuous membrane filtering system for filtering. The process method related to the invention has the advantages of higher easiness for grasping during practical application, continuous efficient running, no need of maturation phase, small influences by seasons and environments, relatively high operability under the natural condition and good outflow water quality, and the problems of poor precipitating performance, complex process, large floor area, wide water body adaptation range and poor manganese removing effect existing in the prior art can be well solved.
Description
[technical field]
The invention belongs to water-treatment technology field.More specifically, the present invention relates to a kind of method of using ferrimanganic in aeration oxidation and the membrane filtration process removal water body through combination.
[background technology]
Begin one's study from the 1950's removal of iron of China, main method has natural oxidation method, contact oxidation method, strong oxidizer oxidation style and biological process.Must pass through abundant aeration when using natural oxidation method and contact oxidation method to handle water body, and use the filter tank of the active filter that contains irony and manganese matter.This treatment process has increased cost of water treatment on the one hand; On the other hand when iron manganese content is improper in the water; For example iron-holder or manganese content are too high or too low, then can't bring into play the due effect of oxidation precipitation, directly cause effluent quality relatively poor; Therefore applicable surface is less, and natural oxidation method and contact oxidation method technical process complicacy.The strong oxidizer oxidation style is to utilize the chemical agent with strong oxidizing property to come ferrous iron and bivalent manganese in the oxidizing water; For example potassium permanganate oxidation, oxychlorination etc.; Therefore the strong oxidizer method has simply effectively, is easy to management, and degree of oxidation is difficult to control, surplus oxidation medicament can bring secondary pollution problem to subsequent technique but exist.Though biological process is considered to the trend of removing of iron and manganese technology from now on, also is not widely used on the engineering at present, and does not build perfect engineering design theory and parameter determination method as yet.
CN200510070771.9 has proposed oxidation reinforced underground water deferrization and demanganization process; It is characterized in that; Underground water makes underground water and air being higher than thorough mixing contact under the atmospheric pressure through pressurization waterfall device of air, also can increase the solubleness of oxygen in water simultaneously; And the water that the waterfall device of air that will pressurize is discharged is sent in the contact reacts jar; Increase the contacting of oxygen and water, dissolution time, the air-water mixture of contact reacts jar discharge is sent in the catalyzed oxidation bed by the mixture as catalyst of manganese sand, magnetite or manganese sand and magnetite.This technology has increased equipment running cost to a certain extent, and has increased the configuration steps of flow process.
CN200510028182.4 proposes a kind of process method and equipment thereof of removing ferrimanganic in the underground water, and underground water through low strength spray aeration tower aeration aerating, is carried out deferrization and demanganization through the biological uniform filtration device of one-level again.Still there are some problems in this invention, as fails to solve preferably the ferrimanganic in the underground water, long ripening period, the problem that limited by natural condition.
CN200510048083.2 proposes a kind of method of removing iron and manganese by double-layer filtering material; Its characteristics are to filter post and do double-layer filter material with silica sand and manganese sand; It is a heavy manganese sand fine filtering material for lightweight silica sand coarse media lower floor at the middle and upper levels, constitutes upper coarse and lower fine size distribution on the whole.This method filtrate still need arrive certain ripening stage, and the cycle of operation is longer, and filtrate also needs problems such as back flushing.
In recent years, because the membrane sepn process is simple, energy-conservation, occupation area of equipment is little, can do advanced treatment to water body, and effluent quality is good etc. characteristics, membrane filtration technique has obtained application widely in WWT and feedwater field.By this; Method according to aeration commonly used both at home and abroad at present and oxygenant oxidation removal ferrimanganic; Advantage in conjunction with Continuous Membrane Filtration technology; The present invention proposes the method that the film combination process is removed ferrimanganic in the water body, with problems such as poor removal effect, technical process are grown in the solution prior art, effluent quality is poor, need certain ripening stage, floor space is big.
[summary of the invention]
The purpose of this invention is to provide the film combination process and can remove the method for ferrimanganic in the water body efficiently, continuously.
