CN107487860A - A kind of fish-farming with sewage microalgae device and preparation method thereof - Google Patents

A kind of fish-farming with sewage microalgae device and preparation method thereof Download PDF

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Publication number
CN107487860A
CN107487860A CN201710938523.4A CN201710938523A CN107487860A CN 107487860 A CN107487860 A CN 107487860A CN 201710938523 A CN201710938523 A CN 201710938523A CN 107487860 A CN107487860 A CN 107487860A
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sewage
microalgae
hollow
adsorption column
parts
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CN107487860B (en
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覃央央
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Tangshan Luan Animal Biotechnology Co. Ltd.
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Guangxi Nanning Rong Weide Amperex Technology Ltd
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00Biological treatment of water, waste water, or sewage
    • C02F3/32Biological treatment of water, waste water, or sewage characterised by the animals or plants used, e.g. algae
    • C02F3/322Biological treatment of water, waste water, or sewage characterised by the animals or plants used, e.g. algae use of algae
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/28Treatment of water, waste water, or sewage by sorption
    • C02F1/281Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/28Treatment of water, waste water, or sewage by sorption
    • C02F1/286Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12MAPPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
    • C12M25/00Means for supporting, enclosing or fixing the microorganisms, e.g. immunocoatings
    • C12M25/10Hollow fibers or tubes
    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12MAPPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
    • C12M29/00Means for introduction, extraction or recirculation of materials, e.g. pumps
    • C12M29/16Hollow fibers
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/10Inorganic compounds
    • C02F2101/20Heavy metals or heavy metal compounds

Abstract

The present invention provides a kind of fish-farming with sewage microalgae device and preparation method thereof, using modification of chitosan, modified montmorillonite used it be prepared into the hollow adsorption column that adsorbed film assembles the metal ion in sewage is adsorbed, sewage is set to pass through adsorption column by pump suction function, sewage stops in adsorption column, contacted with immobilized microalgae, microalgae carries out growth and breeding using the organic nutrient substance in sewage.Carry out sewage disposal using this method, can effectively remove metal ion, carbon, nitrogen, the material such as phosphorus in decontaminated water, at the same can large-scale culturing micro-algae, reach sewage disposal and microdisk electrode dual purpose.Sewage after processing can be used for irrigating, cultivating, cleaning;Turn out the microalgae come and can be used for aquaculture, feed addition, plant oil extract etc..

Description

A kind of fish-farming with sewage microalgae device and preparation method thereof
Technical field
The invention belongs to technical field of sewage, more particularly to a kind of sewage culture microalgae device and preparation method thereof.
Background technology
With China's economic development, livestock and poultry cultivation sewage, municipal wastewater and trade effluent increasingly increase as main pollution Source, these discharges of sewage are big, and COD, carbon, the content of nitrogen and phosphorous are high, simultaneously containing various heavy metal substances.Traditional aerobic activity is dirty Mud treatment technology input cost is high, and operation energy consumption is big, Treatment of Sludge trouble, and dirt can not be fully utilized in the microorganism in activated sludge In the nutriment such as the material in water, most of carbon, nitrogen, phosphorus also residual water.
Microalgae is that have the protophyte of photosynthetic ability, and micro-algae propagation survival ability is extremely strong, can be from waste water Various inorganic elements and organic matter are absorbed, are both domestic and external grind using sewage as cheap culture medium large-scale cultivation processing sewage Study carefully focus.A kind of continuous systems that organic sewage is handled using microalgae of application for a patent for invention CN201310192863.9, including 11 parts such as organic wastewater pre-treatment pond, aerator, organic suspended matter separator, laminar microalgae photosynthetic reactor.Should System architecture is simple, energy consumption is small, realizes organic sewage continuous purification and the cultivation lotus root connection synergy of economic microalgae low-coat scaleization Target.Number of patent application CN201110361451.4, trade effluent are applied to the pretreatment technology flow of both culturing microalgae, utilize nothing Sludge components in machine flocculant alum and organic flocculant chitosan combination technology processing sewage, add sodium hydroxide and adjust The pH value of sewage after section processing, after filtering sedimentation, molecular sieve goes the heavy metal ion in removing water, the work for utilizing this method to handle Industry sewage, retain organic impurities, eliminate inorganic impurity and sludge components, be adapted to both culturing microalgae.Number of patent application A kind of raceway pond microalgae cultivating systems for continuing aerating collecting frustule using microbubble of CN201510418103.4, including runway Pond, the device for turbulent flow carbon compensator is set in raceway pond, continuing air supporting using microbubble and collecting raceway pond frustule, baffle device, Double paddle wheels and the groove structure divided into, by the invention, water circulation in raceway pond is can speed up, is improved between liquid level and air Gas exchanges frequency, can real-time, effectively realize the initial concentration to frustule, improve centrifugal efficiency, reduce centrifugation energy Consumption, reduce harvest cost;The carbon dioxide escape spread can be prevented, improves utilization rate of carbon dioxide, more rapidly regulation Algae solution pH;The exchange between algae solution levels can be effectively facilitated, can prevent the frustule on top layer from, by light injury, can also increase The effective luminous energy total amount for adding the frustule of unit of water body to receive;This raceway pond can realize the continuous culture of microalgae, and cultivate During caused very small amount waste water circulation profit again can be led to after sterilization pool and nutritive salt preparing pool are handled by pipeline With.
