CN102923846B - Combined type biochar enhanced nitrogen removal filler and preparation method thereof - Google Patents
Combined type biochar enhanced nitrogen removal filler and preparation method thereof Download PDFInfo
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Abstract
Discloses a combined type biochar enhanced nitrogen removal filler and a preparation method thereof. The filler comprises modified rice hulls which are filled inside mesh suspended balls and filling rate is 60%. A modified method includes that the rice hulls are thrown into water in proportion of 1g/L : 100g/L, H2O2 is added to enable the water with the rice hulls to be in thickness of 15g/L to 20g/L, and HC1 or H2SO4 is used for adjusting potential of hydrogen (PH) value to 2-3. Besides, FESO4 is added to enable a solution to be in the thickness of 2g/L to 3g/L and then the solution is continuously stirred and reacts for 1.5-2 hours, and the rice hulls are fetched out to be cleaned and dried, and therefore the oxygenated rice hulls can be achieved. Next, in solid and liquid quality volume proportion of 1g/L : 100g/L, the rice hulls after being oxidized are throw into microelement mixed liquor to be soaked for 24 hours and then the solution is continuously stirred so as to enable the surfaces of the rice hulls to be absorbed with microelement. The mixed liquor comprises 1 mol/L FeSO4, 1 mol/L ZnSO4, 1 mol/L CuSO4Na2MoO4, and 1 mol/L MnSO4, and the rice hulls are fetched out to be dried so as to obtain the modified rice hulls.
Description
Technical field
The present invention relates to a kind of combined bio carbon strengthened denitrification filler and preparation method thereof.
Background technology
In recent years, body eutrophication and shortage of water resources problem are day by day serious, and the matter of utmost importance that the caused body eutrophication problem of nitrogen and phosphorus pollution is China's water surrounding.Traditional sewage treatment process is limited in one's ability to the removal of total nitrogen, carries out strengthened denitrification and has carried out a large amount of research, and obtained certain effect by add filler in reactor.But because the carbon-nitrogen ratio in traditional technology is difficult to control, the water-fast biodegradable polymers of synthetic has obtained utilization, is that cost is too high but hinder its reason promoting the use of.
Research shows that agriculture organic solid castoff is the good selection of denitrifying carbon source.China is maximum in the world Rice Cropping country, and rice husk is the main byproduct in the paddy course of processing, accounts for 20% of paddy kernel weight, is very important renewable resources.Data according to statistics, China's rice yield 19510.3 ten thousand t in 2009., within 2009, national rice husk ultimate production is 4009.37 ten thousand t, the 4.57%(2009 whole nation stalk ultimate production that accounts for national stalk ultimate production is 87782.20 ten thousand t).
Carry out certain research about agriculture organic solid castoffs such as rice husks in the application Chinese scholars aspect denitrogenation.
But most of scholar's research only utilizes original agriculture organic solid castoff, do not carry out pre-treatment.Minority scholar has carried out pre-treatment to straw, finds that denitrification effect obviously improves.For example:
" Liaoning chemical industry " the 12nd phase in 2007, " experimental study of rice husk filling biofilter denitrification process ", using rice husk (not pre-treatment) as bio-filter stuffing treatment of simulated sanitary sewage, the denitrification effect of biological filter under different condition is carried out to experimental study.
" China Environmental Science " the 5th phase in 2011, " agricultural waste denitrification solid carbon source preferably ", candidate materials using bagasse, corn cob, rice apple, rice husk, Pericarppium arachidis hypogaeae, 6 kinds of agricultural waste of wood chip as denitrifying carbon source and biofilm carrier, Preliminary Experiment has optimized corn cob, straw, rice husk and can be used as the solid carbon source that substitutes traditional liquid carbon source.(agricultural waste used are not pre-treatment all)
The 4th phase of " Dalian Railway University's journal " calendar year 2001, " cultivating the removal of denitrifying bacteria and nitrate nitrogen taking rice husk as carrier ", cultivates fixing denitrifying bacteria and influence factor thereof taking rice husk (not pre-treatment) as carrier. and carried out the removal experiment of simulated wastewater nitrate nitrogen.
