CN108862610B - Device for cultivating microalgae by using sewage and manufacturing method thereof - Google Patents

Device for cultivating microalgae by using sewage and manufacturing method thereof Download PDF

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CN108862610B
CN108862610B CN201810770215.XA CN201810770215A CN108862610B CN 108862610 B CN108862610 B CN 108862610B CN 201810770215 A CN201810770215 A CN 201810770215A CN 108862610 B CN108862610 B CN 108862610B
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sewage
microalgae
membrane
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hollow fiber
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CN108862610A (en
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不公告发明人
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GUANGDONG ZHONGHUAN ECOLOGICAL TECHNOLOGY Co.,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 invention provides a device for cultivating microalgae by sewage and a manufacturing method thereof. The method for sewage treatment can effectively remove metal ions, carbon, nitrogen, phosphorus and other substances in the sewage, and simultaneously can culture microalgae on a large scale, thereby achieving the dual purposes of sewage treatment and microalgae culture. The treated sewage can be used for irrigation, cultivation, cleaning and the like; the cultured microalgae can be used for aquaculture, feed addition, vegetable oil extraction and the like.

Description

Device for cultivating microalgae by using sewage and manufacturing method thereof
The application is a divisional application of a patent with the application number of 2017109385234 and the application date of 2017, 10 and 11, and the name of the patent is 'a sewage culture microalgae device and a manufacturing method thereof'.
Technical Field
The invention belongs to the technical field of sewage treatment, and particularly relates to a device for culturing microalgae by using sewage and a manufacturing method thereof.
Background
With the economic development of China, livestock and poultry breeding sewage, municipal sewage and industrial sewage are increasing to become main pollution sources, and the sewage has large flow, high COD (chemical oxygen demand), carbon, nitrogen and phosphorus contents and various heavy metal substances. The traditional aerobic activated sludge treatment technology has high input cost, large operation energy consumption and troublesome sludge treatment, microorganisms in the activated sludge cannot fully utilize substances in sewage, and most of nutrient substances such as carbon, nitrogen, phosphorus and the like still remain in water.
Microalgae is a protogenic plant with photosynthesis, has extremely strong propagation and survival ability, can absorb various inorganic elements and organic matters from wastewater, and is a research hotspot at home and abroad for treating wastewater by large-scale culture by taking the wastewater as a cheap culture medium. The invention patent application No. CN201310192863.9 is a continuous system for treating organic sewage by utilizing microalgae, which comprises 11 parts of an organic wastewater pretreatment pool, an aeration device, an organic suspended matter separation device, a layer-type microalgae photosynthetic reactor and the like. The system has simple structure and low energy consumption, and realizes the aims of continuous purification of organic sewage and low-cost large-scale cultivation and coupling synergy of economic microalgae. Patent application No. CN201110361451.4, the pretreatment technical process that industrial sewage was applied to little algae cultivation utilizes inorganic flocculating agent aluminium potassium sulfate and organic flocculating agent chitosan to combine the sludge component in the technology processing sewage, adds the pH value of the sewage after the sodium hydroxide adjustment is handled, filters the back that subsides, and the heavy metal ion in the water is got rid of to the molecular sieve, and the industrial sewage who utilizes this method to handle remains organic impurity, has got rid of inorganic impurity and sludge component, is fit for little algae cultivation. Patent application No. CN201510418103.4 is a runway pool microalgae culture system for harvesting algae cells by using micro-bubble continuous air flotation, which comprises a runway pool, wherein a turbulent flow carbon supplementing device, a device for collecting the algae cells in the runway pool by using micro-bubble continuous air flotation, a flow blocking device, a double-paddle wheel and a groove structure arranged below the double-paddle wheel are arranged in the runway pool; the escape of the scattered carbon dioxide can be prevented, the utilization rate of the carbon dioxide is improved, and the pH value of the algae liquid is adjusted more quickly; the exchange between the upper layer and the lower layer of the algae liquid can be effectively promoted, the surface layer algae cells can be prevented from being damaged by light, and the total amount of effective light energy received by the algae cells in unit water body can be increased; the runway pool can realize continuous culture of microalgae, and a very small amount of wastewater generated in the culture process can be led to the disinfection pool and the nutrient salt blending pool through the pipeline for recycling after treatment.
