CN107585870B - A kind of method of microalgae treated sewage - Google Patents
A kind of method of microalgae treated sewage Download PDFInfo
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- CN107585870B CN107585870B CN201710938493.7A CN201710938493A CN107585870B CN 107585870 B CN107585870 B CN 107585870B CN 201710938493 A CN201710938493 A CN 201710938493A CN 107585870 B CN107585870 B CN 107585870B
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Abstract
The present invention provides a kind of method of microalgae treated sewage, 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 penetrate adsorption column by pumping suction function, sewage stops in adsorption column, it is contacted with immobilized microalgae, microalgae carries out growth and breeding using the organic nutrient substance in sewage.Sewage disposal is carried out using this method, the substances such as metal ion, carbon, nitrogen, the phosphorus in decontaminated water, while energy large-scale culturing micro-algae can be effectively removed, reach sewage disposal and microdisk electrode dual purpose.Treated, and sewage can be used for irrigating, cultivate, clean；It turns out the microalgae come and can be used for aquaculture, feed addition, plant oil extract etc..
Description
Technical field
The invention belongs to technical field of sewage, more particularly to utilize the sewage water treatment method of microalgae.
Background technology
With China's economic development, livestock and poultry cultivation sewage, municipal wastewater and increased become of trade effluent mainly pollute
Source, these discharges of sewage are big, and COD, carbon, the content of nitrogen and phosphorous are high, contain various heavy metal substances simultaneously.Traditional aerobic activity is dirty
Mud treatment technology input cost is high, and operation energy consumption is big, Treatment of Sludge trouble, and dirt cannot be fully utilized in the microorganism in activated sludge
Substance in water, in the nutriments such as 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, is both domestic and external grind using sewage as cheap culture medium large-scale cultivation treated sewage
Study carefully hot spot.A kind of continuous systems handling organic sewage 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.It should
System structure 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
Sodium hydroxide tune is added in sludge components in machine flocculant alum and organic flocculant chitosan combination technology treated sewage
The pH value of section treated sewage, after filtering sedimentation, molecular sieve goes the heavy metal ion in water removal, utilizes the work of this method processing
Industry sewage retains organic impurities, eliminates inorganic impurity and sludge components, is suitble to both culturing microalgae.Number of patent application
A kind of raceway pond microalgae cultivating systems continuing aerating collecting frustule using microbubble of CN201510418103.4, including runway
Pond, set turbulent flow carbon compensator in raceway pond, the device that continues air supporting using microbubble and collect raceway pond frustule, baffle device,
Double paddle wheels and the groove structure divided into can speed up water circulation in raceway pond by the invention, improve 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 reduces harvest cost；The carbon dioxide spread escape can be prevented, utilization rate of carbon dioxide is improved, is more rapidly adjusted
Algae solution pH；The exchange between algae solution levels can be effectively facilitated, the frustule on surface layer can be prevented by light injury, can also be increased
Add effective luminous energy total amount that the frustule of unit of water body receives；This raceway pond can realize the continuous culture of microalgae, and cultivate
The minute quantity waste water generated in the process can be led to after sterilization pool is handled with nutritive salt preparing pool by pipeline and recycle profit again
With.
The research 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 difficulty is detached.
Invention content
For in the prior art, it is unable to scale using microalgae treated sewage, micro algae growth is influenced by high-concentration sewage,
Large-scale microdisk electrode is difficult, and microalgae collects difficult, the undesirable present situation of wastewater treatment efficiency, a kind of utilization of present invention offer
The method of adsorption column combination immobilized microalgae treated sewage.
Using the present invention treated sewage, BOD ＜ 110mg/L, COD ＜ 380mg/L, suspended matter ＜ 20mg/L, ammonia nitrogen
＜ 40mg/L, total phosphorus ＜ 4mg/L.Treated, and sewage can be used for irrigating, cultivate, clean；The microalgae come is turned out to can be used for
Aquaculture, feed addition, plant oil extract etc..