The present invention relates to the film combination process and remove the method for ferrimanganic in the water body.
The present invention realizes through following technical proposals.
Film combination process provided by the invention is removed the method for ferrimanganic in the water body; Comprise water body is carried out the aeration oxidation; Make that dissolved oxygen content maintains 3～15mg/L in the water body, in said water body, add oxygenant simultaneously, said water body residence time in the aeration tank is not less than 1 hour; In said water body, add coagulating agent and coagulant aids again and precipitate, will pass through sedimentary water and deliver in the continuous membrane filter and filter.
Preferably, said oxygenant is selected from potassium permanganate, ozone, dioxide peroxide, chlorine and/or ydrogen peroxide 50.
In the present invention, when water body is carried out the aeration oxidation, can make the pH value of water body maintain 7～10 through adding the pH regulator agent, said pH regulator agent be selected from sodium hydroxide, ammoniacal liquor, sodium hydrogencarbonate and/or yellow soda ash.Generally speaking, when water body was carried out aeration, the pH value of water body was many between 7-8, does not need additional adjustment.But under the situation that contains a large amount of difficult precipitate metal ion in the water body, for example contain a large amount of iron ions, then can precipitate through adding above-mentioned pH regulator agent.
According to a kind of preferred implementation of aforesaid method, said coagulating agent is selected from Poly aluminum Chloride (PAC), Tai-Ace S 150, alum and/or aluminium iron polychloride, and dosage is at 60-200mg/L.Said coagulant aids is selected from SEPIGEL 305, lime, yellow soda ash, clay and/or flyash, and dosage is at 0～10mg/L, precipitate 15-120 minute then after, will pass through sedimentary water again and in delivering to continuous membrane filter, filter.Those skilled in the art can not add coagulant aids, so the addition of coagulant aids can be 0 according to the changing conditions (obvious sediment for example occurring) of adding water body behind the coagulating agent.
Above-mentioned settling step can be chosen in inclined-plate clarifying basin, tube settler, rectangular sedimentation tank, vertical sedimentation basin or the radical sedimentation basin and carry out, or carries out in two kinds of settling tank combinations in said settling tank.
In the present invention, said continuous membrane filter (CMF) system is the membrane filtration system of prior art, and this system generally includes membrane module, pneupress system, back-purge system and PLC robot control system(RCS) and forms.For example adopt the CMF system of record among " application of homemade continuous membrane filter in heat power plant's Water Treatment " people such as (, " Tianjin University of Technology's journal " 03 phase in 2008) Cai Cheng.
Membrane module in the above-mentioned membrane filtration system can be selected micro-filtration type, ultrafiltration type, reverse osmosis type or nanofiltration type membrane module for use, or unites the membrane module of two kinds of uses or above these types.
In the present invention, the film in the said membrane module is existing film, and its material can be Vilaterm (PE), Vestolen PP 7052 (PP), pvdf (PVDF), Vestolen PP 7052 fine (PAN), polyethersulfone (PES) and/or polycarbonate (PC), and membrane pore size is 0.01 μ m-50 μ m.
Membrane module can be selected column-type film components or submerged membrane assembly for use; Membrane element in the membrane module can be selected inner pressed or external-compression type membrane element for use.Column-type film components, submerged membrane assembly, external-compression type membrane element and inner pressed membrane element all are the products that those skilled in the art can obtain or directly buy from market, so its concrete structure is formed and will be repeated no more.
Method of the present invention mainly is applicable to equal height of iron manganese content or water quality relatively than Groundwater with Complicated, and water body can be used as tap water after method of the present invention is handled.Wherein, preferably should adopt to have the method for adding coagulating agent and settling step for the underground water or the trade effluent of the low manganese content of high ferro, like this water body after the processing can as in the situation of water reuse or municipal drainage.
Below technical scheme of the present invention will be described in more detail.