The utilization of microalgae for sewage treatment is a research hotspot of many researchers at present, but the problems of large-scale culture, difficult enrichment and separation and the like exist in the microalgae.
Disclosure of Invention
Aiming at the current situations that sewage treatment by microalgae cannot be scaled, microalgae growth is influenced by high-concentration sewage, the scaling of microalgae culture is difficult, microalgae collection is difficult, and the sewage treatment effect is not ideal in the prior art, the invention provides a device for culturing microalgae by using an adsorption column.
The sewage treated by the method has BOD less than 110mg/L, COD less than 380mg/L, suspended matters less than 20mg/L, ammonia nitrogen less than 40mg/L and total phosphorus less than 4 mg/L. The treated sewage can be used for irrigation, cultivation, cleaning and the like; the cultured microalgae can be used for aquaculture, feed addition, vegetable oil extraction and the like.
A device for culturing microalgae in sewage is composed of a hollow part D consisting of an external layer membrane A and an internal layer membrane B of an adsorption membrane prepared from modified chitosan and modified montmorillonite, and an adsorption column filled with microalgae and arranged in the middle layer of said adsorption membrane for adsorbing the metal ions in sewage.
The device of the invention is prepared by the following steps:
a. dissolving 40-80 parts of polyvinylidene fluoride powder in 25-50 parts of dibutyl phthalate, adding 50-100 parts of modified chitosan powder, 50-100 parts of modified montmorillonite powder and 2-10 parts of genipin, stirring in an oil bath at 210-223 ℃ under the protection of nitrogen for 4-6 hours to form a uniform solution, and standing and defoaming to obtain a polymer; feeding a polymer into a double-screw extruder through a weightless scale feeder with metering precision of 5 per mill, fully and uniformly mixing the materials under the mixing kneading action of 250-300 rpm and 2-5 MPa to obtain a uniform and stable casting solution, accurately metering the casting solution into a spray head through a spinning metering pump at the speed of 90-100 g/min, taking nitrogen with the flow rate of 36-50 ml/min as a hollow support body in an inner cavity, evaporating the nitrogen through an air section with a certain height, then entering a 298K water bath for phase separation and solidification, and collecting a coarse hollow fiber membrane through a collecting wheel at the speed of 25 m/min;
b. c, immersing the coarse hollow fiber membrane obtained in the step c into 95% industrial ethanol for 24 hours, extracting dibutyl phthalate diluent, replacing the ethanol for 2 times in the period, ensuring that the diluent is extracted completely, and rinsing the extracted hollow fiber membrane completely with clear water to obtain the hollow fiber membrane;
c. taking a hollow fiber membrane, assembling into a double-layer membrane column, reserving a space with the width of 3-7 cm in the middle of the double-layer membrane, and arranging a discharge valve at the bottom of the outermost membrane to obtain an adsorption column;
d. vertically fixing a plurality of adsorption columns by using an iron frame, connecting hollow parts of the innermost layer in parallel with a water pump, placing the adsorption columns in a reaction tank, and filling microalgae to perform sewage treatment;
e. operating for 4-7 days; the hollow fiber membrane is cleaned for 2 hours by using 2-5 wt% HCl, then cleaned for 2 hours by using 2000-3000 mg/LNaClO + 1000-2000 mg/LNaOH, the cleaning flux of each component is 15-30L/h, the temperature is 23-25 ℃, and the eluent is collected and used for recovering metal ions.
As a further improvement of the invention, the filling amount of microalgae in the adsorption column is 50-70%, and the hollow part of the adsorption column is not communicated with the middle space part of the two films.
As a further improvement of the invention, the molecular weight of the polyvinylidene fluoride is 30-40 kDa, and the concentration of the polyvinylidene fluoride is 30-35 wt%.
As a further improvement, the weight part ratio of the dibutyl phthalate, the modified chitosan and the modified montmorillonite powder is 1:2: 2-2: 2: 5.