" environmental science " the 4th phase in 2009, " utilizing the research of irradiation pre-treatment straw as denitrification solid carbon source ", adopt through the pretreated stalk of irradiation solid carbon source and the biofilm carrier denitrification denitrogenation as denitrifying microorganism, whether can improve straw as the denitrifying performance of solid carbon source to investigate irradiation pre-treatment.
Study in water treatment about rice husk above, all under pretreated condition, carry out.Though do not carry out pre-treatment, rice husk is all being obtained good effect as biofilm carrier and carbon source aspect strengthened denitrification.Research is unanimously thought: rice husk contains a large amount of robust fibre, xylogen, mineral substance etc., quality is hard, there is a large amount of capillary structures and tiny hole, there is larger specific surface area, be easy to microorganic adhesion, degradation resistant, is a kind of good fixation support, comparatively applicable to being applied to denitrification for Removing Nitrogen engineering.And some scholars research finds that, through pretreated straw, its denitrification effect is had been further upgraded, major cause is through pretreated straw, and utilization can more effectively be degraded by microorganisms.
About the pre-treatment of rice husk, the content of research is little, because the main component of rice husk is xylogen and Mierocrystalline cellulose, though Mierocrystalline cellulose and xylogen can be degraded by microorganisms, but degradation speed is slower, will enumerate rice husk and xylogen and cellulosic pretreatment process below.For example:
The 2nd phase of " Transactions of the Chinese Society of Agricultural Engineering " calendar year 2001, " research of rice husk novel process for recycling ", adopts the quick-fried broken processing of steam boiling, continuously near-critical water processing and burning three steps.
" Chinese agronomy circular " the 10th phase in 2011, " progress of lignocellulose biomass preconditioning technique ", has summed up the pretreated method of lignocellulose biomass.
1) Physical
(1) mechanical disintegration
(2) radiotreatment: gamma-rays, high-velocity electron beam
(3) microwave treatment
(4) ultrasonication
2) physical chemistry processing
(1) steam explosion
(2) SO
2steam explosion
(3) ammonia burst
(4) CO
2explosion
(5) high temperature pyrolysis pre-treatment
3) chemical method
(1) acid treatment
(2) alkaline purification
(3) wet oxidation process
(5) organic solvent processing
(6) ionic liquid processing
4) biological treatment
Pretreatment process for lignocellulose biomass is a lot, but little for the Study on pretreatment of rice husk, studies new pretreatment process and has very large realistic meaning with the bioavailability that improves rice husk.
If rice husk area load is promoted to the trace element of denitrifying bacteria growth, breeding, can make microorganism (especially denitrifying bacteria) in the enrichment fast of rice husk surface.Foreign scholar has carried out correlative study to the trace element that promotes denitrification growth.
" Water Research " the 37th phase in 2003, " Addition of trace metals increasesdenitrification rate in closed marine systems ", points out that the trace elements such as iron, copper and zinc can affect the growing state of denitrification bacterial classification, kind distribution and trophic structure etc.
" Applied and Environmental Microbiology " the 3rd phase in 1998, " Light-mediated nitrite Accumulation during Denitrification by Pseudomonassp.Strain JR12 " added iron in denilrification system, copper, manganese, five kinds of trace elements of zinc and molybdenum, and point two dosage add in reactor, low dosage reactor denitrification rate has increased by 20%, and high dosage reactor denitrification rate has increased by 250%, and find that microorganism does not have transition breeding, show that trace element has obvious pushing effect to denitrification process.
Suspension ball filler is in sewage disposal, to have obtained using widely.The main biofilm carrier that plays a part, have the effect of holding back suspended substance concurrently simultaneously, have that biological attachment power is strong, specific surface area is large, porosity is high, chemistry and Biostatic performance good, durable in use, not stripping nuisance, do not cause secondary pollution, antiultraviolet, the advantage such as anti-aging, hydrophilicity is strong, any soft, half soft, combination, elastic filler cannot realize.
Summary of the invention
The invention provides and a kind ofly can improve nitrogen removal performance, alleviate film and pollute and be conducive to combined bio carbon strengthened denitrification filler that the degraded of microorganism utilizes and preparation method thereof.
