CN203128288U - Combined biochar reinforced denitration filling - Google Patents
Combined biochar reinforced denitration filling Download PDFInfo
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- CN203128288U CN203128288U CN2012205900239U CN201220590023U CN203128288U CN 203128288 U CN203128288 U CN 203128288U CN 2012205900239 U CN2012205900239 U CN 2012205900239U CN 201220590023 U CN201220590023 U CN 201220590023U CN 203128288 U CN203128288 U CN 203128288U
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- rice husk
- husks
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
Abstract
The utility model relates to a combined biochar reinforced denitration filling which comprises modified rice husks filled in meshy suspension spheres, wherein the filling rate is 60 percent and the rice husks are modified by adopting a method comprising the following steps of: putting the rice husks into water according to a proportion of 1: 100g/L, adjusting the solution concentration at 15-20g/L by adding H2O2, then adjusting pH to 2-3 by using HCl or H2SO4, adjusting the solution concentration to 2-3g/L by adding FeSO4, continuously stirring, reacting for 1.5-2 hours, taking the rice husks out, and washing and drying the rice husks to obtain oxidized rice husks; putting the oxidized rice husks to a microelement mixture solution according to a solid-liquid mass volume ratio of 1: 100g/L, soaking for 24 hours, and continuously stirring, so that microelements are adsorbed on the surfaces of the rick husks, wherein the mixture solution consists of FeSO4, ZnSO4, CuSO4, Na2MoO4 and MnSO4 by 1mol/L; and taking the rick husks and drying to obtain the modified rick husks.
Description
Technical field
The utility model relates to a kind of combined bio carbon strengthened denitrification filler.
Background technology
In recent years, body eutrophication and shortage of water resources problem are serious day by day, 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 by add filler in reactor, and obtained certain effect.But because the carbon-nitrogen ratio in the 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.
Studies show that agriculture organic solid castoff is the good selection of denitrifying carbon source.China is maximum in the world paddy rice plantation 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., national rice husk ultimate production was 4009.37 ten thousand t in 2009, the 4.57%(2009 whole nation stalk ultimate production that accounts for national stalk ultimate production is 87782.20 ten thousand t).
Carried out certain research about agriculture organic solid castoffs such as rice husks in the application Chinese scholars aspect the denitrogenation.
But most of scholar's research only utilizes original agriculture organic solid castoff, does 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 ", as bio-filter stuffing treatment of simulated sanitary sewage, the denitrification effect of biological filter under the different condition has been carried out experimental study with rice husk (not pre-treatment).
" China Environmental Science " the 5th phase in 2011, " agricultural waste denitrification solid carbon source preferred ", with bagasse, corn cob, rice apple, rice husk, Pericarppium arachidis hypogaeae, 6 kinds of agricultural waste of the wood chip alternative materials as denitrifying carbon source and biofilm carrier, test has tentatively optimized corn cob, straw, rice husk and can be used as the solid carbon source that substitutes the traditional liquid carbon source.(used agricultural waste are not pre-treatment all)
" Dalian Railway University's journal " the 4th phase of calendar year 2001, " being the removal that carrier is cultivated denitrifying bacteria and nitrate nitrogen with the rice husk " be that carrier is cultivated fixedly denitrifying bacteria and influence factor thereof with rice husk (not pre-treatment). and the removal of having carried out the simulated wastewater nitrate nitrogen is tested.
" environmental science " the 4th phase in 2009, " utilizing irradiation pre-treatment straw as the research of denitrification solid carbon source ", whether employing can improve straw as the denitrifying performance of solid carbon source through solid carbon source and the biofilm carrier denitrification denitrogenation of the pretreated stalk of irradiation as denitrifying microorganism to investigate the irradiation pre-treatment.