Film combination process of the present invention is removed the method for ferrimanganic in the water body, comprises water body is carried out the aeration oxidation that the water that will pass through the aeration oxidation then filters in delivering to continuous membrane filter.When water body was carried out the aeration oxidation, the pH value of water body should be 7～10.When water body is carried out the aeration oxidation; In said water body, add oxygenant (being selected from potassium permanganate, ozone, dioxide peroxide, chlorine and/or ydrogen peroxide 50); In said water body, add coagulating agent and coagulant aids after the aeration oxidation again; Carry out coagulating sedimentation, will pass through sedimentary water again and in delivering to continuous membrane filter, filter.
The purpose of staying water being carried out aeration is: makes on the one hand and contains sufficient dissolved oxygen in the water body, and complete to guarantee the oxidation of can trying one's best of metals ions such as ferrimanganic; The dissolved oxygen that is capacity on the other hand can be removed the CO in the water
2, and then the pH value of raising water body.The influence of pH value is the pH value, and high oxidization rate is fast more more, and the pH value that therefore can remove ferrimanganic in the water body should be more than 7.0, and+greater than 9.0 o'clock, natural oxidation speed is obviously quickening just at pH for divalent manganese.Therefore,, can water pH value be adjusted to 9-10, can quicken the mn ion oxidation for the outstanding especially water body of mn ion content.
Generally should be at aeration oxidation stage use oxygenant according to the water quality situation.The effect of oxygenant is the ferrimanganic in the further exhaustive oxidation water body.Water temperature generally is lower than 10 ℃ or water mesosilicic acid content when higher during from underground extraction such as underground water, and when the oxidation effectiveness of aeration was restricted, tail end added potassium permanganate with further iron-manganese oxide ion in the aeration tank.This is because the redox potential of iron is littler than manganese, and the iron of+divalent hinders+oxidation of divalent manganese greatly, disturbs the removal of manganese, so demanganization after elder generation's deironing during the ferrimanganic coexistence in the water, and depends merely on the dissolved oxygen that the water body aeration produces and be difficult to make the manganese exhaustive oxidation.In addition; In potassium permanganate and the water when iron, manganese generation redox reaction; Generate water-fast intermediate product Manganse Dioxide, Manganse Dioxide has certain adsorptive power, can adsorb organic compound; Very high activity is arranged, coagulate nuclear as new life again and impel suspended particle or colloid generation cohesion back sedimentation to remove.
According to another kind of preferred implementation of the present invention; When described aeration oxidation stage interpolation oxygenant is potassium permanganate; Can take the circumstances into consideration to add by the amount of iron and manganese earlier; Effective volumetric molar concentration like oxygenant is 0.25～1.5 times of iron ion and mn ion volumetric molar concentration summation, and observes the preceding water body color of filter and in time adjust dosage, guarantees effluent color dilution.
When the water quality that will handle is relatively poor; Exist some can with the ion and the condition thereof of ferrimanganic complexing, as silicate content high with water pH value situation on the low side, the Hydrolysis Reactions of Metal-ions after product is difficult to precipitate in the water body after the aeration oxidation; When the turbidity of water body is big after the oxidation; Can select dosing coagulant and coagulant aids according to practical situation, the settling tank of flowing through of the water body behind the coagulation, and the supernatant after the settling tank precipitating action gets into membrane filtration system through overflow weir.
According to another kind of preferred implementation of the present invention, used coagulating agent is mainly a kind of, two or more combination in Poly aluminum Chloride (PAC), Tai-Ace S 150, alum, the aluminium iron polychloride etc.
According to another kind of preferred implementation of the present invention, used coagulant aids can be a kind of, two or more combination in SEPIGEL 305, lime, yellow soda ash, clay, the flyash etc.
Particularly preferably, can add the Poly aluminum Chloride (PAC) of 80～100mg/L earlier, add the SEPIGEL 305 of 0.5～2mg/L again.Generally speaking, the dosage of Poly aluminum Chloride (PAC) should be judged definite according to the turbidity that forms flco profile and supernatant in the settling tank; The dosage of SEPIGEL 305 is generally confirmed according to the profile of the flco that forms in the settling tank, the turbidity of supernatant and the water outlet viscosity of settling tank.