The present invention is to realize in this way：
（1）Band stomata snake pipe is installed at reaction tank bottom, downward, coiled pipe is connect stomata with ozone generating-device；
（2）The preparation and installation of adsorption column：
A. 50 parts of chitosans are weighed, is added in the ethanol solution of 60ml 95% and impregnates, 60 DEG C of swelling 2h of constant temperature；（2）It will
150 parts of vanillic aldehydes are dissolved in the ethyl alcohol of 400ml 95%, and the soak for pouring into chitosan obtains mixed liquor；（3）Mixed liquor is placed
In microwave quick reaction device, 70 DEG C of heating temperature is set, reacts 10min, microwave power 300w, stirring；（4）It has reacted
At cooled and filtered, ethyl alcohol is washed, and washing is dried under vacuum to constant weight, obtains 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 are added 200ml distilled water, and it is 5.6 to adjust pH, and 1h is stirred to react for 60 DEG C in water bath with thermostatic control, the freeze-day with constant temperature at 80 DEG C, carefully
Honed 100 mesh sieve, it is modified montmorillonite used to obtain sodium；
C. it is 10 to take cell concentration5The microalgae solution of/ml, aseptically, with sodium alginate soln, modification of chitosan
1:1:1 be uniformly mixed obtain mixed liquor；Mixed liquor is instilled into calcium chloride solution by syringe and carries out 20 ~ 30min of solidification, is obtained
Calcium alginate coagulates pearl；Calcium alginate is coagulated pearl to be washed with distilled water 2 ~ 3 times, you can obtain immobilized microalgae glueballs；
The sodium alginate concentration is 20 ~ 25mg/ml；The calcium chloride solution concentration is 18 ~ 22mg/ml；
The mixed liquor is 1 with calcium chloride solution volume ratio：（1.5~2）；
D. 40 ~ 80 parts of Kynoar powder is taken, is dissolved in 25 ~ 50 parts of dibutyl phthalates, is added 50 ~ 100 parts
Modification of 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
After 4 ~ 6h of stirring is mixed into uniform solution in bath, standing and defoaming obtains polymer；Polymer is passed through into the weightlessness of 5 ‰ measuring accuracies
Scale feeder feeds double screw extruder, under the mixing kneading effect of 250 ~ 300rpm and 2 ~ 5MPa, material is made to be sufficiently mixed
Uniformly at the casting solution of stable homogeneous, casting solution enters spray by spinning pump with the speed accurate measurement of 90 ~ 100g/min
Head, inner cavity are entered using the nitrogen of 36 ~ 50ml/min flow velocitys as hollow supporting body after the evaporation of the air section of certain altitude
Phase separation and solidification occur in the water-bath of 298K, is collected thick hollow-fibre membrane by collecting wheel with the speed of 25m/min；
E. thick hollow-fibre membrane d being prepared immerses in 95% industrial alcohol 24 hours, extracts two fourth of phthalic acid
Ester diluent, during which needs to change ethyl alcohol 2 times, it is ensured that diluent extraction is clean, and the hollow-fibre membrane that extraction finishes is floated with clear water
Wash clean obtains hollow-fibre membrane.
F. hollow-fibre membrane is taken, is assembled into duplicature column, there are the space of 3 ~ 7cm wide, outermost tunic bottoms among duplicature
Portion is provided with dump valve, obtains adsorption column；
G. multiple adsorption columns are vertically fixed with brandreth, innermost layer hollow space parallel connection is connect with suction pump, is positioned over anti-
Ying Chizhong；
（3）Immobilized microalgae cell is filled in the intermediate space of adsorption column duplicature, seals adsorption column；
（4）It opens sewage pump and sewage is injected into reaction tank, when sewage is not to adsorption column 50 ~ 70%, stop pumping；It opens
Ozone generating-device, ozone aeration quantity are 15 ~ 40g/h, and action time is 10 ~ 20min/h, after ozonization 5h, open and take out
Water pump, adjusting flow are 1 ~ 1.4L/min, and 15 ~ 30min of working time, 40 ~ 60min of time of having a rest make sewage enter adsorption column
After being reacted with immobilized microalgae, the sewage after reaction is discharged into water purifying tank；
（5）After operation 4 ~ 7 days, stopping is filled with ozone, stops sewage pump, stop pumping pump, and immobilized microalgae is passed through suction
Attached column bottom-discharge valve is discharged, and collects；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 is 15 ~ 30L/h, 23 ~ 25 DEG C of temperature, elution
Liquid recycles after collecting for metal ion.