As a further improvement of the invention, the preparation method of the modified chitosan comprises the following steps:
(1) weighing 50 parts of chitosan, adding the chitosan into 60ml of 95% ethanol solution for soaking, and swelling for 2 hours at constant temperature of 60 ℃; (2) dissolving 150 parts of vanillin in 400ml of 95% ethanol, and pouring the solution into a chitosan soak solution to obtain a mixed solution; (3) placing the mixed solution in a microwave rapid reaction device, setting the heating temperature to be 70 ℃, reacting for 10min, and stirring with the microwave power of 300 w; (4) and (3) after the reaction is finished, filtering, washing with ethanol, washing with water, and drying in vacuum to constant weight to obtain modified chitosan powder.
The vanillin grafting modified chitosan has better film forming performance, can well remove Cu2+ and Zn2+ and has the adsorption rate of organic COD up to 25 mg/g;
as a further improvement of the invention, the preparation method of the modified montmorillonite is as follows:
weighing 20 parts of natural montmorillonite, weighing sodium hydroxide which is 5% of the mass of the natural montmorillonite, adding 200ml of distilled water according to the solid-liquid mass ratio of 1:10, adjusting the pH to 5.6, stirring and reacting for 1h in a constant-temperature water bath at 60 ℃, drying at the constant temperature of 80 ℃, and finely grinding through a 100-mesh sieve to obtain the sodium modified montmorillonite.
The sodium modified montmorillonite prepared from the raw materials with specific mixture ratio has adsorption rates of 99.2%, 99.8%, 99.5% and 99.3% for Cu2+, Pb2+, Zn2+ and Cd2 +.
As a further improvement of the invention, the molecular weight of the polyvinylidene fluoride is 30-40 kDa, and the concentration of the polyvinylidene fluoride is 30-35 wt%.
The molecular weight of the polymer affects the viscosity of a polyvinylidene fluoride system and the pore size of a membrane, and further affects the pure water passing rate. When the molecular weight of the polymer is increased, the viscosity of the system is increased, the growth of poor-phase droplets and crystal nuclei is limited, the sizes of the corresponding droplets and spherulites are smaller when the polymer is solidified in a concentrated phase, and the corresponding pore diameter of the membrane is smaller.
As a further improvement, the weight ratio of dibutyl phthalate, modified chitosan and modified montmorillonite powder is 1:2: 2-2: 2: 5.
The weight part ratio of polyvinylidene fluoride ethylene with the molecular weight of 30-40 kDa and the concentration of 30-35 wt% to dibutyl phthalate, modified chitosan and modified montmorillonite powder is 1:2: 2-2: 2:5, and the prepared film has the following properties: the pure water flux is 580-800 Lm-2h-1(298K), the average pore diameter is 0.101-0.115 mu m, the tensile strength is 15.2-20.4N, and the porosity is 70-80%.
According to the invention, chitosan and montmorillonite are modified, then the modified chitosan and montmorillonite are mixed with polyvinylidene fluoride to prepare an adsorption column membrane, immobilized microalgae is used for filling an adsorption column assembled by double-layer membranes, about 98% of heavy metal ions are adsorbed by the adsorption action of the outer layer membrane of the adsorption column, the adsorbed sewage enters the adsorption column to react with the immobilized microalgae, and the microalgae can utilize organic carbon, nitrogen and phosphorus substances in the sewage to grow and reproduce, so that carbon, nitrogen and phosphorus substances in the sewage are further removed. The sewage after the microalgae treatment is discharged after passing through the inner membrane of the adsorption column again, and almost no pollutants such as heavy metal, carbon, nitrogen, phosphorus and the like are contained.
The invention has the advantages that:
1. according to the invention, chitosan and montmorillonite are modified to be used as membrane materials, so that heavy metal ions can be well adsorbed, heavy metal ions such as lead, nickel, molybdenum and the like in wastewater can be effectively adsorbed, and meanwhile, montmorillonite also has a detoxification function, and further purifies sewage.
2. The adsorption column prepared by the invention is an organic-inorganic hybrid membrane, integrates the advantages of the polyvinylidene fluoride separation membrane and the adsorption performance of chitosan and montmorillonite, has stable physical performance, and improves the pure water flux and the hydrophilicity to a certain extent.