When precipitating, used settling tank can be selected inclined-plate clarifying basin or tube settler.Select for use suitable settling tank can save floor space on the one hand, help improving effect of settling on the other hand.In the present invention, aerator, coagulation basin, settling tank and water collecting basin can build up the integral type structures, help further saving floor space and reduce the complicated problem that occurs of pipeline.
At last, the water outlet through the coagulating sedimentation stage gets into membrane filtration system.
In the membrane filtration water outlet stage of the present invention, adopt a cover complete and continuous membrane filtration system.Particularly, continuous membrane filter is that a kind of employing has the two filtering systems of washing Technology of membrane element and air water, is equipped with pipe valve, self-stip unit, dosing unit and Automatic Control Unit etc., forms the closed circuit operate continuously system that a cover is used for water filtration.
Usually, said continuous membrane filter (CMF) comprises compositions such as membrane module, membrane element, pneupress system and back-purge system and PLC robot control system(RCS).
According to another kind of preferred implementation of the present invention; Can before getting into membrane filtration system, increase in the said continuous membrane filter and use strainer; To its objective is the water impact load that gets into membrane filtration system in order cushioning, to avoid water quality badly to quicken the situation generation that film pollutes.
In the present invention, about 20～60min of membrane filtration time, about 20～60s of backwash time.
This is because after long-play; When membrane filtration characteristic is reduced to a certain degree; Should shut down and carry out matting; Those skilled in the art use Hydrocerol A, hydrochloric acid, alkali and Youxiaolin or their mixture usually, look the scavenging solution of contaminated situation configuration different concns of film and pH value.
The cleaning of film belongs to techniques well known; Wherein matting mainly contains: chemical dispersion is cleaned (online matting); Adopt the dosing method of back flushing, used cleaning agent is generally the oxidisability medicament, like Youxiaolin, ydrogen peroxide 50, ozone, Peracetic Acid; Restorative matting (off-line matting), cleaning way are circulation flushing and soak certain hour, a kind of, two or more medicament combination in the matting medicaments such as general employing acid, alkali or oxygenant.
Should be pointed out that the method that comprises coagulation and settling step mainly is applicable to the low manganese of high ferro or only ferruginous underground water or trade effluent, and handle the back water body, promptly to handling the less demanding situation of back water quality as middle water reuse or municipal drainage.In this case, do not need water body is carried out coagulating sedimentation, thereby have advantages such as technology is simple, hydraulic detention time is short, treatment capacity is big, processing cost is low, effluent quality is good.
Compared with prior art, beneficial effect of the present invention is following:
The first, the pre-treatment with Continuous Membrane Filtration technology and common process combines into combination process; Can bring into play the process advantage of each section; Can solve the bad problem of oxidation products sedimentation function in the common process, guarantee that effluent quality is best, delivery turbidity can be less than 0.1NTU.
The second, pretreatment technology flexible operation in the film combination process according to the invention, compact construction, floor space are little.
Three, with the technology of comparing other filtrates, film combination process according to the invention does not need the ripening stage, receives seasonal effect little, and technology does not need the ripening stage, receives seasonal effect little, and is lower to the envrionment conditions requirement, can be handling stronger, and it is wide to adapt to the water body scope.
Four, core is a Continuous Membrane Filtration technology in the film combination process according to the invention; It adopts high pollution-resistant membrane and the two technology of washing of air water with matching; Can realize film do not shut down on-line cleaning; Thereby the uninterrupted continuous stable and ideal membrane flux recovery rate that guarantees water production rate of handling, continuous, the efficient operation of production.
[description of drawings]
Fig. 1 is the process flow sheet of method of the present invention.
Wherein, 1, coagulating agent; 2, coagulant aids; 3, mud effluxes; 4, strainer; 5, reflux.
[embodiment]
Following embodiment combines accompanying drawing that the present invention is described without limitation.Those skilled in the art are under the situation that does not break away from the spirit and scope of the present invention; Can also make variations and modifications to technical scheme of the present invention; But all equivalent technical schemes all belong to category of the present invention, and protection domain of the present invention is to be limited claims.