More than study in water treatment about rice husk, 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 the strengthened denitrification.Study and consistently think: rice husk contains a large amount of robust fibre, xylogen, mineral substance etc., quality is hard, have a large amount of pore structures and tiny hole, bigger specific surface area is arranged, be easy to microorganic adhesion, degradation resistant is a kind of good fixation support, and is comparatively suitable to being applied to the denitrification for Removing Nitrogen engineering.And the part scholar's research finds that through pretreated straw, its denitrification effect is had been further upgraded, and major cause is through pretreated straw, and utilization can more effectively be degraded by microorganisms.
Pre-treatment about rice husk, the content of research seldom 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 ", the quick-fried broken processing of employing steam boiling, continuous near-critical water are handled and were burnt for three steps.
" Chinese agronomy circular " the 10th phase in 2011, " progress of lignocellulose biomass preconditioning technique " summed up the pretreated method of lignocellulose biomass.
1) physics method
(1) mechanical disintegration
(2) radiotreatment: gamma-rays, high-velocity electron beam
(3) microwave treatment
(4) ultrasonication
2) physical chemistry is handled
(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 is handled
(6) ionic liquid is handled
4) biological treatment
Pretreatment process for lignocellulose biomass is a lot, but for the Study on pretreatment of rice husk seldom, studies new pretreatment process and have very big realistic meaning with the biological utilisation that improves rice husk.
If the rice husk area load is promoted denitrifying bacteria growth, the trace element of breeding, can make microorganism (especially denitrifying bacteria) in the enrichment fast of rice husk surface.The foreign scholar has carried out correlative study to the trace element that promotes the denitrification growth.
" Water Research " the 37th phase in 2003, " Addition of trace metals increasesdenitrification rate in closed marine systems " points out that trace elements such as iron, copper and zinc can influence 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 divide two dosage to add in the 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 the transition breeding, show that trace element has tangible pushing effect to denitrification process.
Suspension ball filler is to have obtained using widely in sewage disposal.The main biofilm carrier that plays a part, have the effect of holding back suspended substance simultaneously concurrently, have that biological attachment power is strong, specific surface area is big, porosity is high, chemistry and Biostatic performance be good, durable in use, not stripping nuisance, do not cause secondary pollution, antiultraviolet, anti-aging, advantage such as hydrophilicity is strong, any soft, medium-soft, combination, elastic filler can't realize.
The utility model content
The utility model provides a kind of can improve nitrogen removal performance, alleviate the combined bio carbon strengthened denitrification filler that film pollutes and be conducive to the degraded utilization of microorganism.
The utility model adopts following technical scheme:
A kind of combined bio carbon strengthened denitrification filler described in the utility model, comprise: mesh suspension ball, in mesh suspension ball, be filled with the modification rice husk, make the 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 that described treatment process is by the rice husk after the following disposal methods:
Be the ratio of 1:100 grams per liter in the solid-liquid mass volume ratio, rice husk is dropped in the water, add H again
2O
2Make H
2O
2Mass volume ratio concentration control at 15-20g/L, then with HCl or H
2SO
4To add H
2O
2After the liquid pH regulator be 2-3, then add FeSO
4And with FeSO
4Mass volume ratio concentration control continues to stir with 100r/min with agitator at 2-3g/L, and reaction 1.5-2h after rice husk taken out water and clean 3 times, puts into 60 ℃ of baking ovens and dries, and obtains the rice husk after the oxidation;
Be the ratio of 1:100 grams per liter in the solid-liquid mass volume ratio, rice husk after the oxidation put in the micro-mixed solution soak 24h, simultaneously with 150r/min speed continuously stirring, make the trace element in the micro-mixed solution on the rice husk surface adsorption after the oxidation, described micro-mixed solution is by FeSO
4, ZnSO
4, CuSO
4, Na
2MoO
4And MnSO
4Form FeSO
4, ZnSO
4, CuSO
4Na
2MoO
4And MnSO
4Molecular volume concentration in micro-mixed solution all is 1mol/L, 60 ℃ of baking ovens is put in the rice husk taking-up dried, and obtains the modification rice husk.
