CN106145375A - A kind of preparation and application method for removing sewage and the compositions educating river course again - Google Patents
A kind of preparation and application method for removing sewage and the compositions educating river course again Download PDFInfo
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Abstract
The present invention is a kind of multiple hole material for removing sewage and educate river course again and microbial composite and application process thereof.The immobilization embedded biocatalyzer of the present invention not easily runs off after putting into polluted river channel.This catalyst cannot be only used for the Degradation to sewage Yu river water body pollutant, and this immobilization material also has and can reach to reduce the purpose that overlying water is polluted by bed mud to the absorption fixation of river bottom mud release pollutant.
Description
Technical field
The present invention is a kind of multiple hole material and microbial composite for removing sewage with educate river course again, and said composition is used for controlling the pollution of river, municipal sewage and breeding wastewater.Background technology
Due to long-term settlement, the accumulation of domestic pollutant, causing the black smelly bed mud of city river to deposit, city river sediment pollution is the important sources of black and odorous water, and the external source of black-odor riverway water body is polluted becomes, with sediment pollution, the main source that river water body pollutes.
The black smelly mainly excess of city river is received dirt and is caused oxygen supply of water body and the unbalance result of oxygen consumption, and under water hypoxia or even anaerobic condition, pollutant convert and produce the smelly odorant such as ammonia nitrogen, hydrogen sulfide, VFA and the atrament such as ferrum, manganese sulfide.Sanitary sewage is to cause the black the most universal and topmost smelly polluter of city river.Other polluter also has: house refuse, organic industrial sewage, combined system pipe network overflow sewage, Sewage Plant tail water, livestock and poultry farm fecal sewage etc..
Organic contamination in water body is to cause the black topmost factor of smelly water, pollutant in water body major part again is Organic polluter, organic pollution materials is topmost aerobic substance in water body, these organic pollution materials drain into rivers and creeks, organic material decomposition, under the decomposition of aerobic microbiological, is become CO by early stage2、H2O, causes the dissolved oxygen amount in water to be greatly reduced and causes anoxia, and anaerobe i.e. replaces the organic substance continued in decomposition water, produces sulfide and makes water body blackening, the H that anaerobic effect decomposing organic matter matter produces2S、NH3And CH4The abnormal smells from the patient of multiple micromolecular compound mixes the water surface of blowing out, and makes water body fly away stink.Also research is had to point out, when also having substantial amounts of organic carbon, organic nitrogen and organophosphor to pollute in the middle of water body, no matter the dissolved oxygen amount in water number, the most all by aerobic actinomycetes and the degraded of the microorganism of anaerobism, and different types of material can be generated to cause water body blackening smelly.
Containing large amount of organic matter, nutrient substance, oxygen consumption rate is high, is typically in strong reducing environment, and it is too high that river bottom mud secondary pollution is easily caused the harmful substance contents such as ammonia nitrogen in water body, nitrite, sulfide, excrement be smelly, cause black and odorous water, affect urban look and resident living.Pollution of river bed mud produces big impact to overlying water water quality, the improvement of bed mud can effectively control and reduce the release of the pollutions such as its COD (COD Chemical oxygen demand), nitrogen, phosphorus recycling and the pollution to overlying water, therefore control mercury, be the important step of urban river environmental improvement.
For controlling, the measure of sediment pollution is the thinnest completed desilting in the past, this method is relatively costly, the remarketing of bed mud is also a complicated the difficult problem of environmental protection: by water body aeration oxygen replenishing, can to a certain degree reduce sediment pollution, but shallower river course being easily caused sediments re-suspension: add microorganism formulation in river course, this method has certain effect, shortcoming to be that microorganism formulation is easy to run off in river course to strengthening water body self-purification ability, frequently throw in, high cost.
Biological restoration refers to biology, particularly microbial catalyzed degradation organic pollution, thus repairs contaminated environment or eliminate the process of pollutant in environment.Microbe species in water body is many, metabolic type is various, adaptable, utilize the microorganism remediation polluted-water being originally present in water body, the detergent power of strengthening nature administers contaminated water body, have less investment, consume energy the advantages such as low, convenient management, safety, meets and sets up economy, resource loop, sustainable development society theory.
Microorganism immobilization method refers to the method utilized chemically or physically, is positioned by free microorganism in the area of space limited, and keeps integrity, and the basic fundamental of energy Reusability.Intact cell can be fixed by immobilization technology, enzyme integrity and stability can be maintained to greatest extent, improve microbe density and flow rate in identical element volume, repair process is not limited higher than growth of microorganism rate by dilution rate, immobilization microenvironment is conducive to the adverse effect of shade external environment, the hydraulic property of immobilization particle and settling property can control flexibly, are the pollution law technology of a highly effective.