3. The adsorption column has the advantages of good pressure resistance, no need of a support body, capability of making the membrane component into any size and shape, high packing density in the membrane component, large membrane area and flux per unit volume and the like.
4. The device of the invention utilizes the sewage to culture the microalgae, can purify the sewage, can culture the microalgae on a large scale, is easy to separate the microalgae from the sewage, and can be applied to other aspects, thereby achieving the effects of environmental protection and material recycling.
Drawings
FIG. 1 is a schematic view of an adsorption column of the present invention. Wherein A is an outer layer membrane, B is an inner layer membrane, C is a middle layer part filled with microalgae, and D is a hollow part.
FIG. 2 is a schematic diagram of a reaction cell structure applied to production according to an embodiment of the present invention. Wherein, 1 is an organic wastewater pretreatment tank; 2 is an aeration device; 3 is an organic suspended matter air flotation separation device; 4, a pretreated organic wastewater storage tank; 5 is a layer-type microalgae photosynthetic reactor; 6 is a mixing pool; 7 is a water pump; 8 is a microalgae flocculation tank; 9 is a microalgae continuous harvesting device; 10 is a microalgae spray drying room; 11 is a gas-dissolving type CO2 gas-filling device.
Fig. 3 is an enlarged view of the left portion of the schematic shown in fig. 2. Wherein I is an organic wastewater pretreatment subsystem; II is a photosynthetic reaction subsystem; III is a gas-dissolving CO2 gas-adding subsystem; IV is a microalgae continuous harvesting subsystem.
Detailed Description
The following examples are presented to enable one of ordinary skill in the art to more fully understand the present invention and are not intended to limit the invention in any way.
Example 1
This embodiment is used for the sewage treatment of milk cow plant.
The preparation and installation method of the adsorption column in this example is as follows:
a. dissolving 80 parts of 40kDa and 30 wt% polyvinylidene fluoride powder in 25 parts of dibutyl phthalate, adding 50 parts of modified chitosan powder, 50 parts of modified montmorillonite powder and 2 parts of genipin, stirring in an oil bath at 210 ℃ under the protection of nitrogen for 4 hours to form a uniform solution, and standing and defoaming to obtain a polymer; feeding a polymer into a double-screw extruder through a weightless scale feeder with metering precision of 5 per mill, fully and uniformly mixing the materials under the mixing kneading action of 250rpm and 2MPa to obtain a uniform and stable casting solution, accurately metering the casting solution into a spray head through a spinning metering pump at the speed of 90g/min, taking nitrogen with the flow rate of 36ml/min as a hollow support body in an inner cavity, evaporating the nitrogen through an air section with a certain height, then entering a 298K water bath for phase separation and solidification, and collecting a coarse hollow fiber membrane through a collection wheel at the speed of 25 m/min;
b. and d, immersing the crude hollow fiber membrane obtained in the step d in 95% industrial ethanol for 24 hours, extracting the dibutyl phthalate diluent, replacing the ethanol for 2 times in the process to ensure that the diluent is extracted completely, and rinsing the extracted hollow fiber membrane completely with clear water to obtain the hollow fiber membrane.
c. Taking a hollow fiber membrane, assembling into a double-layer membrane column, wherein a space with the width of 7cm is reserved in the middle of the double-layer membrane, and a discharge valve is arranged at the bottom of the outermost membrane to obtain an adsorption column;
d. vertically fixing a plurality of adsorption columns by using an iron frame, connecting hollow parts of the innermost layer in parallel with a water pump, and placing the adsorption columns in a reaction tank;
after 7 days of operation, stopping filling ozone, stopping a sewage pump, stopping a water pump, discharging the immobilized microalgae through a discharge valve at the bottom of the adsorption column, and collecting the immobilized microalgae; the hollow fiber membranes were washed with 2 wt% HCl for 2 hours and then 2000mg/LNaClO +1000mg/LNaOH for 2 hours at 23 ℃. The cleaning process can improve the retention rate of the tensile strength by 80 percent.
In this example, the loading of immobilized microalgae in the adsorption column was 70%.