In the present invention; The measuring method of all correlation water indexs is write " water and the effluent monitoring analytical procedure " (the 4th edition that " GBT5750-2001 Drinking Water hygienic practice " and State Environmental Protection Administration write according to health ministry; [), measuring method of stipulating in China Environmental Science Press's publication (2002) carries out assay determination.
854 farms, Heilongjiang Province are the typical underground water source ferrimanganic areas that exceed standard; The total iron content that records in the underground water is 7～10mg/L, and total manganese content is 0.1～0.4mg/L, and (total iron is not higher than 0.3mg/L to total iron content considerably beyond China's drinking water standard; Total manganese is not higher than 0.1mg/L); Total manganese is a little more than standard, and this area's silicate content is higher in addition, and water quality is more special.
Utilize film combination process provided by the invention to remove ferrimanganic in the water body.The pilot scale project of a cover 200t/d is set up at groundwater supply station in this area, and is as shown in Figure 2.
Adopting jet-flow aeration is the aerating apparatus of present embodiment, and jet-pump utilizes swiftly flowing current to form negative pressure principle on its surface air is sucked in the water, contained ferrous iron and bivalent manganese and the oxygen reaction generation throw out at high price that is dissolved in the water in the water.At aeration oxidation stage preparation pH is 2.6 sodium hydroxide solution, and dosage is 20L/d, the pH of aeration tank is adjusted into about 7.5, and adds strong oxidizer potassium permanganate in the rear end of aeration tank, and dosage is for to count 4mg/L with the water yield in the aeration tank.Former water through fully oxidation gets into coagulation basin; Successively add coagulant polymeric aluminium chloride and the coagulant aids SEPIGEL 305 that has prepared; Dosage is respectively 80～100mg/L and 1mg/L, is 30min in the residence time of coagulation basin, and mechanical stirring evenly back gets into settling tank 17.Settling tank is an inclined-plate clarifying basin, and the residence time is 30min.Mixed solution is through getting into water collecting basin at the abundant post precipitation supernatant of settling tank through overflow weir.Water collecting basin water is 20 entering CMF continuous membrane filters behind strainer.
The CMF system is made up of ultra-filtration membrane post, pneupress system and back-purge system and PLC robot control system(RCS) etc., and the ultra-filtration membrane post is an external-compression type pillar film.Water outlet gets into clean water basin behind the membrane filtration, and clean water basin also provide the backwash water.The mud that dense water and settling tank are discharged drains into pipe network through plumbing drain.During normal the operation, chemical dispersion is cleaned 3 days once, and restorative matting cleaning frequency cleaned once according to the water quality situation in general 1～3 month.
Through long-term observation, this pilot process system operational excellence, and iron level is 0.05～0.2mg/L in the water outlet; Manganese content is 0.005～0.08mg/L; It is thus clear that the underground water of overproof water quality is after art breading according to the invention, iron manganese content all can reach China's drinking water standard in the water outlet.
The discharge of wastewater of Shijiazhuang City, Hebei Province city iron and steel enterprise, total iron content 14～18mg/L in the waste water, total manganese content is 0.4～0.7mg/L, is mainly iron level and far surpasses China's industrial wastewater discharge standard.
Steel wastewater discharges the pilot scale project that a cover 100t/d is set up at the station in this area to utilize film combination process provided by the invention; It is the aerating apparatus of this technology that this project adopts jet-flow aeration; Jet-pump utilizes swiftly flowing current to form negative pressure principle on its surface air is sucked in the water, and contained in the water+divalent iron and+divalent manganese and the oxygen reaction that is dissolved in the water generate the throw out of high price.The aeration oxidation stage is adjusted into the pH of aeration tank about 8, and adds strong oxidizer potassium permanganate in the rear end of aeration tank, and addition is 8mg/L.Oxidation stage is adjusted into water body pH about 8 with sodium hydroxide.Former water through fully oxidation forms deposition in the rear end, aeration tank, supernatant gets into water collecting basin through overflow weir.