Compared with prior art, the utlity model has following advantage:
The utility model is based on carrier and the carbon source function of rice husk, strengthen the function of its denitrogenation by the microorganism usability of pre-treatment raising rice husk, and and suspension ball filler combine, solve the pollution of membrane bioreactor, realize the recycling of pollutant removal and agricultural wastes simultaneously.Rice husk is through after the pre-treatment, and nitrogen removal performance is improved, and main variation performance is as follows:
Find rice husk main component (as Mierocrystalline cellulose etc.) carbochain fracture by rice husk oxidation front and rear surfaces Fourier Infrared spectroscopy, cellulosic degree of polymerization reduces.Fig. 1 is the infrared analysis result on rice husk surface.Rice husk surface tissue infrared analysis curve through the Fenton reagent oxidation has had very big variation 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
-1The place 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 makes the cellulose chain fracture after the Fenton reagent oxidation, and the two keys of C=O increase, and this variation makes that rice husk is easier and utilized by microorganism just.
Confirm respectively that by static denitrification experiment the rice husk after the oxidation is conducive to the degraded utilization of microorganism and utilizes the denitrification capability of rice husk to get a promotion through microorganism after the micro-load.
Static denitrification test method is as follows:
The 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 (cleaning centrifugal removal supernatant liquor with distilled water) and 100mL nutrient solution, and clog with soft rubber ball with holes (or absorbent cotton), be positioned on the gas bath constant temperature oscillator and vibrate 12h(25 ℃, 140r/min), every 2h gets suspension filtered or centrifugal, NO in the monitoring filtrate
3-N content calculates average denitrification rate.
As shown in Figure 2, do not carry out the rice husk of any processing, denitrification rate difference after the rice husk of Fenton reagent oxidation and the micro-load of process: 3.95mg/(L.h), 5.14mg/(L.h) and 5.46mg/(L.h), utilize the denitrification rate of rice husk to improve 30.13% and 38.23% respectively with respect to microorganism after untreated rice husk process Fenton reagent oxidation and the micro-load.
Description of drawings
Fig. 1 is rice husk infrared scan figure.
Fig. 2 is the denitrification capability comparison diagram.
Fig. 3 is combined bio carbon strengthened denitrification filler synoptic diagram.
1. modification rice husk, ball 2. suspends
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.
Embodiment
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 the 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 the following disposal methods:
Be the ratio of 1:100 grams per liter in the solid-liquid mass volume ratio, rice husk is dropped in the water, add H again
2O
2Make H
2O
2Mass volume ratio concentration control at 15-20g/L, then with HCl or H
2SO
4To add H
2O
2After the liquid pH regulator be 2-3, then add FeSO
4And with FeSO
4Mass volume ratio concentration control continues to stir with 100r/min with agitator at 2-3g/L, and reaction 1.5-2h after rice husk taken out water and clean 3 times, puts into 60 ℃ of baking ovens and dries, and obtains the rice husk after the oxidation;
Be the ratio of 1:100 grams per liter in the solid-liquid mass volume ratio, rice husk after the oxidation put in the micro-mixed solution soak 24h, simultaneously with 150r/min speed continuously stirring, make the trace element in the micro-mixed solution on the rice husk surface adsorption after the oxidation, described micro-mixed solution is by FeSO
4, ZnSO
4, CuSO
4, Na
2MoO
4And MnSO
4Form FeSO
4, ZnSO
4, CuSO
4, Na
2MoO
4And MnSO
4Molecular volume concentration in micro-mixed solution all is 1mol/L, 60 ℃ of baking ovens is put in the rice husk taking-up dried, and obtains the modification rice husk.
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 enhanced biological denitrogenation in sewage disposal, and can alleviate film pollute in membrane bioreactor, increases effluent flux, also is the recycling of agriculture organic solid castoff (rice husk) simultaneously.