Example 2
The embodiment is used for domestic sewage treatment.
The preparation and installation method of the adsorption column in the embodiment is as follows:
a. dissolving 40 parts of 30kDa and 35 wt% polyvinylidene fluoride powder in 30 parts of dibutyl phthalate, adding 30 parts of modified chitosan powder, 75 parts of modified montmorillonite powder and 5 parts of genipin, stirring in an oil bath at 215 ℃ under the protection of nitrogen for 5 hours to form a uniform solution, and standing and defoaming to obtain a polymer; feeding a polymer into a double-screw extruder through a weightless scale feeder with metering precision of 5 per mill, fully and uniformly mixing the materials under the mixing and kneading action of 280rpm and 4MPa to obtain uniform and stable casting solution, accurately metering the casting solution into a spray head through a spinning metering pump at the speed of 100g/min, taking nitrogen with the flow rate of 45ml/min as a hollow support body in an inner cavity, evaporating the nitrogen through an air section with a certain height, then entering a 298K water bath for phase separation and solidification, and collecting a coarse hollow fiber membrane through a collecting wheel at the speed of 25 m/min;
b. and (b) immersing the crude hollow fiber membrane obtained in the step a in 95% industrial ethanol for 24 hours, extracting the dibutyl phthalate diluent, replacing the ethanol for 2 times in the process to ensure that the diluent is extracted completely, and rinsing the extracted hollow fiber membrane completely with clear water to obtain the hollow fiber membrane.
c. Taking a hollow fiber membrane, assembling into a double-layer membrane column, wherein a space with the width of 3cm is reserved in the middle of the double-layer membrane, and a discharge valve is arranged at the bottom of the outermost membrane to obtain an adsorption column;
d. vertically fixing a plurality of adsorption columns by using an iron frame, connecting hollow parts of the innermost layer in parallel with a water pump, and placing the adsorption columns in a reaction tank;
the specific operation steps of this embodiment are as follows:
starting a sewage pump to inject domestic sewage into the reaction tank, and stopping pumping water when the sewage is 50% of the adsorption column; opening an ozone generating device, wherein the aeration quantity of ozone is 15g/h, the acting time is 10min/h, after the ozone acts for 5h, a water pump is opened, the flow is adjusted to be 1L/min, the working time is 15min, the rest time is 40min, after the sewage enters an adsorption column and reacts with immobilized microalgae, the sewage after reaction is discharged into a water purifying tank;
after running for 4 days, stopping filling ozone, stopping a sewage pump, stopping a water pump, discharging the immobilized microalgae through a discharge valve at the bottom of the adsorption column, collecting, cleaning the hollow fiber membrane with 4 wt% HCl for 2 hours, and then cleaning with 2500mg/LNaClO +1500mg/LNaOH for 2 hours, wherein the cleaning flux of each component is 22L/h, and the temperature is 24 ℃. The cleaning process can improve the retention rate of the tensile strength to 81.6%.
In this example, the loading of immobilized microalgae in the adsorption column was 50%.
Example 3
The embodiment is used for urban sewage treatment.
The preparation and installation method of the adsorption column in the embodiment is as follows:
a. dissolving 80 parts of 35kDa and 30 wt% polyvinylidene fluoride powder in 50 parts of dibutyl phthalate, adding 100 parts of modified chitosan powder, 100 parts of modified montmorillonite powder and 10 parts of genipin, stirring in 223 ℃ oil bath under the protection of nitrogen for 6 hours to form a uniform solution, and standing and defoaming to obtain a polymer; feeding a polymer into a double-screw extruder through a weightless scale feeder with metering precision of 5 per mill, fully and uniformly mixing the materials under the mixing kneading action of 300rpm and 5MPa to obtain a uniform and stable casting solution, accurately metering the casting solution into a spray head through a spinning metering pump at the speed of 100g/min, taking nitrogen with the flow rate of 50ml/min as a hollow support body in an inner cavity, evaporating the nitrogen through an air section with a certain height, then entering a 298K water bath for phase separation and solidification, and collecting a coarse hollow fiber membrane through a collection wheel at the speed of 25 m/min;
b. and (b) immersing the crude hollow fiber membrane obtained in the step a in 95% industrial ethanol for 24 hours, extracting the dibutyl phthalate diluent, replacing the ethanol for 2 times in the process to ensure that the diluent is extracted completely, and rinsing the extracted hollow fiber membrane completely with clear water to obtain the hollow fiber membrane.