The present invention adopts following technical scheme:
A kind of combined bio carbon strengthened denitrification filler of the present invention, comprise: mesh suspension ball, in mesh suspension ball, be filled with modification rice husk, make modification rice husk occupy 60% of the interior space of mesh suspension ball, the mesh aperture of mesh suspension ball is 2-3mm, described modification rice husk is by the rice husk after following disposal methods, and described treatment process is:
Be the ratio of 1:100 grams per liter in solid-liquid mass volume ratio, rice husk is dropped in water, then add H
2o
2make H
2o
2mass volume ratio concentration be controlled at 15-20g/L, then with HCl or H
2sO
4to add H
2o
2after liquid pH regulator be 2-3, then add FeSO
4and by FeSO
4mass volume ratio concentration is controlled at 2-3g/L, and with agitator, with the lasting stirring of 100r/min, reaction 1.5-2h, takes out water by rice husk and clean after 3 times, puts into 60 DEG C of baking ovens and dries, and obtains the rice husk after oxidation;
It is the ratio of 1:100 grams per liter in solid-liquid mass volume ratio, rice husk after oxidation is put in micro-mixed solution and soaked 24h, simultaneously with 150r/min speed continuously stirring, make the trace element in micro-mixed solution in the rice husk surface adsorption after oxidation, described micro-mixed solution is by FeSO
4, ZnSO
4, CuSO
4, Na
2moO
4and MnSO
4composition, FeSO
4, ZnSO
4, CuSO
4na
2moO
4and MnSO
4molecular volume concentration in micro-mixed solution is all 1mol/L, rice husk taking-up is put into 60 DEG C of baking ovens and dry, and obtains modification rice husk.
The preparation method of combined bio carbon strengthened denitrification filler of the present invention, get the mesh suspension ball that rice husk and mesh aperture are 2-3mm, then rice husk is carried out to modification, the modification rice husk again modification being obtained is inserted mesh suspension ball, and make modification rice husk occupy 60% of the interior space of mesh suspension ball, the modification that rice husk is carried out adopts following methods:
Be the ratio of 1:100 grams per liter in solid-liquid mass volume ratio, rice husk is dropped in water, then add H
2o
2make H
2o
2mass volume ratio concentration be controlled at 15-20g/L, then with HCl or H
2sO
4to add H
2o
2after liquid pH regulator be 2-3, then add FeSO
4and by FeSO
4mass volume ratio concentration is controlled at 2-3g/L, and with agitator, with the lasting stirring of 100r/min, reaction 1.5-2h, takes out water by rice husk and clean after 3 times, puts into 60 DEG C of baking ovens and dries, and obtains the rice husk after oxidation;
It is the ratio of 1:100 grams per liter in solid-liquid mass volume ratio, rice husk after oxidation is put in micro-mixed solution and soaked 24h, simultaneously with 150r/min speed continuously stirring, make the trace element in micro-mixed solution in the rice husk surface adsorption after oxidation, described micro-mixed solution is by FeSO
4, ZnSO
4, CuSO
4, Na
2moO
4and MnSO
4composition, FeSO
4, ZnSO
4, CuSO
4na
2moO
4and MnSO
4molecular volume concentration in micro-mixed solution is all 1mol/L, rice husk taking-up is put into 60 DEG C of baking ovens and dry, and obtains modification rice husk.
Compared with prior art, tool of the present invention has the following advantages:
The present invention is taking the carrier of rice husk and carbon source function as basis, the microorganism usability that improves rice husk by pre-treatment is strengthened the function of its denitrogenation, and combine with suspension ball filler, solve the pollution of membrane bioreactor, realize the recycling of pollutant removal and agricultural wastes simultaneously.Rice husk is after pre-treatment, and nitrogen removal performance is improved, and Main change performance is as follows:
Be oxidized front and rear surfaces Fourier Infrared spectroscopy by rice husk and find rice husk main component (as Mierocrystalline cellulose etc.) carbochain fracture, cellulosic degree of polymerization reduces.Fig. 1 is the infrared analysis result on rice husk surface.There is very large variation through the rice husk surface tissue infrared analysis curve of Fenton reagent oxidation as seen from the figure.The rice husk surface of oxidation is at wave number 1023cm
-1the absorption peak at place is slightly high, and wave number 1023cm
-1place belongs to the stretching vibration of carbohydrate C=O, and in all the other wave-number ranges, all absorption peaks all reduce, and this shows to make cellulose chain fracture after Fenton reagent oxidation, and the two keys of C=O increase, and this variation is more easily utilized rice husk by microorganism just.