The study hotspot that processing is current many researchers is carried out to sewage using microalgae, but there is extensive for microalgae The problems such as cultivating, being enriched with separating difficulty.
The content of the invention
For in the prior art, scale being unable to using microalgae processing sewage, micro algae growth is influenceed by high-concentration sewage, Large-scale microdisk electrode is difficult, and microalgae collects difficult, the undesirable present situation of wastewater treatment efficiency, and the present invention provides a kind of utilize The device of adsorption column cultivating microalgae.
Sewage after being handled using the present invention, BOD < 110mg/L, COD < 380mg/L, suspension < 20mg/L, ammonia nitrogen < 40mg/L, total phosphorus < 4mg/L.Sewage after processing can be used for irrigating, cultivating, cleaning;The microalgae come is turned out to can be used for Aquaculture, feed addition, plant oil extract etc..
A kind of fish-farming with sewage microalgae device, by modification of chitosan, the modified montmorillonite used outer membrane A for being prepared into adsorbed film and in The hollow space D and the middle layer segment C adsorption columns of filling microalgae that tunic B assembles inhale to the metal ion in sewage It is attached, sewage is passed through adsorption column by pump suction function, sewage is stopped in adsorption column, contacted with immobilized microalgae, microalgae profit Growth and breeding is carried out with the organic nutrient substance in sewage.
The device of the present invention is through the following steps that be prepared:
A. 40 ~ 80 parts of Kynoar powder is taken, is dissolved in 25 ~ 50 parts of dibutyl phthalates, adds 50 ~ 100 parts of modifications Chitosan powder, 50 ~ 100 parts of modified montmorillonite used powder, 2 ~ 10 parts of Geniposides, under nitrogen protection in 210 ~ 223 DEG C of oil baths After 4 ~ 6h of stirring is mixed into uniform solution, standing and defoaming obtains polymer;Polymer is fed by the Weightlessness balance of 5 ‰ measuring accuracies Material machine feeds double screw extruder, under 250 ~ 300rpm and 2 ~ 5MPa mixing kneading effect, material is sufficiently mixed uniformly Into the casting solution of stable homogeneous, casting solution enters shower nozzle by spinning pump with 90 ~ 100g/min speed accurate measurement, interior Chamber is using the nitrogen of 36 ~ 50ml/min flow velocitys as hollow supporting body, into 298K's after the air section evaporation of certain altitude Occur to be separated and solidify in water-bath, collected thick hollow-fibre membrane by collecting wheel with 25m/min speed;
B. thick hollow-fibre membrane c being prepared is immersed in 95% industrial alcohol 24 hours, and extraction dibutyl phthalate is dilute Agent is released, during which need to change ethanol 2 times, it is ensured that diluent extraction is clean, and it is dry with clear water rinsing will to extract the hollow-fibre membrane finished It is net to obtain hollow-fibre membrane;
C. hollow-fibre membrane is taken, is assembled into duplicature post, the wide spaces of 3 ~ 7cm are left among duplicature, outermost tunic bottom is set Dump valve is equipped with, obtains adsorption column;
D. multiple adsorption columns are vertically fixed with brandreth, hollow space parallel connection in innermost layer is connected with suction pump, is positioned over reaction tank In, fill microalgae, you can carry out sewage disposal;
E. after running 4 ~ 7 days;Hollow-fibre membrane is cleaned 2 hours with 2 ~ 5wt%HCl, then with 2000 ~ 3000mg/L NaClO+ 1000 ~ 2000mg/L NaOH are cleaned 2 hours, and every component cleaning flux be 15 ~ 30L/h, 23 ~ 25 DEG C of temperature, eluent collection It is used to metal ion afterwards reclaim.