The conservation rate that the cleaning can improve tensile strength is 80% ~ 82.9%.
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 the ethanol solution of 60ml 95% and impregnates, 60 DEG C of swelling 2h of constant temperature；（2）It will
150 parts of vanillic aldehydes are dissolved in the ethyl alcohol of 400ml 95%, and the soak for pouring into chitosan obtains mixed liquor；（3）Mixed liquor is placed
In microwave quick reaction device, 70 DEG C of heating temperature is set, reacts 10min, microwave power 300w, stirring；（4）It has reacted
At cooled and filtered, ethyl alcohol is washed, and washing is dried under vacuum to constant weight, obtains modification of chitosan powder.
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
200ml distilled water is added, it is 5.6 to adjust pH, and 1h is stirred to react for 60 DEG C in water bath with thermostatic control, the freeze-day with constant temperature at 80 DEG C, fine grinding
Son is sieved with 100 mesh sieve, it is modified montmorillonite used to obtain sodium.
As a further improvement on the present invention, the immobilized microalgae preparation method is as follows：
It is 10 to take cell concentration5The microalgae solution of/ml, aseptically, with sodium alginate soln, modification of chitosan 1:
1:1 be uniformly mixed obtain mixed liquor；Mixed liquor is instilled into calcium chloride solution by syringe and carries out 20 ~ 30min of solidification, obtains sea
Calcium alginate coagulates pearl；Calcium alginate is coagulated pearl to be washed with distilled water 2 ~ 3 times, you can obtain immobilized microalgae glueballs.The alginic acid
Na concn is 20 ~ 25mg/ml；The calcium chloride solution concentration is 18 ~ 22mg/ml；The mixed liquor and calcium chloride solution body
Product is than being 1：（1.5~2）.
As a further improvement on the present invention, the Kynoar ethylene molecule amount is 30KDa ~ 40Kda, gathers inclined fluorine
Ethylene concentration is 30 ~ 35wt%.
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.
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 cures
Corresponding drop and spherulite size are smaller, and corresponding membrane aperture is smaller.
Molecular weight is the Kynoar ethylene of 30KDa ~ 40Kda, a concentration of 30 ~ 35wt%, with two fourth of phthalic acid
Ester, modification of chitosan, modified montmorillonite used powder weight part ratio 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%。
As a further improvement on the present invention, adsorption column hollow space is not communicated with two membranes intermediate space part.
As a further improvement on the present invention, immobilized microalgae loading 50 ~ 70% in the adsorption column.
As a further improvement on the present invention, the ozonization time is 5h/ days.
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 adsorbed, the sewage after absorption enters 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 removes the carbon nitrogen phosphorus substance in decontaminated water.After microalgae processing
Sewage again pass by adsorption column inner layer film after be discharged, be almost free of the polluters such as heavy metal, carbon, nitrogen, phosphorus.
Advantages of the present invention：
1. the present invention by being modified to chitosan and montmorillonite is used as membrane material, can adsorb well heavy metal from
Son can effectively adsorb Pb In Exhausted Water, every, heavy metal ion such as nickel, molybdenum, while montmorillonite also has except malicious function, further net
Change sewage.
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 adsorption column of the present invention has 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. the present invention using sewage progress microdisk electrode, can be purified to sewage and large-scale culturing micro-algae, place
Sewage after reason also can apply to other aspects with the microalgae come is turned out, and have the function that environmental protection, substance recycle.