By the experiment of static denitrification confirm respectively that rice husk after oxidation is conducive to the degraded utilization of microorganism and after micro-load microorganism utilize the denitrification capability of rice husk to get a promotion.
Static denitrification test method is as follows:
Test nutrient solution adopts and add NaNO in distilled water
3and K
2hPO
4, be configured NO by N:P=5:1
3-N concentration is 100mg/L.In every group of 250mL Erlenmeyer flask, add corresponding pre-treatment rice husk 10g, add 100mL active sludge (with the clean centrifugal removal supernatant liquor of distilled water) and 100mL nutrient solution, and clog with soft rubber ball with holes (or absorbent cotton), be positioned over the 12h(25 DEG C that vibrates on gas bath constant temperature oscillator, 140r/min), every 2h gets suspension filtered or centrifugal, NO in monitoring filtrate
3-N content, calculates average denitrification rate.
test active sludge is taken from Wujin of Changzhou Cao Qiao sewage work anoxic pond.
As shown in Figure 2, do not carry out the rice husk of any processing, the rice husk of Fenton reagent oxidation and the difference of the denitrification rate after micro-load: 3.95mg/(L.h), 5.14mg/(L.h) and 5.46mg/(L.h), utilize the denitrification rate of rice husk to improve respectively 30.13% and 38.23% with respect to untreated rice husk microorganism after Fenton reagent oxidation and micro-load.
Brief description of the drawings
Fig. 1 is rice husk infrared scan figure.
Fig. 2 is denitrification capability comparison diagram.
Fig. 3 is combined bio carbon strengthened denitrification filler schematic diagram.
1. modification rice husk, 2. suspension ball
Fig. 4 is rice husk pretreatment process figure.
Fig. 5 is combined bio carbon filler preparation flow figure.
Fig. 6 is that effluent flux is with variation diagram working time.
Fig. 7 is rice husk surface SEM figure.
Embodiment
Embodiment 1
A kind of combined bio carbon strengthened denitrification filler, comprise: mesh suspension ball 1, in mesh suspension ball 1, be filled with modification rice husk 2, make modification rice husk occupy 60% of mesh suspension ball 1 interior space, the mesh aperture of mesh suspension ball 1 is 2-3mm, described modification rice husk 2 is that described treatment process is by the rice husk after following disposal methods:
Be the ratio of 1:100 grams per liter in solid-liquid mass volume ratio, rice husk is dropped in water, then add H
2o
2make H
2o
2mass volume ratio concentration be controlled at 15-20g/L, then with HCl or H
2sO
4to add H
2o
2after liquid pH regulator be 2-3, then add FeSO
4and by FeSO
4mass volume ratio concentration is controlled at 2-3g/L, and with agitator, with the lasting stirring of 100r/min, reaction 1.5-2h, takes out water by rice husk and clean after 3 times, puts into 60 DEG C of baking ovens and dries, and obtains the rice husk after oxidation;
It is the ratio of 1:100 grams per liter in solid-liquid mass volume ratio, rice husk after oxidation is put in micro-mixed solution and soaked 24h, simultaneously with 150r/min speed continuously stirring, make the trace element in micro-mixed solution in the rice husk surface adsorption after oxidation, described micro-mixed solution is by FeSO
4, ZnSO
4, CuSO
4, Na
2moO
4and MnSO
4composition, FeSO
4, ZnSO
4, CuSO
4, Na
2moO
4and MnSO
4molecular volume concentration in micro-mixed solution is all 1mol/L, rice husk taking-up is put into 60 DEG C of baking ovens and dry, and obtains modification rice husk.