As a further improvement on the present invention, microalgae loading is 50 ~ 70% in the adsorption column, adsorption column hollow space It is not communicated with two membranes intermediate space part.
As a further improvement on the present invention, described Kynoar molecular weight is 30KDa ~ 40Kda, Kynoar Concentration is 30 ~ 35wt%.
As a further improvement on the present invention, the dibutyl phthalate, modification of chitosan, modified montmorillonite used powder Ratio of weight and number is 1:2:2~2:2:5.
As a further improvement on the present invention, the preparation method of the modification of chitosan is as follows:
(1)50 parts of chitosans are weighed, is added in 60ml 95% ethanol solution and soaks, 60 DEG C of swelling 2h of constant temperature;(2)By 150 Part vanillic aldehyde is dissolved in 400ml 95% ethanol, and the soak for pouring into chitosan obtains mixed liquor;(3)Mixed liquor is positioned over In microwave quick reaction device, 70 DEG C of heating-up temperature is set, reacts 10min, microwave power 300w, stirring;(4)Reaction is completed, Cooled and filtered, ethanol are washed, and washing, are dried under vacuum to constant weight, are obtained modification of chitosan powder.
The chitosan of vanillic aldehyde graft modification, there is more preferable filming performance, while Cu can be removed very well2+、Zn2+, to having Machine thing COD adsorption rate can reach 25mg/g;
As a further improvement on the present invention, the modified montmorillonite used preparation method is as follows:
20 parts of natural smectite is weighed, 5% sodium hydroxide of natural smectite quality is weighed, by solid-liquid mass ratio 1:10 add 200ml distilled water, regulation pH are 5.6,60 DEG C of stirring reaction 1h in water bath with thermostatic control, the freeze-day with constant temperature at 80 DEG C, and fine grinding crosses 100 Mesh sieve, it is modified montmorillonite used to obtain sodium.
The raw material of specific proportioning carries out the property montmorillonite that sodium changes, to Cu2+、Pb2+、Zn2+、Cd2+Adsorption rate it is reachable respectively 99.2%th, 99.8%, 99.5% and 99.3%.
As a further improvement on the present invention, described Kynoar ethylene molecule amount is 30KDa ~ 40Kda, gathers inclined fluorine Ethylene concentration is 30 ~ 35wt%.
Polymer molecular weight size influences Kynoar system viscosity and membrane aperture size, and then influences pure water and pass through Rate.When polymer molecular weight increases, system viscosity increases, and the growth of stingy drop and nucleus is limited, when polymer concentrated phase solidifies Corresponding drop and spherulite size are smaller, and corresponding membrane aperture is smaller.
As a further improvement on the present invention, dibutyl phthalate, modification of chitosan, modified montmorillonite used powder weight Score ratio is 1:2:2~2:2:5.
The Kynoar ethene that molecular weight is 30KDa ~ 40Kda, concentration is 30 ~ 35wt%, with the fourth of phthalic acid two Ester, modification of chitosan, modified montmorillonite used powder ratio of weight and number are 1:2:2~2:2:5, the performance of the film prepared is:Pure water 580 ~ 800Lm of flux-2h-1(298K), 0.101 ~ 0.115 μm, 15.2 ~ 20.4N of tensile strength of average pore size, porosity 70 ~ 80%。
Then the present invention is mixed and made into adsorption column film by being modified to chitosan and montmorillonite with Kynoar, Using the adsorption column that is assembled into of immobilized microalgae filling duplicature, sewage passes through the suction-operated of adsorption column outer membrane, and 98% or so Heavy metal ion be adsorbed, the sewage after absorption is entered inside adsorption column to be reacted with immobilized microalgae, and microalgae can be sharp Growth and breeding is carried out with the Organic Carbon And Total Nitrogen phosphorus substance in sewage, further except the carbon nitrogen phosphorus substance in decontaminated water.After microalgae processing Sewage again pass by adsorption column inner layer film after discharge, almost without the polluter such as heavy metal, carbon, nitrogen, phosphorus.