Establish strainer before the CMF continuous membrane filter, water collecting basin water is gone into continuous membrane filter through strainer is laggard.Form by the outer press mold of submerged, pneupress system and back-purge system and PLC robot control system(RCS) etc.During normal the operation, chemical dispersion is cleaned 2 days once, and restorative matting cleaning frequency cleaned once according to the water quality situation in general 1～3 month.
Through long-term observation, this pilot process system operational excellence, and iron level is less than 2mg/L in the water outlet, and manganese content is less than 0.2mg/L.
With embodiment 2 identical runnings, after difference is to adjust the pH of water body, in water body, add aluminum chloride and the 2mg/L lime of 60mg/L.
The observation operation result, iron level MV is 1.6mg/L in the water outlet, manganese content is less than 0.2mg/L.
Embodiment 4
With embodiment 2 identical runnings, after difference is to adjust the pH of water body, in water body, add Tai-Ace S 150 and the 10mg/L flyash of 200mg/L.
The observation operation result, iron level MV is about 1.9mg/L in the water outlet, and manganese content is less than 0.2mg/L.It is thus clear that the trade effluent that ferrimanganic exceeds standard is after art breading according to the invention, iron manganese content all can reach the emission standard of China's trade effluent in the water outlet.
Claims (9)
1. a film combination process is removed the method for ferrimanganic in the water body; It is characterized in that said method comprises carries out the aeration oxidation to water body; Make that dissolved oxygen content maintains 3～15mg/L in the water body, in said water body, add oxygenant simultaneously, said water body residence time in the aeration tank is not less than 1 hour; In said water body, add coagulating agent and/or coagulant aids again and precipitate, will pass through sedimentary water and deliver in the continuous membrane filter and filter.
2. method according to claim 1; It is characterized in that said oxygenant is selected from potassium permanganate, ozone, dioxide peroxide, chlorine and/or ydrogen peroxide 50, the volumetric molar concentration of oxygenant in water body is iron ion and mn ion volumetric molar concentration summation 0.25～1.5 times in the said water body.
3. method according to claim 1 when it is characterized in that water body carried out the aeration oxidation, makes the pH value of water body maintain 7～10 through adding the pH regulator agent, and said pH regulator agent is selected from sodium hydroxide, ammoniacal liquor, sodium hydrogencarbonate and/or yellow soda ash.
4. method according to claim 1 is characterized in that said coagulating agent is selected from Poly aluminum Chloride (PAC), Tai-Ace S 150, alum and/or aluminium iron polychloride, and said coagulating agent addition is with water body volumeter 60-200mg/L; Said coagulant aids is selected from SEPIGEL 305, lime, yellow soda ash, clay and/or flyash; Said coagulant aids addition is with water body volumeter 0-10mg/L.
5. method according to claim 4; It is characterized in that said settling step carries out in inclined-plate clarifying basin, tube settler, rectangular sedimentation tank, vertical sedimentation basin or radical sedimentation basin, or carry out in two kinds of settling tank combinations in said settling tank.
6. method according to claim 1 is characterized in that said continuous membrane filter comprises membrane module, pneupress system, back-purge system and PLC robot control system(RCS) composition.
7. method according to claim 6 is characterized in that said membrane module is micro-filtration type, ultrafiltration type, reverse osmosis type and/or nanofiltration type membrane module.
8. method according to claim 6 is characterized in that membrane material in the said membrane module is selected from that Vilaterm, Vestolen PP 7052, pvdf, Vestolen PP 7052 are fine, polyethersulfone and/or polycarbonate, and the membrane pore size in the said membrane module is 0.01 μ m-50 μ m.
9. method according to claim 6 is characterized in that being in the said membrane module column-type film components or submerged membrane assembly.
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| CN109336292A (en) * | 2018-11-20 | 2019-02-15 | 湖北省黄麦岭磷化工有限责任公司 | A kind of processing method of Mn-bearing waste water |
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