Embodiment 2
A kind of preparation method of combined bio carbon strengthened denitrification filler, get the mesh suspension ball 1 that rice husk and mesh aperture are 2-3mm, then rice husk is carried out to modification, the modification rice husk 2 again modification being obtained is inserted mesh suspension ball 1, and make modification rice husk occupy 60% of mesh suspension ball 1 interior space, the modification that rice husk is carried out adopts following methods:
Be the ratio of 1:100 grams per liter in solid-liquid mass volume ratio, rice husk is dropped in water, then add H
2o
2make H
2o
2mass volume ratio concentration be controlled at 15-20g/L, then with HCl or H
2sO
4to add H
2o
2after liquid pH regulator be 2-3, then add FeSO
4and by FeSO
4mass volume ratio concentration is controlled at 2-3g/L, and with agitator, with the lasting stirring of 100r/min, reaction 1.5-2h, takes out water by rice husk and clean after 3 times, puts into 60 DEG C of baking ovens and dries, and obtains the rice husk after oxidation;
It is the ratio of 1:100 grams per liter in solid-liquid mass volume ratio, rice husk after oxidation is put in micro-mixed solution and soaked 24h, simultaneously with 150r/min speed continuously stirring, make the trace element in micro-mixed solution in the rice husk surface adsorption after oxidation, described micro-mixed solution is by FeSO
4, ZnSO
4, CuSO
4, Na
2moO
4and MnSO
4composition, FeSO
4, ZnSO
4, CuSO
4, Na
2moO
4and MnSO
4molecular volume concentration in micro-mixed solution is all 1mol/L, rice husk taking-up is put into 60 DEG C of baking ovens and dry, and obtains modification rice husk.In the present embodiment, the rice husk dropping in water is the rice husk after steam explosion, described steam explosion is: water in high-pressure steam sterilizing pan is added to working water level, first rice husk is wrapped with bundle, put into high-pressure steam sterilizing pan, rice husk accounts for 20% of high-pressure steam sterilizing pan useful volume, open high-pressure steam sterilizing pot, in the time that high-pressure steam sterilizing pan is heated to 120 DEG C, after maintaining 120 DEG C of saturation steams and depressing and continue rice husk heating 30min, open snifting valve, take out rice husk and naturally cool to room temperature, remove the gauze of parcel rice husk, again the rice husk that removes gauze is placed in 60 DEG C of baking ovens and is dried.
Example
Combined bio carbon strengthened denitrification filler, wherein " biological carbon " refers to rice husk (through pre-treatment), and the implication of " combination " is the combination of rice husk and suspension ball.The filler that both are combined into can be in sewage disposal enhanced biological nitrogen removal, and can in membrane bioreactor, alleviate film and pollute, increase effluent flux, be also the recycling of agriculture organic solid castoff (rice husk) simultaneously.
Core of the present invention is the pre-treatment of rice husk, and the pre-treatment integrated approach of employing is: steam explosion+Fenton reagent oxidation+micro-load, wherein Fenton reagent oxidation and micro-carrying method are first and use.Fig. 4 is the pretreatment process figure of rice husk, and concrete grammar is as follows:
1) steam explosion
Steam explosion is to use saturated vapor heating raw, is then suddenly down to the preprocessing means of normal pressure after effect certain hour.Its mechanism of action is in steam explosion process, and high pressure steam infiltrated fiber inside discharges from blind hole gap in the mode of air-flow, makes Mierocrystalline cellulose that certain mechanical breaking occur.Meanwhile, the destruction of the inner hydrogen bond of High Temperature High Pressure aggravation Mierocrystalline cellulose, the free hydroxyl making new advances, in Mierocrystalline cellulose, ordered structure changes, and fibrous material short texture has increased specific surface area and the porosity of biomass greatly.
The method that the present invention adopts: water in high-pressure steam sterilizing pan is added to working water level, first rice husk is wrapped with bundle, put into high-pressure steam sterilizing pan, rice husk accounts for 20% of high-pressure steam sterilizing pan useful volume, opens high pressure steaming cooking vessel, in the time that high-pressure steam sterilizing pan is heated to 120 DEG C, maintain 120 DEG C of constant continuing after rice husk heating 30min of saturated vapor pressure, drop to rapidly normal pressure, take out rice husk and naturally cool to room temperature, be placed in 60 DEG C of baking ovens and dry.