The criteria for classification that immobilization method of microorganism is the most unified at present, method is the most varied, but mainly have surface adsorption (in conjunction with) immobilization, crosslinking (binding) immobilization, the several method such as (polymer) embedded immobilization and self immobilization (self-crosslinking immobilization between microbial cell).In immobilized microorganism technique, most commonly seen with investment.Investment is microorganism to be enclosed in the networking of natural macromolecule amylose class or synthesis high-molecular gel, so that microbial immobilized.It is characterized in immobilized microorganism can be prepared as variously-shaped (spherical, block, cylindric, membranaceous, cloth-like, tubulose etc.), and the microorganism after immobilization can be rised in value, so the most study to it, applies the widest.The material used in investment mainly has sodium alginate, polyvinyl alcohol, triacetate fiber, agar etc., and adds auxiliary material such as activated carbon, rectorite, limestone etc. to improve the performance of embedded material.In the antimicrobial treatment process of waste water, mainly utilize the biological chemistry action of microorganism, organic pollution in waste water is as nutrient substance required in microbial life active procedure, and be absorbed and used during the vital movement of microorganism, and it be converted into and be easily isolated or harmless material.Microorganism has improvement water quality, biological self cleaning, suppression algae excessive propagation in water body, controls body eutrophication, increases dissolved oxygen, reduces COD, reduces ammonia nitrogen, reduces phosphorus content, improves the functions such as water environment ecological balance.There are some researches show, in the case of not administering river bottom mud, through the improvement of the measures such as oxidation pond pretreatment, river water body oxygen supplement, water body in-situ bioremediation, river course downstream water the most gradually recovers black smelly.After river bottom mud carries out biological reinforced oxidation reparation, polluted river water water quality is significantly improved and improves.
Embedded immobilization biocatalyzer (IBC, immobilized biocatalysts) advantage include: low cost, immobilization easily operate and can be made into variously-shaped, can, immobilization rear bearing cells in vivo harmless to microorganism in being fixed, immobilization under normal temperature and pressure spill few, in environment, other microorganisms are not easily accessible, substrate permeability is good, physical strength and chemically stability good (Wang Jianlong, 2002).
Biocatalyzer (Biocatalyst) refers to protease or the living biological cell with catalytic capability, it is also likely to be nucleic acid (Cech under special circumstances, 1993), enzyme is material necessary in all life entities, and enzyme can be with effective percentage and be selectively catalyzed the chemical conversion in various life entity.1839, Payen and Persozu have studied the process that Fructus Hordei Vulgaris hydrolysis starch is dextrin and sugar being in germination state, and is purified into amylase (Payen, 1839).When 1973, Japan's thousand cigarette one Lang Liyong polyacrylamide gel embedded immobilizations had escherichia coli (Escherichia coli) aspartic acid (thousand cigarette one youths, 1975) of high activity aspartase.The correlational study of immobilized biocatalyst (Immobilized biocatalyst) developing rapidly after this.
Zeolite is the carrier of a kind of common biocatalyzer, by solid absorption method, microbial cell is adsorbed onto zeolite surface, and the structure of zeolite is the tetrahedral framework (SiO with silicon or aluminum oxide4Or AlO4) as ultimate unit, form a kind of three-dimensional space framing structure (Oliveira and Rubio, 2007, Malekian et al., 2011) by oxygen atom link silicon, the tetrahedron of aluminum.Because aluminum atom band three valence charge, it is combined into AlO with oxygen atom4During tetrahedral framework, total presents electronegative state, therefore the negatively charged ions near arround adsorbing is electrical to neutralize it, also because such a kind of skeleton construction creates many holes and cavity, zeolite has the biggest surface area of other mineral (400-800m2/g), such structure makes zeolite have powerful absorption affinity and ion-exchange capacity, the hole size of zeolite surface is uniform, average at 0.3mm-1.0mm, (Popov et al., 2012) all can be adsorbed less than the material of this diameter.Zeolite is utilized to do living things catalysis agent carrier, amass big except zeolite surface has many well table, microbial cell do not had nocuity, in biological denitrification process, on the one hand zeolite self can also adsorb the ammonia nitrogen in water during exchanging via ion, on the other hand by zeolite electrostatic interaction, nitrifier is fixed and at zeolite surface one layer of biomembrane of formation, biomembrane can be by the ammonia nitrogen in zeolite self absorption water via being chemically converted to nitrate, a kind of oneself absorbs and the circulation of oneself's nitrification occurs on the surface of zeolite, the ability of zeolite ammonia nitrogen is because the effect of surface microorganism constantly regenerates, so utilizing zeolite to do microorganism catalysis agent carrier in the technique of biological denitrificaion, during composed physical absorption for the most double, ion exchange and biological nitration three processes (Bai et al., 2010).