Core of the present utility model 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 the saturated vapor heating raw, is down to the preprocessing means of normal pressure behind the effect certain hour then suddenly.Its mechanism of action is in the steam explosion process, and high pressure steam infiltrated fiber inside discharges from the blind hole crack in the mode of air-flow, makes Mierocrystalline cellulose that certain mechanical breaking take place.Simultaneously, the destruction of the inner hydrogen bond of High Temperature High Pressure aggravation Mierocrystalline cellulose, the free hydroxyl that makes new advances, ordered structure changes in the Mierocrystalline cellulose, and the fibrous material short texture has increased specific surface area and the porosity of biomass greatly.
The method that the utility model adopts: water in the high-pressure steam sterilizing pan is added to working water level, earlier 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 the high compressed steam pot, when treating that high-pressure steam sterilizing pan is heated to 120 ℃, keep 120 ℃ of constant continuing behind the rice husk heating 30min of saturated vapor pressure, drop to normal pressure rapidly, take out rice husk and naturally cool to room temperature, be placed in 60 ℃ 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 +Mix a kind of strong oxidizer that obtains, can produce the very strong OH free radical of oxidation capacity.
The optimum oxidation mix proportion scheme has been determined in test: be the ratio of 1:100 in the solid-liquid mass volume ratio, rice husk is dropped in the water, add H again
2O
2Make H
2O
2Mass volume ratio concentration control at 15-20g/L, then with HCl or H
2SO
4To add H
2O
2After the liquid pH regulator be 2-3, then add FeSO
4And with FeSO
4Mass volume ratio concentration control continues to stir with 100r/min with agitator at 2-3g/L, and reaction 1.5-2h after rice husk taken out water and clean 3 times, puts into 60 ℃ of baking ovens and dries, and obtains the rice husk after the oxidation.
3) micro-load
Be the ratio of 1:100 in the solid-liquid mass volume ratio, rice husk after the oxidation put in the micro-mixed solution soak 24h, simultaneously with 150r/min speed continuously stirring, make the trace element in the micro-mixed solution on the rice husk surface adsorption after the oxidation, described micro-mixed solution is by FeSO
4, ZnSO
4, CuSO
4Na
2MoO
4And MnSO
4Form FeSO
4, ZnSO
4, CuSO
4Na
2MoO
4And MnSO
4Molecular volume concentration in micro-mixed solution all is 1mol/L, 60 ℃ of baking ovens is put in the rice husk taking-up dried, and obtains the modification rice husk.
4) combined bio carbon strengthened denitrification filler
Pretreated rice husk and suspension ball filler (the lucky energy of Yixing City environmental protection equipment company limited produces) are made up, combined method is as follows: open suspension ball filler, add pretreated rice husk, making the filling ratio of rice husk in the suspension ball is that 60% assurance rice husk is in the inner fluidized state that forms of suspension ball, close up the suspension ball, form combined bio carbon strengthened denitrification filler, Fig. 5 is the preparation flow of combined bio carbon strengthened denitrification filler.
Suspension ball performance perameter such as following table that this utility model adopts:
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 |
Can directly be added to the combined bio carbon filler in the reactor during use, filler begins to be suspended in the mud mixed liquid surface, the 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 the 10-20min filler along with the hole of mud mixed liquid by gauze enters.Filler can carry out the 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, the combined bio carbon filler washes away, collides the film surface under the effect of aeration, stirring simultaneously, accelerated the renewal of film surface biological film, alleviate the film pollution, increased effluent flux.
Below in conjunction with a specific embodiment, the utility model is further understood in exemplary illustration and help.
The utility model group membership has set up the bioreactor of dynamic membrane pilot scale plant of a cover day output 100t in sewage work, adds the effect that the variation of pollutant removal and membrane flux before and after the filler illustrates combined bio carbon strengthened denitrification filler by investigating in reactor.
Pilot scale plant treatment scale 100t/d, residence time 8h, intaking is 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 sludge concentration maintains about 8000mg/L in the steady running process.The effluent adopting gravity-elution, head pressure reduction is about 1m.