2) Fenton reagent oxidation
Fenton reagent is found in 1894 by French scientist H.J.H.Fenton, by H
2o
2and Fe
2 +a kind of strong oxidizer being mixed to get, can produce the OH free radical that oxidation capacity is very strong.
Optimum oxidation mix proportion scheme has been determined in test: the ratio that is 1:100 in solid-liquid mass volume ratio, drops into rice husk in water, then adds H
2o
2make H
2o
2mass volume ratio concentration be controlled at 15-20g/L, then with HCl or H
2sO
4to add H
2o
2after liquid pH regulator be 2-3, then add FeSO
4and by FeSO
4mass volume ratio concentration is controlled at 2-3g/L, and with agitator, with the lasting stirring of 100r/min, reaction 1.5-2h, takes out water by rice husk and clean after 3 times, puts into 60 DEG C of baking ovens and dries, and obtains the rice husk after oxidation.
3) micro-load
The ratio that is 1:100 in solid-liquid mass volume ratio, rice husk after oxidation is put in micro-mixed solution and soaked 24h, with 150r/min speed continuously stirring, make the trace element in micro-mixed solution in the rice husk surface adsorption after oxidation, described micro-mixed solution is by FeSO simultaneously
4, ZnSO
4, CuSO
4na
2moO
4and MnSO
4composition, FeSO
4, ZnSO
4, CuSO
4na
2moO
4and MnSO
4molecular volume concentration in micro-mixed solution is all 1mol/L, rice husk taking-up is put into 60 DEG C of baking ovens and dry, and obtains modification rice husk.
4) combined bio carbon strengthened denitrification filler
Pretreated rice husk and suspension ball filler (production of Yixing City Ji Neng environmental protection equipment company limited) are combined, combined method is as follows: open suspension ball filler, add pretreated rice husk, making the filling ratio of rice husk in suspension ball is that 60% guarantee rice husk is in the inner fluidized state that forms of suspension ball, close up suspension ball, form combined bio carbon strengthened denitrification filler, Fig. 5 is the preparation flow of combined bio carbon strengthened denitrification filler.
The suspension ball performance perameter that this invention adopts is as following table:
Table 1 suspension ball performance perameter
| Structure formation | Specification | Specific surface area (m 2/m 3) | Porosity | Material proportion | Number of elements/m 3 |
| Spherical | Φ80 | 800 | ≥95 | 0.92 | 2000 |
When use, combined bio carbon filler directly can be added in reactor, filler starts to be suspended in mud mixed liquid surface, along with mud mixed liquid enters by the hole of gauze, suspension ball is inner fully to be contacted with rice husk and under the effect of aeration (dissolved oxygen 2.5mg/L), stirring (500r/min), can realize complete fluidisation through 10-20min filler.Filler can carry out synchronous nitration and denitrification strengthened denitrification through biofilm at suspension ball and rice husk surface formation microbial film, rice husk also can be denitrification process carbon source is provided, combined bio carbon filler washes away, collides film surface under the effect of aeration, stirring simultaneously, accelerate the renewal of film surface biological film, alleviate film pollution, increased effluent flux.
Below in conjunction with a specific embodiment, the present invention is further understood in exemplary illustration and help.
Group membership of the present invention has set up the bioreactor of dynamic membrane pilot scale plant of a set of day output 100t in Wujin of Changzhou Cao Qiao sewage work, the variation that adds filler front and back pollutant removal and membrane flux by investigating in reactor illustrates the effect of combined bio carbon strengthened denitrification filler.
Pilot scale plant is positioned at Cao Qiao sewage work of changzhou city, treatment scale 100t/d, and residence time 8h, intakes as this factory's anoxic pond water outlet, provides oxygen by rotary blower, and aerating system adopts boring aeration, and gas-water ratio is controlled at 10:1.Seed sludge is taken from sewage work's Aerobic Pond, and in steady running process, sludge concentration maintains 8000mg/L left and right.Effluent adopting gravity-elution, head pressure reduction is about 1m.