c. Taking a hollow fiber membrane, assembling into a double-layer membrane column, leaving a space with the width of 5cm in the middle of the double-layer membrane, and arranging a discharge valve at the bottom of the outermost membrane to obtain an adsorption column;
d. vertically fixing a plurality of adsorption columns by using an iron frame, connecting hollow parts of the innermost layer in parallel with a water pump, and placing the adsorption columns in a reaction tank;
the specific operation steps of this embodiment are as follows:
starting a sewage pump to inject domestic sewage into the reaction tank, and stopping pumping water when the sewage is 60% of the adsorption column; opening an ozone generating device, wherein the aeration quantity of ozone is 25g/h, the acting time is 20min/h, after the ozone acts for 5h, a water pump is opened, the flow is adjusted to be 1.2L/min, the working time is 20min, the rest time is 50min, after the sewage enters an adsorption column and reacts with the immobilized microalgae, the sewage after the reaction is discharged into a water purifying tank;
after running for 6 days, stopping filling ozone, stopping a sewage pump, stopping a water pump, discharging the immobilized microalgae through a discharge valve at the bottom of the adsorption column, and collecting; the hollow fiber membranes were washed with 5 wt% HCl for 2 hours and then with 3000mg/LNaClO +2000mg/LNaOH for 2 hours at a cleaning flux of 30L/h per module and a temperature of 25 ℃. The cleaning process can improve the retention rate of the tensile strength to 82.9%. In this example, the loading of immobilized microalgae in the adsorption column was 60%.
Example 4
The device for cultivating microalgae by using the sewage prepared in the embodiment 1-3 of the invention and the continuous system for treating organic sewage by using the microalgae disclosed in the invention patent CN201310192863.9 are used for comparison in treating pig-raising wastewater.
The method for treating the pig raising wastewater by the sewage culture microalgae device prepared in the embodiment 1-3 is the same as the treatment method described in the embodiment 1-3.
The mode for treating the pig raising wastewater by the continuous system for treating the organic sewage by using the microalgae disclosed in the patent CN201310192863.9 is as follows:
1. a pig raising enterprise with 5 tens of thousands of live pig stocklines discharges about 200 tons of biogas slurry every day, and the biogas slurry flows into a biogas slurry pretreatment tank after primary sedimentation, the treatment tank is formed by connecting 100 cement tanks in series, the width of each tank is 6m, the length of each tank is 8m, the depth of each tank is 1.5m, the effective volume of each tank is about 60m3, and the total volume of the whole tank sub-groups is 6000m 3. The biogas slurry enters the first tank and flows out of the last tank, and the retention time is about 30 days. A dissolved air type intermittent aeration oxygen supply device is arranged at the upper layer 50cm of each single pool, and an isolation net cage is matched; the net cage is implanted with the fungus-algae symbiotic film-hanging floating ball, and the pool is provided with a shading and rain-shielding shed frame which allows 20-30% of scattered light to penetrate through, thereby creating good micro-ecological conditions for the harmonious symbiosis of the fungus and the algae. The symbiotic biofilm culturing floating ball is fixed with a symbiotic mixed population of various aquatic fungi, nitrobacteria and algae. The organisms are common organisms in a biogas liquid pool ecological system, and no special requirement is required. The treatment capacity per hour of 8m is arranged at the tail end of the series-connected tanks3The dissolved air flotation machine removes organic suspended matters remained in organic wastewater and heavy metal components adsorbed on the organic suspended matters through flocculation separation, improves the light transmittance of the organic wastewater, and collects the pretreated organic wastewater obtained from the water outlet of the flotation machine into a large organic wastewater storage tank to form a biogas liquid culture medium which can be directly used for microalgae culture.