Advantages of the present invention:
1. the present invention is used as membrane material by being modified to chitosan and montmorillonite, heavy metal ion can be adsorbed well, Pb In Exhausted Water can effectively be adsorbed, every, the heavy metal ion such as nickel, molybdenum, while montmorillonite also has and remove malicious function, further purification dirt Water.
2. adsorption column prepared by the present invention is hybrid organic-inorganic film, the advantages of having concentrated polyvinylidene fluoride separation membrane with And the absorption property of chitosan, montmorillonite, film stable physical property, pure water flux and hydrophily are improved to some extent.
3. the present invention adsorption column there is good pressure-resistant performance, arbitrary size can be made without supporter, membrane module and shape, The advantages that loading density is big in membrane module, unit volume membrane area and flux is big.
4. carrying out microdisk electrode using sewage by apparatus of the present invention, sewage can be purified, and can is trained on a large scale Microalgae is supported, is easily isolated microalgae and sewage, the sewage after processing also can apply to other aspects with next microalgae is turned out, and reach The effect that environmental protection, material recycle.
Brief description of the drawings
Fig. 1 is the schematic diagram of adsorption column of the present invention.Wherein A is outer membrane, and B is nexine film, and C is the middle level portion of filling microalgae Point, D is hollow space.
Fig. 2 is the reaction tank structural representation that one embodiment of the invention is applied in production.Wherein, 1 is before organic wastewater Processing pond;2 be aerator;3 be organic suspended matter gas floatation separation device;4 be organic wastewater storage pool after pre-treatment;5 be layer Decline algae photosynthetic reactor;6 be mixing pit;7 be water pump;8 be microalgae flocculation basin;9 be the continuous harvesting apparatus of microalgae;10 be microalgae It is spray-dried room;11 be air-dissolved CO2Aerator.
Fig. 3 is the enlarged drawing of schematic diagram left-hand component shown in Fig. 2.Wherein I is organic wastewater pre-treatment subsystem;II is light Close reaction subsystem;III is air-dissolved CO2 aerating subsystems;IV is that microalgae continuously harvests subsystem.
Embodiment
The following examples can make those skilled in the art that the present invention be more fully understood, but not limit in any way The present invention.
Embodiment 1
The present embodiment is used for dairy cow farm sewage disposal.
The preparation of adsorption column and installation method are as follows in the present embodiment:
A. 40Kda, 30wt% 80 parts of Kynoar powder are taken, is dissolved in 25 parts of dibutyl phthalates, 50 parts is added and changes Property Chitosan powder, 50 parts of modified montmorillonite used powder, 2 parts of Geniposides, under nitrogen protection in 210 DEG C of oil baths stir 4h mixing Into after uniform solution, standing and defoaming obtains polymer;Polymer is fed into double spiral shells by the Weightlessness balance feeding machine of 5 ‰ measuring accuracies Bar extruder, under 250rpm and 2MPa mixing kneading effect, material is set to be sufficiently mixed uniformly into the casting solution of stable homogeneous, Casting solution enters shower nozzle by spinning pump with 90g/min speed accurate measurement, and inner chamber is with the nitrogen of 36ml/min flow velocitys As hollow supporting body, it is separated and solidifies into generation in 298K water-bath after the air section evaporation of certain altitude, with 25m/min speed is collected thick hollow-fibre membrane by collecting wheel;
B. thick hollow-fibre membrane d being prepared is immersed in 95% industrial alcohol 24 hours, and extraction dibutyl phthalate is dilute Agent is released, during which need to change ethanol 2 times, it is ensured that diluent extraction is clean, and it is dry with clear water rinsing will to extract the hollow-fibre membrane finished It is net to obtain hollow-fibre membrane.
C. hollow-fibre membrane is taken, is assembled into duplicature post, the wide spaces of 7cm, outermost tunic bottom are left among duplicature Dump valve is provided with, obtains adsorption column;
D. multiple adsorption columns are vertically fixed with brandreth, hollow space parallel connection in innermost layer is connected with suction pump, is positioned over reaction tank In;
After operation 7 days, stopping is filled with ozone, stops sewage pump, and stop pumping pump, and immobilized microalgae is arranged by adsorbing column bottom Go out valve discharge, collect;Hollow-fibre membrane is cleaned 2 hours with 2wt%HCl, then with 2000mg/L NaClO+1000mg/L NaOH Cleaning 2 hours, 23 DEG C of temperature.The conservation rate that the cleaning can improve tensile strength is 80%.