The immobilization compound probiotic agent (CBM of the present invention, complex beneficial microorganism) put into after polluted river channel, not easily run off, not only strengthen the microbial bacterial agent Degradation to pollutant, its immobilization matrix may additionally facilitate the absorption fixation to sediment release pollutant, pollutes overlying water further up to reducing bed mud.
The present invention selects zeolite to be carrier, and zeolite mean specific gravity is 2.12, and volume is at 0.05-0.15cm3Scope is appropriate, and its porosity is suitable for the absorption of micro-cattle umbrella thing to be fixed, and can be fixed complete microbial cell, it is to avoid the integrity of artificial destruction enzyme and the stability of biochemical reaction；Growth rate is fast, effective.Zeolite be carrier immobilized cell particle for static or unhurried current polluted-water in bed mud, directly can add according to pollution level, simple to operate, it is not necessary to change natural environment and build extensive structures, do not produce secondary pollution.Zeolite abundance, low price.Reduce investment outlay, simple flow, safe and reliable in practice, economically low cost, the 30-50% that construction investment is only Physical, chemical method is repaired.
Carrier used in the present invention can replace with spherical algin.Use compound bacteria (nitrifier and denitrifying bacterium), plus the algin embedding using biphase (aerobic and anoxia), its principle is to utilize this oxygen within spherical algin distribution difference, and due to the penetration of oxygen, algin is internal is anoxic zone (anaerobic zone)；Algin is outside is aerobic district (aerobic zone).Effectively remove ammonia nitrogen in sewage and be divided into two steps: Nitrification (nitrification；Aerobic state) product is nitric acid (NO3), with nitrous acid (NO2)；Denitrification (denitrification；Anaerobic state) product is nitrogen (N2).Aerobic environment, can only carry out Nitrification；Otherwise, Denitrification can only be carried out.General polluted river channel or treatment tank, be difficult to maintain with place aerobic and anaerobic state simultaneously, or be only to embed single nitrification strain, and it is the best except ammonia nitrogen effect；The algin that the present invention uses has the algin embedding compound bacteria compositions of biphase (aerobic and anoxia), for ammonia nitrogen in sewage more efficiently
The microorganism that the present invention selects is amphimicrobian mixed vaccine, the microorganism energy long-lasting cleanliness after immobilization；The microenvironment of immobilized cell particle is conducive to shade original inhabitants' probiotics, toxicant to the harmful competition of microbial body, swallows and poison so that it is play consistently high-effect under complicated environmental condition.The present invention uses biological restoration to refer mainly to microorganism remediation, specially inorganic carrier zeolite adsorption fixation of microbe, fast to compound bacteria adsorption rate, cultivation effect good.
The present invention falls within bed mud bioremediation agents, is made up of complex micro organism fungicide, oxygenation agent and fixation support, may also include biological nutritive agent and biologic detoxication agent ancillary drug, reaches efficiently to remove the purpose of dirty water pollutant.Owing to most pollution of river regions are big, tool mobility, primary type microorganism is hardly formed dominant degradation bacteria group, the special nature of polluted bed mud proposes higher requirement to biological restoration undoubtedly, combination advantage degradation flora must be screened, and its density of microbe immobilized particles, advantage degrading microorganism flora just can be made to touch polluted bed mud, reach the purpose of removal organic polluter.
Ecological dredging agent is the environmental purifying agent of a kind of excellent performance, by improving vitality and the self-purification capacity of water body, promptly improves water quality, is the purification method of a kind of economy.Ecological dredging agent has the function of precipitation, and itself and the microorganism adhered to thereof not easily run off, even if in the river course of water flowing, lakes and marhshes, reservoir and the places such as the seabeach of ebb, bay of rising, can effectively work.Even if in the deepest waters, bottom can be sunk to, the Organic substance in mud be absorbed and decomposes, and reach the effects such as water purification, oxygen supplement, elimination stench.In actual application, other bio-carrier needs in river course to fix just can work, and is often washed away by current and need to carry out reduction, uses ecological dredging agent the most not have this phenomenon.
Discharge ecological dredging agent, without machines for mud clearage, clear mud, there is no reeky desilting scene.Owing to pollution condition is different with mud situation, according to application example before, discharging an ecological dredging agent, the mud 4-6 in river course month can reduce 20-30 centimetre.After discharging ecological dredging agent, it is not necessary to the black smelly river course of aeration aerating equipment, originally anoxia quickly purifies.It can be seen that a lot of aquatic animal after water quality is purified, promote hydrobiological food chain reparation.This process, without throwing in fry and other species, has just grown many aquatiles and the shoal of fish for tens days, is therefore well suited for purifying substrate pollution and water ecology reparation.