Description of the drawings
Fig. 1 is the sewage disposal reaction tank structural schematic diagram that one embodiment of the invention is applied in production.Wherein, 1 is to have
Machine waste water pre-treatment pond；2 be aerator；3 be organic suspended matter gas floatation separation device；4 store for organic wastewater after pre-treatment
Pond；5 be laminar microalgae photosynthetic reactor；6 be mixing pit；7 be water pump；8 be microalgae flocculation basin；9 be the continuous harvesting apparatus of microalgae；
10 are spray-dried room for microalgae；11 be air-dissolved CO2Aerator.
Fig. 2 is the enlarged drawing of schematic diagram left-hand component shown in Fig. 1.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.
Specific implementation mode
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. 80 parts of Kynoar powder for taking 40Kda, 30wt%, is dissolved in 25 parts of dibutyl phthalates, is added 50
Part modification of chitosan powder, 50 parts of modified montmorillonite used powder, 2 parts of Geniposides stir 4h in 210 DEG C of oil baths under nitrogen protection
After being mixed into uniform solution, standing and defoaming obtains polymer；Polymer is fed by the Weightlessness balance feeder of 5 ‰ measuring accuracies
Double screw extruder makes material be sufficiently mixed the uniformly casting at stable homogeneous under the mixing kneading effect of 250rpm and 2MPa
Film liquid, casting solution enter nozzle by spinning pump with the speed accurate measurement of 90g/min, and inner cavity is with 36ml/min flow velocitys
Nitrogen is as hollow supporting body, into generation phase separation in the water-bath of 298K and admittedly after the evaporation of the air section of certain altitude
Change, is collected thick hollow-fibre membrane by collecting wheel with the speed of 25m/min；
B. thick hollow-fibre membrane d being prepared immerses in 95% industrial alcohol 24 hours, extracts two fourth of phthalic acid
Ester diluent, during which needs to change ethyl alcohol 2 times, it is ensured that diluent extraction is clean, and the hollow-fibre membrane that extraction finishes is floated with clear water
Wash clean obtains hollow-fibre membrane.
C. hollow-fibre membrane is taken, is assembled into duplicature column, there are the space of 7cm wide, outermost tunic bottoms among duplicature
It is provided with dump valve, obtains adsorption column；
D. multiple adsorption columns are vertically fixed with brandreth, innermost layer hollow space parallel connection is connect with suction pump, is positioned over anti-
Ying Chizhong；
The present embodiment concrete operation step is as follows：
Immobilized microalgae is filled into adsorption column, adsorption column is sealed, opens sewage pump by dairy cow farm level-one grid
Treated, and sewage injection reaction tank stops pumping when sewage is not to adsorption column 70%；Ozone generating-device is opened, ozone fills
Tolerance is 40g/h, action time 20min/h, after ozonization 5h, opens suction pump, adjusting flow is 1.4L/min, work
Make time 30min, time of having a rest 60min, so that sewage is entered after adsorption column reacted with immobilized microalgae, by the dirt after reaction
Water is discharged into water purifying tank；After operation 7 days, stopping is filled with ozone, stops sewage pump, stop pumping pump, and immobilized microalgae is passed through suction
Attached column bottom-discharge valve is discharged, and collects；Hollow-fibre membrane is cleaned 2 hours with 2wt%HCl, then uses 2000mg/L NaClO+
1000mg/L NaOH are cleaned 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, is added 30 parts
It is mixed to stir 5h in 215 DEG C of oil baths under nitrogen protection for modification of chitosan powder, 75 parts of modified montmorillonite used powder, 5 parts of Geniposides
After synthesizing uniform solution, standing and defoaming obtains polymer；Polymer is double by the Weightlessness balance feeder feeding of 5 ‰ measuring accuracies
Screw extruder makes material be sufficiently mixed the uniformly casting film at stable homogeneous under the mixing kneading effect of 280rpm and 4MPa
Liquid, casting solution enter nozzle by spinning pump with the speed accurate measurement of 100g/min, and inner cavity is with 45ml/min flow velocitys
Nitrogen is as hollow supporting body, into generation phase separation in the water-bath of 298K and admittedly after the evaporation of the air section of certain altitude
Change, is collected thick hollow-fibre membrane by collecting wheel with the speed of 25m/min；
B. thick hollow-fibre membrane d being prepared immerses in 95% industrial alcohol 24 hours, extracts two fourth of phthalic acid
Ester diluent, during which needs to change ethyl alcohol 2 times, it is ensured that diluent extraction is clean, and the hollow-fibre membrane that extraction finishes is floated with clear water
Wash clean obtains hollow-fibre membrane.