In the present embodiment, immobilized microalgae loading 70% in adsorption column.
Embodiment 2
The present embodiment is used for sanitary sewage disposal.
Adsorption column is prepared as follows with installation method in the present embodiment:
A. 40 parts of 30Kda, 35wt% Kynoar powder is taken, is dissolved in 30 parts of dibutyl phthalates, adds 30 parts of modifications Chitosan powder, 75 parts of modified montmorillonite used powder, 5 parts of Geniposides, 5h is stirred in 215 DEG C of oil baths under nitrogen protection and is mixed into After uniform solution, standing and defoaming obtains polymer;Polymer is fed into twin-screw by the Weightlessness balance feeding machine of 5 ‰ measuring accuracies Extruder, under 280rpm and 4MPa mixing kneading effect, material is set to be sufficiently mixed uniformly into the casting solution of stable homogeneous, casting Film liquid enters shower nozzle by spinning pump with 100g/min speed accurate measurement, and inner chamber is made with the nitrogen of 45ml/min flow velocitys For hollow supporting body, it is separated and solidifies into generation in 298K water-bath after the air section evaporation of certain altitude, with 25m/min speed is collected thick hollow-fibre membrane by collecting wheel;
B. thick hollow-fibre membrane d being prepared is immersed in 95% industrial alcohol 24 hours, and extraction dibutyl phthalate is dilute Agent is released, during which need to change ethanol 2 times, it is ensured that diluent extraction is clean, and it is dry with clear water rinsing will to extract the hollow-fibre membrane finished It is net to obtain hollow-fibre membrane.
C. hollow-fibre membrane is taken, is assembled into duplicature post, the wide spaces of 3cm, outermost tunic bottom are left among duplicature Dump valve is provided with, obtains adsorption column;
D. multiple adsorption columns are vertically fixed with brandreth, hollow space parallel connection in innermost layer is connected with suction pump, is positioned over reaction tank In;
The present embodiment concrete operation step is as follows:
Open sewage pump and sanitary sewage is injected into reaction tank, when sewage is not to adsorption column 50%, stop pumping;Open ozone hair Generating apparatus, ozone aeration quantity is 15g/h, action time 10min/h, after ozonization 5h, opens suction pump, adjusts flow For 1L/min, working time 15min, time of having a rest 40min, sewage is set to enter after adsorption column reacted with immobilized microalgae, Reacted sewage is discharged into water purifying tank;
After operation 4 days, stopping is filled with ozone, stops sewage pump, and stop pumping pump, and immobilized microalgae is arranged by adsorbing column bottom Go out valve discharge, collect, hollow-fibre membrane is cleaned 2 hours with 4wt%HCl, then with 2500mg/L NaClO+1500mg/L NaOH Cleaning 2 hours, every component cleaning flux are 22L/h, 24 DEG C of temperature.The conservation rate that the cleaning can improve tensile strength is 81.6%。
In the present embodiment, immobilized microalgae loading 50% in adsorption column.
Embodiment 3
The present embodiment is used for municipal sewage treatment.
Adsorption column is prepared as follows with installation method in the present embodiment:
A. 80 parts of 35Kda, 30wt% Kynoar powder is taken, is dissolved in 50 parts of dibutyl phthalates, 100 parts is added and changes Property Chitosan powder, 100 parts of modified montmorillonite used powder, 10 parts of Geniposides, under nitrogen protection in 223 DEG C of oil baths stir 6h mix After synthesizing uniform solution, standing and defoaming obtains polymer;Polymer is double by the Weightlessness balance feeding machine feeding of 5 ‰ measuring accuracies Screw extruder, under 300rpm and 5MPa mixing kneading effect, material is set to be sufficiently mixed uniformly into the casting film of stable homogeneous Liquid, casting solution enter shower nozzle by spinning pump with 100g/min speed accurate measurement, and inner chamber is with 50ml/min flow velocitys Nitrogen is as hollow supporting body, into generation phase separation in 298K water-bath and admittedly after the air section evaporation of certain altitude Change, collected thick hollow-fibre membrane by collecting wheel with 25m/min speed;
B. thick hollow-fibre membrane d being prepared is immersed in 95% industrial alcohol 24 hours, and extraction dibutyl phthalate is dilute Agent is released, during which need to change ethanol 2 times, it is ensured that diluent extraction is clean, and it is dry with clear water rinsing will to extract the hollow-fibre membrane finished It is net to obtain hollow-fibre membrane.