2. The photosynthetic reactor of the embodiment is formed by connecting 225 sets of photosynthetic reactors in parallel, the photosynthetic bioreactor of the single frame is a multi-layer runway type self-flow structure formed by gluing an angle steel bracket and toughened colorless glass according to the principle of bionics, 8 layers of the reactor are arranged, and the distance between the layers is 40 cm; the width of the runway is 70cm, the length is 2000cm, the water storage thickness is 20cm, the pretreated biogas slurry flows out of the photosynthetic reactor from the photosynthetic reactor, and the retention time is kept for 36 hours. The biogas slurry (which is 40 percent of the total amount of the effluent) treated by the organic wastewater pretreatment subsystem I and the circulating reflux part (which accounts for 60 percent of the total amount of the effluent) of the effluent rich in algae cells in the photosynthetic reaction subsystem II. After being mixed in the mixing pool, the mixture is pressurized by a water pump and then is conveyed by a pipeline and evenly distributed to the uppermost layer of all the parallel single frames, and the circulation driven by gravity is started. The layered microalgae photosynthetic bioreactor is arranged under the protection of the facility of the light-transmitting greenhouse. The layered microalgae photosynthetic bioreactor is started for the first time and needs to be inoculated with chlorella pure culture seeds, and rapid domestication is carried out by gradually increasing the biogas slurry proportion. The Chlorella (Chlorella Vulgaris) FACHB-7 strain used in this example was purchased directly from fresh water algae seed bank of the institute of aquatic organisms, department of sciences, south road 7, east lake, mountain Lo, Wuhan Lojia.
3. The waste gas (mainly CO2 and H2O steam) generated by biogas power generation is compressed to the bottom of a stainless steel cylindrical container with the height of 6 meters and the diameter of 40cm by adopting a gas-dissolving type CO2 gas-adding device in a gas compression mode, is mixed and dissolved with the pumped circulating inlet water of the photosynthetic reaction subsystem II, and is finally conveyed to each part of the microalgae photosynthetic reactor in the form of carbonic acid for utilization by microalgae.
4. The continuous microalgae harvesting device in the embodiment comprises a mixing tank 6, a microalgae flocculation tank 8 and a continuous microalgae harvesting device 9. Effluent which is from the photosynthetic reaction subsystem II and is partially rich in algae cells (which is equal to 40 percent of the total amount of the effluent of the photosynthetic reaction subsystem II) is sent to a microalgae flocculation tank 8, treated by a flocculating agent and then sent to a microalgae continuous harvesting device 9, and the harvested high-water-content chlorella mud is sent to a spray drying machine room 10 for spray drying treatment. The processing capacity of the spray dryer was 1 ton per hour, and the material inlet temperature was set at 160 ℃ and the material outlet temperature at 75 ℃. And carrying out damp-proof packaging on the spray-dried chlorella powder for later use. After harvesting the microalgae, the purified water is discharged from the microalgae continuous harvesting device 9 after reaching the standard.
The indexes of the discharged water after the sewage culture microalgae device prepared in the embodiment 1-3 and the continuous system for treating organic sewage by microalgae in the invention patent CN201310192863.9, the dry weight of the cultured microalgae and the performances of the membrane of the sewage culture microalgae device prepared in the embodiment 1-3 are measured, and the data are shown in tables 1-3.
TABLE 1 contents of substances in discharged water after treatment by each apparatus
Figure BDA0001730061080000131
TABLE 2 microalgae Dry weight after treatment of wastewater from pig farming
Processing apparatus EXAMPLE 1 apparatus EXAMPLE 2 apparatus EXAMPLE 3 device Continuous system
Dry weight of microalgae(g/L) 50 40 42 35
TABLE 3 film Properties of the devices
Figure BDA0001730061080000132
As can be seen from tables 1 to 3, compared with the continuous system for treating organic sewage by utilizing the microalgae of the patent CN201310192863.9, the device for culturing microalgae in sewage has better sewage treatment capability and higher microalgae concentration after culture.
The above-described embodiment of the present invention is merely illustrative of the present invention and is not restrictive thereof, and any changes within the meaning and scope equivalent to the claims of the present invention should be construed as being included in the scope of the claims.