80 areas plate film assembly identical with structure adopted in test, and every membrane module is of a size of 1m * 0.5m, total about 70m of effective cross sectional area
2Mould material adopts gac sponge, the about 500 μ m in aperture, thick 1cm; The membrane module arrangement mode is laterally, vertically respectively 2 arranges the independent water outlet of every row.
Test divides two stages: the fs does not add filler, and subordinate phase adds combination biological carbon filler, and injected volume is 2000, and after this filler was added to reactor, 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 by 4%, improves.Because the filler quantity that test is thrown in is very little, 4% total nitrogen reduction shows that the strengthened denitrification of combination biological carbon filler is respond well.
Table 2 pollutant removal table (n=35)
Annotate: data are mean value ± square root of the variance
In order to keep the stable flux of bioreactor of dynamic membrane, this research is stablized effluent flux by the mode that strengthens the aeration back flushing.The concrete operations mode is: system's operation about month, close into water and water outlet every 8h every day, opens two typhoon machine back flushing 30-45min simultaneously, reopens into water and water outlet afterwards.Find in the process of the test, when the starting stage that reopens flowing water Valve, the water outlet muddiness, but after the 5-10min, effluent quality recovers, and flux also obtains recovery to a certain degree.Concrete variations of flux is seen shown in Figure 6.
As seen from Figure 6, operation effluent flux in early stage is slow downtrending, and flux is by initial 48L/(m
2H) drop to the 17L/(m of 40d
2H).After this by strengthening the aeration back flushing, flux has obtained certain recovery, and flux was all at 30L/(m in preceding ten days
2H) about, flux reduces gradually until 18L/(m afterwards
2H).70d adds combined bio carbon strengthened denitrification filler in reactor, effluent flux rises and is stabilized in 20L/(m
2H), the lasting 60d of this flux does not descend.This explanation combined bio carbon strengthened denitrification filler carries out strong waterpower and mechanical erosion to the film surface under the effect of aeration, accelerated the biomembranous renewal that comes off on film surface, has alleviated the film pollution.
Take out the rice husk in the suspension ball after 4 months, the rice husk surface growth a large amount of coccus and bacillus, microorganism is very abundant mutually, 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, also be the new way of agriculture organic solid castoff recycling simultaneously.
Claims (1)
1. combined bio carbon strengthened denitrification filler, it is characterized in that, comprising: mesh suspension ball (1) is filled with modification rice husk (2) in mesh suspension ball (1), make the 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.
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|---|---|---|---|
| CN2012205900239U CN203128288U (en) | 2012-11-09 | 2012-11-09 | Combined biochar reinforced denitration filling |
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|---|---|---|---|
| CN2012205900239U CN203128288U (en) | 2012-11-09 | 2012-11-09 | Combined biochar reinforced denitration filling |
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| CN203128288U true CN203128288U (en) | 2013-08-14 |
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ID=48936286
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102923846A (en) * | 2012-11-09 | 2013-02-13 | 江苏百纳环境工程有限公司 | Combined type biochar enhanced nitrogen removal filler and preparation method thereof |
| CN108191005A (en) * | 2018-02-01 | 2018-06-22 | 桐乡市易清环保科技有限公司 | A kind of Modified Iron charcoal electrolysis micro nano structure preparation method and sewage water treatment method |
-
2012
- 2012-11-09 CN CN2012205900239U patent/CN203128288U/en not_active Withdrawn - After Issue
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102923846A (en) * | 2012-11-09 | 2013-02-13 | 江苏百纳环境工程有限公司 | Combined type biochar enhanced nitrogen removal filler and preparation method thereof |
| CN108191005A (en) * | 2018-02-01 | 2018-06-22 | 桐乡市易清环保科技有限公司 | A kind of Modified Iron charcoal electrolysis micro nano structure preparation method and sewage water treatment method |
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|---|---|---|---|
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| GR01 | Patent grant | ||
| AV01 | Patent right actively abandoned |
Granted publication date: 20130814 Effective date of abandoning: 20140917 |
|
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