Eliminate mud replacement desilting with ecological dredging agent and repair aquatic ecological simultaneously, can dock with original river course comprehensive control task, greatly reduce difficulty of governance, raising regulation effect, and non-secondary pollution.After discharging ecological dredging agent, the microbes biomass of cleanser and absorption set thereof is huge, can absorb and decompose ammonia nitrogen, nitrate, nitrite, hydrogen sulfide, sulphur compound and other nutritional labeling, the cause sordes contained in water body and mud.The effect of ecological dredging agent is to absorb to decompose the Organic substance contained in mud, and after Organic substance is completely absorbed decomposition, bed mud surface is exactly one layer of sandstone inorganic matter not decomposed by absorption, and mud face becomes canescence.Ecological dredging agent can also be rendered in treatment tank, sludge-tank, can decompose removing residue mud, purify water, eliminates stench etc..Ecological dredging agent is purifying seabeach sludge, is decomposing aquatic farm mud, improves the water quality of sewage disposal, removes stink, removes poisonous algae and purify water body in lake etc., has outstanding detergent power.
Summary of the invention
A kind of compositions for removing sewage with educate river course again, said composition includes modified zeolite and microbial composite.
A kind of compositions for removing sewage with educate river course again, said composition includes algin and microbial composite.
The co-cultivation condition of this microbial composite be with 28 DEG C, rotating speed 200rpm, under the intensity of illumination illumination as 1000lux, cultivate 7 days continuously；After adding 5% molasses, 0.4% carbamide and 0.15% potassium dihydrogen phosphate, temperature is controlled in 28 DEG C and with fermentation tank continuous fermentation 5 days.
This modified zeolite manufacture method is that (mordenite, chemical formula is (Ca, Na by modenite2,K2)Al2Si10O24·7H2O) clean with distilled water and dry, then zeolite is soaked in 5% hydrochloric acid 2 hours；Clean to pH value as neutrality with distilled water again and dry, and zeolite being soaked in 5% sodium hydroxide 2 hours, clean to pH value as neutrality with distilled water and dry.
A kind of method using composition removing sewage and educate river course again, said composition includes modified zeolite and microbial composite.
Said composition is put in sewage or in river course, i.e. pollutant in degradable water.
It is that every liter of sewage adds 3-8 gram that said composition makes an addition to sewage quantity.
This sewage refers to the sewage at ditch, cistern, Sewage System, river course.
It is that every square centimeter of river area adds 400-750 gram that said composition makes an addition to streamflow.
The method that this removing is polluted includes reducing amine ion, nitrite ion, sulfur-containing compound, phosphorus-containing compound, solid-state aerosol concentration, with reduction BOD, COD.
The invention have the benefit that the occasion that technique is particularly well suited for carrying out dredging operation.Overcome somewhat expensive, noise is excessive, easily give an offensive smell, be difficult to the difficult problems such as handling problems.Use compound substrate cleanser heavy metal and phosphorus can play certain stable, harmless effect.Proceed to bed mud as chromium and phosphorus could act as deposit and reduce the release to overlying water.Use novel substrate cleanser that the river course of severe contamination can carry out muddy water integration ecological reparation.This technical operation is simple, to river flood control without any adverse effect, without extra charge in running.
Accompanying drawing explanation
Fig. 1 be sweep electron microscope shooting modified zeolite and zeolite cladding CBM (A is the SEM figure of the zeolite that NaOH/HCl processes, B be process after the SEM figure of zeolite covered composite yarn probiotics)；
Fig. 2 is to analyze modified zeolite for ammonia nitrogen absorption with bright mould isothermal adsorpting equation formula；
Figure is the ability of 3 compound bio catalyst and zeolite adsorption ammonia nitrogen；
Figure is that 4 immobilized biocatalysts process (A) ammonia nitrogen concentration of fresh water waste water, (B) nitrite ion concentration；
Fig. 5 is that immobilized biocatalyst processes (A) ammonia nitrogen concentration of sea water waste water, (B) nitrite ion concentration；
Fig. 6 is that immobilized biocatalyst processes (A) ammonia nitrogen concentration of sea-farming sewage, (B) nitrite ion concentration, (C) COD concentration, (D) sulfur-containing molecules concentration；
Fig. 7 is that immobilized biocatalyst processes (A) ammonia nitrogen concentration of black foul sewage water, (B) nitrite ion concentration, (C) COD concentration, (D) suspended solid particle concentration, (E) phosphorous molecular concentration, (F) sulfur-containing molecules concentration at the bottom of river course；
Fig. 8 is for being compounded with each strain quantitative analysis of each culture period of beneficial microorganism.