C. hollow-fibre membrane is taken, is assembled into duplicature column, there are the space of 3cm wide, outermost tunic bottoms among duplicature
It is provided with dump valve, obtains adsorption column；
D. multiple adsorption columns are vertically fixed with brandreth, innermost layer hollow space parallel connection is connect with suction pump, is positioned over anti-
Ying Chizhong；
The present embodiment concrete operation step is as follows：
It opens sewage pump and sanitary sewage is injected into reaction tank, when sewage is not to adsorption column 50%, stop pumping；It opens smelly
Oxygengenerating plant, ozone aeration quantity is 15g/h, action time 10min/h, after ozonization 5h, opens suction pump, adjusts
Flow is 1L/min, working time 15min, time of having a rest 40min, so that sewage is entered adsorption column and is reacted with immobilized microalgae
Afterwards, the sewage after reaction is discharged into water purifying tank；
After operation 4 days, stopping is filled with ozone, stops sewage pump, stop pumping pump, and immobilized microalgae is passed through adsorption column bottom
Portion's dump valve discharge, is collected, and hollow-fibre membrane is cleaned 2 hours with 4wt%HCl, then uses 2500mg/L NaClO+1500mg/L
NaOH is cleaned 2 hours, and every component cleaning flux is 22L/h, 24 DEG C of temperature.The cleaning can improve the holding of tensile strength
Rate 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, is added 100
Part modification of chitosan powder, 100 parts of modified montmorillonite used powder, 10 parts of Geniposides stir in 223 DEG C of oil baths under nitrogen protection
After 6h is mixed into uniform solution, standing and defoaming obtains polymer；Polymer is fed by the Weightlessness balance feeder of 5 ‰ measuring accuracies
Enter double screw extruder, under the mixing kneading effect of 300rpm and 5MPa, material is made to be sufficiently mixed uniformly into stable homogeneous
Casting solution, casting solution enter nozzle by spinning pump with the speed accurate measurement of 100g/min, and inner cavity is flowed with 50ml/min
Speed nitrogen be used as hollow supporting body, by certain altitude air section evaporation after into 298K water-bath in occur phase separation with
Solidification, is collected thick hollow-fibre membrane by collecting wheel with the speed of 25m/min；
B. thick hollow-fibre membrane d being prepared immerses in 95% industrial alcohol 24 hours, extracts two fourth of phthalic acid
Ester diluent, during which needs to change ethyl alcohol 2 times, it is ensured that diluent extraction is clean, and the hollow-fibre membrane that extraction finishes is floated with clear water
Wash clean obtains hollow-fibre membrane.
C. hollow-fibre membrane is taken, is assembled into duplicature column, there are the space of 5cm wide, outermost tunic bottoms among duplicature
It is provided with dump valve, obtains adsorption column；
D. multiple adsorption columns are vertically fixed with brandreth, innermost layer hollow space parallel connection is connect with suction pump, is positioned over anti-
Ying Chizhong；
The present embodiment concrete operation step is as follows：
It opens sewage pump and sanitary sewage is injected into reaction tank, when sewage is not to adsorption column 60%, stop pumping；It opens smelly
Oxygengenerating plant, ozone aeration quantity is 25g/h, action time 20min/h, after ozonization 5h, opens suction pump, adjusts
Flow is 1.2L/min, working time 20min, time of having a rest 50min, so that sewage is entered adsorption column and is carried out instead with immobilized microalgae
Sewage after reaction is discharged into water purifying tank by Ying Hou；
After operation 6 days, stopping is filled with ozone, stops sewage pump, stop pumping pump, and immobilized microalgae is passed through adsorption column bottom
Portion's dump valve discharge, is collected；Hollow-fibre membrane is cleaned 2 hours with 5wt%HCl, then uses 3000mg/L NaClO+2000mg/L
NaOH is cleaned 2 hours, and every component cleaning flux is 30L/h, 25 DEG C of temperature.The cleaning can improve the holding of tensile strength
Rate is 82.9%.In the present embodiment, immobilized microalgae loading 60% in adsorption column.