Test adopts the plate film assembly that 80 areas are identical with structure, and every membrane module is of a size of 1m × 0.5m, total about 70m of effective cross sectional area
2.Mould material adopts gac sponge, aperture approximately 500 μ m, thick 1cm; Membrane module arrangement mode is laterally, longitudinally each 2 arranges the independent water outlet of every row.
In test point two stages: the first stage does not add filler, subordinate phase adds combination biological carbon filler, and injected volume is 2000, and this filler is added to after reactor, and 15-20min can complete fluidisation.
As can be seen from Table 2, add filler after system to COD, NH
3the clearance of-N and TP changes little, all in 1% scope, and the removal effect of TN has been increased to 4%, improves.The filler quantity of throwing in due to test is very little, and it is respond well that 4% total nitrogen reduction shows to combine the strengthened denitrification of biological carbon filler.
Table 2 pollutant removal table (n=35)
Note: data are mean value ± square root of the variance
In order to maintain the stable flux of bioreactor of dynamic membrane, this research is stablized effluent flux by the mode that strengthens aeration back flushing.Concrete operations mode is: system operation about month, close into water and water outlet every day every 8h, opens two Fans back flushing 30-45min simultaneously, reopens afterwards into water and water outlet.In process of the test, find, when reopening the starting stage of flowing water Valve, water outlet muddiness, but after 5-10min, effluent quality recovers, flux also recovery to a certain extent.Concrete variations of flux as shown in Figure 6.
As seen from Figure 6, operation effluent flux in early stage is slow decreasing trend, and flux is by initial 48L/(m
2h) drop to the 17L/(m of 40d
2h).After this by strengthening aeration back flushing, flux has obtained certain recovery, and within front ten days, flux is all at 30L/(m
2h) left and right, flux reduces gradually until 18L/(m afterwards
2h).70d adds combined bio carbon strengthened denitrification filler in reactor, and effluent flux rises and is stabilized in 20L/(m
2h), the lasting 60d of this flux does not decline.This explanation combined bio carbon strengthened denitrification filler, under the effect of aeration, carries out strong waterpower and mechanical erosion to film surface, has accelerated the biomembranous renewal that comes off on film surface, has alleviated film pollution.
After 4 months, take out the rice husk in suspension ball, will can find out by rice husk surface SEM figure (Fig. 7), rice husk surface growth a large amount of coccus and bacillus, microbial is very abundant, is the good carrier of microorganism growth breeding.
In sum, combined bio carbon strengthened denitrification filler has certain effect aspect strengthened denitrification, and can alleviate film simultaneously and pollute, be also the new way of agriculture organic solid castoff recycling simultaneously.
Claims (3)
1. a combined bio carbon strengthened denitrification filler, it is characterized in that, comprise: mesh suspension ball (1), in mesh suspension ball (1), be filled with modification rice husk (2), make modification rice husk occupy 60% of the interior space of mesh suspension ball (1), the mesh aperture of mesh suspension ball (1) is 2-3mm, and described modification rice husk (2) is that described treatment process is by the rice husk after following disposal methods:
Be the ratio of 1:100 grams per liter in solid-liquid mass volume ratio, rice husk is dropped in water, then add H
2o
2make H
2o
2mass volume ratio concentration be controlled at 15-20g/L, then with HCl or H
2sO
4to add H
2o
2after liquid pH regulator be 2-3, then add FeSO
4and by FeSO
4mass volume ratio concentration is controlled at 2-3g/L, and with agitator, with the lasting stirring of 100r/min, reaction 1.5-2h, takes out water by rice husk and clean after 3 times, puts into 60 DEG C of baking ovens and dries, and obtains the rice husk after oxidation;
It is the ratio of 1:100 grams per liter in solid-liquid mass volume ratio, rice husk after oxidation is put in micro-mixed solution and soaked 24h, simultaneously with 150r/min speed continuously stirring, make the trace element in micro-mixed solution in the rice husk surface adsorption after oxidation, described micro-mixed solution is by FeSO
4, ZnSO
4, CuSO
4, Na
2moO
4and MnSO
4composition, FeSO
4, ZnSO
4, CuSO
4, Na
2moO
4and MnSO
4molecular volume concentration in micro-mixed solution is all 1mol/L, absorption is had rice husk after micro-oxidation to take out to put into 60 DEG C of baking ovens and dry, and obtains modification rice husk.