Detailed description of the invention
Prepared by CBM composite probiotics ferment
nullUse purchased from Hsinchu food industry institute living resources and the purebred bacterial strain at the center of preservation (BCRC)，Enrichment amplification culture photosynthetic bacteria、Bacillus subtilis、Nitrifier、Lactic acid bacteria、Der Pilz、Actinomycetes、Yeast，7 big class bacterial strains prepare compound probiotic (CBM) with commensalism cultivation，This compound bacteria includes following strain: Rhodopseudomonas palustris、Rhodospirillum rubrum、Rhodobacter sphaeroides、Lactobacillus pentosus、Lactococcus lactis、Bacillus subtilis、Saccharomycopsis fibuligera、Ochrobactrum anthropi、Thiosphaera pantotropha、Achromobacter denitrificans、Pseudomonas stutzeri、Penicillium citrinum、Chaetomium globosum、Aspergillus oryzae、Aspergillus niger、Myrothecium verrucaria、Pichia psedopastoris、Streptomyces albulus.Culture medium and the best growing condition according to each bacterial strain are cultivated；Culture medium prescription is as follows:
YM MEDIUM(Saccharomycopsis fibuligera)
YPD MEDIUM(Pichia psedopastoris)
YEAST STARCH MEDIUM II(Streptomyces albulus)
LACTOBACILLI MRS BROTH(Lactobacillus pentosus、Lactococcus lactis)
NURIENT MEDIUM(Rhodopseudomonas palustris、Rhodospirillum rubrum、Rhodobacter sphaeroides、Achromobacter denitrificans、Ochrobactrum anthropi、Pichia psedopastoris、Bacillus subtilis)
NS(non-sulfur)MEDIUM(Rhodopseudomonas palustris、Rhodospirillum rubrum、Rhodobacter sphaeroides)
Mineral mixed liquor: magnesium sulfate hydrate (MgSO4·H2O): 0.2g, potassium hydrogen phosphate (K2HPO4): 1.0g ferrous sulfate hydrate (FeSO4·H2O): 0.5g calcium chloride CaCl2: 0.02g manganous chloride (MnCl2·H2O): 0.002g sodium molybdate (NaMoO4·H2O): 0.001g finally adds distilled water to 1.0L.
MALT EXTRACT MEDIUM I(Blakeslaa’s Formula)(Aspergillus oryzae、Chaetomium globosum、Penicillium citrinum)
Glucose it is initially charged before sterilizing
POTATO DEXTROSE MEDIUM(PDA)(Aspergillus niger)
After above-mentioned each purebred bacterial strain reaches 109cfu/ml, through by each purebred bacterium solution mixed in equal amounts, cultivating the cultivation that coexists (symbiotic culture) with anaerobism 5～7 days with 60Lux illumination, agitation 50rpm mode again, this purpose is to make mixing anaerobic bacterium be supplied to the desired substance of different flora from the culture fluid of aerobic bacteria (to include: carbon source and nitrogen source；Aminoacid, saccharide, fat, vitamin), these nutrient matrixes, it can be ensured that these microorganism species form a Mutualism, the stable Microbial ecosystem of commensalism existence.
Front step commensalism mixed culture flora again with 28 DEG C, rotating speed 200rpm, under the intensity of illumination illumination as 1000lux, cultivate 7 days continuously.This step is to amplify (first amplification) for the first time.
Front step commensalism mixed culture is after flora adds 5% molasses, 0.4% carbamide and 0.15% potassium dihydrogen phosphate, and temperature is controlled in 28 DEG C and with fermentation tank continuous fermentation 5 days, CBM compound probiotic liquid.This step is that second time amplifies (second amplification).
Prepared by carrier zeolite
HCl-NaOH method of modifying: zeolite is cleaned with distilled water and dries, then zeolite is immersed in 5%HCl 2 hours.It is washed till pH value with distilled water as neutrality and to dry, the most again zeolite is immersed in 5%NaOH 2 hours, be washed till pH value as neutrality and dry for standby with distilled water.
Novel immobilization is combined bed mud cleanser and is microbial immobilized main matrix with zeolite and adds slow release oxygenation agent and activated carbon.Zeolite successively increases specific surface area and porosity, the organically-modified raising absorbability to anion through heat modification.Zeolite its rack-like inside configuration after modified is filled with micropore and passage, huge biological attachment surface area, internal hole can be provided also to have the effect of screening molecule for microbiologic population, it is possible to selection advantage microbial population and help they procreations.In order to make bed mud exists micro-oxygen conditions, slow release oxygenation agent calper calcium peroxide also can be used.Its effective content 80%, theoretical oxygen supplement amount 0.22O2Mg/mg, and 1.38mg/mg basicity can be produced.This patent carries out the screening of bacterial strain from the bed mud of native country, is enriched with 8 big more than the 20 kind of bacterial strains of class such as amplification culture photosynthetic bacteria, bacillus subtilis, nitration denitrification antibacterial in commensalism mode to preparing compound probiotic (CBM).Immobilization is combined substrate cleanser and makes graininess, moisture content 15%, average density 2.6.