Each content of material such as table 1 in treated in above example sewage, microalgae dry weight such as table 2, doughnut film property
It can be such as table 3.
Each content of material in sewage after the processing of 1 each embodiment of table
2 each embodiment culture microalgae concentration of table
3 each embodiment doughnut film properties of table
The above embodiment of the present invention scheme is only the description of the invention and cannot limit the present invention, in the power with the present invention
Any change in the sharp comparable meaning and scope of claim, is all considered to be and is included within the scope of the claims.
Claims (6)
1. a kind of method of microalgae treated sewage, which is characterized in that include the following steps：
（1）Band stomata snake pipe is installed at reaction tank bottom, downward, coiled pipe is connect stomata with ozone generating-device；
（2）The preparation and installation of adsorption column：
A. 50 parts of chitosans are weighed, is added in the ethanol solution of 60mL 95% and impregnates, 60 DEG C of swelling 2h of constant temperature；By 150 parts of perfume (or spice)
Oxalaldehyde is dissolved in the ethyl alcohol of 400mL 95%, 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 temperature is set, reacts 10min, microwave power 300w, stirring；Reaction is completed, cooled and filtered,
Ethyl alcohol is washed, and washing is dried under vacuum to constant weight, obtains 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, it is 5.6 to adjust pH, and 1h is stirred to react for 60 DEG C 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. it is 10 to take cell concentration5The microalgae solution of/mL, aseptically, with sodium alginate soln, modification of chitosan 1:1:1
It is uniformly mixed and obtains mixed liquor；Mixed liquor is instilled into calcium chloride solution by syringe and carries out 20 ~ 30min of solidification, obtains seaweed
Sour calcium coagulates pearl；Calcium alginate is coagulated pearl to be washed with distilled water 2 ~ 3 times, you can obtain immobilized microalgae glueballs；
The sodium alginate concentration is 20 ~ 25mg/mL；The calcium chloride solution concentration is 18 ~ 22mg/mL；
The mixed liquor is 1 with calcium chloride solution volume ratio：（1.5~2）；
D. 40 ~ 80 parts of Kynoar powder is taken, is dissolved in 25 ~ 50 parts of dibutyl phthalates, 50 ~ 100 parts of modifications are added
Chitosan powder, 50 ~ 100 parts of modified montmorillonite used powder of sodium, 2 ~ 10 parts of Geniposides, under nitrogen protection in 210 ~ 223 DEG C of oil baths
After 4 ~ 6h of middle stirring is mixed into uniform solution, standing and defoaming obtains polymer；Polymer is passed through into the Weightlessness balance of 5 ‰ measuring accuracies
Feeder feeds double screw extruder, under the mixing kneading effect of 250 ~ 300rpm and 2 ~ 5MPa, material is made to be sufficiently mixed
The even casting solution at stable homogeneous, casting solution enter nozzle by spinning pump with the speed accurate measurement of 90 ~ 100g/min,
Inner cavity enters 298K using the nitrogen of 36 ~ 50mL/min flow velocitys as hollow supporting body after the evaporation of the air section of certain altitude
Water-bath in occur phase separation and solidification, thick hollow-fibre membrane is collected by collecting wheel with the speed of 25m/min；
E. thick hollow-fibre membrane d being prepared immerses in 95% industrial alcohol 24 hours, and extraction dibutyl phthalate is dilute
Agent is released, during which needs to change ethyl alcohol 2 times, it is ensured that diluent extraction is clean, and the hollow-fibre membrane that extraction is finished clear water rinses dry
It is net to obtain hollow-fibre membrane；