C. hollow-fibre membrane is taken, is assembled into duplicature post, the wide spaces of 5cm, outermost tunic bottom are left among duplicature Dump valve is provided with, obtains adsorption column;
D. multiple adsorption columns are vertically fixed with brandreth, hollow space parallel connection in innermost layer is connected with suction pump, is positioned over reaction tank In;
The present embodiment concrete operation step is as follows:
Open sewage pump and sanitary sewage is injected into reaction tank, when sewage is not to adsorption column 60%, stop pumping;Open ozone hair Generating apparatus, ozone aeration quantity is 25g/h, action time 20min/h, after ozonization 5h, opens suction pump, adjusts flow For 1.2L/min, working time 20min, time of having a rest 50min, sewage is set to be reacted into adsorption column with immobilized microalgae Afterwards, reacted sewage is discharged into water purifying tank;
After operation 6 days, stopping is filled with ozone, stops sewage pump, and stop pumping pump, and immobilized microalgae is arranged by adsorbing column bottom Go out valve discharge, collect;Hollow-fibre membrane is cleaned 2 hours with 5wt%HCl, then with 3000mg/L NaClO+2000mg/L NaOH Cleaning 2 hours, every component cleaning flux are 30L/h, 25 DEG C of temperature.The conservation rate that the cleaning can improve tensile strength is 82.9%.In the present embodiment, immobilized microalgae loading 60% in adsorption column.
Embodiment 4
With the microalgae of the fish-farming with sewage microalgae device prepared by the embodiment of the present invention 1 ~ 3 and patent of invention CN201310192863.9 The continuous system of organic sewage is handled, processing Pig raising wastewater is as a comparison.
Fish-farming with sewage microalgae device prepared by the embodiment of the present invention 1 ~ 3 handles Pig raising wastewater mode with described in embodiment 1 ~ 3 Processing mode.
The continuous system processing Pig raising wastewater mode of patent of invention CN201310192863.9 microalgae processing organic sewage It is as follows:
1st, the pig enterprise of certain pigs in stock 50,000, about 200 tons of biogas slurry is discharged daily, biogas slurry is flowed into after primary settling Pre-treatment pond, the processing pond is in series by 100 cement pit, and the wide 6m in single pond, long 8m, deep 1.5m, dischargeable capacity is about 60m3, whole pond group total measurement (volume) is 6000m3.Biogas slurry enters the outflow of last pond, residence time from first pond About 30 days.Air-dissolved intermittent aerating apparatus of oxygen supply, supporting isolation net cage are installed at the upper strata 50cm per single pond;Net cage Be implanted into helotism biofilm ball float, on pond installation shade keep off the rain frame, it is allowed to 20-30% scattering light passes through, be bacterium algae and Good environment factor is created in humorous symbiosis.A variety of aquatic fungis, nitrobacteria, algae are fixed with helotism biofilm ball float Symbiosis population mixture.Above-mentioned biology is all common biology in biogas slurry pond ecological system, is not specially required.In series connection pond most End is provided with the dissolved air type air-float machine that treating capacity per hour is 8m3, by the organic suspended matter remained in organic wastewater, absorption Heavy metal component flocculation separation on organic suspended matter removes, and improves the translucency of organic wastewater, is obtained from air floatation machine delivery port To pretreated organic wastewater be collected into a large-scale organic wastewater storage pool, turn into and be used directly for microalgae and support The marsh liquid culture medium grown.