Prepared by carrier algin
It is that underlying carrier adds water to 100 grams with 10% polyvinyl alcohol (PVA) and 2% sodium alginate (sodium alginate), it is heated to after PVA is completely dissolved adding 2 grams of modified zeolite powders in 80 DEG C, in 121 DEG C, 1.5 atmospheric pressures (atm) carry out sterilizing 20 minutes, place be cooled to room temperature.Bacterium mud after addition 10% is centrifugal, pours the mixture in 50mL syringe, slowly instills containing 2% calcium chloride (CaCl2) boric acid saturated solution at 4 DEG C immobilization formed diameter 3 millimeters (mm) bead, the set time is 24 hours, 2 to 3 times can be standby with physiology distilled water flushing after taking-up.
Embodiment 1 modified zeolite surface ratio is relatively
Modified zeolite is shot the surface ratio surface compared with unmodified zeolite with sweep electron microscope (SEM) by this experiment, experimental result represents that modified zeolite surface has the vestige corroded by strong acid and strong base, surface significantly extends expansion, hole aperture becomes big, illustrate increase through modified zeolite surface area, and then increase the absorbability (the 1st figure) of ammonia nitrogen.The surface area that can make zeolite during sodium hydroxide modification reduces with total pore volume ratio to have research to point out, represent that the aperture of zeolite surface hole also can increase, that ion is conducive to replace, and then improve the zeolite absorbability (Zhu Fenghua etc. for ammonia nitrogen, 2010), Sun Xingbin et al. utilizes modified zeolite to study the ability of its dephosphorization, result of study represents that unmodified zeolite surface is in irregularly, hole space is less, although surface has been covered with duct, but major part duct is blocked by other materials, the case shell of modified zeolite becomes distinct, the hole on surface becomes big, form a kind of coralloid surface texture, such surface texture adds the surface area of zeolite surface, also improve the absorbability (Sun Xingbin etc. of zeolite, 2010).
Bright mould isothermal adsorpting equation formula (Langmuir isotherm)
Among, q in equationeUnit adsorbent amount (mg/g) during for reaching adsorption equilibrium, C is the equilibrium concentration of adsorbate, qmFor adsorbent saturated extent of adsorption (mg/g), KLIt it is then constant.By inverted for Langmuir equation:
With 1/qe1/C is mapped, obtains the saturated extent of adsorption q of adsorbent from intercept and slopem=17.89mg/g, absorption constant KL=3.42L/mol.
The linear regression R Spuare value of Langmuir isothermal adsorption patterns is high, represents the modified mordenite absorption mode for ammonia nitrogen, meets Langmuir isothermal adsorption patterns, absorption constant KLThe highest represent adsorbent ability the highest (the 2nd figure).The absorbability of ammonia nitrogen to the characteristic of natural intelligence zeolite (being mainly composed of oblique method zeolite and modenite) and is made a search by Englert et al., and result of study represents that natural Chile zeolite table surface area is 177m2/ g, is 1.02m to ammonia nitrogen ion exchange capacityeq/ g, is then illustrating that to the result of study of ammonia nitrogen absorption ability natural Chile zeolite is quite fast to the rate of adsorption of ammonia nitrogen, and adsorption capacity can reach 0.68meq/ g, and absorption mode can be consistent (Englert and Rubio, 2005) with Langmuir absorption mode.
Embodiment 2 surface adsorption immobilization CBM complex microorganism zeolite treatment sewage analaysis
Utilizing modified modenite and complex biological catalyst to process ammonia nitrogen simulated wastewater to compare both control groups with not Zeolite Addition and carry out the comparison of ammonia nitrogen absorption ability, the ammonia nitrogen absorption ability of experimental result display complex biological catalyst is substantially strong than the ammonia nitrogen absorption ability of modified modenite.And by experimental result learn the ammonia nitrogen removal frank of zeolite up to 52%, the ammonia nitrogen removal frank of compound bio catalyst is up to 63% (the 3rd figure).
CBM embedded immobilization biocatalyzer processes fresh water waste water.Ammonia nitrogen fresh water simulated wastewater adds CBM embedded immobilization biocatalyzer, NH4+Original content is 4.5ppm, and addition is 5g/L, control group without, every day detects NH4+Concentration, carries out 3 repetitions continuous seven days, and result display CBM has the ability of ammonium ion in notable degradation water, and effect can continue more than 7 days (the 4th figure A).Nitrous acid fresh water waste water adds CBM embedded immobilization biocatalyzer, NO2-Original content is 0.4ppm, and addition is 5g/L, control group without, every day detects NO2-Concentration, carries out 3 repetitions continuous seven days, and result display CBM has the ability of nitrite ion in notable degradation water, and effect can continue more than 7 days (the 4th figure B).