F. hollow-fibre membrane is taken, is assembled into duplicature column, there are the spaces of 3 ~ 7cm wide, outermost tunic bottom to set among duplicature
It is equipped with dump valve, obtains adsorption column；
G. multiple adsorption columns are vertically fixed with brandreth, innermost layer hollow space parallel connection is connect with suction pump, is positioned over reaction tank
In；
（3）Immobilized microalgae glueballs is filled in the intermediate space of adsorption column duplicature, seals adsorption column；
（4）It opens sewage pump and sewage is injected into reaction tank, when sewage is not to adsorption column 50 ~ 70%, stop pumping；Open ozone
Generating means, ozone aeration quantity are 15 ~ 40g/h, and action time is 10 ~ 20min/h, after ozonization 5h, open suction pump,
Adjusting flow is 1 ~ 1.4L/min, and 15 ~ 30min of working time, 40 ~ 60min of time of having a rest make sewage enter adsorption column and fixation
After change microalgae glueballs is reacted, the sewage after reaction is discharged into water purifying tank；
（5）After operation 4 ~ 7 days, stopping is filled with ozone, stops sewage pump, stop pumping pump, and immobilized microalgae glueballs is passed through suction
Attached column bottom-discharge valve is discharged, and collects；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 is 15 ~ 30L/h, 23 ~ 25 DEG C of temperature, elution
Liquid recycles after collecting for metal ion.
2. a kind of method of microalgae treated sewage according to claim 1, it is characterised in that：It is provided with the sun outside adsorption column
Energy LED lamp provides power supply using solar energy power accumulating plate, light source, the intensity of light source is provided for micro algae growth in rainy weather
For 6000 ~ 10000lux.
3. a kind of method of microalgae treated sewage according to claim 1, it is characterised in that：Immobilized microalgae in adsorption column
Glueballs loading 50 ~ 70%, adsorption column hollow space are not communicated with two membranes intermediate space part.
4. a kind of method of microalgae treated sewage according to claim 1, it is characterised in that：The ozonization time is 5h/
It.
5. a kind of method of microalgae treated sewage according to claim 1, it is characterised in that：The Kynoar point
Son amount is 30KDa ~ 40Kda, a concentration of 30 ~ 35wt% of Kynoar.
6. a kind of method of microalgae treated sewage according to claim 1, it is characterised in that：Dibutyl phthalate,
The modified montmorillonite used powder weight part ratio of modification of chitosan, sodium is 1:2:2~2:2:5.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104609498A (en) * | 2015-02-21 | 2015-05-13 | 桂林理工大学 | Method for dynamically adsorbing and purifying heavy metal ions in water |
| CN104630295A (en) * | 2015-03-08 | 2015-05-20 | 中国海洋大学 | Method for treating municipal secondary wastewater and producing grease by using immobilized microalgae |
| CN106186352A (en) * | 2016-07-25 | 2016-12-07 | 江苏星鑫分离设备制造有限公司 | A kind of method utilizing porous cellulose aeroge immobilized microorganism bacterium to process ammonia nitrogen waste water |
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| CN104609498A (en) * | 2015-02-21 | 2015-05-13 | 桂林理工大学 | Method for dynamically adsorbing and purifying heavy metal ions in water |
| CN104630295A (en) * | 2015-03-08 | 2015-05-20 | 中国海洋大学 | Method for treating municipal secondary wastewater and producing grease by using immobilized microalgae |
| CN106186352A (en) * | 2016-07-25 | 2016-12-07 | 江苏星鑫分离设备制造有限公司 | A kind of method utilizing porous cellulose aeroge immobilized microorganism bacterium to process ammonia nitrogen waste water |
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