2nd, the photosynthetic reactor of this example is composed in parallel using 225 groups of photosynthetic reactor single rack, the photosynthetic organism of its single rack is anti- It is to use angle bar frame, the cementing multilayer racetrack gravity flow structure formed of tempering flint glass according to bionics principle to answer device, 8 layers of reactor, interfloor distance 40cm;Runway width 70cm, length 2000cm, water storage thickness is in 20cm, natural pond after pretreatment Liquid is from the photosynthetic reactor is entered to the outflow photosynthetic reactor, residence time holding 36 hours.By organic wastewater pre-treatment The biogas slurry of subsystem I processing(Equivalent to going out the 40% of water inventory), the water outlet with being rich in frustule in photosynthetic response subsystem II Circulating reflux part(Account for out the 60% of water inventory).After being mixed in mixing pit, by pipeline and equal after being pressurizeed by water pump The even the superiors for being distributed to all single rack in parallel, start the circulation of weight-driven.Laminar microalgae photosynthesis physiological target is placed in Under the facilities protection of printing opacity greenhouse.Laminar microalgae photosynthesis physiological target starts first to be needed to be inoculated with chlorella pure culture seed, And quickly tamed by increasing biogas slurry ratio step by step.Chlorella used in this example (Chlorella Vulgaris) FACHB-7 strains Directly bought from positioned at aquatile research institute of the Chinese Academy of Sciences algae kind storehouse of Wuhan Luo Jia Shan East Lake South Road 7.
3rd, using air-dissolved CO2 aerators, waste gas is produced in marsh gas power generation in a manner of gas compression(With CO2And H2O Based on steam)One high 6 meters, the bottom of diameter 40cm stainless steel cylindrical container is compressed to, herein the light with being pumped into Reaction subsystem II circulation water inlet mixed dissolution is closed, and microalgae photosynthetic reactor is finally transported in the form of carbonic acid Each position is utilized by microalgae.
4th, the continuous harvesting apparatus of microalgae described in this example is by mixing pit 6, microalgae flocculation basin 8, the continuous harvesting apparatus 9 of microalgae Composition.The water outlet of frustule is partly rich in photosynthetic response subsystem II(It is total equivalent to photosynthetic response subsystem II water outlets The 40% of amount), microalgae flocculation basin 8 is admitted to, after flocculant process, the continuous harvesting apparatus 9 of microalgae is then sent through, is harvested High-moisture percentage bead algal gel is transported to spray drying computer room 10 and carries out spray drying treatment.The disposal ability of spray dryer is 1 ton per hour, 160 DEG C of setting material inlet temperature, 75 DEG C of material outlet temperature.The moistureproof bag of chlorella powder by spray drying Equipment is used.Go out purified water from the continuous qualified discharge of harvesting apparatus 9 of microalgae after harvesting microalgae.
Determine at the fish-farming with sewage microalgae device of the preparation of embodiment 1 ~ 3 and patent of invention CN201310192863.9 microalgae The continuous system heel row of reason organic sewage discharges water microalgae dry weight and the sewage prepared by embodiment 1 ~ 3 after indices, culture The film properties of cultivating microalgae device, data such as table 1 ~ 3.
Each content of material during 1 each device of table processing heel row discharges water
Microalgae dry weight after the processing of the Pig raising wastewater of table 2
The film properties of 3 each device of table
It is by table 1 ~ 3 as can be seen that organic using patent CN201310192863.9 of the present invention microalgae processing with patent of invention The continuous system of sewage is compared, and fish-farming with sewage microalgae device prepared by the present invention has more preferable sewage treatment capacity, after culture Microalgae concentration it is higher.
The above embodiment of the present invention scheme is only the description of the invention and can not limit the present invention, in the power with the present invention Any change in sharp claim suitable implication and scope, is all considered to be and is included within the scope of the claims.

Claims (5)

1. a kind of fish-farming with sewage microalgae device, it is characterised in that by modification of chitosan, modified montmorillonite used be prepared into the outer of adsorbed film The hollow space D and fill the middle layer segment C adsorption columns of microalgae to the metal in sewage that tunic A and nexine film B assemble Ion is adsorbed, and sewage is passed through adsorption column by pump suction function, sewage is stopped in adsorption column, connect with immobilized microalgae Touch, microalgae carries out growth and breeding using the organic nutrient substance in sewage.