CBM embedded immobilization biocatalyzer processes sea water waste water.Ammonia nitrogen sea water waste water adds CBM embedded immobilization biocatalyzer, NH4+Original content is 4.5ppm, and addition is 5g/L, control group without, every day detects NH4+Concentration, carries out 3 repetitions continuous 7 days, and result display CBM has the ability of ammonium ion in notable degradation water, and effect can continue more than 7 days (the 5th figure A).Nitrous acid sea water simulation waste water adds CBM embedded immobilization biocatalyzer, NO2-Original content is 0.4ppm, and addition is 5g/L, control group without, every day detects NO2-Concentration, carries out 3 repetitions continuous 7 days, and result display CBM has the ability of nitrite ion in notable degradation water, and effect can continue more than 7 days (the 5th figure B).
CBM embedded immobilization biocatalyzer processes sea-farming sewage.Ammonia nitrogen sea-farming sewage adds CBM embedded immobilization biocatalyzer, NH4+Original content is 1.38ppm, and addition is 5g/L, control group without, every day detects NH4+Concentration, carries out 3 repetitions continuous 15 days, and result display CBM has the ability of ammonium ion in notable degradation water, and effect can continue more than 15 days (the 6th figure A).Nitrous acid sea water simulation waste water adds CBM embedded immobilization biocatalyzer, NO2-Original content is 0.73ppm, and addition is 5g/L, control group without, detect NO2-concentration every day, carry out 3 repetitions continuous 15 days, result display CBM has the ability of nitrite ion in notable degradation water, and effect can continue more than 15 days (the 6th figure B).
Sea-farming sewage adds CBM embedded immobilization biocatalyzer, COD original content is 2.54ppm, addition is 5g/L, control group without, detect COD concentration every day, carrying out 3 repetitions continuous 15 days, result display CBM has the ability of COD in notable degradation water, and effect can continue more than 15 days (the 6th figure C).Sea water simulation waste water adds CBM embedded immobilization biocatalyzer, sulfide (sulfide) original content is 41ppb, addition is 5g/L, control group without, every day detects sulfide concentration, carrying out 3 repetitions continuous 15 days, result display CBM has the ability of notable Sulfide in water of degrading, and effect can continue more than 15 days (the 6th figure D).
Embodiment 3 improves black foul sewage water with novel C BM compound bio catalyst
CBM embedded immobilization biocatalyzer processes black foul sewage water.Bottom of river channel black foul sewage water adds CBM embedded immobilization biocatalyzer, add the experimental result of immobilized biocatalyst and add modified modenite for the comparison (the 7th figure A) of ammonia clearance in sewage, and add the experimental result of immobilized biocatalyst and add the comparison (the 7th figure B) for Nitrite In Polluted Water nitric acid clearance of the modified modenite, each experimental group includes three repetitions, and experimental data represents with standard deviation with meansigma methods.
Bottom of river channel black foul sewage water adds CBM embedded immobilization biocatalyzer, add the experimental result of immobilized biocatalyst and add modified modenite for the comparison (the 7th figure C) of COD clearance in sewage, and add the experimental result of immobilized biocatalyst and add modified modenite for the comparison (the 7th figure D) of suspended solid particle clearance in sewage, suspended particles unit is water turbidity (NTU, nephelometric turbidity unit), each experimental group includes three repetitions, and experimental data represents with standard deviation with meansigma methods.
Bottom of river channel black foul sewage water adds CBM embedded immobilization biocatalyzer, add the experimental result of immobilized biocatalyst and add the comparison (the 7th figure E) for molecule clearance phosphorous in sewage of the modified modenite, and add the experimental result of immobilized biocatalyst and add modified modenite for the comparison (the 7th figure F) of sulfur-containing molecules clearance in sewage, each experimental group includes three repetitions, and experimental data represents with standard deviation with meansigma methods.
The in situ restoration of the ecosystem application Tong Bu with bed mud of embodiment 4 water body
By the fixing substrate cleanser 400-750g/m being compounded with beneficial microorganism (CBM)2, uniform broadcasting is in river bed.And setting 2 power 2.2KW water carrying type aerators, aerator operates 8 hours every day.After 17 days, water body eliminates black smelly phenomenon, from upstream to downstream, presents lead-lark-yellowish green progressive formation, and transparency brings up to downstream part about 45cm from about the 12cm of upstream water body, and presents and be from upstream to the trend that downstream steps up.After 30 days, there are a large amount of yellowish-brown floating sludges in upstream.After 60 days, bed mud degrades 45cm, and upstream floating brown mud gradually decreases.At land and water boundary, now plant 0.3-0.5m sink water and emergent vegetation zone, and supplement and add 250g/m2Enter water quality after substrate cleanser and safeguard the phase.