2. the preparation method of combined bio carbon strengthened denitrification filler described in a claim 1, it is characterized in that, get the mesh suspension ball (1) that rice husk and mesh aperture are 2-3mm, then rice husk is carried out to modification, the modification rice husk (2) again modification being obtained is inserted mesh suspension ball (1), and make modification rice husk occupy 60% of the interior space of mesh suspension ball (1), the modification that rice husk is carried out adopts following methods:
Be the ratio of 1:100 grams per liter in solid-liquid mass volume ratio, rice husk is dropped in water, then add H
2o
2make H
2o
2mass volume ratio concentration be controlled at 15-20g/L, then with HCl or H
2sO
4to add H
2o
2after liquid pH regulator be 2-3, then add FeSO
4and by FeSO
4mass volume ratio concentration is controlled at 2-3g/L, and with agitator, with the lasting stirring of 100r/min, reaction 1.5-2h, takes out water by rice husk and clean after 3 times, puts into 60 DEG C of baking ovens and dries, and obtains the rice husk after oxidation;
It is the ratio of 1:100 grams per liter in solid-liquid mass volume ratio, rice husk after oxidation is put in micro-mixed solution and soaked 24h, simultaneously with 150r/min speed continuously stirring, make the trace element in micro-mixed solution in the rice husk surface adsorption after oxidation, described micro-mixed solution is by FeSO
4, ZnSO
4, CuSO
4, Na
2moO
4and MnSO
4composition, FeSO
4, ZnSO
4, CuSO
4, Na
2moO
4and MnSO
4molecular volume concentration in micro-mixed solution is all 1mol/L, rice husk taking-up is put into 60 DEG C of baking ovens and dry, and obtains modification rice husk.
3. the preparation method of combined bio carbon strengthened denitrification filler according to claim 2, it is characterized in that, the rice husk dropping in water is the rice husk after steam explosion, described steam explosion is: water in high-pressure steam sterilizing pan is added to working water level, first rice husk is wrapped with bundle, put into high-pressure steam sterilizing pan, rice husk accounts for 20% of high-pressure steam sterilizing pan useful volume, open high-pressure steam sterilizing pot, in the time that high-pressure steam sterilizing pan is heated to 120 DEG C, after maintaining 120 DEG C of saturation steams and depressing and continue rice husk heating 30min, open snifting valve, take out rice husk and naturally cool to room temperature, remove the gauze of parcel rice husk, again the rice husk that removes gauze is placed in 60 DEG C of baking ovens and is dried.
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| CN103359829B (en) * | 2013-07-31 | 2014-10-08 | 环境保护部南京环境科学研究所 | Biological carbonaceous composite porous filler and preparation method thereof |
| CN105347477B (en) * | 2015-11-13 | 2018-06-08 | 南京工业大学 | A kind of wastewater treatment bionical fluidisation carrier used for biological fluidized bed and its preparation method and application |
| CN108569686B (en) * | 2018-06-13 | 2020-07-21 | 南京农业大学 | Method for removing USEPA PAHs in biochar by Fenton oxidation |
| CN109052634B (en) * | 2018-08-21 | 2021-05-18 | 重庆渝桑环保科技有限公司 | Aerobic microbial filler |
| CN109607779A (en) * | 2019-02-21 | 2019-04-12 | 合肥工业大学 | A kind of method of anerobic sowage ammoxidation coupling solid phase denitrification efficient denitrification |
| CN112047490B (en) * | 2020-08-24 | 2022-11-18 | 上海理工大学 | Method and device for removing ammonia nitrogen in urban river water body by using biochar in cooperation with composite bacteria |
| CN112174293A (en) * | 2020-08-25 | 2021-01-05 | 兰州理工大学 | Electric-enhanced bioretention system for removing low-concentration antibiotics |
| CN115088564B (en) * | 2022-05-24 | 2023-07-07 | 山东省农业科学院 | Ecological efficient cultivation method for inhibiting water and salt of asparagus in coastal saline-alkali soil |
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