2. a kind of preparation method of fish-farming with sewage microalgae device, it is characterised in that comprise the following steps:
A. 50 parts of chitosans are weighed, is added in 60ml 95% ethanol solution and soaks, 60 DEG C of swelling 2h of constant temperature;By 150 parts of perfume (or spice) Oxalaldehyde is dissolved in 400ml 95% ethanol, and the soak for pouring into chitosan obtains mixed liquor;It is quick that mixed liquor is positioned over microwave In reaction unit, 70 DEG C of heating-up temperature is set, reacts 10min, microwave power 300w, stirring;Reaction is completed, cooled and filtered, Ethanol is washed, and washing, is dried under vacuum to constant weight, is obtained modification of chitosan powder;
B. 20 parts of natural smectite is weighed, 5% sodium hydroxide of natural smectite quality is weighed, by solid-liquid mass ratio 1:10 add Enter 200ml distilled water, regulation pH is 5.6,60 DEG C of stirring reaction 1h in water bath with thermostatic control, the freeze-day with constant temperature at 80 DEG C, fine grinding 100 mesh sieve, it is modified montmorillonite used to obtain sodium;
C. 40 ~ 80 parts of Kynoar powder is taken, is dissolved in 25 ~ 50 parts of dibutyl phthalates, adds 50 ~ 100 parts of modifications Chitosan powder, 50 ~ 100 parts of modified montmorillonite used powder, 2 ~ 10 parts of Geniposides, under nitrogen protection in 210 ~ 223 DEG C of oil baths After 4 ~ 6h of stirring is mixed into uniform solution, standing and defoaming obtains polymer;Polymer is fed by the Weightlessness balance of 5 ‰ measuring accuracies Material machine feeds double screw extruder, under 250 ~ 300rpm and 2 ~ 5MPa mixing kneading effect, material is sufficiently mixed uniformly Into the casting solution of stable homogeneous, casting solution enters shower nozzle by spinning pump with 90 ~ 100g/min speed accurate measurement, interior Chamber is using the nitrogen of 36 ~ 50ml/min flow velocitys as hollow supporting body, into 298K's after the air section evaporation of certain altitude Occur to be separated and solidify in water-bath, collected thick hollow-fibre membrane by collecting wheel with 25m/min speed;
D. thick hollow-fibre membrane c being prepared is immersed in 95% industrial alcohol 24 hours, and extraction dibutyl phthalate is dilute Agent is released, during which need to change ethanol 2 times, it is ensured that diluent extraction is clean, and it is dry with clear water rinsing will to extract the hollow-fibre membrane finished It is net to obtain hollow-fibre membrane;
E. hollow-fibre membrane is taken, is assembled into duplicature post, the wide spaces of 3 ~ 7cm are left among duplicature, outermost tunic bottom is set Dump valve is equipped with, obtains adsorption column;
F. multiple adsorption columns are vertically fixed with brandreth, hollow space parallel connection in innermost layer is connected with suction pump, is positioned over reaction tank In, fill microalgae, you can carry out sewage disposal;
G. after running 4 ~ 7 days;Hollow-fibre membrane is cleaned 2 hours with 2 ~ 5wt%HCl, then with 2000 ~ 3000mg/L NaClO+ 1000 ~ 2000mg/L NaOH are cleaned 2 hours, and every component cleaning flux be 15 ~ 30L/h, 23 ~ 25 DEG C of temperature, eluent collection It is used to metal ion afterwards reclaim.
A kind of 3. fish-farming with sewage microalgae device according to claim 1, it is characterised in that:Microalgae loading is in adsorption column 50 ~ 70%, adsorption column hollow space is not communicated with two membranes intermediate space part.
A kind of 4. preparation method of fish-farming with sewage microalgae device according to claim 2, it is characterised in that:Described is poly- inclined PVF molecular weight is 30KDa ~ 40Kda, and Kynoar concentration is 30 ~ 35wt%.
A kind of 5. preparation method of fish-farming with sewage microalgae device according to claim 2, it is characterised in that:Phthalic acid Dibutyl ester, modification of chitosan, modified montmorillonite used powder ratio of weight and number are 1:2:2~2:2:5.
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CN113578943A (en) * 2021-07-19 2021-11-02 武汉理工大学 Method for repairing lead-polluted soil by using microalgae-montmorillonite compound
CN114988951A (en) * 2022-06-21 2022-09-02 广西南宁昇华农业科技有限公司 Water-soluble fertilizer for improving fruit quality

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CN114988951A (en) * 2022-06-21 2022-09-02 广西南宁昇华农业科技有限公司 Water-soluble fertilizer for improving fruit quality

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