Relatively adding the river water quality after substrate cleanser, every water pollution factor is in as follows listed by table 1, table 2:
Table 1
Table 2
CODcr: with dichromic acid ion measurement COD
BOD: BOD, biological oxygen demand
Not throwing in substrate cleanser, bed mud is black and has extremely strong stink.Throwing in after substrate cleanser 3 months, bed mud is purified and is destitute of smell, and river bed mud reduces 45-60 centimetre with ss suspended solid.Every cause the biotic factor of river stink in as follows listed by table 3:
Table 3
MPN: maximum possible bacterium number, maximum probability number
MLSS:mixed liquor suspended solid
MLVSS:mixed liquor volatile suspended solid
The each strain quantitative analysis of embodiment 5 complex microorganism
For confirming to be compounded with each strain content among beneficial microorganism (CBM), with quantitative nucleic acid polymerase chain reaction (quantitative PCR), quantitative analysis is combined in effective microorganism preparation each culture period (cultivation that coexists, for the first time cultivation, second time are cultivated) each strain quantity (copies) and ratio.Quantitatively converging of each culture period is whole in the 8th figure.
Technique is particularly well suited for carrying out the occasion of dredging operation.Overcome somewhat expensive, noise is excessive, easily give an offensive smell, be difficult to the difficult problems such as handling problems.Use compound substrate cleanser heavy metal and phosphorus can play certain stable, harmless effect.Proceed to bed mud as chromium and phosphorus could act as deposit and reduce the release to overlying water.Use novel substrate cleanser that the river course of severe contamination can carry out muddy water integration ecological reparation.This technical operation is simple, to river flood control without any adverse effect, without extra charge in running.
Above-mentioned multinomial effect, the real Statutory Invention patent requirement fully complying with novelty and progressive that belongs to, filing an application in whence in accordance with the law, earnestly asks your office and check and approve this part application for a patent for invention case to encourage invention.
Claims (10)
1. one kind is used for the compositions removed sewage with educate river course again, it is characterised in that this combination
Thing includes multiple hole material and microbial composite.
Compositions the most according to claim 1, it is characterised in that this multiple hole material is
Modified zeolite or algin.
Compositions the most according to claim 1, it is characterised in that this antimicrobial composition
Thing obtains with following method: co-cultivation condition for 28 DEG C, rotating speed 200rpm, illumination strong
Under the degree illumination for 1000lux, cultivate 7 days continuously；Add 5% molasses, 0.4% carbamide
And 0.15% after potassium dihydrogen phosphate, temperature is controlled in 28 DEG C and with fermentation tank continuous fermentation 5 days
。
4. a modified zeolite manufacture method for compositions according to claim 2, it is special
Levying and be, this manufacture method includes cleaning modenite with distilled water drying, then is soaked by zeolite
Steep in 5% hydrochloric acid 2 hours；Clean to pH value as neutrality with distilled water again and dry, and
Zeolite is soaked in 5% sodium hydroxide 2 hours, finally cleans to pH value with distilled water and be
Neutrality is also dried.
5. use compositions to put into sewage and remove the method polluted, by claim 1 indication
Compositions put into sewage remove pollute.
Method the most according to claim 5, it is characterised in that this sewage refers to fresh water waste water
, sea water waste water, freshwater aquiculture sewage or sea-farming sewage.
Method the most according to claim 6, it is characterised in that said composition makes an addition to dirt
The water yield is that every liter of sewage puts into 3-8 gram.
Method the most according to claim 5, it is characterised in that this sewage refers to ditch, storage
Sewage at pond, Sewage System, river course.
Method the most according to claim 8, it is characterised in that said composition makes an addition to dirt
The water yield is that every square centimeter of sewage area puts into 400-750 gram.
Method the most according to claim 5, it is characterised in that the side that this removing is polluted
Method includes that reduction amine ion, nitrite ion, sulfur-containing compound, phosphorus-containing compound, solid-state are hanged
Floating particle concentration, with reduction BOD, COD.
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| CN110204061A (en) * | 2019-07-05 | 2019-09-06 | 深圳利都科技有限公司 | A kind of sewage treatment reagent can be used for mud thawing |
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| CN111470739A (en) * | 2020-05-28 | 2020-07-31 | 王志斌 | Method for inhibiting endogenous pollution release by coupling compound minerals with benthic algae |
| CN117187088A (en) * | 2023-11-08 | 2023-12-08 | 吉林省中科兆翔生态科技集团有限公司 | Microbial preparation for surface water pollutant treatment, preparation method and application |
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| CN111470739A (en) * | 2020-05-28 | 2020-07-31 | 王志斌 | Method for inhibiting endogenous pollution release by coupling compound minerals with benthic algae |
| CN117187088A (en) * | 2023-11-08 | 2023-12-08 | 吉林省中科兆翔生态科技集团有限公司 | Microbial preparation for surface water pollutant treatment, preparation method and application |
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