Claims (9)

1. A sewage culture microalgae device is characterized by comprising: outer membrane A and nexine membrane B, outer membrane A and nexine membrane B are the hollow fiber membrane that is prepared by modified chitosan, modified montmorillonite and polyvinylidene fluoride and forms, outer membrane A and nexine membrane B intussuseption equipment form a hollow portion D and a middle level part C, hollow portion D comprises nexine membrane B, middle level part C is located between outer membrane A and the nexine membrane B, middle level part C fills little algae, and sewage gets into middle level part C through outer membrane A and contacts with little algae, flows out hollow portion D through nexine membrane B again, discharges from hollow portion D.
2. The sewage culture microalgae device of claim 1, wherein the preparation method of the modified chitosan comprises: weighing 50 parts of chitosan, adding the chitosan into 60mL of 95% ethanol solution for soaking, and swelling for 2 hours at the constant temperature of 60 ℃; dissolving 150 parts of vanillin in 400mL of 95% ethanol, and pouring the solution into a chitosan soaking solution to obtain a mixed solution; placing the mixed solution in a microwave rapid reaction device, setting the heating temperature to be 70 ℃, reacting for 10min, and stirring with the microwave power of 300 w; and (3) after the reaction is finished, filtering, washing with ethanol, washing with water, and drying in vacuum to constant weight to obtain modified chitosan powder.
3. The sewage culture microalgae device according to claim 1, wherein the preparation method of the modified montmorillonite is as follows: weighing 20 parts of natural montmorillonite, weighing sodium hydroxide which is 5% of the mass of the natural montmorillonite, adding 200mL of distilled water according to the solid-liquid mass ratio of 1:10, adjusting the pH to 5.6, stirring and reacting for 1h in a constant-temperature water bath at 60 ℃, drying at the constant temperature of 80 ℃, and finely grinding through a 100-mesh sieve to obtain the sodium modified montmorillonite.
4. The device for cultivating microalgae in sewage as claimed in any of claims 1-3, wherein the preparation method of the hollow fiber membrane comprises: dissolving 40-80 parts of polyvinylidene fluoride powder in 25-50 parts of dibutyl phthalate, adding 50-100 parts of modified chitosan powder, 50-100 parts of modified montmorillonite powder and 2-10 parts of genipin, stirring in an oil bath at 210-223 ℃ under the protection of nitrogen for 4-6 hours to form a uniform solution, and standing and defoaming to obtain a polymer; feeding a polymer into a double-screw extruder through a weightless scale feeder with metering precision of 5 per mill, mixing and kneading under the mixing and kneading effects of 250-300 rpm and 2-5 MPa, fully and uniformly mixing the materials to form a uniform and stable casting solution, accurately metering the casting solution into a spray head through a spinning metering pump at the speed of 90-100 g/min, taking nitrogen with the flow rate of 36-50 mL/min as a hollow support body in an inner cavity, evaporating through an air section with a certain height, then entering a 298K water bath for phase separation and solidification, and collecting a coarse hollow fiber membrane through a collecting wheel at the speed of 25 m/min; and (3) immersing the crude hollow fiber membrane into 95% industrial ethanol for 24 hours, extracting the dibutyl phthalate diluent, replacing the ethanol for 2 times in the process to ensure that the diluent is completely extracted, and rinsing the extracted hollow fiber membrane with clear water to obtain the hollow fiber membrane.
5. The device for cultivating microalgae in sewage of claim 1, wherein the width of the middle layer C is 3-7 cm.
6. The sewage culture microalgae device of claim 1, characterized in that: the microalgae filling amount is 50-70%.
7. The sewage culture microalgae device of claim 1, characterized in that: the hollow part D is not communicated with the middle layer part C.
8. The sewage culture microalgae device of claim 4, wherein: the molecular weight of the polyvinylidene fluoride is 30-40 kDa, and the concentration of the polyvinylidene fluoride is 30-35 wt%.
9. The sewage culture microalgae device of claim 4, wherein: the weight part ratio of dibutyl phthalate, modified chitosan and modified montmorillonite powder is 1:2: 2-2: 2: 5.
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